4-Methylbenzoic acid (p-Toluic acid) by Asch

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Conditions

References A

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100

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D: 93%

101

With boron trifluoride diethyl etherate; water

T=80°C; 2 h; regioselective reaction;

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Zhang, Shuting; Zhang, Xiaohui; Ling, Xuege; He, Chao; Huang, Ruofeng; Pan, Jing; Li, Jiaqiang; Xiong, Yan

RSC Advances, 2014 , vol. 4, # 58 p. 30768 - 30774 Title/Abstract Full Text View citing articles Show Details

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Rx-ID: 38398434 Find similar reactions

With 1-iso-propyl-4-methylbenzene

University of Tennessee Research Foundation; Bozell, Joseph J.; Chatterjee, Sabornie

Patent: US2014/249300 A1, 2014 ; Location in patent: Page/Page column ;

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Title/Abstract Full Text Show Details

Oxidation of p-cymene

Oxidation of p-cymene p-cymene (1.34 g, 10 mmol) was mixed with Mn(NO3)2*H2O (0.06 g, 0.2 mmol) and Fe(NO3)3*9H2O (0.08 g, 0.3 mmol) according to the general procedure. Standard workup gave 0.27 g (20percent) of 4-methylbenzoic acid. The product identity was confirmed by comparing the NMR and IR spectra of the product with the reference. A

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102

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With vanadium pentoxide

T=160°C; 1 h; Hide Experimental Procedure

PERSTORP AB; LUNDMARK, Stefan; KANGAS, Matias; HÄGGMAN, Bo

Patent: WO2014/133433 A1, 2014 ; Location in patent: Page/Page column 6 ; Title/Abstract Full Text Show Details

1.1:Step 1 - gas phase oxidations

Example 1 (Step 1 - gas phase oxidations) Into a tubular reactor 2.5 cm in internal diameter and 3.5 m in length, the catalyst was packed together with an inert carrier. The tubular reactor was heated and a mixed gas containing p- cymene preheated to at least 135°C and air with an inlet temperature of 170°C, in a ratio of 100 g Nm3 (100 gram of cymene relative to 1 m3 of air at standard temperature and pressure) was fed to into the tubular reactor at a rate of 4.0 Nm3/hr. Results are given in Table 1. Three experiments (Experiment 1-3) were performed using the following reaction temperatures and reaction time: Experiment 1 : 160°C. Experiment 2: 180°C. Experiment 3: 200°C. One hour reaction time. Yielded reaction mixtures are in enclosed Table 1 reported as percent by weight.

103

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With ammonium cerium (IV) nitrate; oxygen in acetonitrile

T=20 - 50°C; 4 h; Hide Experimental Procedure

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Rx-ID: 38878301 Find similar reactions

Chang, Meng-Yang; Tsai, Chung-Yu

Tetrahedron Letters, 2014 , vol. 55, # 40 p. 5548 - 5550 Title/Abstract Full Text View citing articles Show Details

A representative synthetic procedure of skeletons 3 and 5 is as follows

General procedure: Ce(NH4)2(NO3)6 (CAN, 274 mg, 0.5 mmol) was added to a solution of β-ketosulfones 2 (0.5 mmol) in MeCN (10 mL) at rt. The reaction mixture was stirred at 50 oC for 4 h, cooled to rt, and the solvent was concentrated. The residue was diluted with water (10 mL) and the mixture was extracted with EtOAc (3 x 20 mL). The combined organic layers were washed with brine, dried, filtered and evaporated to afford crude product. Products 3 and 5 were isolated and recrystalised from EtOAc and THF.

104

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Rx-ID: 38903023 Find similar reactions

85%

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With copper(l) iodide; potassium carbonate in dimethyl sulfoxide

T=100°C; 24 h; Inert atmosphere; Hide Experimental Procedure

Zheng, Rui; Zhou, Qizhong; Gu, Haining; Jiang, Huajiang; Wu, Jiashou; Jin, Zhengneng; Han, Deman; Dai, Guoliang; Chen, Rener

Tetrahedron Letters, 2014 , vol. 55, # 41 p. 5671 - 5675 Title/Abstract Full Text View citing articles Show Details

2.1 Typical procedure for thesynthesis of aromatic carboxylic acids from arylboronic acids and acetylacetate:

General procedure: Phenylboronic acid (0.12 g, 1.0 mmol)acetyl acetate (650mg, 5.0 mmol)CuI (19 mg, 10 molpercent)K2CO3(0.28 g, 2.0 mmol) were dissolved in DMSO (5 mL, anhydrous). The solution was stirred at 100 °C under nitrogen atmosphere for 24h and then cooled and the solution was poured into HCl (40 mL, 1 mol/L). The mixture was extracted with CH2Cl2 (40 mL). Then, the solution was washed with HCl (40 mL, 1 mol/l), and dried over sodium sulfate. Upon removal of the solvent with a rotavapor, the resulting residue was subjected to column chromatography (petroleum ether/AcOEt 20:1) to give the desired product 3a(117 mg, 96percent) as a white solid. A

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105

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With ceria; oxygen in water

T=30°C; P=750.075 Torr; 24 h; Green chemistry; Catalytic behavior;

Deori, Kalyanjyoti; Gupta, Dinesh; Saha, Basudeb; Deka, Sasanka

ACS Catalysis, 2014 , vol. 4, # 9 p. 3169 - 3179 Title/Abstract Full Text View citing articles Show Details

106

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Rx-ID: 38996815 Find similar reactions

14%

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With Sn silica-based Lewis acid *BEA structure catalyst (Sn-BEA) in 1,4-dioxane

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DAVIS, MARK E.; PACHECO, JOSHUA

Patent: US2014/364631 A1, 2014 ; Location in patent: Paragraph 0180-0182 ;

T=225°C; P=52476.2 Torr; 6 h; High pressureAutoclave; Hide Experimental Procedure

Title/Abstract Full Text Show Details

4.2:Example 4.2

Four additional examples of the reactions of substituted furans are shown in FIG. 7. These are the Diels-Alder/aromatization reactions between ethylene and furoic acid, 2-acetyl-5-methylfuran, 5-methyl-2-furoic acid, and methyl 5-methyl-2-furoate to produce benzoic acid, 4-methylacetophenone, p-toluic acid, and methyl p-toluate, respectively. Each of these furanic dienes can be obtained from known methods starting from furfural, and furfural can be produced from xylose analogous to HMF production from glucose. [0181] Table 5 summarizes experiment conditions and results for these four new Diels-Alder/aromatization reactions. When methy 5-methyl-2-furoate is used as the diene, nearly 100percent selectivity to the methyl p-toluate product can be achieved. The last line shows an experiment in which pure silica *BEA catalyst was used instead of Sn-BEA and the result was no conversion, therefore showing that a Lewis acid site in the silica catalyst such as tin is required for the Diels-Alder/aromatization reaction to occur. [TABLE-US-00005] TABLE 5 Experimental conditions and results for Diels-Alder/Aromatization reactions shown in FIG. 7. In each case, reactant concentration was 0.4M in 1,4-dioxane; reaction temperature was 225° C.; total pressure was 1000 psig. For FA to BA conversion, reactant concentration was 0.2M Catalyst Time, Reactant Product (mg) hr Conversion Yield Sn-BEA (102) 6 55percent 2percent Sn-BEA (200) 6 4-Methyl- acetophenone was confirmed product in 1H NMR spectrum, but conversion and yield not quantified Sn-BEA (200) 6 82percent 14percent Sn-BEA (200) Sn-MCM- 41 (200) Sn—SiO2 (200) Si-BEA (200) 6 6 6 6 13percent 12percent 11percent 0percent 13percent 12percent 11percent

0percent The Diels-Alder/aromatization catalysts Sn-MCM-41 and Sn—SiO2 are pure silica MCM-41 containing tin and amorphous silica containing tin, respectively. Si-BEA is a pure silica-based catalyst structure. Like the experiments summarized in Table 5, the solvent used for these reactions was dioxane. The reactions are conducted in a batch reactor pressurized with ethylene gas. Conversions and yields have been determined using quantitative 1H NMR with an internal standard. [0182] This is the first report for each of these reactions in Table P1-2. Therefore, this invention allows for completely novel routes to producing these chemical products, and likely others, from biomass-derived furans such as furfural and HMF as shown in FIG. 8.

12%

Pacheco, Joshua J.; Davis, Mark E.

Proceedings of the National Academy of Sciences of the United States of America, 2014 , vol. 111, # 23 p. 8363 - 8367 Title/Abstract Full Text View citing articles Show Details

in 1,4-dioxane

T=20 - 190°C; Diels-Alder Cycloaddition; P=27752.8 - 52505.3 Torr; 6 h; Inert atmosphere; Hide Experimental Procedure

Diels-Alder Dehydration Reactions

General procedure: Experiments were carried out in a 50-mL high pressure stainless steel batch reactor (Parr Series 4590) equipped with a magnetic stirrer and heater. The reactor setup allowed for ethylene gas(Matheson, 99.995percent purity) or helium to be charged to the reactor. In a typical experiment, 100 mg of catalyst and 10 g of a 0.1 M diene solution in dioxane (Sigma-Aldrich, 99.8percent) was loaded into the reactor. The magnetic stirrer was operated at 200 rpm and the head space of the reactor was purged with helium gas with a fill/vent cycle (10×). Next, the reactor was pressurized to 37 bar (room temperature) with ethylene gas, the inlet valve was closed, and the reaction was performed in batch operation. The reactor was heated to 190 °C within 15 min while the pressure increased autogenously to 70 bar. At the end of the reaction time, the reactor was allowed to cool to room temperature and the reactor gases were vented. The product was then collected for analysis. A

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107

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Rx-ID: 39057711 Find similar reactions

With tetrakis(triphenylphosphine) palladium(0); cesium fluoride in methanol; ethylene glycol dimethyl ether

T=90°C; 16 h; Inert atmosphere;

Bunescu, Ala; Wang, Qian; Zhu, Jieping

Chemistry - A European Journal, 2014 , vol. 20, # 45 p. 14633 - 14636 Title/Abstract Full Text View citing articles Show Details

108

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Rx-ID: 9458592 Find similar reactions

97%

With dihydrogen peroxide; methyltrioxorhenium (VII); magnesium sulfate in acetonitrile

3 h; Heating;

Jain, Suman L.; Sharma, Vishal B.; Sain, Bir

Synthetic Communications, 2003 , vol. 33, # 22 p. 3875 - 3878 Title/Abstract Full Text View citing articles Show Details

85%

With sodium hypochlorite in acetonitrile

T=20°C; 5 h;

Khurana; Sharma; Gogia; Kandpal

Organic Preparations and Procedures International, 2007 , vol. 39, # 2 p. 185 - 189 Title/Abstract Full Text View citing articles Show Details

69 %Chromat.

With g-C3N4; oxygen; acetic acid in water; acetonitrile

T=100°C; P=2250.23 Torr; 16 h; AutoclaveIrradiationGreen chemistry; Hide Experimental Procedure

Zhan, Haiying; Liu, Wenjie; Fu, Minling; Cen, Jinghe; Lin, Jingxin; Cao, Hua

Applied Catalysis A: General, 2013 , vol. 468, p. 184 - 189 Title/Abstract Full Text View citing articles Show Details

General procedure for synthesis of benzil (2a)

General procedure: In a typical procedure, mpg-C3N4 (60 mg) and 2-hydroxy-1,2-diphenylethanone (1a, 1.0 mmol) were added to CH3CN (10 mL) in a 100 mL stainless steel autoclave. The O2 (3 bar) source was introduced and the closed autoclave was heated to 100 °C, followed by visible light irradiation for 16 h. The reaction mixture turned clear and the catalysts were deposited on the button, which was recovered by filtration. And then the solvent was removed, and the residue was separated by column chromatography to give the pure sample 2a.

109

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Rx-ID: 11000337 Find similar reactions

With perchloric acid; N-chlorosaccharin in water; acetic acid

T=29.84°C; 24 h; Kinetics; Further Variations:Temperaturesvarious concentrations of substrate, reagents and rations of solvents;

Farook, N. A. Mohamed

Journal of Solution Chemistry, 2007 , vol. 36, # 3 p. 345 - 356 Title/Abstract Full Text View citing articles Show Details

With potassium bromate; sulfuric acid; H2O*O(2-)*O4S(2-)*V(4+); mercury(II) diacetate; acetic acid in water

T=49.84°C; Darkness; Kinetics; ConcentrationTemperature;

Reddy, Cherkupally Sanjeeva; Manjari, Padma Sunitha

Journal of Molecular Catalysis A: Chemical, 2010 , vol. 328, # 1-2 p. 76 - 87 Title/Abstract Full Text View citing articles Show Details

With potassium bromate; manganese(II) sulfate dihydrate; sulfuric acid; mercury(II) diacetate; acetic acid in water

T=39.84°C; 24 h; KineticsMechanism; Reagent/catalystTemperatureSolventConcentration;

Reddy, Cherkupally Sanjeeva; Manjari, Padma Sunitha

Indian Journal of Chemistry - Section A Inorganic, Physical, Theoretical and Analytical Chemistry, 2011 , vol. 50, # 7 p. 979 - 990 Title/Abstract Full Text View citing articles Show Details

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With potassium bromate; ruthenium trichloride; sulfuric acid; mercury(II) diacetate in water; acetic acid

T=39.84°C; 12 h; MechanismKinetics; ConcentrationReagent/catalystTemperature;

Manjari, Padma Sunitha; Reddy, Cherkupally Sanjeeva

Transition Metal Chemistry, 2011 , vol. 36, # 7 p. 707 - 719 Title/Abstract Full Text View citing articles Show Details

With NBSacc; water; acetic acid

T=29.84°C; Kinetics; Temperature;

Mohamed Farook; Manochitra; Afroos Banu

Journal of Solution Chemistry, 2013 , vol. 42, # 1 p. 239 - 250 Title/Abstract Full Text View citing articles Show Details

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110

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A: 89.2%

With carbon dioxide; oxygen; N-hydroxysuccinimide; anhydrous cobalt diacetate in acetic acid

T=60°C; P=44269 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

University of Kansas

Patent: US2008/139841 A1, 2008 ; Location in patent: Page/Page column 4 ; Title/Abstract Full Text Show Details

Example 4; Oxidation of p-Xylene Using CAT and NHSI at 60° C.; In this example, a solution of 0.1168 g (1.01 mmol) of N-hydroxysuccinimide, 0.5348 g (5.05 mmol) p-xylene and 0.0756 g (0.3 mmol) of CAT in 40 ml of acetic acid was heated to 60° C. in a Parr Hastelloy reactor with a temperature and pressure transducer. After the temperature reached 60° C., 506 psi of CO2 was introduced to the reactor, then 350 psi of O2 was slowly added to the reactor. A rapid temperature rise (due to heat generated by the exothermic oxidation) within roughly six minutes following O2 introduction, accompanied by a drop in reactor pressure (due to consumption of O2 in the liquid phase reaction) indicated rapid reaction after induction. These profiles are steep and level off within minutes after induction. The mixture was stirred under pressure for one hour at 60° C., then cooled to room temperature after releasing the pressure. The white solid TPA was filtered, the filtrate analyzed by HPLC using biphenyl as an internal standard. The solid TPA product was washed by acetic acid (20 ml) and dried in an oven at 120° C. for six hours to yield TPA (0.75 g, 89.2percent). A similar product analysis was found, see example 2.

A: 79.77% B: 0.67% C: 0.3%

With oxygen; N-hydroxysuccinimide; anhydrous cobalt diacetate in acetic acid

T=25 - 125°C; P=12049.9 - 44475.9 Torr; 1 - 6 h; Product distribution / selectivity; Hide Experimental Procedure

University of Kansas

Patent: US2008/139841 A1, 2008 ; Location in patent: Page/Page column 4; 9 ; Title/Abstract Full Text Show Details

2; 3; 26:

Example 2; Oxidation of p-Xylene Using CAT and NHSI at 100° C.; In this example, a solution of 0.1158 g (1.01 mmol) of N-hydroxysuccinimide, 0.5199 g (4.9 mmol) of p-xylene and 0.1273 g (0.511 mmol) CAT in 40 ml of acetic acid was heated to 100° C. in a Parr Hastelloy reactor fitted with temperature and pressure controllers. After the temperature reached 100° C., 860 psi of air was slowly introduced into the reactor. The mixture was stirred under pressure for one hour at 100° C., the pressure was released, and the mixture cooled to room temperature. Within roughly 15 minutes following O2 introduction, a rapid temperature rise occurred (due to heat generated by the exothermic oxidation) accompanied by a drop in reactor pressure (due to consumption of O2 in the liquid phase reaction) indicating rapid reaction. These profiles are steep and level off within minutes after induction (typical T and P profiles will be provided in the patent application). The white solid of terephthalic acid (TPA) was filtered, and the filtrate analyzed by HPLC using biphenyl as the internal standard. The solid TPA product was washed with additional acetic acid (20 ml) and dried in an oven at 120° C. for six hours to obtain 0.795 g of TPA (yield: 98percent based on the initial moles of p-xylene reacted). Analysis: 97.7percent TPA, 2.0percent carboxybenzaldehyde (CBA), and 0.3percent p-toluic acid (PTA).; Example 3; Oxidation of p-Xylene Using CAT and NHSI at 60° C.; In this example, a solution of 0.1208 g (1.05 mmol) of N-hydroxysuccinimide, 0.5291 g (4.99 mmol) of p-xylene and 0.1142 g (0.46 mmol) of CAT in 40 ml of acetic acid was heated to 60° C. in a Parr Hastelloy reactor with temperature and pressure transducer. After the temperature reached 60° C., 233 psi of air was slowly introduced into the reactor. The mixture was stirred under pressure for one hour at 60° C., then the pressure was released, and the mixture was cooled to room temperature. A rapid temperature rise (due to heat generated by the exothermic oxidation) within roughly 20 minutes following O2 introduction, accompanied by a drop in reactor pressure (due to consumption of O2 in the liquid phase reaction) indicated rapid reaction. The white solid TPA was filtered, and the filtrate analyzed by HPLC using biphenyl as the internal standard. The solid TPA product was washed with acetic acid (20 ml) and dried in an oven at 120° C. for six hours to yield TPA (0.75 g, 95percent). Analytical solid component results: 96.4percent TPA, 0.78percent CBA, and 2.81percent PTA.; Example 26; Temperature Effect; In this example, the effect of temperature on yield was investigated. The reaction comprised p-xylene 0.32 mol/L, Co(OAc)2 1.01.x.10-2 mol/L, NHSI 2.1.x.10-2 mol/L oxygen, 30 ml acetic acid in a 50 ml Parr Hastelloy reactor for six hours. The results are in Table 2.

A: 74%

With carbon dioxide; oxygen; N-hydroxysuccinimide; cobalt(II) 2,4-pentanedionate in acetic acid

T=60°C; P=49337.2 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

University of Kansas

Patent: US2008/139841 A1, 2008 ; Location in patent: Page/Page column 4-5 ; Title/Abstract Full Text Show Details

Example 5; Oxidation of p-Xylene Using Anhydrous Cobalt Acetate and NHSI at 60° C.; In this example, a solution of 0.1168 g (1.01 mmol) of N-hydroxysuccinimide, 0.5256 g (4.96 mmol) p-xylene and 0.078 g (0.3 mmol) of Co(acac)2 in 40 ml of acetic acid was heated to 60° C. in a Parr Hastelloy reactor with a temperature and pressure transducer. After the temperature reached 60° C., 614 psi of CO2 was introduced to the reactor, then 340 psi of O2 was slowly added to the reactor. The mixture was stirred under pressure for one hour at 60° C., then cooled to room temperature after releasing the pressure. A rapid temperature rise (due to heat generated by the exothermic oxidation) within roughly six minutes following O2 introduction, accompanied by a drop in reactor pressure (due to consumption of O2 in the liquid phase reaction) indicates rapid reaction after induction. The white solid TPA was filtered, the filtrate was analyzed by HPLC using biphenyl as the internal standard. The solid TPA product was washed with acetic acid (20 ml) and dried in an oven at 120° C. for six hours to yield TPA (0.75 g, 74percent). The product analysis was similar to that given in Example 2. Hide Details

A: 16% B: 13% C: 38%

With hydrochlorid acid; oxygen; [Acr+-Mes]ClO4- in acetonitrile

T=4.84°C; 13 h; Irradiation;

Ohkubo, Kei; Mizushima, Kentaro; Fukuzumi, Shunichi

Research on Chemical Intermediates, 2013 , vol. 39, # 1 p. 205 - 220 Title/Abstract Full Text View citing articles Show Details

A: 28.8%

With ([MnIII(5,10,15,20-tetra(4-chlorophenyl)porphyrin)]chloride); [Co(O2CCH3)2]*4H2O

T=190°C; P=9000.9 Torr; 5 h; Neat (no solvent)Autoclave;

Xiao, Yang; Zhang, Xiaoyan; Wang, Qin Bo; Tan, Ze; Guo, Can Cheng; Deng, Wei; Liu, Zhi Gang; Zhang, He Fei

Chinese Chemical Letters, 2011 , vol. 22, # 2 p. 135 - 138 Title/Abstract Full Text View citing articles Show Details

A: 26%

With carbon dioxide; oxygen; N-hydroxysuccinimide; zirconium tetraacetylacetonate; anhydrous cobalt diacetate in acetic acid

T=80°C; P=48613.2 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

University of Kansas

Patent: US2008/139841 A1, 2008 ; Location in patent: Page/Page column 5 ; Title/Abstract Full Text Show Details

Example 6; Oxidation of p-Xylene Using CAT and NHSI at 80° C.; In this example, a solution of 0.1032 g (0.9 mmol) of N-hydroxysuccinimide, 0.5165 g (4.87 mmol) p-xylene, 0.1137 g (0.46 mmol) of CAT and 0.0591 g (0.12 mmol) of Zr(acac)4 in 40 ml of acetic acid was heated to 80° C. in a Parr Hastelloy reactor with a temperature and pressure transducer. After the temperature reached 80° C., 580 psi of CO2 was introduced into the reactor, then 360 psi of O2 was slowly added to the reactor. A rapid temperature rise (due to heat generated by the exothermic oxidation) within roughly three minutes following O2 introduction, accompanied by a drop in reactor pressure (due to consumption of O2 in the liquid phase reaction) indicates rapid reaction induction. These profiles are steep and level off within minutes after induction. The mixture was stirred under pressure for one hour at 80° C., then cooled to room temperature after releasing the pressure. The white solid of TPA was filtered, and the filtrate analyzed by HPLC using biphenyl as the internal standard. The solid TPA product was washed with extra acetic acid (20 ml) and dried in an oven at 120° C. for six hours to yield TPA (0.75 g, 26percent). A product analysis was similar to that obtained in Example 2. A: 17.3% B: 0.9% C: 5.3%

With oxygen; Manganese (II) acetate; cobalt(II) dibromide in water; acetic acid

T=115 - 190°C; P=11400.8 Torr; 0.666667 - 3 h; Product distribution / selectivity; Hide Experimental Procedure

1; 2; 3; 4; 5; 4; 9; 6; 7; 8; 9:

KOCAT INC.

Patent: US2008/91043 A1, 2008 ; Location in patent: Page/Page column 3-4; 6 ; Title/Abstract Full Text Show Details

Comparative Example 1The experiment was conducted same as in Example 1 except that the volumetric ratio of O2/CO2 in the O2/CO2 mixed gas was changed to 21percent/79percent. The final products were also analyzed as described in Example 1.The yield of TA was increased to 58.2percent, and 2.7percent of 4-CBA and 30.1percent of p-toluic acid were observed. It was ascertained that the conversion and the selectivity are drastically lowered as compared to Examples 1-3.; Comparative Example 2The experiment was conducted same as in Example 1 except that the volumetric ratio of O2/CO2 in the O2/CO2 mixed gas was changed to 26percent/74percent. The final products were also analyzed as described in Example 1.The yield of TA was increased to 67.1percent, and 3.9percent of 4-CBA and 21.2percent of p-toluic acid were observed. It was ascertained that the conversion and the selectivity are drastically lowered as compared to Examples 1-3.; Comparative Example 3The experiment was conducted same as in Example 1 except that the volumetric ratio of O2/CO2 in the O2/CO2 mixed gas was changed to 28percent/72percent. The final products were also analyzed as described in Example 1.The yield of TA was increased to 69.7percent, and 2.5percent of 4-CBA and 12.7percent of ptoluic acid were observed. It was ascertained that the conversion and the selectivity are drastically lowered as compared to Examples 1-3.; Example 4The experiment was conducted same as in Example 1 except that the oxidation temperature was changed to 135° C. The final products were also analyzed as described in Example 1.As shown in TABLE 3, the yield of TA is 78.5percent, and traces of impurities such as 4-CBA and p-toluic acid were observed, which were completely removed by increasing the reaction time to 3 hours. It was ascertained that the conversion is much improved as compared to Comparative Example 4. The color of the products (i.e. white) is also advantageous over Comparative Example 5 despite the relatively lower conversion and selectivity. The dark yellow color of solid products in Comparative Example 5 is due to large amount of color impurities such as 2,6-DCAq (2,6-dicarboxyanthraquinone).; Example 5The experiment was conducted same as in Example 1 except that the oxidation temperature was changed to 145° C. The final products were also analyzed as described in Example 1.The yield of TA is 89.7percent, and traces of impurities such as 4-CBA and p-toluic acid were observed, which were completely removed by increasing the reaction time to 3 hours. It was ascertained that the conversion and the selectivity are much improved as compared to Comparative Example 4. The color of the products (i.e. white) is also advantageous over Comparative Example 5.; Comparative Example 4The experiment was conducted same as in Example 1 except that the oxidation temperature was changed to 115° C. The final products were also analyzed as described in Example 1.The yield of TA is 17.3percent, and 2.6percent of 4-CBA and 29.3percent of p-toluic acid were observed. It was ascertained that the conversion and the selectivity are drastically lowered as compared to Examples 4-8, and that the color impurities were not completely removed although the reaction is conducted for 3 hours.; Example 9The experiment was conducted same as in Example 1 except that the content of the O2/CO2 mixed gas was changed to 30percent of O2, 40percent of CO2 and 30percent of Ar. The final products were also analyzed as described in Example 1.The yield of TA was 80.3percent, and small amounts of impurities such as 4-CBA and p-toluic acid were observed, which were completely removed by increasing the reaction time to 1.5 hours. It was ascertained that the conversion is much improved as compared to Comparative Example 6, where N2 was used instead of Ar. This result shows that the oxidation reaction is not inhibited by Ar but by N2.; Comparative Example 6The experiment was conducted same as in Example 9 except that the content of the O2/CO2 mixed gas was changed to 30percent of O2, 40percent of CO2 and 30percent of N2. The final products were also analyzed as described in Example 1.The yield of TA was 41.0percent, and 1.8percent of 4-CBA and 31.7percent of p-toluic acid were observed, which were not completely removed although the reaction is conducted for 2 hours. This result shows that N2 inhibits the oxidation reaction regardless of the reaction time.; Comparative Example 7The experiment was conducted same as in Example 9 except that the content of the O2/CO2 mixed gas was changed to 30percent of O2 and 70percent of N2. The final products were also analyzed as described in Example 1.The yield of TA was 39.1percent, and 4.0percent of 4-CBA and 54.8percent of p-toluic acid were observed, which were not completely removed although the reaction is conducted for 2 hours. In particular, 4-CBA was produced in a remarkably large amount as compared to Comparative Example 6.; Comparative Example 8The experiment was conducted same as in Example 10 except the oxidation time was changed to 40 minutes. The final products were also analyzed as described in Example 1.As shown in TABLE 5, the yield of TA was 60.8percent, and 3.3percent of 4-CBA and 19.1percent of p-toluic acid were observed.; Comparative Example 9The experiment was conducted same as in Example 10 except the volumetric ratio of O2/CO2 was changed to 30percent/70percent and that the oxidation time was changed to 40 minutes. The final products were also analyzed as described in Example 1.As shown in TABLE 5, the yield of TA was 42.2percent, and small amounts of 4-CBA and p-toluic acid were observed, which were completely removed by increasing the reaction time to 1 hour.

With oxygen; anhydrous cobalt diacetate in water

T=130°C; 6 h; Product distribution / selectivity; Hide Experimental Procedure

Saxena, Mahendra Pratap; Gupta, Ashok Kumar; Sharma, Satish Kumar; Bangwal, Dinesh Prasad; Kumar, Krishan

Patent: US2006/247464 A1, 2006 ; Location in patent: Page/Page column 2-3 ; Title/Abstract Full Text Show Details

1; 2; 5; 7; 8:

EXAMPLE-1; p-Xylene, (30 g), p-toluic acid (5.0 g), cobaltous acetate (5.0 g) and water (150 g) were charged in an autoclave. This reactor was then pressurized with oxygen to about 15 kg/cm2 pressure and heated to 130° C. The pressure of the reactor was maintained at 20 kg/cm2 with continuous stirring and exit oxygen flow rate at 75 ml/min. After 6 hr of reaction, the reactor was cooled, the contents were filtered and washed with toluene. Total unreacted p-xylene was determined from organic phase and content of a toluene trap (kept after the reactor where through exit gases passed during the reaction) by analyzing these by gas chromatography. Solid product was also analysed by G.C. Analysis of reaction products/stream indicated 65.41percent conversion of p-xylene into oxygenated products (mole percent) as p-toluic acid (p-TA), 82.39percent, 4carboxybenzaldehyde (4-CBA) 1.82percent, terephthalic acid (TPA), 13.50percent and others 1.35percent.; EXAMPLE-2; p-Xylene (30.0 g), was oxidized with oxygen at 150° C. in the presence of 5.0 g p-TA, 5.0 g cobaltous acetate and 150 g water. The reaction was carried out as in Example-1. 78.23percent Of p-xylene was converted into p-TA, 90.56percent; 4-CBA, 2.75percent; TPA, 6.32percent and others 0.30percent.; EXAMPLE-5; p-Xylene (30.0 g) was oxidized with molecular oxygen at 130° C. in the presence of 10.04 g p-TA, 5.0 g of cobaltous acetate as catalyst and 150 g of water as solvent. The reaction was carried out and worked up as in example-1. 72.2percent Of p-xylene was converted into oxygenated compounds as p-TA, 77.53percent, 4CBA, 4.75percent, TPA, 16.98percent and others 0.73percent.; EXAMPLE-7; p-Xylene (30.0 g) was oxidized with oxygen at 130° C. in the presence of 10.0 g p-TA, 5.0 g of cobaltous acetate as catalyst and 150 g water as solvent. Reaction was carried out at 10 kg/cm2 pressure and worked up as in example-1. 73.38percent Of p-xylene was converted into oxygenated compounds as p-TA, 82.88percent, 4-CBA, 2.87percent and TPA, 14.25percent.; EXAMPLE -8; p-Xylene (30.0 g) was oxidized with oxygen at 130° C. in the presence of 5.0 g of p-TA, 5.02 g of cobaltous acetate and 50 g of water as solvent. Reaction was carried out at 20 kg/cm2 pressure and worked up as in example-1. 67.46percent Of p-xylene was converted into oxygenated compounds as p-TA, 78.99percent; 4-CBA, 1.46percent; TPA, 16.24percent and others 3.3percent.

With oxygen; anhydrous cobalt diacetate; cerium triacetate in water

T=130°C; 6 h; Product distribution / selectivity; Hide Experimental Procedure

Saxena, Mahendra Pratap; Gupta, Ashok Kumar; Sharma, Satish Kumar; Bangwal, Dinesh Prasad; Kumar, Krishan

Patent: US2006/247464 A1, 2006 ; Location in patent: Page/Page column 3 ; Title/Abstract Full Text Show Details

EXAMPLE-6; p-Xylene (30.0 g) was oxidized with molecular oxygen at 130° C., under the experimental conditions mentioned in example-5 except that a mixture of 0.31 g of cerous acetate and 4.48 g of cobaltous acetate was used as catalyst. 67.34percent Of p-xylene got converted into oxygenated compounds as p-TA, 84.68percent, 4-CBA, 2.04percent and TPA, 13.22percent.

With oxygen; anhydrous cobalt diacetate in water

T=130 - 150°C; 6 h; Acidic conditions; Product distribution / selectivity; Hide Experimental Procedure

COUNCIL OF SCIENTIFIC and INDUSTRIAL RESEARCH

Patent: WO2006/103693 A1, 2006 ; Location in patent: Page/Page column 6-8 ; Title/Abstract Full Text Show Details

1; 2; 5; 7; 8:

Example -1 p-Xylene, (30 g), p-toluic acid (5.0 g), cobaltous acetate (5.0 g) and water (150 g) were charged in an autoclave. This reactor was then pressurized with oxygen to about 15 kg/cm2 pressure and heated to 13O C. The pressure of the reactor was maintained at 20 kg/cm2 with continuous stirring and exit oxygen flow rate at 75 ml/min. After 6 hr of reaction, the reactor was cooled, the contents were filtered and washed with toluene.Total unreacted p-xylene was determined from organic phase and content of a toluene trap (kept after the reactor where through exit gases passed during the reaction) by analyzing these by gas chromatography. Solid product was also analysed by G. C.Analysis -of reaction products/ stream indicated 65.41percent conversion of p-xylene into oxygenated products (molepercent) as p-toluic acid (p-TA), 82.39percent, 4carboxybenzaldehyde(4-CBA) 1.82percent, terephthalic acid (TPA), 13.50percent and others 1.35percent.Example - 2 p-Xylene (30.Og), was oxidized with oxygen at 150 C in the presence of 5.0 g p-TA, 5.0 g cobaltous acetate and 150 g water. The reaction was carried out as in Example-1.78.23percent Of p-xylene was converted into p-TA, 90.56percent; 4-CBA, 2.75percent; TPA, 6.32percent and others 0.30percent.Example -5 p-Xylene (30.Og) was oxidized with molecular oxygen at 13O C in the presence of 10.04 g p-TA, 5.0 g of cobaitous acetate as catalyst and 150 g of water as solvent. The reaction was carried out and worked up as in example-1. 72.2percent Of p-xylene was converted into oxygenated compounds as p-TA, 77.53percent, 4CBA, 4.75percent, TPA, 16.98percent and others 0.73percent.Example -7 p-Xylene (30.Og) was oxidized with oxygen at 13O C in the presence of 10.0 g p-TA, 5.0 g of cobaltous acetate as catalyst and 15O g water as solvent. Reaction was carried out at 10 kg/cm2 pressure and worked up as in example-1. 73.38percent Of p-xylene was converted into oxygenated compounds as p-TA, 82.88percent, 4-CBA, 2.87percent and TPA,14.25percent.Example -8 p-Xylene (30.Og) was oxidized with oxygen at 13O C in the presence of 5.Og of p-TA,5.02 g of cobaltous acetate and 50 g of water as solvent. Reaction was carried out at20 kg/cm2 pressure and worked up as in example-1. 67.46percent Of p-xylene was converted into oxygenated compounds as p-TA, 78.99percent; 4-CBA, 1.46percent; TPA, 16.24percent and others 3.3percent.

With oxygen; anhydrous cobalt diacetate; cerium triacetate

T=130 - 150°C; 6 h; Acidic conditions; Product distribution / selectivity; Hide Experimental Procedure

COUNCIL OF SCIENTIFIC and INDUSTRIAL RESEARCH

Patent: WO2006/103693 A1, 2006 ; Location in patent: Page/Page column 7 ; Title/Abstract Full Text Show Details

4; 6:

Example-4 p-Xylene (30.01 g) was oxidized with oxygen at 15O C in the presence of 4.4 g cobaltous acetate and 0.3 g cerium(lll)acetate as catalyst in 15O g of water. The reaction was carried out and worked up as in example-1. In the absence of p-TA but in the presence of cerium with cobalt. 20.05percent Of p-xylene was converted into oxygenated compounds. White solid product was found consisting of p-TA 96.62percent terephthalic acid0.42percent and others 2.96percent.Example -6 p-Xylene (30.Og) was oxidized with molecular oxygen at 13O0C, under the experimental conditions mentioned in example-5 except that a mixture of 0.31 g of cerous acetate and 4.48 g of cobaltous acetate was used as catalyst. 67.34percent Of p-xylene got converted into oxygenated compounds as p-TA, 84.68percent, 4-CBA, 2.04percent and TPA,13.22percent.

With hydrogen bromide; oxygen; acetic acid; zirconium tetraacetate; anhydrous cobalt diacetate; Manganese (II) acetate in water

T=195 - 235°C; 0.3 - 0.8 h; Product distribution / selectivity; Hide Experimental Procedure

COBARR S.P.A.

Patent: WO2007/66365 A1, 2007 ; Location in patent: Page/Page column 9-10; 11-12; 13 ; Title/Abstract Full Text Show Details

1; 4; 5; 6; 10; 12; 13; 14; 15; 16; 17; 18; 19; 8; 9; 11:

Example 1The reactor was charged with 2.5 g p-xylene, 150 g acetic acid containing 10 wtpercent H2O, 0.100 g Co (CH3COO)2.4H2O and Mn (II) acetate, Zr (IV) acetate, HBr (47percent solution in H2O) in the atomic ratio Co:Mn: Zr:Br = 1:0.6:0.05:1.7. The mixture was oxidized with air (flow 0.5 1/min) at 195°C for 20 minutes, then during 3 min the temperature was increased to 2100C and at this temperature oxidation proceeded for 22 min to reach complete conversion of p-xylene. The HPLC analysis of terephthalic acid determined that it contained 11 ppm of 4-CBA and 4 ppm of p- toluic acid. The color parameter L* was 95.8.Examples 4 to 7The procedure of Example 1 was repeated except that the mixture was oxidized with air at 195 0C for 15 min and at 210 0C for 7 min. The composition of the catalysts in the experiments was changed as illustrated in Table

1.Table 1The results unambiguously demonstrate the very high influence of the catalyst composition on the purity of the formed terephthalic acid. A very high purity of PTA is reached only if the concentration of manganese varies in a certain range. In the absence of manganese (Exp. No. 7) the rate of oxidation is very low and PTA is practically not formed.Examples 8 to 11The procedure of example 4 was repeated except that the composition of the catalysts in the experiment was changed as is illustrated in Table 2 <n="12"/>Table 2These results clearly show that the synergistic effect of zirconium is strongly influenced by the atomic ratio of Co:Mn in the oxidation catalysts. When the ratio of Co:Mn is 1:1.2, the synergistic effect of zirconium on the purity of terephthalic acid is negligible.Example 12The reactor was charged with 2.5 g p-xylene, 150 g acetic acid containing 5 wtpercent H2O, 0.120 g cobalt acetate tetrahydrate and Mn (II) acetate, Zr (IV) acetate, HBr (47percent solution in H2O) in the atomic ratio Co:Mn: Zr:Br = 1: 0.2:0.1:1.35. The flow of air used for oxidation of p-xylene was during the oxidation changed in the range 1.5 to 0.05 1/min depending on the oxygen content in the off-gas. The mixture was oxidized at 1950C for 7 min, then during 2 min the temperature was

increased to 2050C and at this temperature oxidation proceeded for 9 min (total reaction time 18 min) . The obtained terephthalic acid contained 24 ppm of 4-CBA and 6 ppm of p- toluic acid. <n="13"/>The experiment demonstrates that at specific reaction conditions and composition of the catalyst it is possible to obtain high purity PTA at the temperature 205 0C in the last stage of oxidationExample 13 (comparative)The procedure of Example 12 was repeated except that oxidation of p-xylene was carried out isothermally at 2050C for 18 min. The terephthalic acid contained 42 ppm of 4-CBA and 6 ppm of p-toluic acid. The color parameter L* is 93.1.The comparison of results of experiments 12 and 13 confirms that isothermal oxidation of p-xylene produces terephthalic acid with lower purity than step-wise oxidation at different temperatures .Examples 14 to 17The procedure of Example 4 was repeated except that the composition of the catalysts in experiments was Co:Mn:Zr = 1:0.6:0.1 and the atomic ratio Co:Br was changed as is described in Table 3.Table 3 <n="14"/>As is seen from the results, the concentration of bromine in the reaction system must be optimal in order to obtain high purity PTA.Example 18The reactor was charged with 5.0 g p-xylene, 150 g acetic acid containing 5 wtpercent water, 0.20 g cobalt acetate tetrahydrate and Mn (II) acetate, Zr (IV) acetate, HBr (47percent solution in H2O) in the atomic ratio Co:Mn:Zr:Br = 1:0.6:0.1:2.3. The flow of air was during oxidation changed in the range 1.5 to 0.05 1/min depending on the oxygen content in the off-gas. The mixture was oxidized at 1900C for 10 min, then during 5 min the temperature increased to 22O0C and at this temperature oxidation

proceeded for 5 min. In the next step the inlet of air flow was stopped and during 8 min the reaction mixture is heated to 235 0C and at this temperature stirred for 20 min. The formed terephthalic acid contained 33 ppm of 4-CBA and 5 ppm of p-toluic acid.Example 19 (Comparative)The procedure of Example 18 was repeated except that the reaction mixture after the oxidation reaction was not heated to 2350C. The formed terephthalic acid contains 117 ppm of 4-CBA and 27 ppm of p-toluic acid. The results of Examples 18 and 19 confirm that the subsequent heating of the reaction mixture in the absence of air increases its purity.Examples 8 to 11The procedure of example 4 was repeated except that the composition of the catalysts in the experiment was changed as is illustrated in Table 2 <n="12"/>Table 2These results clearly show that the synergistic effect of zirconium is strongly influenced by the atomic ratio of Co:Mn in the oxidation catalysts. When the ratio of Co:Mn is 1:1.2, the synergistic effect of zirconium on the purity of terephthalic acid is negligible.

With hydrogen bromide; oxygen; acetic acid; anhydrous cobalt diacetate; Manganese (II) acetate in water

T=195 - 210°C; 0.75 h; Product distribution / selectivity; Hide Experimental Procedure

COBARR S.P.A.

Patent: WO2007/66365 A1, 2007 ; Location in patent: Page/Page column 9 ; Title/Abstract Full Text Show Details

Example 2The procedure of Example 1 was repeated except that hafnium was employed instead of zirconium in the amount corresponding to the atomic ratio Co:Mn:Hf:Br = 1:0.6:0.1:1.7. The terephthalic acid contained 14 ppm of 4-CBA and 5 ppm of p-toluic acid.

With hydrogen bromide; oxygen; acetic acid; anhydrous cobalt diacetate; Manganese (II) acetate in water

T=195 - 210°C; 0.75 h; Product distribution / selectivity; Hide Experimental Procedure

COBARR S.P.A.

Patent: WO2007/66365 A1, 2007 ; Location in patent: Page/Page column 9-10 ; Title/Abstract Full Text Show Details

Example 3 (Comparative)The procedure of Example 1 was repeated except that no zirconium was added. The quality of produced terephthalic acid in <n="11"/>the absence of Zr or Hf is lower. The PTA contained 89 ppm of 4-CBA and 6 ppm of p-toluic acid.

With oxygen; acetic acid; hydrogen bromide; anhydrous cobalt diacetate; Manganese (II) acetate in water

T=195°C; P=36978.7 Torr; 0.333333 h; Product distribution / selectivity; Hide Experimental Procedure

BP CORPORATION NORTH AMERICA INC.

Patent: WO2008/67112 A2, 2008 ; Location in patent: Page/Page column 22 ; Title/Abstract Full Text Show Details

10; 11:

Examples 10-16A series of oxidations was conducted similar to that described for Example 1 , except that the concentration of catalyst was varied, while the molar ratio of Co/Mn/Br catalyst components was fixed at 1/1/1. The results are shown in Table 3.

With oxygen; anhydrous cobalt diacetate; Manganese (II) acetate; 1-ethyl-3-methylimidazolium chloride in acetic acid

T=215 - 220°C; P=13501.4 - 14251.4 Torr; 2 h; Conversion of starting material; Hide Experimental Procedure

SAUDI BASIC INDUSTRIES CORPORATION; SABIC PETROCHEMICALS B.V.

Patent: WO2008/74497 A1, 2008 ; Location in patent: Page/Page column 9-10 ; Title/Abstract Full Text Show Details

Example 1; The experimental set-up includes a 1000 ml continuous stirred tank reactor, provided with mechanical stirrers, a gas delivery tube, a reflux condensor, a thermocouple, and a rupture disc. The reactor is heated by 5 circulating hot oil from a temperature controlled oil bath. The exit gases are passed through a trap for further analyses. The reactor and other relevant equipment are made from Hastealloy C.In this experiment pxylene was oxidised with air as oxidant, using acetic acid as solvent, a combination of cobalt acetate tetrahydrate and o manganese acetate tetrahydrate as catalyst, and 1-ethyl-3-methylimidazolium bromide as promoter.The following experimental procedure was applied: a) Perform a leak test by filling the reactor with nitrogen at 2.0 MPa for 30 min and check for leaks; 5 b) Charge 40 g of p-xylene to the reactor using a dosing pump at rate of 5 ml/min; c) Charge 200 g of acetic acid to the reactor at rate of 10 ml/min; d) Charge 10 g of catalyst and promoter solution [having Co+2 concentration of 0.02 wtpercent (on solvent), Co+2 / Mn+2 mass ratio of 1/5, and BrV (Co+2 + Mn+2) o ratio of 1.0/1.0] to the reactor at a rate of 1.0 ml/min; e) Start the agitator slowly and set at 100-150 rpm; f) Set the condenser temperature at 850C by circulating the hot oil from the bath; g) Inject nitrogen at flow rate of 50 ml/hr and maintain reactor pressure at 1.8 5 MPa; h) Heat the reactor to 2150C by circulating hot oil from the bath and maintain pressure of 1.8 MPa with a pressure control valve; i) After temperature has reached 215 0C close nitrogen line and inject air at1.8 MPa, at a flow rate of 50 ml/hr; 0 j) Check the O2 and CO2 concentration in the off-gas with online gas analyzers; adjust air flow rate or

temperature such that [O2] is in the range of2.0-2.5 vol percent and [CO2] is 1.3-1.5 vol percent; <n="11"/>k) Continue the reaction for 120 min, and maintain the reactor temperature between 215-22O0C and pressure 1.8-1.9 MPa (monitor temperature and pressure continuously);I) Record the temperature and control the exothermicity of reaction; stop air flow if reactor temperature increase above 2250C; m) After 120 minutes start cooling the reactor down to 2O0C by lowering hot oil bath temperature; n) Vent the gases slowly by opening valve; o) Remove the slurry product by opening bottom drain valve and collect it in a glass beaker; p) Filter using buchner funnel and separate the solid CTA product and mother liquor at room temperature in hood; q) Dry wet cake at 9O0C in oven for 2 hours; r) Sample product and mother liquor for analysis.The conversion of pxylene was found to be virtually 100percent. Gas chromatography on exit gas showed no detectable methylbromide. A further qualitative experiment was performed by passing the vent gases through silver nitrate solution; up on which no change in solution occurred, indicating that presumably no methylbromide was formed. In Table 1 the analyses results of the recovered solid product as determined by HPLC are given. HMWC means higher molecular weights compounds.From the observation that no methylbromide nor brominated by products were found, it can be concluded that the bromide remains bounded in the ionic liquid compound, and does not form bromine-containing compounds that can cause corrosion. In addition the ionic liquid can be separated from the solid product stream, such that no bromine-containing compounds will be present in the product stream.

With oxygen; caesium acetate; anhydrous cobalt diacetate; Manganese (II) acetate; 1-ethyl-3-methylimidazolium chloride in acetic acid

T=215 - 220°C; P=13501.4 - 14251.4 Torr; 2 h; Conversion of starting material; Hide Experimental Procedure

SAUDI BASIC INDUSTRIES CORPORATION; SABIC PETROCHEMICALS B.V.

Patent: WO2008/74497 A1, 2008 ; Location in patent: Page/Page column 10-11 ; Title/Abstract Full Text Show Details

Example 2; The procedure as described for Example 1 was repeated, but additionally cesium acetate was added, in such amount that BrVCs+ molar ratio <n="12"/>was 1. The results on the recovered TPA product are depicted in Table 1 , and demonstrate that addition of an alkali metal like cesium further improves catalyst performance; e.g. reduces the level of undesirable impurities.

With hydrogen bromide; oxygen; anhydrous cobalt diacetate; Manganese (II) acetate; benzoic acid in water

T=234.99°C; P=36961.4 Torr; 0.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2008/194866 A1, 2008 ; Location in patent: Page/Page column 4-5 ; Title/Abstract Full Text Show Details

With oxygen; acetic acid; palladium diacetate; stannous acetate in water

T=169°C; P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 13-14; 22 ; Title/Abstract Full Text Show Details

EXAMPLES 1-4; Weighed amounts of palladium(II) acetate, antimony(III) acetate and tin(II) acetate salts or stock solutions in various combinations were measured into a 10 mL Teflon reaction tube together with amounts of para-xylene, acetic acid and water (95percent acetic acid and 5percent water by weight of the combination thereof) providing a total liquid volume of 7.5 mL. A Teflon stir bar was inserted into the reaction tube and the reaction tube was placed into a thermostatted reactor block. The reactor block was closed, sealing the reaction tube. Headspace in the reaction tube was purged with nitrogen under pressure of 14 bars. The reactor block was used to heat the reaction tube to 170° C., after which air flow into the reaction tube at 1.8 L/min and mixing at 1000 rpm were begun. After 60 minutes, stirring and air flow were stopped and the reactor block and reaction tube were allowed to cool to room temperature. Contents of the reaction tube were removed and dissolved in dimethyl sulfoxide. Samples were analyzed for major product intermediates and impurities by high pressure liquid chromatography (HPLC).Conditions and results of the oxidations are reported in TABLE 1. Amounts of metals and metalloids used in the oxidations are expressed in parts per million by weight of the acetic acid and water used in the oxidations. Para-xylene ("PX") conversions reported in the table are expressed as moles of converted para-xylene per mole of para-xylene starting material reduced by para-xylene contents of condensed overhead vapors from the oxidations, which typically ranged up to 5percent of the initial charge. Selectivities shown in the table are percentages, by weight, of terephthalic acid ("TA"), 4carboxybenzaldehyde ("4CBA") and p-toluic acid ("PTOL"), respectively, of the converted products weight. As seen from the table, conversions of para-xylene to carboxylic acid derivatives using binary combinations of palladium with tin or antimony without bromine in Examples 1 and 2 were far greater than that with tin and antimony in Control 1. Conversions in Examples 1 and 2 were also significantly greater than those in trials using each of palladium, antimony and tin alone in Controls 11-13 reported below. Surprisingly, the catalytic compositions used in Examples 4 and 5, which contained palladium, antimony and tin, showed still greater conversion of the para-xylene feed to carboxylic acid derivatives, including nearly quantitative conversion in Example 3, in combination with low levels of carbon oxides.

With oxygen; acetic acid; palladium diacetate; tris(acetylacetonato)vanadium(III); nickel diacetate; antimony triacetate in water

T=171°C; P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 21-22 ; Title/Abstract Full Text Show Details

43-8:

EXAMPLE 43; Following the procedure of Examples 1-4, a series of para-xylene oxidation trials in aqueous acetic acid solvent was conducted using compositions prepared from various combinations of one or more acetic acid soluble salts of palladium, platinum, vanadium, titanium, molybdenum, chromium, tin, antimony and, in some cases, acetic acid-soluble salts of one or more of additional metal or metalloid or standardized solutions thereof in aqueous acetic acid in amounts providing the metals or metalloids in about equal parts by weight corresponding to about 500 ppmw based on weight of acetic acid solvent used in the oxidations. Metal and metalloid combinations, temperatures and oxidation results are reported in TABLE 14; results of Examples 1-4 are also included for reference.

With oxygen; acetic acid; tris(acetylacetonato)vanadium(III); diacetoxy-platinum; silver(I) acetate in water

P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

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43-21:

With oxygen; acetic acid; palladium diacetate; tris(acetylacetonato)vanadium(III); antimony triacetate; chromium (III) ethanoate in water

T=171°C; P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

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43-9:

With oxygen; acetic acid; palladium diacetate; tris(acetylacetonato)vanadium(III); stannous acetate; antimony triacetate in water

T=170°C; P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

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43-6:

With oxygen; acetic acid; palladium diacetate; tris(acetylacetonato)vanadium(III); [Mo2(acetate)4]; antimony triacetate in water

T=175°C; P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

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43-5:

thereof in aqueous acetic acid in amounts providing the metals or metalloids in about equal parts by weight corresponding to about 500 ppmw based on weight of acetic acid solvent used in the oxidations. Metal and metalloid combinations, temperatures and oxidation results are reported in TABLE 14; results of Examples 1-4 are also included for reference.

With oxygen; acetic acid; tris(acetylacetonato)vanadium(III); diacetoxy-platinum; antimony triacetate in water

P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

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43-15:

With oxygen; acetic acid; titanium(IV) oxide bis(2,4-pentanedionate); tris(acetylacetonato)vanadium(III); diacetoxy-platinum in water

P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

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43-14:

With oxygen; acetic acid; tris(acetylacetonato)vanadium(III); diacetoxy-platinum in water

P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

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43-16:

With oxygen; acetic acid; tris(acetylacetonato)vanadium(III); diacetoxy-platinum; [Mo2(acetate)4] in water

P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

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43-12:

With oxygen; acetic acid; tris(acetylacetonato)vanadium(III); diacetoxy-platinum; gallium acetate in water

P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

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43-19:

With oxygen; acetic acid; tris(acetylacetonato)vanadium(III); diacetoxy-platinum in water

P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

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43-22:

43-7:

With oxygen; acetic acid; palladium diacetate; [Mo2(acetate)4]; anhydrous calcium acetate; antimony triacetate in water

T=173°C; P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

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With oxygen; acetic acid; palladium diacetate; stannous acetate; antimony triacetate; chromium (III) ethanoate in water

T=170°C; P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

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43-4:

With oxygen; acetic acid; palladium diacetate; [Mo2(acetate)4]; stannous acetate; chromium (III) ethanoate in water

T=172°C; P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

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43-10:

With oxygen; acetic acid; palladium diacetate; [Mo2(acetate)4]; stannous acetate; antimony triacetate in water

T=170°C; P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

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43-1:

With oxygen; acetic acid; palladium diacetate; stannous acetate; antimony triacetate in water

T=147 - 168°C; P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

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3; 4:

With oxygen; acetic acid; titanium(IV) oxide bis(2,4-pentanedionate); palladium diacetate; antimony triacetate in water

T=166 - 170°C; P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

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43-2; 43-3:

With oxygen; acetic acid; titanium(IV) oxide bis(2,4-pentanedionate); palladium diacetate; diacetoxy-platinum in water

P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

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43-24:

With oxygen; acetic acid; palladium diacetate; diacetoxy-platinum; [Mo2(acetate)4] in water

P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 21-22 ;

Title/Abstract Full Text Show Details

43-20:

Stage #1: With sodium hydroxide; hydrogen bromide; anhydrous cobalt diacetate; Manganese (II) acetate

Samsung General Chemicals Co., Ltd.

Patent: EP1140765 B1, 2005 ; Location in patent: Page/Page column 13; 14 ;

Stage #2: para-xylene With oxygen in water; acetic acid

T=185°C; 1.01667 h; Hide Experimental Procedure

Title/Abstract Full Text Show Details

24; 25:

To a 10 liter capacity titanium pressure reactor, the reactants and oxidation feed gas, air, were introduced to carry out an oxidation reaction in a continuous manner. The composition of the reactants was 4percent of water, 13percent of para-xylene and 81percent of acetic acid. The catalyst was comprised of, on the basis of the total weight of the reactants, 100 ppm of cobalt, 200 ppm of manganese and 300 ppm of bromine. Cobalt acetate tetrahydrate, manganese acetate tetrahydrate, and hydrogen bromide were used. The reaction temperature was 185°C, and the residence time in the reactor was 61 minutes. Air was supplied therein so that the flow rate of air corresponded to the amount that the mole ratio of oxygen to para-xylene was 3.0. As for the additive alkali metal or alkaline earth metal components, the amount of sodium hydroxide was adjusted so that the concentration of Na became 30 ppm. After reaching a steady state, the reaction was carried out for 8 hours. Table 4 shows the compositions of the solid which was obtained after cooling and solid-liquid separation. In comparison with the case without sodium (Comparative Example 6), it showed that the concentration of the terephthalic acid product was increased in the products, and that of para-toluic acid was decreased. Further, the analytic results of oxygen, carbon dioxide and carbon monoxide in the vent gas are shown in Table 4. The oxygen concentration in vent gas decreased, and this means that the catalytic activity increased with the addition of an alkali additive metal, sodium. Judging from the results on the same level of oxygen consumption, it is clear that the side reactions are also suppressed at least attributing to a decrease in the production rates of carbon dioxide and carbon monoxide (refer to the COx/O2 conversion)

Stage #1: With hydrogen bromide; potassium acetate; anhydrous cobalt diacetate; Manganese (II) acetate

Samsung General Chemicals Co., Ltd.

Patent: EP1140765 B1, 2005 ; Location in patent: Page/Page column 13; 14 ;

Stage #2: para-xylene With oxygen in water; acetic acid

T=185°C; 1.01667 h; Hide Experimental Procedure

Title/Abstract Full Text Show Details

26; 27:

The oxidation of para-xylene was carried out in the identical manner to Example 24, except that the additive metals and its concentrations were varied as described in Table 4, respectively. The results of these runs are summarized in Table 4 and are compared with the case without additive metals (Comparative Example 6, Table 4). It showed that the amounts of terephthalic acid contained in the products increased while those of paratoluic acid were decreased. The concentrations of oxygen remained in the vent gas were decreased, revealing that the catalytic activity increased with an alkali additive metal, sodium or potassium. The content of terephthalic acid contained in the solid products increased as the additive concentration increased from 50 ppm to 100 ppm (see Example 26 and 27), whereas the amount of both para-toluic acid and 4-CBA included in the product were correspondingly declined. This trend becomes much more conspicuous if the results of these runs are compared with that of Comparative Example 6

Stage #1: With hydrogen bromide; anhydrous cobalt diacetate; Manganese (II) acetate

Samsung General Chemicals Co., Ltd.

Patent: EP1140765 B1, 2005 ; Location in patent: Page/Page column 14 ;

Stage #2: para-xylene With oxygen in water; acetic acid

T=185°C; 1.01667 h; Hide Experimental Procedure

Title/Abstract Full Text Show Details

6:Comparative Example 6

The oxidation reaction of para-xylene was carried out in the identical manner to Example 24, except that the reaction was conducted without additive metals. Judging from the amount of oxygen remained in the vent gas stream and the composition of the harvested solid product, it is safe to conclude that the catalytic activity is low. The contents of terephthalic acid and p-toluic acid in the solid product obtained in this control run were 44.3percent (against 54.~59.3percent for Examples 24~27, Table 4) and 51.3percent (against 36.3percent~40.8percent for Examples 27~24, Table 4), respectively

With N-(t-butoxycarbonyloxy)-phthalimide; oxygen; anhydrous cobalt diacetate; Manganese (II) acetate; acetic acid

T=99.84°C; P=750.075 Torr; 24 h;

Falcon; Campos-Martin; Al-Zahrani; Fierro

Catalysis Communications, 2010 , vol. 12, # 1 p. 5 - 8 Title/Abstract Full Text View citing articles Show Details

A: 73.4 %Chromat. B: 8.6 %Chromat. C: 5.7 %Chromat.

With oxygen; acetic acid

T=120°C; P=123762 Torr; 2 h; Supercritical conditions;

Zuo, Xiaobin; Niu, Fenghui; Snavely, Kirk; Subramaniam, Bala; Busch, Daryle H.

Green Chemistry, 2010 , vol. 12, # 2 p. 260 - 267 Title/Abstract Full Text View citing articles Show Details

A: 35 %Chromat. B: 9 %Chromat. C: 52 %Chromat.

With cerium(IV) oxide; oxygen in water

T=70°C; P=750.075 Torr; 25 h; Catalytic behaviorKinetics; TimeConcentration;

Deori, Kalyanjyoti; Gupta, Dinesh; Saha, Basudeb; Awasthi, Satish K.; Deka, Sasanka

Journal of Materials Chemistry A, 2013 , vol. 1, # 24 p. 7091 - 7099 Title/Abstract Full Text View citing articles Show Details

111

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A: 17 %Spectr. B: 60 %Spectr. C: 17 %Spectr.

With oxygen

T=80°C; pH=9; 4 h; aq. buffer;

Saio, Daisuke; Amaya, Toru; Hirao, Toshikazu

Advanced Synthesis and Catalysis, 2010 , vol. 352, # 13 p. 2177 - 2182 Title/Abstract Full Text View citing articles Show Details

With Au0.95Ag0.05; oxygen; sodium carbonate

T=39.84°C; 1 h; Catalytic behavior; Hide Experimental Procedure

Huang, Xuemin; Wang, Xueguang; Tan, Mingwu; Zou, Xiujing; Ding, Weizhong; Lu, Xionggang

Applied Catalysis A: General, 2013 , vol. 467, p. 407 - 413 Title/Abstract Full Text View citing articles Show Details

Catalyst reaction

General procedure: The oxidation of alcohols was carried out with O2 in a three-necked flask of 50 mL with a reflux condenser with a magnetic stirrer. Typically, 3 mmol of Na2CO3 was firstly dissolved in 30 mL of metal nanoparticle colloid completely. The solution was heated at the set temperature with an accuracy of ± 0.1 K and bubbled with pure O2 (30 mL/min) for 60 min. Then, the desired amount of alcohol was added into the reaction mixture and started the oxidation reaction under vigorous stirring by bubbling O2. The reactions were monitored by sampling the reaction mixture (0.5 mL) at fixed intervals. The reaction mixture was immediately quenched with a 2 M HCl aqueous solution (0.5 mL) and extracted with ethyl acetate (5 mL) for 3 times. The obtained organic layer was dried with Na2SO4 and analyzed by a CP-3800 gas chromatography with FID detector using the external standard method. The overall organic mass balance based on the starting reactants was more than 95percent. A

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112

Synthesize Find similar Rx-ID: 34669144 Find similar reactions

Multi-step reaction with 2 steps 1: sodium azide / N,N-dimethyl-formamide / 0.5 h / 10 - 15 °C 2: trichlorophosphate / N,N-dimethyl-formamide / 10 - 95 °C View Scheme

Shah, Shailesh R.; Navathe, Sudhanva S.; Dikundwar, Amol G.; Guru Row, Tayur N.; Vasella, Andrea T.

European Journal of Organic Chemistry, 2013 , # 2 p. 264 - 267 Title/Abstract Full Text View citing articles Show Details

113

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With trichlorophosphate in N,N-dimethyl-formamide

T=10 - 95°C; Vilsmeier Reaction;

Shah, Shailesh R.; Navathe, Sudhanva S.; Dikundwar, Amol G.; Guru Row, Tayur N.; Vasella, Andrea T.

European Journal of Organic Chemistry, 2013 , # 2 p. 264 - 267 Title/Abstract Full Text View citing articles Show Details

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114

Synthesize Find similar Rx-ID: 35848569 Find similar reactions

A: 61 %Chromat. B: 6 %Chromat. C: 19 %Chromat. D: 11 %Chromat.

With cerium(IV) oxide; oxygen in water

T=95°C; P=750.075 Torr; 12 h; Catalytic behaviorKinetics; TimeTemperatureConcentration;

Deori, Kalyanjyoti; Gupta, Dinesh; Saha, Basudeb; Awasthi, Satish K.; Deka, Sasanka

Journal of Materials Chemistry A, 2013 , vol. 1, # 24 p. 7091 - 7099 Title/Abstract Full Text View citing articles Show Details

115

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Multi-step reaction with 2 steps 1.1: potassium carbonate / 0.25 h / 20 °C 1.2: 63 °C

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Rx-ID: 35996454 Find similar reactions

Khaibulova, T. Sh.; Boyarskaya; Boyarskii

Russian Journal of Organic Chemistry, 2013 , vol. 49, # 3 p. 360 - 365 Zh. Org. Khim., 2013 , vol. 49, # 3 p. 373 - 378

2.1: potassium hydroxide / methanol / 2 h / 63 °C View Scheme

Title/Abstract Full Text View citing articles Show Details

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116

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Rx-ID: 36031121 Find similar reactions

With acetic acid in water

T=30°C; KineticsMechanism; ConcentrationTemperature;

Mohamed Farook; Alhaji; Uduman Mohideen; Seyed Dameen; Mitu, Liviu; Abshana Begam

Journal of Solution Chemistry, 2013 , vol. 42, # 6 p. 1183 - 1193 Title/Abstract Full Text View citing articles Show Details

117

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87%

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Rx-ID: 36212096 Find similar reactions

With tert.-butylhydroperoxide; potassium tert-butylate in water

T=80°C; 8 h; Hide Experimental Procedure

Shaikh, Tanveer Mahammadali; Hong, Fung-E

Tetrahedron, 2013 , vol. 69, # 42 p. 8929 - 8935 Title/Abstract Full Text View citing articles Show Details

4.1.2 Typical experimental procedure for oxidation of diols to carboxylic acids (3a–t)

General procedure: In a 25mL round-bottom flask, t-BuOK (1.5mmol) was dissolved in water (0.5mL), and diol (0.5mmol) was added. Subsequently, aq 70percent TBHP (2mmol) was slowly added to this flask. The resulting suspension was then heated at 80°C (using oil bath) for 8h. After completion of reaction this slurry was cooled to room temperature. The slurry was then acidified with 2M hydrochloric acid until the aqueous layer was strongly acidic by pH paper. This on simple filtration resulted in pure carboxylic acids. Note: alternate work-up procedure: The reaction mixture was then cooled to room temperature and then extracted with ethyl acetate (2×10mL) and combined organic phase was washed with saturated brine solution and dried over anhydrous Na2SO4. After removal of the solvent under reduced pressure to afford carboxylic acids. A

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118

Synthesize Find similar Rx-ID: 36449137 Find similar reactions

Multi-step reaction with 2 steps 1: ethyl acetate / 20 °C / |Heating 2: sodium carbonate / 5 h / 145 °C View Scheme

Tamboli, Majid I.; Krishnaswamy, Shobhana; Gonnade, Rajesh G.; Shashidhar, Mysore S.

Chemistry - A European Journal, 2013 , vol. 19, # 38 p. 12867 - 12874 Title/Abstract Full Text View citing articles Show Details

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119

Synthesize Find similar Rx-ID: 36449138 Find similar reactions

A: 19% B: 67% C: 46% D: 14%

With sodium carbonate

T=145°C; 5 h;

Tamboli, Majid I.; Krishnaswamy, Shobhana; Gonnade, Rajesh G.; Shashidhar, Mysore S.

Chemistry - A European Journal, 2013 , vol. 19, # 38 p. 12867 - 12874 Title/Abstract Full Text View citing articles Show Details

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120

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Rx-ID: 36461714 Find similar reactions

A: 74%

With potassium phosphate; copper quinolate; tetra-(n-butyl)ammonium iodide in water; dimethyl sulfoxide

T=120°C; 24 h;

Zhu, Yan; Yan, Hong; Lu, Linhua; Liu, Defu; Rong, Guangwei; Mao, Jincheng

Journal of Organic Chemistry, 2013 , vol. 78, # 19 p. 9898 - 9905 Title/Abstract Full Text View citing articles Show Details

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121

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Find similar

Rx-ID: 36709724 Find similar reactions

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With oxygen; potassium carbonate in tetrahydrofuran

T=60°C; 12 h; Green chemistry; Reagent/catalyst;

Soule, Jean-Francois; Miyamura, Hiroyuki; Kobayashi, Shu

Chemistry - An Asian Journal, 2013 , vol. 8, # 11 p. 2614 - 2626 Title/Abstract Full Text View citing articles Show Details

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122

Synthesize Find similar

Rx-ID: 3536996 Find similar reactions

With palladium diacetate; acetic acid

T=100°C; P=11250.9 Torr; 20 h; Yield given. Yields of byproduct given. Title compound not separated from byproducts;

Jintoku, Tetsuro; Fujiwara, Yuzo; Kawata, Itaru; Kawauchi, Tomio; Taniguchi, Hiroshi

Journal of Organometallic Chemistry, 1990 , vol. 385, # 2 p. 297 - 306 Title/Abstract Full Text View citing articles Show Details

A: 1.2 % Chromat. B: 92.6 % Chromat. C: 6.2 % Chromat.

With oxygen; tetracarbonylbis(μ-chloro)dirhodium(I); trifluoroacetic acid; trifluoroacetic anhydride

T=138 - 140°C; 2 h;

Kalinovskii, I. O.; Lescheva, A. A.; Kuteinikova, M. M.; Gel'bshtein, A. I.

J. Gen. Chem. USSR (Engl. Transl.), 1990 , vol. 60, # 1.2 p. 123 - 130,108 - 113 Title/Abstract Full Text Show Details

With palladium diacetate; dipotassium peroxodisulfate; trifluoroacetic acid

P=760 Torr; 20 h; Ambient temperature; Yield given. Yields of byproduct given. Title compound not separated from byproducts;

Taniguchi, Yuki; Yamaoka, Yoshinori; Nakata, Kazuyuki; Takaki, Ken; Fujiwara, Yuzo

Chemistry Letters, 1995 , # 5 p. 345 - 346 Title/Abstract Full Text Show Details

Hide Details

With oxygen; trifluoroacetic acid; trifluoroacetic anhydride; tetracarbonylbis(μ-chloro)dirhodium(I); anhydrous copper acetate

T=107 - 156°C; 2 h; analogous reaction of other benzene derivatives; other Rh complexes; Pd complexes; other Cu salts; Fe, Co and Ni compounds; acetic acid and acetic anhydride instead of CF3COOH and (CF3CO)2O; different pCO and pO2; Product distribution;

Kalinovskii, I. O.; Lescheva, A. A.; Kuteinikova, M. M.; Gel'bshtein, A. I.

J. Gen. Chem. USSR (Engl. Transl.), 1990 , vol. 60, # 1.2 p. 123 - 130,108 - 113 Title/Abstract Full Text Show Details

A: 1.6 % Chromat. B: 76.6 % Chromat. C: 21.8 % Chromat.

With oxygen; copper diacetate; tetracarbonylbis(μ-chloro)dirhodium(I); trifluoroacetic acid; trifluoroacetic anhydride

T=140°C; 2 h;

Kalinovskii, I. O.; Lescheva, A. A.; Kuteinikova, M. M.; Gel'bshtein, A. I.

J. Gen. Chem. USSR (Engl. Transl.), 1990 , vol. 60, # 1.2 p. 123 - 130,108 - 113 Title/Abstract Full Text Show Details

A: 25.0 % Chromat. B: 68.2 % Chromat. C: 11.8 % Chromat.

With oxygen; copper diacetate; tetracarbonylbis(μ-chloro)dirhodium(I); trifluoroacetic acid; trifluoroacetic anhydride

T=139°C; 2 h;

Kalinovskii, I. O.; Lescheva, A. A.; Kuteinikova, M. M.; Gel'bshtein, A. I.

J. Gen. Chem. USSR (Engl. Transl.), 1990 , vol. 60, # 1.2 p. 123 - 130,108 - 113 Title/Abstract Full Text Show Details

With palladium diacetate; dipotassium peroxodisulfate in trifluoroacetic acid

20 h; Ambient temperature; Yield givenYields of byproduct given. Title compound not separated from byproducts;

Lu, Wenjun; Yamaoka, Yoshinori; Taniguchi, Yuki; Kitamura, Tsugio; Takaki, Ken; Fujiwara, Yuzo

Journal of Organometallic Chemistry, 1999 , vol. 580, # 2 p. 290 - 294 Title/Abstract Full Text View citing articles Show Details

With ammonium metavanadate; palladium (II) trifluoroacetate; oxygen; trifluoroacetic acid; trifluoroacetic anhydride

T=79.84°C; P=5175.52 Torr; 4 h; Autoclave; Kinetics;

Behn, Andrew; Zakzeski, Joseph; Head-Gordon, Martin; Bell, Alexis T.

Journal of Molecular Catalysis A: Chemical, 2012 , vol. 361-362, p. 91 - 97 Title/Abstract Full Text View citing articles Show Details

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123

Synthesize Find similar Rx-ID: 8750257 Find similar reactions

With tert.-butylhydroperoxide; air; K6[SiW11Co(H2O)O39]*14H2O in water

T=180°C; catalytic liquid phase oxidation; P=20685.9 Torr; Product distribution; Further Variations:TemperaturesReagentsSolvents;

Alekar; Gopinathan

Indian Journal of Chemistry - Section A Inorganic, Physical, Theoretical and Analytical Chemistry, 2000 , vol. 39, # 4 p. 439 - 441 Title/Abstract Full Text View citing articles Show Details

With C41H37BrCl2MnN3O6; oxygen

T=120°C; 14 h; Kinetics; Reagent/catalyst;

Li, Jian-Zhang; Yang, Zhu-Zhu; He, Xi-Yang; Zeng, Jun; Zhang, Jin

Journal of Chemical Research, 2012 , vol. 36, # 7 p. 425 - 428 Title/Abstract Full Text View citing articles Show Details

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124

Synthesize Find similar Rx-ID: 11141809 Find similar reactions

125

With air; cyclohexene; carbon

24 h; Heating;

Sereda, Grigoriy; Rajpara, Vikul

Tetrahedron Letters, 2007 , vol. 48, # 19 p. 3417 - 3421 Title/Abstract Full Text View citing articles Show Details

With 4-(N,N-dimethlyamino)pyridine; oxygen; benzyl bromide

T=160°C; P=7500.75 Torr; 3 h; Autoclaveneat (no solvent);

Zhang, Zhan; Gao, Jin; Wang, Feng; Xu, Jie

Molecules, 2012 , vol. 17, # 4 p. 3957 - 3968 Title/Abstract Full Text View citing articles Show Details

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96 %Chromat.

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Rx-ID: 32439886 Find similar reactions

With water in acetonitrile

Photolysis; Hide Experimental Procedure

Jana, Avijit; Ikbal, Mohammed; Singh, N.D. Pradeep

Tetrahedron, 2012 , vol. 68, # 4 p. 1128 - 1136 Title/Abstract Full Text View citing articles Show Details

4.8. Preparative photolysis

General procedure: A solution of caged compound (4a-h) and (7b-d) (0.05 mmol) in acetonitrile/H2O (75/25) individually was irradiated using the procedure described under deprotection photolysis. The irradiation was monitored by TLC at regular intervals. After completion of photolysis, solvent was removed under vacuum and the photoproducts (3-(hydroxymethyl)perylene, and the corresponding carboxylic acid or alcohol) were isolated by column chromatography using increasing percentage of EtOAc in hexane as an eluant. A

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126

Synthesize Find similar Rx-ID: 33041753 Find similar reactions

Wang, Zhi-Zhong; Ma, Xuan-Ping; Wei, Xiao-Gang

E-Journal of Chemistry, 2012 , vol. 9, # 3 p. 1562 - 1568 Title/Abstract Full Text View citing articles Show Details

Hydrolysis;

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127

Synthesize Find similar Rx-ID: 33041754 Find similar reactions

Hydrolysis;

Wang, Zhi-Zhong; Ma, Xuan-Ping; Wei, Xiao-Gang

E-Journal of Chemistry, 2012 , vol. 9, # 3 p. 1562 - 1568 Title/Abstract Full Text View citing articles Show Details

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128

Synthesize Find similar Rx-ID: 33456272 Find similar reactions

With 4-(N,N-dimethlyamino)pyridine; oxygen; benzyl bromide

T=170°C; P=7500.75 Torr; 3 h; Autoclaveneat (no solvent);

Zhang, Zhan; Gao, Jin; Wang, Feng; Xu, Jie

Molecules, 2012 , vol. 17, # 4 p. 3957 - 3968 Title/Abstract Full Text View citing articles Show Details

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129

Synthesize Find similar Rx-ID: 33456273 Find similar reactions

With 1-bromo-butane; 4-(N,N-dimethlyamino)pyridine; oxygen

T=160°C; P=7500.75 Torr; 3 h; Autoclaveneat (no solvent);

Zhang, Zhan; Gao, Jin; Wang, Feng; Xu, Jie

Molecules, 2012 , vol. 17, # 4 p. 3957 - 3968 Title/Abstract Full Text View citing articles Show Details

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130

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Rx-ID: 33456274 Find similar reactions

With 4-(N,N-dimethlyamino)pyridine; oxygen; benzyl bromide

T=160°C; P=7500.75 Torr; 3 h; Autoclave;

Zhang, Zhan; Gao, Jin; Wang, Feng; Xu, Jie

Molecules, 2012 , vol. 17, # 4 p. 3957 - 3968

Title/Abstract Full Text View citing articles Show Details

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131

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Rx-ID: 33611541 Find similar reactions

With water

T=25°C; Solvolysis; Kinetics; Concentration;

Bentley, T. William; Koo, In Sun

Arkivoc, 2012 , vol. 2012, # 7 p. 25 - 34 Title/Abstract Full Text View citing articles Show Details

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132

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Rx-ID: 34033595 Find similar reactions

Multi-step reaction with 2 steps 1: triethylamine / dichloromethane / 12 h / 20 °C 2: water; methanol / |UV-irradiation; |Photolysis View Scheme

Ikbal, Mohammed; Banerjee, Rakesh; Atta, Sanghamitra; Jana, Avijit; Dhara, Dibakar; Anoop, Anakuthil; Singh, N. D. Pradeep

Chemistry - A European Journal, 2012 , vol. 18, # 38 p. 11968 - 11975 Title/Abstract Full Text View citing articles Show Details

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133

Synthesize Find similar Rx-ID: 34033609 Find similar reactions

B: 92%

Ikbal, Mohammed; Banerjee, Rakesh; Atta, Sanghamitra; Jana, Avijit; Dhara, Dibakar; Anoop, Anakuthil; Singh, N. D. Pradeep

Chemistry - A European Journal, 2012 , vol. 18, # 38 p. 11968 - 11975 Title/Abstract Full Text View citing articles Show Details

in methanol; water

UV-irradiationPhotolysis; Quantum yield;

134

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Rx-ID: 34280738 Find similar reactions

Matic, Mirela; Denegri, Bernard; Kronja, Olga

Journal of Organic Chemistry, 2012 , vol. 77, # 20 p. 8986 - 8998,13 Title/Abstract Full Text Show Details

in ethanol; dichloromethane

T=25°C; Kinetics;

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135

Synthesize Find similar Rx-ID: 34500711 Find similar reactions

Ikbal, Mohammed; Banerjee, Rakesh; Atta, Sanghamitra; Dhara, Dibakar; Anoop, Anakuthil; Singh, N. D. Pradeep

Journal of Organic Chemistry, 2012 , vol. 77, # 23 p. 10557 - 10567 Title/Abstract Full Text View citing articles Show Details

in acetonitrile

4 h; IrradiationPhotolysis; Quantum yield;

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136

Synthesize Find similar Rx-ID: 34767608 Find similar reactions

A: 27% B: 31%

With Mn(OAc)3*H2O in ethanol; water

T=50°C; 6 h;

Wang, Chao; Li, Zhilong; Ju, Yeming; Koo, Sangho

European Journal of Organic Chemistry, 2012 , # 35 p. 6976 - 6985

C: 12%

Title/Abstract Full Text View citing articles Show Details

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137

Synthesize Find similar Rx-ID: 34767617 Find similar reactions

Multi-step reaction with 3 steps 1.1: sodium hydride / toluene / 0.5 h / |Reflux 2.1: sodium hydride / tetrahydrofuran / 1 h / 0 °C 2.2: 20 °C 3.1: Mn(OAc)3*H2O / ethanol; water / 6 h / 50 °C View Scheme

Wang, Chao; Li, Zhilong; Ju, Yeming; Koo, Sangho

European Journal of Organic Chemistry, 2012 , # 35 p. 6976 - 6985 Title/Abstract Full Text View citing articles Show Details

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138

Synthesize Find similar Rx-ID: 34767618 Find similar reactions

Multi-step reaction with 2 steps 1.1: sodium hydride / tetrahydrofuran / 1 h / 0 °C 1.2: 20 °C 2.1: Mn(OAc)3*H2O / ethanol; water / 6 h / 50 °C View Scheme

Wang, Chao; Li, Zhilong; Ju, Yeming; Koo, Sangho

European Journal of Organic Chemistry, 2012 , # 35 p. 6976 - 6985 Title/Abstract Full Text View citing articles Show Details

139

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Rx-ID: 2009283 Find similar reactions

97%

With tetrabutylammomium bromide; dicobalt octacarbonyl in sodium hydroxide; benzene

T=65°C; 1 h; Irradiation;

Brunet, Jean-Jacques; Sidot, Christian; Caubere, Paul

Journal of Organic Chemistry, 1983 , vol. 48, # 8 p. 1166 - 1171 Title/Abstract Full Text View citing articles Show Details

97%

With sodium hydroxide; tetrabutylammomium bromide; dicobalt octacarbonyl in water; benzene

T=65°C; P=760 Torr; 1.5 h; Irradiation;

Brunet, Jean-Jacques; Sidot, Christian; Caubere, Paul

Tetrahedron Letters, 1981 , vol. 22, p. 1013 - 1016 Title/Abstract Full Text View citing articles Show Details

77%

With palladium diacetate; caesium carbonate; α,α'-bis(di-t-butylphosphino)-o-xylene in water; N,N-dimethyl-formamide

T=80°C; P=2068.65 Torr; Inert atmosphere;

McNulty, James; Nair, Jerald J.; Sliwinski, Marcin; Robertson, Al J.

Tetrahedron Letters, 2009 , vol. 50, # 20 p. 2342 - 2346 Title/Abstract Full Text View citing articles Show Details

Hide Details

75%

With water; triethylamine; 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate

T=60°C; P=760.051 Torr;

McNulty, James; Nair, Jerald J.; Robertson, Al

Organic Letters, 2007 , vol. 9, # 22 p. 4575 - 4578 Title/Abstract Full Text View citing articles Show Details

54%

With sodium hydroxide; tetra-(n-butyl)ammonium iodide; bis(benzonitrile)palladium(II) dichloride; triphenylphosphine in xylene

T=90°C; Carbonylation; 4 h;

Lapidus; Petrovskii; Bruk; Beletskaya

Russian Journal of Organic Chemistry, 1999 , vol. 35, # 11 p. 1636 - 1639 Title/Abstract Full Text View citing articles Show Details

87 % Chromat.

With water; sodium acetate; triethylamine; Pd-bis(1-methylbenzothiazole-2-carbene) in N,N-dimethyl acetamide

T=130°C; 12 h;

Calo, Vincenzo; Giannoccaro, Potenzo; Nacci, Angelo; Monopoli, Antonio

Journal of Organometalic Chemistry, 2002 , vol. 645, # 1-2 p. 152 - 157 Title/Abstract Full Text View citing articles Show Details

98 % Chromat.

With tetra-(n-butyl)ammonium iodide; triphenylphosphine; bis(benzonitrile)palladium(II) dichloride in water; xylene

T=98°C; Carbonylation; P=760 Torr; 7.5 h;

Beletskaya; Lapidus; Petrovskii

Russian Journal of Organic Chemistry, 1998 , vol. 34, # 10 p. 1464 - 1470 Title/Abstract Full Text View citing articles Show Details

With water; sodium acetate; dppdmp; palladium diacetate in N,N-dimethyl-formamide

T=140°C; P=11251.1 Torr; 16 h; Inert atmosphere; Product distribution / selectivity; Hide Experimental Procedure

BASF SE

Patent: US2011/172456 A1, 2011 ; Location in patent: Page/Page column 10-11 ; Title/Abstract Full Text Show Details

The catalyst Pd(PhCN)2Cl2 (0.5 mol percent) and the ligand 2,2-dimethyl-1,3-bis(diphenyl-phosphanyl)propane (Pepstar, 1.5 mol percent) were weighed out in a glovebox under a protective gas and dissolved in 5 ml of degassed DMF. Subsequently, 20 ml of degassed DMF, the substrate 4-acetylchlorobenzene (10 mmol), aniline (15 mmol) and base (15 mmol) were added to the charge.The reaction charge was transferred into an autoclave purged with argon and the autoclave was purged three times with carbon monoxide. Subsequently, the reaction solution was heated to 130° C. Subsequently, a CO pressure of 15 bar was applied. The reaction was run at 15 bar and 130° C. or 150° C. for 24 h. The autoclave was cooled down and opened. A gas chromatography analysis of the reaction output was carried out according to the following table No. 2. A

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140

Synthesize Find similar Rx-ID: 9642253 Find similar reactions

With hydrogenchloride; water; N-hexadecyl-N,N,N-trimethylammonium bromide

T=25°C; Kinetics; Further Variations:Reagents;

Buurma, Niklaas J.; Serena, Paola; Blandamer, Michael J.; Engberts, Jan B. F. N.

Journal of Organic Chemistry, 2004 , vol. 69, # 11 p. 3899 - 3906 Title/Abstract Full Text View citing articles Show Details

With water; sodium lauryl sulfate in acetonitrile

T=25°C; pH=5.3; Micellar solution; Kinetics; ConcentrationReagent/catalystTimepH-value;

Onel, Lavinia; Buurma, Niklaas J.

Journal of Physical Chemistry B, 2011 , vol. 115, # 45 p. 13199 - 13211 Title/Abstract Full Text View citing articles Show Details

141

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Rx-ID: 28226122 Find similar reactions

81%

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Stage #1: para-bromotoluene With bromobenzene; trifluoroacetic acid; cobalt(II) dibromide; zinc dibromide; zinc in acetonitrile

Inert atmosphere; Stage #2: carbon dioxide With palladium diacetate; tri-cyclo-hexyl-phosphine in tetrahydrofuran; acetonitrile

T=0°C; P=760.051 Torr; Inert atmosphere; Stage #3: With hydrogenchloride in tetrahydrofuran; water; ethyl acetate; acetonitrile

Yeung, Charles S.; Dong, Vy M.

Journal of the American Chemical Society, 2008 , vol. 130, # 25 p. 7826 - 7827 Title/Abstract Full Text View citing articles Show Details

62 %Chromat.

With tetra-(n-butyl)ammonium iodide in N,N-dimethyl-formamide

T=0°C; Electrochemical reaction;

Zhang, Jingbo; Niu, Dongfang; Lan, Yangchun; Wang, Huan; Zhang, Guirong; Lu, Jiaxing

Synthetic Communications, 2011 , vol. 41, # 24 p. 3720 - 3727 Title/Abstract Full Text View citing articles Show Details

142

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Rx-ID: 30222721 Find similar reactions

47%

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Stage #1: With copper(l) iodide; caesium carbonate; L-proline in dimethyl sulfoxide

T=130°C; Ullmann type reaction; 24 h; Inert atmosphere; Stage #2: in dimethyl sulfoxide

T=140°C; 12 h; Stage #3: With hydrogenchloride in water

pH=2 - 3;

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Yang, Daoshan; Yang, Haijun; Fu, Hua

Chemical Communications, 2011 , vol. 47, # 8 p. 2348 - 2350 Title/Abstract Full Text View citing articles Show Details

143

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Rx-ID: 30222722 Find similar reactions

61%

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Stage #1: With copper(l) iodide; caesium carbonate; L-proline in dimethyl sulfoxide

T=130°C; Ullmann type reaction; 24 h; Inert atmosphere; Stage #2: in dimethyl sulfoxide

T=140°C; 12 h; Stage #3: With hydrogenchloride in water

pH=2 - 3;

Yang, Daoshan; Yang, Haijun; Fu, Hua

Chemical Communications, 2011 , vol. 47, # 8 p. 2348 - 2350 Title/Abstract Full Text View citing articles Show Details

144

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Rx-ID: 30222723 Find similar reactions

41%

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Stage #1: With copper(l) iodide; caesium carbonate; L-proline in dimethyl sulfoxide

T=130°C; Ullmann type reaction; 24 h; Inert atmosphere; Stage #2: in dimethyl sulfoxide

T=140°C; 12 h; Stage #3: With hydrogenchloride in water

pH=2 - 3;

Yang, Daoshan; Yang, Haijun; Fu, Hua

Chemical Communications, 2011 , vol. 47, # 8 p. 2348 - 2350 Title/Abstract Full Text View citing articles Show Details

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145

Synthesize Find similar Rx-ID: 30514143 Find similar reactions

With hydrogen; 0.5 wtpercent Pd on carbon

BP CORPORATION NORTH AMERICA INC.; NUBEL, Philip, O.; BARTOS, Thomas, M.; TALREJA, Sameer; BRUGGE, Stephen, P.

Patent: WO2011/41151 A2, 2011 ; Location in patent: Page/Page column 22-25 ;

T=275 - 282°C; P=7500.75 Torr; Inert atmosphereSealed tube; Product distribution / selectivity; Hide Experimental Procedure

Title/Abstract Full Text Show Details

General Procedures for Examples 1 and 2; Catalysts in Examples 1 and 2, including Catalysts 1-4 and Comparative A , were supported catalysts prepared by an incipient wetness technique. Aqueous solutions of iridium acetate, palladium nitrate and rhodium acetate, each from W. C. Heraeus, and a granular, coconut shell carbon from Norit designated GCN 3070 were used. The carbon had pore volume of 0.60 mL/g determined by water absorption.Impregnations were conducted by placing in glass vials weighed amounts of the carbon, which had been dried at 120°C in air before weighing, and adding to the bottles volumes of one or both of the metals salt solutions equal to the pore volumes of the support samples. After adding the solutions to the carbon samples the bottles were tumbled on a rolling bench for at least 1 hour to evenly spread excess moisture on the outside of the carbon particles and allow the solution(s) to penetrate the pores of the carbon. After tumbling the catalyst samples were dried in air for 2 hours at 110 °C, calcined under a nitrogen flow at 100 m.Jmin for 2 hours at 300 °C, reduced in a flow of 7percent hydrogen in nitrogen at 100 mL/min for 5 hours at 250 °C, and ground to powder using a mechanical grinding mill. Catalysts were prepared with iridium, rhodium and palladium weight percents and mole ratios as reported in the following table.Catalytic hydrogenation experiments were conducted using parallel magnetically-stirred, stainless steel batch reactors with a volume of 50 mL each. The reactors were fitted with Teflon insert liners. Reactors were charged with solid catalyst, 15 mL deionized water and about 15 mg (about 0.1 mmol) 4-carboxybenzaldehyde at room temperature. In Example 2 the charge to the reactor also included about 1.5 g (about 9 mmol) terephthalic acid. The reactors were then purged with nitrogen, tested for leaks by pressuring to 30 bar with nitrogen followed by releasing the pressure and pressurizing with hydrogen to 10 bar, heated to 275 °C over 30-45 minutes, held at 275-282 °C for 20 minutes, and then allowed to cool. During heating back pressure regulators with which the reactors were equipped were set at 90 bar, effectively sealing the reactors.After cooling, reactor contents were diluted with dimethyl sulfoxide ("DMSO") to dissolve the organic solids. The solutions were analyzed for 4CBA, terephthalic acid (TA), pTOL, benzoic acid (BA), and pHMBA by high- pressure liquid chromatography ("HPLC").; Example 1; Hydrogenation reactions of 4CBA in water were performed using Comparative A and Catalysts 2 and 3. Results are reported in Table 1.; All catalysts exhibited essentially 100percent conversion of 4CBA but they differed in selectivity. Catalysts 2 and 3, containing iridium and palladium, showed much higher selectivity for pHMBA than Comparative catalyst A, which contained only palladium and yielded primarily pTOL. The iridium and palladium-containing catalysts both yielded more pHMBA than pTOL.

With hydrogen; 0.45 wtpercent Ir and 0.5 wtpercent Pd on carbon T=275 - 282°C; P=7500.75 Torr; Inert atmosphereSealed tube; Product distribution / selectivity; Hide Experimental Procedure

BP CORPORATION NORTH AMERICA INC.; NUBEL, Philip, O.; BARTOS, Thomas, M.; TALREJA, Sameer; BRUGGE, Stephen, P.

Patent: WO2011/41151 A2, 2011 ; Location in patent: Page/Page column 22-25 ; Title/Abstract Full Text Show Details

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146

Synthesize Find similar Rx-ID: 30514144 Find similar reactions

With hydrogen; 1.8 wtpercent Ir and 0.5 wtpercent Pd on carbon T=275 - 282°C; P=7500.75 Torr; Inert atmosphereSealed tube; Product distribution / selectivity; Hide Experimental Procedure

BP CORPORATION NORTH AMERICA INC.; NUBEL, Philip, O.; BARTOS, Thomas, M.; TALREJA, Sameer; BRUGGE, Stephen, P.

Patent: WO2011/41151 A2, 2011 ; Location in patent: Page/Page column 22-26 ; Title/Abstract Full Text Show Details

General Procedures for Examples 1 and 2; Catalysts in Examples 1 and 2, including Catalysts 1-4 and Comparative A , were supported catalysts prepared by an incipient wetness technique. Aqueous solutions of iridium acetate, palladium nitrate and rhodium acetate, each from W. C. Heraeus, and a granular, coconut shell carbon from Norit designated GCN 3070 were used. The carbon had pore volume of 0.60 mL/g determined by water absorption.Impregnations were conducted by placing in glass vials weighed amounts of the carbon, which had been dried at 120°C in air before weighing, and adding to the bottles volumes of one or both of the metals salt solutions equal to the pore volumes of the support samples. After adding the solutions to the carbon samples the bottles were tumbled on a rolling bench for at least 1 hour to evenly spread excess moisture on the outside of the carbon particles and allow the solution(s) to penetrate the pores of the carbon. After tumbling the catalyst samples were dried in air for 2 hours at 110 °C, calcined under a nitrogen flow at 100 m.Jmin for 2 hours at 300 °C, reduced in a flow of 7percent hydrogen in nitrogen at 100 mL/min for 5 hours at 250 °C, and ground to powder using a mechanical grinding mill. Catalysts were prepared with iridium, rhodium and palladium weight percents and mole ratios as reported in the following table.Catalytic hydrogenation experiments were conducted using parallel magnetically-stirred, stainless steel batch reactors with a volume of 50 mL each. The reactors were fitted with Teflon insert liners. Reactors were charged with solid catalyst, 15 mL deionized water and about 15 mg (about 0.1 mmol) 4-carboxybenzaldehyde at room temperature. In Example 2 the charge to the reactor also included about 1.5 g (about 9 mmol) terephthalic acid. The reactors were then purged with nitrogen, tested for leaks by pressuring to 30 bar with nitrogen followed by releasing the pressure and pressurizing with hydrogen to 10 bar, heated to 275 °C over 30-45 minutes, held at 275-282 °C for 20 minutes, and then allowed to cool. During heating back pressure regulators with which the reactors were equipped were set at 90 bar, effectively sealing the reactors.After cooling, reactor contents were diluted with dimethyl sulfoxide ("DMSO") to dissolve the organic solids. The solutions were analyzed for 4CBA, terephthalic acid (TA), pTOL, benzoic acid (BA), and pHMBA by high- pressure liquid chromatography ("HPLC").; Example 2; Hydrogenation reactions of 4CBA in water were performed as described above but in the presence of TA using Comparative Catalyst A, Catalysts 2, 3 and 4, and, for comparative purposes, a commercial 0.5 wtpercent Pd/carbon catalyst identified as BASF "Type D" that had been dried and ground to powder.; As seen from the table, the reactions proceeded to 97-99percent 4CBA conversion. The reactions with the Pd-lr catalysts and the Pd-Rh catalyst yielded much higher amounts of pHMBA than pTOL whereas the comparative catalysts without Ir or Rh yielded more pTOL than pHMBA.

With hydrogen; 2:1 Ir/Pd atom ration, 1.807 wtpercent Ir on carbon T=290°C; P=25858.1 Torr; Inert atmosphereAutoclave; Product distribution / selectivity; Hide Experimental Procedure

BP CORPORATION NORTH AMERICA INC.; NUBEL, Philip, O.; BARTOS, Thomas, M.; TALREJA, Sameer; BRUGGE, Stephen, P.

Patent: WO2011/41151 A2, 2011 ; Location in patent: Page/Page column 26-28 ; Title/Abstract Full Text Show Details

General Procedures for Examples 3 and 4; Catalyst samples were prepared from stock solutions of Pd(N03)2 (14 wtpercent Pd) and iridium acetate (5 wtpercent Ir, in 50percent acetic acid solution) obtained from Johnson Matthey and from hexa(acetato)-mu- oxotris(aqua)trirhodium(lll) acetate ([Rh3(OOCCH3)6-M-0(H20)3]OAc) obtained from Alfa Aesar.Catalytic hydrogenation experiments were conducted with the Catalysts in these

examples using 435 grams crude terephthalic acid containing about 0.25 wtpercent 4CBA and about 0.1 wtpercent other impurities such as pTOL, pHMBA and benzoic acid ("BA") and 1015 grams of water. The crude terephthalic acid and water were charged to a one-gallon titanium autoclave reactor. Reactor contents were stirred at 300 revolutions per minute and hydrogen gas at 20°C in a volume corresponding to 0.42 moles was added to the reactor from a 300 ml vessel by lowering the vessel pressure by 500 psi (~690kPa). The reactor was heated to 290°C to dissolve the terephthalic acid, after which the stirring rate was increased to 1000 revolutions per minute and the catalyst sample being tested was added to the reactor as described in more detail in the individual examples.Liquid samples were withdrawn at various times after catalyst addition and analyzed for the following compounds: 4-carboxybenzaldehyde (4CBA), 4-hydroxymethyl benzoic acid (pHMBA), p-toluic acid (pTOL), and benzoic acid (BA). The results are presented in Tables 3 and 4. Samples were selected where 4CBA conversions were between 93 and 98percent to allow comparisons of catalysts on a common 4CBA conversion basis. Selectivities were defined as the moles produced divided by the number of moles of 4CBA converted. As an example, selectivity to p-hydroxymethyl benzoic acid (pHMBA) was determined as follows: moles of pHMBA produced pHMBA Selectivity = - initial moles 4CBA - final moles 4CBA; Example 3Catalysts 5-8 and Comparative B were prepared from 30-70 mesh carbon particles (Norit GCN3070) which had been dried in air at 110°C in an oven for at least 2 hours prior to use and stored in a sealed container in a desiccated environment until use. Water absorption of the carbon, measured by addition of water to the incipient wetness point, was determined to be 1.0 cc water / gram carbon.For catalyst preparations, portions of the dried support were impregnated at room temperature with the Pd(N03)2 solution or a solution containing both dissolved Pd(N03)2 and iridium acetate. The solutions contained amounts of metals to yield finished catalysts with 0.5 wtpercent Pd and iridium contents reported in Table 3. Deionized water contents were such that solution volumes were equal to the water absorption volume of the quantities of carbon support being impregnated. Impregnations were performed by adding metal solutions to the carbon slowly and evenly using a pipette, with frequent mixing of the carbon during impregnations.The impregnated materials were dried in an oven in air at 110°C for 2 hours and were then loaded into a stainless steel tube inside a furnace. A 100 standard cm3 / minute ("seem") flow of helium through the tube was begun. The tube was then heated to 300°C and held at 300°C for 2 hours under helium flow. Temperature was reduced to 200°C, helium flow was discontinued and a flow of hydrogen gas at 100 seem was initiated. The tube was heated to 275°C and held at that temperature under hydrogen flow for 2 hours, cooled to room temperature under helium flow, then unloaded.In the hydrogenation trials, catalyst samples were released directly into the liquid phase reaction mixtures from a solids holding device fitted in the reactors in the headspace above the liquid level. Results of the trials are reported in Table 3.; As can be seen from Table 3, pHMBA selectivities increased as the atom ratio of iridium to palladium decreased over the range of 1 : 10 to 25 and exceeded that of Comparative B in which palladium was the sole hydrogenation metal. BA selectivities also decreased over that range.

With hydrogen; 5 Pd/C

T=275 - 282°C; P=7500.75 Torr; Inert atmosphereSealed tube; Product distribution / selectivity; Hide Experimental Procedure

BP CORPORATION NORTH AMERICA INC.; NUBEL, Philip, O.; BARTOS, Thomas, M.; TALREJA, Sameer; BRUGGE, Stephen, P.

Patent: WO2011/41151 A2, 2011 ; Location in patent: Page/Page column 22-26 ; Title/Abstract Full Text Show Details

General Procedures for Examples 1 and 2; Catalysts in Examples 1 and 2, including Catalysts 1-4 and Comparative A , were supported catalysts prepared by an incipient wetness technique. Aqueous solutions of iridium acetate, palladium nitrate and rhodium acetate, each from W. C. Heraeus, and a granular, coconut shell carbon from Norit designated GCN 3070 were used. The carbon had pore volume of 0.60 mL/g determined by water absorption.Impregnations were conducted by placing in glass vials weighed amounts of the carbon, which had been dried at 120°C in air before weighing, and adding to the bottles volumes of one or both of the metals salt solutions equal to the pore volumes of the support samples. After adding the solutions to the carbon samples the bottles were tumbled on a rolling bench for at least 1 hour to evenly spread excess moisture on the outside of the carbon particles and allow the solution(s) to penetrate the pores of the carbon. After tumbling the catalyst samples were dried in air for 2 hours at 110 °C, calcined under a nitrogen flow at 100 m.Jmin for 2 hours at 300 °C, reduced in a flow of 7percent hydrogen in nitrogen at 100 mL/min for 5 hours at 250 °C, and ground to powder using a mechanical grinding mill. Catalysts were prepared with iridium, rhodium and palladium weight percents and mole ratios as reported in the following table.Catalytic hydrogenation experiments were conducted using parallel magnetically-stirred, stainless steel batch reactors with a volume of 50 mL each. The reactors were fitted with Teflon insert liners. Reactors were charged with solid catalyst, 15 mL deionized water and about 15 mg (about 0.1 mmol) 4-carboxybenzaldehyde at room temperature. In Example 2 the charge to the reactor also included about 1.5 g (about 9 mmol) terephthalic acid. The reactors were then purged with nitrogen, tested for leaks by pressuring to 30 bar with nitrogen followed by releasing the pressure and pressurizing with hydrogen to 10 bar, heated to 275 °C over 30-45 minutes, held at 275-282 °C for 20 minutes, and then allowed to cool. During heating back pressure regulators with which the reactors were equipped were set at 90 bar, effectively sealing the reactors.After cooling, reactor contents were diluted with dimethyl sulfoxide ("DMSO") to dissolve the organic solids. The solutions were analyzed for 4CBA, terephthalic acid (TA), pTOL, benzoic acid (BA), and pHMBA by high- pressure liquid chromatography ("HPLC").; Example 2; Hydrogenation reactions of 4CBA in water were performed as described above but in the presence of TA using Comparative Catalyst A, Catalysts 2, 3 and 4, and, for comparative purposes, a commercial 0.5 wtpercent Pd/carbon catalyst identified as BASF "Type D" that had been dried and ground to powder.; As seen from the table, the reactions proceeded to 97-99percent 4CBA conversion. The reactions with the Pd-lr catalysts and the Pd-Rh catalyst yielded much higher amounts of pHMBA than pTOL whereas the comparative catalysts without Ir or Rh yielded more pTOL than pHMBA. A

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147

Synthesize Find similar Rx-ID: 30828129 Find similar reactions

B: 90 %Chromat.

With water in methanol

0.833333 h; UV-irradiation; Hide Experimental Procedure

Ikbal, Mohammed; Jana, Avijit; Singh, N.D. Pradeep; Banerjee, Rakesh; Dhara, Dibakar

Tetrahedron, 2011 , vol. 67, # 20 p. 3733 - 3742 Title/Abstract Full Text View citing articles Show Details

6.4. Photogeneration of carboxylic acids and its quantum yield measurement

General procedure: Carboxylates (3a-h and 6a-c) (0.05 mmol) was dissolved in MeOH/H2O (9:1), and it was irradiated using 125 W medium pressure Hg lamp using quartz filter. In each case the photolysis was stopped when conversion reached at least 95percent (as indicated by HPLC). After the completion of the photolysis, the solvent was removed under vacuum and the photoproducts (carboxylic acids and carboxyanilide) were separated by column chromatography using ethyl acetate/hexane as eluant.The quantum yield of photogeneration of carboxylic acids was analyzed by employing valerophenone as an actinometer. The progress of the photolysis was monitored by taking 5 μl of aliquot at regular interval of time and analyzed by HPLC, using eluant hexane/isopropanol (9:1), at a flow rate of 1 ml/min (detection: UV 254 nm). The percent of carboxylic acid generated was determined by calculating the gradual increase in the peak area of the carboxylic acid. A

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148

Synthesize Find similar Rx-ID: 30828130 Find similar reactions

A: 60 %Chromat.

With water in methanol

0.833333 h; UV-irradiation; Hide Experimental Procedure

Ikbal, Mohammed; Jana, Avijit; Singh, N.D. Pradeep; Banerjee, Rakesh; Dhara, Dibakar

Tetrahedron, 2011 , vol. 67, # 20 p. 3733 - 3742 Title/Abstract Full Text View citing articles Show Details

6.4. Photogeneration of carboxylic acids and its quantum yield measurement

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149

Synthesize Find similar Rx-ID: 30828153 Find similar reactions

A: 65 %Chromat.

With water in methanol

T=20°C; 0.833333 h; UV-irradiation; Hide Experimental Procedure

Ikbal, Mohammed; Jana, Avijit; Singh, N.D. Pradeep; Banerjee, Rakesh; Dhara, Dibakar

Tetrahedron, 2011 , vol. 67, # 20 p. 3733 - 3742 Title/Abstract Full Text View citing articles Show Details

6.4. Photogeneration of carboxylic acids and its quantum yield measurement

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150

Synthesize Find similar Rx-ID: 30828257 Find similar reactions

B: 95 %Chromat.

With water in methanol

0.833333 h; UV-irradiation; Hide Experimental Procedure

Ikbal, Mohammed; Jana, Avijit; Singh, N.D. Pradeep; Banerjee, Rakesh; Dhara, Dibakar

Tetrahedron, 2011 , vol. 67, # 20 p. 3733 - 3742 Title/Abstract Full Text View citing articles Show Details

6.4. Photogeneration of carboxylic acids and its quantum yield measurement

151

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Rx-ID: 31034829 Find similar reactions

A: 60% C: 28%

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Aggarwal, Ranjana; Sumran, Garima; Garg, Neelam; Aggarwal, Ashok

European Journal of Medicinal Chemistry, 2011 , vol. 46, # 7 p. 3038 - 3046 Title/Abstract Full Text View citing articles Show Details

in water

pH=0.8; 4 h; Reflux; regioselective reaction; Hide Experimental Procedure

5.1. Synthesis of 2-(3',5'-disubstituted pyrazol-1'-yl)-5,7-disubstituted pyrazolo[1,5-a]pyrimidines (7)

General procedure: To H2O (20 ml) were added 3(5)-amino-5(3)-hydrazinopyrazole dihydrochloride (5) (0.93 g, 0.005 mol) and CH3COCH2COC6H5 (6b) (0.81 g, 0.005 mol). This reaction mixture was found to have pH 0.8 at 25 °C. Then the reaction mixture was refluxed for 4 h. After completion of the reaction (monitored by TLC), the reaction mixture was cooled to room temperature and extracted using 2 .x. 30 ml portions of ethyl acetate. The combined organic layers were successively washed with brine, dried over anhydrous Na2SO4, filtered and concentrated to give a residual mass. The residue obtained on cooling was found to be a mixture of three products as predicted by TLC and 1H NMR spectrum. The residue was column chromatographed over silica gel (100-200 mesh) using petroleum ether followed by petroleum ether/CHCl3 of increasing polarity as eluent to yield three compounds- benzoic acid 10b m.p. 120-121 °C (lit. [35] m.p. 121-123 °C) in the first fraction, followed by 3-methyl-5-phenyl-1H-pyrazole (9b) m.p. 129-130 °C; (lit. [26], [27] and [28] m.p. 128 °C); yield 8percent and finally 2-(3'-methyl-5'-phenylpyrazol-1'-yl)-5-methyl-7-phenylpyrazolo[1,5-a]pyrimidine (7b). A

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152

Synthesize Find similar Rx-ID: 31130758 Find similar reactions

A: 66% B: 81%

With TEMPO; oxygen in acetonitrile

T=50°C; P=760.051 Torr; 12 h;

Song, Ren-Jie; Liu, Yu; Hu, Rui-Xiang; Liu, Yan-Yun; Wu, Ji-Cheng; Yang, Xu-Heng; Li, Jin-Heng

Advanced Synthesis and Catalysis, 2011 , vol. 353, # 9 p. 1467 - 1473 Title/Abstract Full Text View citing articles Show Details

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153

Synthesize Find similar Rx-ID: 31622046 Find similar reactions

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A: 78% B: 8%

With oxygen; potassium carbonate in acetonitrile

T=30°C; 24 h;

Yasukawa, Tomohiro; Miyamura, Hiroyuki; Kobayashi, Shu

Chemistry - An Asian Journal, 2011 , vol. 6, # 2 p. 621 - 627 Title/Abstract Full Text View citing articles Show Details

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154

Synthesize Find similar Rx-ID: 31644465 Find similar reactions

A: 18.4 mol % B: 36.1 mol %

With manganese bromide tetrahydrate; water; dihydrogen peroxide

T=380°C; P=172517 Torr;

Perez, Eduardo; Fraga-Dubreuil, Joan; Garcia-Verdugo, Eduardo; Hamley, Paul A.; Thomas, W. Barry; Housley, Duncan; Partenheimer, Walt; Poliakoff, Martyn

Green Chemistry, 2011 , vol. 13, # 9 p. 2389 - 2396 Title/Abstract Full Text View citing articles Show Details

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155

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Rx-ID: 32167213 Find similar reactions

A: 63 %Chromat. B: 25 %Chromat. C: 12 %Chromat.

With oxygen; sodium hydroxide in tetrahydrofuran; water

T=40°C; 12 h;

Soule, Jean-Francois; Miyamura, Hiroyuki; Kobayashi, Shu

Journal of the American Chemical Society, 2011 , vol. 133, # 46 p. 18550 - 18553 Title/Abstract Full Text View citing articles Show Details

156

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Rx-ID: 32317572

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82%

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Find similar reactions

Stage #1: With anhydrous iron chloride in tetrachloromethane

T=85°C; 24 h; Inert atmosphere; Stage #2: With hydrogenchloride; water in tetrachloromethane

Inert atmosphere;

Lian, Xiaoyan; Fu, Shaomin; Ma, Tongmei; Li, Shunbin; Zeng, Wei

Applied Organometallic Chemistry, 2011 , vol. 25, # 6 p. 443 - 447 Title/Abstract Full Text View citing articles Show Details

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157

Synthesize Find similar Rx-ID: 32381366 Find similar reactions

With oxygen in acetonitrile

20 h; Photolysis;

Allpress, Caleb J.; Arif, Atta M.; Houghton, Dylan T.; Berreau, Lisa M.

Chemistry - A European Journal, 2011 , vol. 17, # 52 p. 14962 - 14973 Title/Abstract Full Text View citing articles Show Details

158

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Rx-ID: 32490740 Find similar reactions

With water; dimethyl sulfoxide

T=25°C; Kinetics;

Um, Ik-Hwan; Kim, Eun-Hee; Kang, Ji-Sun

Organic and Biomolecular Chemistry, 2011 , vol. 9, # 23 p. 8062 - 8067 Title/Abstract Full Text View citing articles Show Details

159

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Multi-step reaction with 2 steps

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Rx-ID: 32490757 Find similar reactions

Um, Ik-Hwan; Kim, Eun-Hee; Kang, Ji-Sun

1: hydrogenchloride / water; acetonitrile 2: water; dimethyl sulfoxide / 25 °C View Scheme

Organic and Biomolecular Chemistry, 2011 , vol. 9, # 23 p. 8062 - 8067 Title/Abstract Full Text View citing articles Show Details

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160

Synthesize Find similar Rx-ID: 32586302 Find similar reactions

A: 58% B: 22%

With hydrogenchloride; water

2 h; Reflux;

Pak; Tyrkov

Russian Journal of Organic Chemistry, 2011 , vol. 47, # 12 p. 1908 - 1910 Title/Abstract Full Text View citing articles Show Details

161

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Rx-ID: 32783581 Find similar reactions

With rat cecal content T=37°C; pH=6.8; aq. phosphate buffer;

Kong, Hyesik; Kim, Hyunjeong; Do, Heejeong; Lee, Yonghyun; Hong, Sungchae; Yoon, Jeong-Hyun; Jung, Yunjin; Kim, Young Mi

Biopharmaceutics and Drug Disposition, 2011 , vol. 32, # 6 p. 343 - 354 Title/Abstract Full Text View citing articles Show Details

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162

Synthesize Find similar Rx-ID: 9248734 Find similar reactions

With sodium hydroxide; sodium hydrogencarbonate; sodium carbonate; potassium hexacyanoferrate(III); osmium(VIII) oxide in water

T=36.85°C; pH=10.33; Kinetics; Further Variations:pH-values;

Gnana Rani, D. Freeda; Pushparaj, F. J. Maria; Alphonse; Rangappa

Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2002 , vol. 41, # 10 p. 2153 - 2159

Title/Abstract Full Text View citing articles Show Details

With KBrO3; sulfuric acid; mercury(II) diacetate; acetic acid in water

T=39.84°C; KineticsMechanism; ConcentrationSolventTemperature; regioselective reaction;

Reddy, Cherkupally Sanjeeva; Manjari, Padma Sunitha

Indian Journal of Chemistry - Section A Inorganic, Physical, Theoretical and Analytical Chemistry, 2010 , vol. 49, # 4 p. 418 - 424 Title/Abstract Full Text View citing articles Show Details

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163

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Rx-ID: 10435454 Find similar reactions

With chloro-trimethyl-silane; aluminum tri-bromide

T=20°C; P=22501.8 Torr; 3 h; Product distribution; Further Variations:Reagents;

Nemoto, Koji; Yoshida, Hiroki; Suzuki, Yutaka; Morohashi, Naoya; Hattori, Tetsutaro

Chemistry Letters, 2006 , vol. 35, # 7 p. 820 - 821 Title/Abstract Full Text View citing articles Show Details

With chloro-trimethyl-silane; aluminum tri-bromide

T=20°C; P=22502.3 Torr; 3 h; Autoclave;

Nemoto, Koji; Yoshida, Hiroki; Egusa, Naoki; Morohashi, Naoya; Hattori, Tetsutaro

Journal of Organic Chemistry, 2010 , vol. 75, # 22 p. 7855 - 7862 Title/Abstract Full Text View citing articles Show Details

164

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Rx-ID: 29000695 Find similar reactions

81%

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Stage #1: carbon dioxide With tin(IV) chloride

Stage #2: toluene T=79.84°C; P=44254.4 Torr; 18 h; Product distribution / selectivity; Hide Experimental Procedure

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UNIVERSITY OF PITTSBURGH

Patent: WO2005/73159 A2, 2005 ; Location in patent: Page/Page column 8-9 ; Title/Abstract Full Text Show Details

EXAMPLE B Several additional reactions were conducted using various Lewis acids. Runs 14-23 were conducted in the same manner as Runs 1-13 with the reaction conducted at a pressure of 5.9MPa, temperature of 353K, and time of 18 hours. The results are shown in Table II below. Table II Run No. Lewis Acid Mmol Used percent Yield 14 AIC13 5. 37 80 15 NaAlCl4 4.66 60 16 TiC14 3. 34 71 17 Ti (OEt) 4 5.22 25 18 Zn (OT2 5. 10 30 19 Zn(OAc)2 5.62 55 20 CuBr2 4. 91 50 21 SnCI4 5. 00 81 22 MoCl5 4.42 76 The results in Table II show that the method of this invention resulted in appreciable yield for a variety of Lewis Acids without adding zinc or aluminum powder and at significantly lower pressures than the method of Calfee et al.

76%

Stage #1: carbon dioxide With [MoCl5]

Stage #2: toluene T=79.84°C; P=44254.4 Torr; 18 h; Product distribution / selectivity; Hide Experimental Procedure

UNIVERSITY OF PITTSBURGH

Patent: WO2005/73159 A2, 2005 ; Location in patent: Page/Page column 8-9 ; Title/Abstract Full Text Show Details

71%

Stage #1: carbon dioxide With titanium tetrachloride

Stage #2: toluene T=79.84°C; P=44254.4 Torr; 18 h; Product distribution / selectivity; Hide Experimental Procedure

UNIVERSITY OF PITTSBURGH

Patent: WO2005/73159 A2, 2005 ; Location in patent: Page/Page column 8-9 ; Title/Abstract Full Text Show Details

60%

Stage #1: carbon dioxide With sodium tetrachloroaluminate

Stage #2: toluene T=79.84°C; P=44254.4 Torr; 18 h; Product distribution / selectivity; Hide Experimental Procedure

UNIVERSITY OF PITTSBURGH

Patent: WO2005/73159 A2, 2005 ; Location in patent: Page/Page column 8-9 ; Title/Abstract Full Text Show Details

Stage #1: carbon dioxide With zinc diacetate

Stage #2: toluene T=79.84°C; P=44254.4 Torr; 18 h; Product distribution / selectivity; Hide Experimental Procedure

UNIVERSITY OF PITTSBURGH

Patent: WO2005/73159 A2, 2005 ; Location in patent: Page/Page column 8-9 ; Title/Abstract Full Text Show Details

Stage #1: carbon dioxide With copper(ll) bromide

Stage #2: toluene T=79.84°C; P=44254.4 Torr; 18 h; Product distribution / selectivity; Hide Experimental Procedure

UNIVERSITY OF PITTSBURGH

Patent: WO2005/73159 A2, 2005 ; Location in patent: Page/Page column 8-9 ; Title/Abstract Full Text Show Details

Stage #1: carbon dioxide With zinc trifluoromethanesulfonate

Stage #2: toluene T=79.84°C; P=44254.4 Torr; 18 h; Product distribution / selectivity; Hide Experimental Procedure

UNIVERSITY OF PITTSBURGH

Patent: WO2005/73159 A2, 2005 ; Location in patent: Page/Page column 8-9 ; Title/Abstract Full Text Show Details

Stage #1: carbon dioxide With titanium tetraethoxide

Stage #2: toluene T=79.84°C; P=44254.4 Torr; 18 h; Product distribution / selectivity; Hide Experimental Procedure

UNIVERSITY OF PITTSBURGH

Patent: WO2005/73159 A2, 2005 ; Location in patent: Page/Page column 8-9 ; Title/Abstract Full Text Show Details

Stage #1: carbon dioxide With AlCl3, aluminium chloride

T=79.84°C; 1 h; Stage #2: toluene T=26.84 - 149.84°C; P=10351 - 51755.2 Torr; 5 - 30 h; Product distribution / selectivity;

UNIVERSITY OF PITTSBURGH

Patent: WO2005/73159 A2, 2005 ; Location in patent: Page/Page column 7-9 ;

Hide Experimental Procedure

Title/Abstract Full Text Show Details

A; B:

EXAMPLE A Several reactions in accordance with this invention were run using varying temperatures, pressures, and reaction times. In each of Runs 1-13, a weighed amount of anhydrous AtCts corresponding to the indicated molar amount of anhydrous AIC13 was added to a 31 mL high pressure reaction vessel with a Teflon stir bar constructed at the University of Pittsburgh and has a useful operating pressure range from 0 to about 50 MPa at temperatures below 423K. The vessel was sealed and C02 was added using a Haskell Gas Booster compressor until the vessel reached the indicated pressure. Stirring at about 400 rpm was started and the temperature was raised to 353K. The contents were allowed to incubate for 1 hour. At the end of the incubation period, excess toluene (approximately 4 times on a molar basis with respect to AIC13) was added using a high pressure syringe pump from High Pressure Equipment Co. , Erie, PA. The reaction was allowed to run for the indicated number of hours at the temperature and pressure listed, after which it was stopped via the slow introduction of 5mL of 1 M HCI. The vessel was then slowly depressurized while cooling to room temperature. Yield of toluic acid (relative to moles of AIC13) was measured. The results are included in Table I below. Table I Run A . Cb Pressure Reaction Time Reaction Temp. Yield No. mmol MPa Hours K percent 1 4.81 1.38 18 353 12 2 5. 6 3. 45 18 353 41 3 3. 9 5. 52 18 353 63 4 4. 21 6. 90 18 353 83 5 4. 80 6. 90 18 300 10 6 4. 00 6. 90 18 313 35 7 5. 11 6. 90 18 323 57 8 4. 43 6. 90 18 373 85 9 4. 53 6. 90 18 423 40 10 4. 11 6. 90 5 353 27 11 3. 96 6. 90 15 353 60 12 4. 20 6. 90 20 353 82 13 4. 66 6. 90 30 353 80 The results shown in Table I show that the method of this invention can be used to achieve higher yields at significantly lower pressure, without using zinc or aluminum powder, than the results achieved according to Calfee et al., (USPN 3,138, 626).; EXAMPLE B Several additional reactions were conducted using various Lewis acids. Runs 14-23 were conducted in the same manner as Runs 1-13 with the reaction conducted at a pressure of 5.9MPa, temperature of 353K, and time of 18 hours. The results are shown in Table II below. Table II Run No. Lewis Acid Mmol Used percent Yield 14 AIC13 5. 37 80 15 NaAlCl4 4.66 60 16 TiC14 3. 34 71 17 Ti (OEt) 4 5.22 25 18 Zn (OT2 5. 10 30 19 Zn(OAc)2 5.62 55 20 CuBr2 4. 91 50 21 SnCI4 5. 00 81 22 MoCl5 4.42 76 The results in Table II show that the method of this invention resulted in appreciable yield for a variety of Lewis Acids without adding zinc or aluminum powder and at significantly lower pressures than the method of Calfee et al.

10%

With aluminum tri-bromide

T=20°C; P=22502.3 Torr; 3 h; Autoclave;

Nemoto, Koji; Yoshida, Hiroki; Egusa, Naoki; Morohashi, Naoya; Hattori, Tetsutaro

Journal of Organic Chemistry, 2010 , vol. 75, # 22 p. 7855 - 7862 Title/Abstract Full Text View citing articles Show Details

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165

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Rx-ID: 29725030 Find similar reactions

With 1-n-butyl-2,3-dimethylimidazolium bistrifluoromethylsulfonylamide in methanol

T=24.84°C; Equilibrium constant; Reagent/catalyst;

D'Anna, Francesca; Marullo, Salvatore; Vitale, Paola; Noto, Renato

Journal of Organic Chemistry, 2010 , vol. 75, # 14 p. 4828 - 4834 Title/Abstract Full Text View citing articles Show Details

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166

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Yuan, Yu; Ji, Xiang; Zhao, Dongbo

European Journal of Organic Chemistry, 2010 , # 27 p. 5274 - 5278 Title/Abstract Full Text View citing articles Show Details

With [NEt3Me]I; water; dihydrogen peroxide in acetonitrile

T=20°C; 15 h;

167

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With oxygen; Mn(CH3COO)2*4H2O; [Co(O2CCH3)2]*4H2O

T=100°C; P=15001.5 Torr; 15 h; Product distribution / selectivity; Hide Experimental Procedure

Ishii, Yasutaka; Takano, Minoru; Hirai, Naruhisa

Patent: US2010/317869 A1, 2010 ; Location in patent: Page/Page column 15 ; Title/Abstract Full Text Show Details

3:Example 3

Example 3 In an autoclave equipped with a Teflon (registered trademark) inner cylinder, was prepared an acetic acid solution (3 mL) of 7.0 mg of manganese(II) acetate tetrahydrate, 6.6 mg of cobalt(II) acetate tetrahydrate, and 2.1 g (20 mmol) of p-xylene. To the solution was suspended 418 mg of an immobilized N-hydroxyphthalimide catalyst prepared according to the procedure of Example 1. The resulting mixture was stirred at 100° C. under pressurized air (at 20 atmospheres, i.e., 2 MPa) for 15 hours. The reaction solution was analyzed to find that, in a conversion from p-xylene of 52percent, there were produced p-methylbenzaldehyde in a selectivity of 12percent, p-methylbenzoic acid in a selectivity of 58percent, and terephthalic acid in a selectivity of 4percent. After the completion of the reaction, the immobilized catalyst was separated by filtration, washed with ethyl acetate, dried under reduced pressure, and recovered as an immobilized catalyst. The recovered immobilized catalyst was reused in an oxidation reaction according to the same procedure, but the conversion was decreased to 26percent, demonstrating that the activity of the catalyst was decreased.

With oxygen; Mn(CH3COO)2*4H2O; [Co(O2CCH3)2]*4H2O

T=100°C; P=15001.5 Torr; 4 h; Product distribution / selectivity; Hide Experimental Procedure

Ishii, Yasutaka; Takano, Minoru; Hirai, Naruhisa

Patent: US2010/317869 A1, 2010 ; Location in patent: Page/Page column 15 ; Title/Abstract Full Text Show Details

5:Example 5

Example 5 In an autoclave equipped with a Teflon (registered trademark) inner cylinder was prepared an acetic acid solution (5 mL) of 7.3 mg of manganese(II) acetate tetrahydrate, 8.4 mg of cobalt(II) acetate tetrahydrate, and 221 mg (2 mmol) of p-xylene; and 134 mg of an immobilized N-hydroxysuccinimide catalyst prepared by the procedure of Example 2 was suspended in the solution. The resulting mixture was stirred at 100° C. under pressurized air (at 20 atmospheres, i.e., 2 MPa) for 4 hours. The reaction solution was analyzed to find that, in a conversion from p-xylene of 97percent, there were produced p-methylbenzaldehyde in a selectivity of 1percent, p-methylbenzoic acid in a selectivity of 50percent, and terephthalic acid in a selectivity of 20percent. After the completion of the reaction, the products were dissolved in N,N-dimethylformamide (DMF), from which the immobilized catalyst was separated by filtration, washed with ethyl acetate, dried, and thereby recovered. A

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168

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Rx-ID: 30026376 Find similar reactions

B: 5%

With aluminum tri-bromide in benzene

T=20°C; P=22502.3 Torr; 3 h; Autoclave;

Nemoto, Koji; Yoshida, Hiroki; Egusa, Naoki; Morohashi, Naoya; Hattori, Tetsutaro

Journal of Organic Chemistry, 2010 , vol. 75, # 22 p. 7855 - 7862 Title/Abstract Full Text View citing articles Show Details

169

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With water in acetonitrile

pH=7.5; 0.266667 h; UV-irradiationaq. buffer; KineticsQuantum yield; TimeWavelength;

Jana, Avijit; Atta, Sanghamitra; Sarkar, Sujan K.; Singh, N.D. Pradeep

Tetrahedron, 2010 , vol. 66, # 52 p. 9798 - 9807 Title/Abstract Full Text View citing articles Show Details

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170

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B: 45%

With hydrogenchloride; water in diethyl ether; ethanol

pH=2;

Kayukova; Orazbaeva; Gapparova; Beketov; Espenbetov; Faskhutdinov; Tashkhodjaev

Chemistry of Heterocyclic Compounds, 2010 , vol. 46, # 7 p. 879 - 886 Title/Abstract Full Text View citing articles Show Details

171

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Rx-ID: 31232764 Find similar reactions

With sodium perchlorate; water; sodium hydroxide

T=25°C; Kinetics; Reagent/catalyst;

Nummert, Vilve; Piirsalu, Mare; Koppel, Ilmar A.

Journal of Physical Organic Chemistry, 2010 , vol. 23, # 6 p. 497 - 504 Title/Abstract Full Text View citing articles Show Details

172

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With oxygen; acetic acid; palladium diacetate; stannous acetate; antimony triacetate in water

T=182 - 195°C; P=20929.4 Torr; 1 - 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

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BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 16-17 ; Title/Abstract Full Text Show Details

16; 17:

EXAMPLES 13-20; In these examples palladium-antimony-tin compositions according to the invention were used for semi-continuous oxidations of various feed materials using a 300 mL titanium Parr reactor outfitted with a Magnadrive impeller agitator, reflux condensers, a back pressure regulator, a mass flow controller, on-line vent gas analyzers (CO, O2, and CO2), one pump for adding liquid feedstock and another pump for adding supplemental solvent.The reactor bottom was preloaded with weighed amounts of palladium(II) acetate (1.208 g), antimony(III) acetate (1.407 g), and tin(II) acetate (1.143 g), and 95percent aqueous acetic acid (72.6 g). The reactor was sealed, pressurized to 390 psig with nitrogen and agitation was begun. The reactor contents were heated to 182° C. At initiation, the nitrogen flow was replaced by a mixture of 8percent oxygen in nitrogen flowing at 15 standard cubic feet per hour ("SCFH"), and the feedstock and supplemental solvent were added. The feedstock and the aqueous, 95 wt percent acetic acid as supplemental solvent were added for 60 minutes at 0.567 mL/min and 0.633 mL/min, respectively. Thirty seconds after initiation, the temperature set-point was increased to 194° C. Twenty minutes after initiation, the set-point temperature was increased again to 195° C. After 60 minutes, feedstock and solvent additions were terminated and, in each of Examples 13-15, a 30 minute tailout period was begun. During that period, the 8percent oxygen in nitrogen gas mixture was added at 15 SCFH. At the end of the tailout period, the flow of 8percent oxygen in nitrogen was replaced by a flow of only nitrogen gas. Example 16 was carried out as in Examples 13-15 except the tailout step was omitted. In all examples, the reactor was sequentially removed from the heat source, cooled, depressurized, and unsealed. Representative samples of the total reactor product slurries were collected and analyzed by HPLC and Karl Fisher (water) analyses.Results of semi-continuous oxidations using para-xylene feed in Examples 13-16 are reported in TABLE 8. The oxidations in Examples 13-15 produced TA in an average selectivity of almost 82percent. The average total selectivities of less fully oxidized carboxylic acid derivatives (4CBA+PTOL) in the oxidations using para-xylene feed was 14.05 mole percent. Results of semi-continuous oxidations using alternate feed materials in Examples 16-19 are reported in TABLE 9. TABLE 9 displays oxidation results using liquid feedstocks, p-tolualdehyde and p-methylacetophenone. The duplicate p-tolualdehyde oxidations in Examples 16 and 17 generated very similar results, demonstrating good reproducibility of the oxidations. The p-tolualdehyde feed was converted to TA, although at lower efficiency and with greater levels of partial carboxylic acid derivatives as compared to the para-xylene feed in Examples 13-15. However, the total COx generated was much lower than in the para-xylene oxidations. The p-methylacetophenone oxidations in Examples 18 and 19 had similar results, including low TA yields. The total COx generated in those examples was higher than the amount made in the p-tolualdehyde oxidations, consistent with a higher activity of the catalyst for oxidation of the p-methylacetophenone feed material to carbon oxides than the p-tolualdehyde and p-xylene feeds. A

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173

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With oxygen; acetic acid; palladium diacetate; stannous acetate; antimony triacetate in water

T=182 - 195°C; P=20929.4 Torr; 1 - 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 16-17 ; Title/Abstract Full Text Show Details

18; 19:

174

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With oxygen; acetic acid; palladium diacetate; stannous acetate; antimony triacetate in water

T=100 - 195°C; P=20929.4 Torr; 1 - 1.5 h; Product distribution / selectivity; Hide Experimental Procedure

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BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 16-17; 18-19 ; Title/Abstract Full Text Show Details

13; 14; 15; 16; 26; 27; 28; 29:

EXAMPLES 13-20; In these examples palladium-antimony-tin compositions according to the invention were used for semi-continuous oxidations of various feed materials using a 300 mL titanium Parr reactor outfitted with a Magnadrive impeller agitator, reflux condensers, a back pressure regulator, a mass flow controller, on-line vent gas analyzers (CO, O2, and CO2), one pump for adding liquid feedstock and another pump for adding supplemental solvent.The reactor bottom was preloaded with weighed amounts of palladium(II) acetate (1.208 g), antimony(III) acetate (1.407 g), and tin(II) acetate (1.143 g), and 95percent aqueous acetic acid (72.6 g). The reactor was sealed, pressurized to 390 psig with nitrogen and agitation was begun. The reactor contents were heated to 182° C. At initiation, the nitrogen flow was replaced by a mixture of 8percent oxygen in nitrogen flowing at 15 standard cubic feet per hour ("SCFH"), and the feedstock and supplemental solvent were added. The feedstock and the aqueous, 95 wt percent acetic acid as supplemental solvent were added for 60 minutes at 0.567 mL/min and 0.633 mL/min, respectively. Thirty seconds after initiation, the temperature set-point was increased to 194° C. Twenty minutes after initiation, the set-point temperature was increased again to 195° C. After 60 minutes, feedstock and solvent additions were terminated and, in each of Examples 13-15, a 30 minute tailout period was begun. During that period, the 8percent oxygen in nitrogen gas mixture was added at 15 SCFH. At the end of the tailout period, the flow of 8percent oxygen in nitrogen was replaced by a flow of only nitrogen gas. Example 16 was carried out as in Examples 13-15 except the tailout step was omitted. In all examples, the reactor was sequentially removed from the heat source, cooled, depressurized, and unsealed. Representative samples of the total reactor product slurries were collected and analyzed by HPLC and Karl Fisher (water) analyses.Results of semi-continuous oxidations using para-xylene feed in Examples 13-16 are reported in TABLE 8. The oxidations in Examples 13-15 produced TA in an average selectivity of almost 82percent. The average total selectivities of less fully oxidized carboxylic acid derivatives (4CBA+PTOL) in the oxidations using para-xylene feed was 14.05 mole percent.; XAMPLES 20-23; In these examples palladium-antimony-tin compositions according to the invention were used in batch oxidations of various feed materials in solid form at ambient temperature using the 300 mL reactor used in Examples 13-20. Batch oxidations were conducted by loading the reactor with palladium(II) acetate (1.208 g), antimony(III) acetate (1.407 g), and tin(II) acetate (1.143 g), weighed amounts of solid feed materials and 95percent aqueous acetic acid (114.5 g). In Examples 20 and 21, the feed was 42.4 g p-toluic acid and in Examples 22 and 23 the feed was 41.7 g terephthaldehyde. The reactor was sealed, pressurized to 390 psig by addition of nitrogen gas and agitation was started. The reactor contents were heated to 182° C. and the nitrogen flow was replaced by flow of a mixture of oxygen and nitrogen containing 8percent oxygen at 15 SCFH. Thirty seconds after initiation, the temperature set-point was increased to 194° C. Twenty minutes after initiation, the temperature set-point was increased to 195° C. After 90 minutes, the 8percent oxygen in nitrogen flow was replaced by a flow of only nitrogen. The reactor was removed from the heat source, cooled, depressurized, and unsealed. Representative samples of the total reactor product slurries from each run were collected and analyzed by HPLC and Karl Fisher analyses. Results are reported in TABLE 10. Inconsistent results in Examples 20 and 21 appear to have resulted from the presence of a contaminant(s) carried over from a previous oxidation experiment. When the ptoluic acid feed was oxidized a second time as in Example 21, there was very little measured activity. Therefore, Example 21 is believed to represent the more accurate results of p-toluic acid oxidation. Examples 22 and 23 produced reproducible results in oxidation of a terephthaldehyde feed. TA product selectivity averaged about 57percent with 4-CBA as the only intermediate carboxylic acid derivative at about 31percent. Total COx generated in these examples was high.

With oxygen; palladium diacetate; [Mo2(acetate)4]; stannous acetate; antimony triacetate in water

T=193 - 199°C; P=20929.4 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 20 ; Title/Abstract Full Text Show Details

37:

EXAMPLES 34-37; A series of oxidations experiments was conducted substantially as in Examples 30-32 except that concentrations of palladium, antimony, tin and molybdenum salts charged to the reactor were varied and the 95 wt percent aqueous acetic acid solution charged to the reactor with the catalyst metal salts and as supplemental solvent was diluted or replaced with water. Water contents in weight percent based on total solvent charged and results of analyses of the reactor contents in each of these experiments, including metals concentrations in the supernatant liquid from each run determined by inductive coupled plasma analyses ("ICP") are reported in Table 15. These examples and the table illustrate effectiveness of the catalyst composition in oxidations with increasing water contents from 5 to 100 wt percent. Of course, at 100percent, the solvent is only water. In oxidations using bromine-promoted cobalt-manganese catalyst compositions conventionally used in commercial manufacture of terephthalic acid, and also those using bromine free catalysts as in US Patent Application No. 2002/0188155, even small increases in water content of the liquid phase reaction mixtures can adversely affect both conversions and selectivity to desired terephthalic acid products. Surprisingly, however, Examples 34-36 and Table 15 illustrate that oxidations progressed actively, and with high selectivities to terephthalic acid, at water contents as high as 40 wt percent. It also was surprising that selectivities to intermediate oxidation products such as 4CBA, PTAL and PTOL decreased slightly with increases in water concentration to 40 wt percent. The decreases in selectivities for these intermediates are indicative of higher catalyst activity in the conversion of the intermediates to terephthalic acid. At 100 wt percent water as liquid medium for the oxidation in Example 37, conversion was lower than expected due to ineffective mixing of para-xylene and water in the apparatus used, but even with that difficulty, selectivity to carboxylic acid derivatives of the para-xylene feed was greater than 50percent and selectivity to terephthalic acid was 6percent. Oxidations in water with significantly higher conversions to oxidized para-xylene derivatives and selectivities to terephthalic acid are illustrated in the Examples 38-41 below.

With hydrogen bromide; oxygen; acetic acid; palladium diacetate; stannous acetate; antimony triacetate in water

T=182 - 195°C; P=20929.4 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 19 ; Title/Abstract Full Text Show Details

22; 23:

CONTROLS 22-23; Semi-continuous oxidations without tailouts were conducted as in Example 16 but with addition of 48 wt percent aqueous hydrobromic acid, which is a common bromine source used as a promoter in commercial manufacture of terephthalic acid by oxidation of para-xylene using cobalt-manganese catalysts. Results are reported in TABLE 13. Results from Example 16 are included for reference. In contrast to Example 16 in which no bromine was added, under otherwise identical conditions the oxidations in Controls 22 and 23 were impeded by the presence of the aqueous hydrogen bromide. The TA product selectivity fell by an order of magnitude and the main product was PTOL in Control 22. In Control 23, in which the bromine concentration was double the amount used in Control 22, only a trace of TA was made. Hide Details

With oxygen; acetic acid; palladium diacetate; [Mo2(acetate)4]; stannous acetate; antimony triacetate in water

T=193 - 199°C; P=20929.4 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 19-20 ; Title/Abstract Full Text Show Details

30; 31; 32; 34; 35; 36:

EXAMPLES 30-33; A catalyst composition of palladium, tin, antimony and molybdenum was used in a series of semi-continuous para-xylene oxidations conducted substantially as in Examples 6-9 except that in Examples 48-50 the reaction temperatures ranged from 193 to 199° C. Catalyst compositions were prepared by charging weighed amounts of palladium(II) acetate, antimony(III) acetate, tin(II) acetate, molybdenum(II) acetate

dimer and 95percent aqueous acetic acid to the reactor in amounts providing 4000 ppmw palladium, 2000 ppmw antimony, 2000 ppmw tin and 5000 ppmw molybdenum, calculated as metals and based on weight of aqueous acetic acid. Contents of the reactor were removed after each oxidation run and were analyzed as in Examples 6-9 to assess products and selectivities. Results of Examples 48-50, together with selectivities averaged over the three experiments, are reported in Table 14. Reactor contents from each run also included darkly colored solid particles. As seen from these examples and the table, terephthalic acid selectivity of the palladium, tin, antimony and molybdenum containing catalytic composition was exceptionally high and results of the three runs were highly reproducible.In Example 33, the procedure of Examples 30-32 was followed except that the temperature was increased to 203-209° C. The oxidation proceeded vigorously with even greater selectivity to terephthalic acid (97percent) than in Examples 30-32, 1.2percent 4CBA and 0.1percent each of PTOL and PTAL. Feedstock burning and generation of carbon oxides at the higher temperature were about 1.5-2 times the average of Examples 30-32; EXAMPLES 34-37; A series of oxidations experiments was conducted substantially as in Examples 30-32 except that concentrations of palladium, antimony, tin and molybdenum salts charged to the reactor were varied and the 95 wt percent aqueous acetic acid solution charged to the reactor with the catalyst metal salts and as supplemental solvent was diluted or replaced with water. Water contents in weight percent based on total solvent charged and results of analyses of the reactor contents in each of these experiments, including metals concentrations in the supernatant liquid from each run determined by inductive coupled plasma analyses ("ICP") are reported in Table 15. These examples and the table illustrate effectiveness of the catalyst composition in oxidations with increasing water contents from 5 to 100 wt percent. Of course, at 100percent, the solvent is only water. In oxidations using bromine-promoted cobalt-manganese catalyst compositions conventionally used in commercial manufacture of terephthalic acid, and also those using bromine free catalysts as in US Patent Application No. 2002/0188155, even small increases in water content of the liquid phase reaction mixtures can adversely affect both conversions and selectivity to desired terephthalic acid products. Surprisingly, however, Examples 34-36 and Table 15 illustrate that oxidations progressed actively, and with high selectivities to terephthalic acid, at water contents as high as 40 wt percent. It also was surprising that selectivities to intermediate oxidation products such as 4CBA, PTAL and PTOL decreased slightly with increases in water concentration to 40 wt percent. The decreases in selectivities for these intermediates are indicative of higher catalyst activity in the conversion of the intermediates to terephthalic acid. At 100 wt percent water as liquid medium for the oxidation in Example 37, conversion was lower than expected due to ineffective mixing of para-xylene and water in the apparatus used, but even with that difficulty, selectivity to carboxylic acid derivatives of the para-xylene feed was greater than 50percent and selectivity to terephthalic acid was 6percent. Oxidations in water with significantly higher conversions to oxidized para-xylene derivatives and selectivities to terephthalic acid are illustrated in the Examples 38-41 below. A

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175

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With oxygen; acetic acid; [Mo2(acetate)4]; 5-palladium/activated carbon; antimony triacetate in water

T=200 - 205°C; P=24290.9 Torr; 1.75 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 20-21 ; Title/Abstract Full Text Show Details

38; 39:

EXAMPLES 38-41; Semi-continuous para-xylene oxidations were conducted in water using supported and unsupported catalysts in 300 mL titanium Parr reactors linked to two liquid feed systems and outfitted with a Magnadrive stirrer and two parallel water-cooled titanium condensers for receiving overhead gas vented from the reactor. Gas feed to the reactor was controlled by a mass flow controller, the pressure was regulated by a back pressure regulator and vent gases were continuously analyzed for carbon monoxide, carbon dioxide and oxygen by a bank of three analyzers. The reactor was heated using a heating mantel with control over the heating profile managed by a Parr controller.The catalyst composition used in Examples 40 and 41 were supported catalyst compositions composed of palladium, antimony and molybdenum loaded at levels reported in TABLE 16 on titania and were prepared by calcining in air at 650° C. a mixed anatase and rutile phase titania powder identified as P25 having average primary particle size of 21 nm and BET surface area of 50 m2/g obtained from Degussa, cooling the titania, and wet impregnating it by excess liquid impregnation at room temperature using an aqueous solution containing palladium nitrate, antimony acetate, and ammonium heptamolybdate which was prepared by mixing individual stock solutions of the salts in relative proportions corresponding to the loading levels of the final supported catalyst compositions. The palladium nitrate stock solution was an aqueous 35 wt percent solution of palladium nitrate. The antimony acetate stock solution was prepared by mixing 5 grams antimony acetate with 10 grams citric acid monohydrate and 30 grams water at 60° C. for 1 hour and then cooling to room temperature. The ammonium heptamolybdate stock solution consisted of 10 grams ammonium heptamolybdate that had been mixed in 20 grams citric acid monohydrate and 60 grams water at 60° C. for 1 hour and then allowed to cool to room temperature. After addition of the impregnating solution to the titania, the slurry was homogenized by shaking briefly. The slurry was then dried at 50° C. for 60 hours, heated to 120° C. at a rate of 2° C. per minute, and held at 120° C. for 2 hours. The dried solid was then calcined under flowing air (100 mL/min) by heating slowly (0.4° C./min) to 400° C. and holding at 400° C. for 2 hours under air flow. The calcined solid was ground to a free-flowing powder and transferred to a crucible. The calcined solid was then reduced with hydrogen by exposure to a flow of dilute hydrogen (7 vol percent H2 in nitrogen) for 1 hour at room temperature and heating in an oven to 250° C. with increases in oven temperature at a rate of 0.4° C./min, after which the temperature was held at 250° C. for 5 hours under dilute hydrogen flow.The carbon-supported palladium used in combination with antimony and molybdenum acetate salt solutions in Examples 38 and 39 was a commercially available carbon-supported palladium in powder form containing 5 wt percent palladium and was obtained from Aldrich Corporation.Oxidations were begun by charging the reactor bottom with weighed amounts of catalyst or catalyst components and of distilled and deionized water ("DD Water") as liquid medium for the reaction. In each of the examples, 2.0 g of p-toluic acid were also added to the reaction mixture. After affixing the reactor bottom to the reactor head the reactor was filled and pressurized to 450 psig using high pressure bottled nitrogen. The reactor contents then were stirred and heating to a target initiation temperature, reported in TABLE 16, was begun. Once the reactor contents reached the target initiation temperature, reactions were begun by discontinuing the nitrogen flow and beginning a flow of a mixture of 8 vol percent oxygen and 92 vol percent nitrogen. Feed of liquid para-xylene at rates shown in TABLE 16 was then started. Semi-continuous oxidations were conducted for pre-determined periods of time, also reported in the table, and then the liquid feed addition was stopped while continuing the 8percent oxygen and 92percent nitrogen flow and heating for an additional period of time as reported in the table.After the oxidation periods ended, the 8percent oxygen plus 92percent nitrogen flow was stopped and nitrogen flow was resumed at 15 SCFH. The heating mantel was shut off and the reactor and its contents were allowed to cool to room temperature. At that point, the reactor was depressurized, the reactor bottom was detached and a sample of the total reactor effluent was collected for analysis by HPLC. Reaction conditions and results are shown in TABLE 16. Feedstock conversions in the table do not take into account unreacted feedstock that entered the vapor phase in the reactor such that it was unavailable for conversion to oxidized aromatic products. Unreacted feedstock in the vapor phase was estimated to be no more than about 5percent by weight of feed material.

With oxygen; acetic acid; 5 Pd/2.5 Sb/5 Mo/TiO2 in water

T=200 - 205°C; P=24290.9 Torr; 1.75 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 20-21 ; Title/Abstract Full Text Show Details

40:

With oxygen; acetic acid; 5 Pd/5 Sb/2.5 Mo/TiO2 in water

T=200 - 205°C; P=24290.9 Torr; 1.75 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 20-21 ; Title/Abstract Full Text Show Details

41:

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176

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With oxygen; acetic acid; palladium diacetate; antimony triacetate in water

T=167°C; P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 13-14; 22 ; Title/Abstract Full Text Show Details

With oxygen; acetic acid; palladium diacetate; V(acac)3; anhydrous calcium acetate; antimony triacetate in water

T=175°C; P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 21-22 ; Title/Abstract Full Text Show Details

43-18:

With oxygen; acetic acid; palladium diacetate; C8H12HfO8; cerium triacetate; antimony triacetate in water

T=171 - 174°C; P=10501.1 Torr; 1 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2009/69594 A1, 2009 ; Location in patent: Page/Page column 21-22 ; Title/Abstract Full Text Show Details

43-11; 43-14:

177

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With tetrabutylammomium bromide; tetra(n-butyl)ammonium hydroxide; water

T=25°C; Kinetics; Concentration;

Nummert, Vilve; Piirsalu, Mare; Vahur, Signe; Travnikova, Oksana; Koppel, Ilmar A.

Collection of Czechoslovak Chemical Communications, 2009 , vol. 74, # 1 p. 29 - 42 Title/Abstract Full Text View citing articles Show Details

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178

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Rx-ID: 28416006 Find similar reactions

Achmatowicz, Michal; Thiel, Oliver R.; Wheeler, Philip; Bernard, Charles; Huang, Jinkun; Larsen, Robert D.; Faul, Margaret M.

Journal of Organic Chemistry, 2009 , vol. 74, # 2 p. 795 - 809 Title/Abstract Full Text View citing articles Show Details

Stage #1: With tris-(dibenzylideneacetone)dipalladium(0); N-cyclohexyl-cyclohexanamine; 2-(dicyclohexylphosphino)-2'-methylbiphenyl in water; butan-1-ol

T=85°C; Suzuki coupling; 20 h; Inert atmosphere; Stage #2: With sodium hydroxide in water; butan-1-ol

T=60°C; 0.5 h; Inert atmosphere; Stage #3: With hydrogenchloride; water in butan-1-ol

pH=6 - 7; Inert atmosphere; A

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179

Synthesize Find similar Rx-ID: 28416007 Find similar reactions

A: 77%

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Stage #1: With sodium hydroxide; tris-(dibenzylideneacetone)dipalladium(0); 2-(dicyclohexylphosphino)-2'-methylbiphenyl in ethanol; water

T=78 - 80°C; Suzuki coupling; Inert atmosphere;

Achmatowicz, Michal; Thiel, Oliver R.; Wheeler, Philip; Bernard, Charles; Huang, Jinkun; Larsen, Robert D.; Faul, Margaret M.

Journal of Organic Chemistry, 2009 , vol. 74, # 2 p. 795 - 809

Title/Abstract Full Text View citing articles Show Details

Stage #2: With hydrogenchloride; water in ethanol

T=20°C; pH=3.4; Inert atmosphere; A

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180

Synthesize Find similar Rx-ID: 28416023 Find similar reactions

A: 54% B: 15% C: 10%

Stage #1: With isopropylmagnesium chloride in tetrahydrofuran

T=-50°C; 1 h; Inert atmosphere; Stage #2: With tri-isopropoxy-borane in tetrahydrofuran

T=-40 - -10°C; Inert atmosphere; Stage #3: With hydrogenchloride; water in tetrahydrofuran

T=20°C; pH=1 - 2; Inert atmosphere;

Achmatowicz, Michal; Thiel, Oliver R.; Wheeler, Philip; Bernard, Charles; Huang, Jinkun; Larsen, Robert D.; Faul, Margaret M.

Journal of Organic Chemistry, 2009 , vol. 74, # 2 p. 795 - 809 Title/Abstract Full Text View citing articles Show Details

181

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Rx-ID: 28533742 Find similar reactions

Stage #1: With 1,8-diazabicyclo[5.4.0]undec-7-ene in dichloromethane

T=22°C; 1 h; Stage #2: With hydrogenchloride in dichloromethane; water

Lipshutz, Bruce H.; Ghorai, Subir; Leong, Wendy Wen Yi

Journal of Organic Chemistry, 2009 , vol. 74, # 7 p. 2854 - 2857 Title/Abstract Full Text View citing articles Show Details

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182

Synthesize Find similar Rx-ID: 28612828 Find similar reactions

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A: 1.87 g

Stage #1: 9H-fluorene With ethanol; potassium tert-butylate

Reflux; Stage #2: 4-formyl-benzoic acid Reflux; Stage #3: With hydrogenchloride; water

Cooling with ice;

Dane, Eric L.; Maly, Thorsten; Debelouchina, Galia T.; Griffin, Robert G.; Swager, Timothy M.

Organic Letters, 2009 , vol. 11, # 9 p. 1871 - 1874 Title/Abstract Full Text View citing articles Show Details

183

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Rx-ID: 28613054 Find similar reactions

89%

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Stage #1: With lithium chloride in N,N-dimethyl-formamide

T=50°C; P=760.051 Torr; 24 h; Stage #2: With hydrogenchloride; water in N,N-dimethyl-formamide

Kobayashi, Koji; Kondo, Yoshinori

Organic Letters, 2009 , vol. 11, # 9 p. 2035 - 2037 Title/Abstract Full Text View citing articles Show Details

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184

Synthesize Find similar Rx-ID: 28693916 Find similar reactions

A: 2 %Spectr. B: 80%

With N-bromosuccinmide in water

T=27°C; 25 h; Irradiation;

Podgorsek, Ajda; Stavber, Stojan; Zupan, Marko; Iskra, Jernej

Tetrahedron, 2009 , vol. 65, # 22 p. 4429 - 4439 Title/Abstract Full Text View citing articles Show Details

185

Rx-ID: 28773480

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Find similar reactions

74%

With palladium diacetate; caesium carbonate; (Me)CgPPh in N,N-dimethyl-formamide

T=80°C; P=2327.23 Torr;

McNulty, James; Nair, Jerald J.; Capretta, Alfredo

Tetrahedron Letters, 2009 , vol. 50, # 28 p. 4087 - 4091 Title/Abstract Full Text View citing articles Show Details

186

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92%

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Rx-ID: 28785775 Find similar reactions

Khurana, Jitender M.; Arora, Reema

Synthesis, 2009 , # 7 art. no. Z23308SS, p. 1127 - 1130 Title/Abstract Full Text View citing articles Show Details

With methanol; sodium tetrahydroborate; NiII chloride hexahydrate

T=20°C; 0.166667 h; chemoselective reaction;

187

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Rx-ID: 28848995 Find similar reactions

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With ammonium metavanadate; rhodium(III) acetylacetonate; difluorochloroacetic anhydride; oxygen; Chlorodifluoroacetic acid

T=79.84°C; P=2587.76 Torr; 4 h; Inert atmosphere; Kinetics; Reagent/catalyst;

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188

Synthesize Find similar Rx-ID: 29082501 Find similar reactions

Zakzeski, Joseph; Behn, Andrew; Head-Gordon, Martin; Bell, Alexis T.

Journal of the American Chemical Society, 2009 , vol. 131, # 31 p. 11098 - 11105 Title/Abstract Full Text View citing articles Show Details

With potassium chloride; potassium hydroxide in water; dimethyl sulfoxide

T=25°C; KineticsMechanism; Reagent/catalystpH-value;

Murphy, John L.; Tenn III, William J.; Labuda, Joseph J.; Nagorski, Richard W.

Tetrahedron Letters, 2009 , vol. 50, # 52 p. 7358 - 7361 Title/Abstract Full Text View citing articles Show Details

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189

Synthesize Find similar Rx-ID: 29126955 Find similar reactions

A: 81%

With potassium superoxide; tetraethylammonium bromide in N,N-dimethyl-formamide

T=20°C; 2 h;

Singh, Satish Kumar; Singh, Krishna Nand

Phosphorus, Sulfur and Silicon and the Related Elements, 2009 , vol. 184, # 9 p. 2339 - 2343 Title/Abstract Full Text View citing articles Show Details

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190

Synthesize Find similar Rx-ID: 29348340 Find similar reactions

With oxygen in water

T=80°C; P=3750.38 Torr; 12 h;

Feng, Bo; Hou, Zhenshan; Wang, Xiangrui; Hu, Yu; Li, Huan; Qiao, Yunxiang

Green Chemistry, 2009 , vol. 11, # 9 p. 1446 - 1452 Title/Abstract Full Text View citing articles Show Details

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191

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A: 13.7% B: 59.2%

With 2,4-di-Nitrobenzene; sodium hydroxide in water

T=100°C; 2.5 h; Sealed tube;

Bjorsvik, Hans-Rene; Liguori, Lucia; Minisci, Francesco

Organic Process Research and Development, 2001 , vol. 5, # 2 p. 136 - 140 Title/Abstract Full Text View citing articles Show Details

With 2-hydroxy-1,3-isoindolinedione; oxygen; Mn(CH3COO)2*4H2O; [Co(O2CCH3)2]*4H2O in acetic acid

T=100°C; P=760.051 Torr; 15 h;

Nakamura, Ryota; Obora, Yasushi; Ishii, Yasutaka

Advanced Synthesis and Catalysis, 2009 , vol. 351, # 10 p. 1677 - 1684 Title/Abstract Full Text View citing articles Show Details

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192

Synthesize Find similar Rx-ID: 25972835 Find similar reactions

Bley, Filiz; Schaper, Klaus; Goerner, Helmut

Photochemistry and Photobiology, 2008 , vol. 84, # 1 p. 162 - 171 Title/Abstract Full Text View citing articles Show Details

T=25°C; KineticsQuantum yield; Further Variations:Solvents;

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193

Synthesize Find similar Rx-ID: 25972838 Find similar reactions

194

Bley, Filiz; Schaper, Klaus; Goerner, Helmut

Photochemistry and Photobiology, 2008 , vol. 84, # 1 p. 162 - 171 Title/Abstract Full Text View citing articles Show Details

T=25°C; KineticsQuantum yieldActivation energy; Further Variations:Solvents;

Synthesize Find similar Rx-ID: 25972845 Find similar reactions

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Bley, Filiz; Schaper, Klaus; Goerner, Helmut

Photochemistry and Photobiology, 2008 , vol. 84, # 1 p. 162 - 171 Title/Abstract Full Text View citing articles Show Details

T=25°C; KineticsQuantum yieldActivation energy; Further Variations:Solvents;

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195

Synthesize Find similar Rx-ID: 25972846 Find similar reactions

Bley, Filiz; Schaper, Klaus; Goerner, Helmut

Photochemistry and Photobiology, 2008 , vol. 84, # 1 p. 162 - 171 Title/Abstract Full Text View citing articles Show Details

T=25°C; KineticsQuantum yieldActivation energy; Further Variations:Solvents;

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196

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Bley, Filiz; Schaper, Klaus; Goerner, Helmut

Photochemistry and Photobiology, 2008 , vol. 84, # 1 p. 162 - 171 Title/Abstract Full Text View citing articles Show Details

T=25°C; KineticsQuantum yield; Further Variations:Solvents;

197

Synthesize Find similar Rx-ID: 27787361 Find similar reactions

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With oxygen; acetic acid; hydrogen bromide; anhydrous cobalt diacetate; Manganese (II) acetate in water

T=195 - 232°C; P=17326.7 - 36978.7 Torr; 0.333333 h; Product distribution / selectivity; Hide Experimental Procedure

BP CORPORATION NORTH AMERICA INC.

Patent: WO2008/67112 A2, 2008 ; Location in patent: Page/Page column 18-20; 21-24 ; Title/Abstract Full Text Show Details

1; 2; 3; 4; 5; A1; A2; A3; A4; A5; A6; A7; A8; B; 12; 13; 14; 15; 16; 18; 19; 20; 21; 22; 23; 24:

A series of oxidations of p-xylene using an MC catalyst was conducted in a volumetrically expanded liquid reaction mixture in a reaction vessel pressurized with carbon dioxide. The oxidations were conducted in a 78-milliliter liter titanium batch reactor fitted a valve for introduction of gas and equipped with an external shaker for agitation and an internal thermocouple for monitoring temperature of the reactor contents. The thermocouple also aided in evaluating expansion of the liquid oxidation reaction mixtures in the reactor because solid particles, primarily of terephthalic acid reaction product, from the reaction mixtures coated or clung to the thermocouple over the course of the oxidations such that observations of the initial liquid levels in the reactor at the start of the oxidations and of reactor volumes corresponding to heights of particles on the thermocouple at the end of the oxidations could be used to calculate expansion of the liquid body. The reactor was charged initially with catalyst solution in acetic acid and p-xylene feed and pressurized with the desired gas mixture. The reactor was placed in the shaker and immersed in a sand bath to bring the internal temperature to the desired reaction temperature within 1.5 minutes with shaking at a rate of 340 cycles per minute. After the desired oxidation time (typically 20 minutes), the reactor was cooled to room temperature with water directed into contact with its exterior surfaces from jets. The total product from the reactor was analyzed for carboxylic acid product content, as well as content of major intermediates (4-CBA and p-toluic acid). Off-gas was analyzed for CO, methyl bromide and oxygen.Preliminary to running oxidation experiments, the reactor was pressured with a 80/20 by volume mixture of CO2 and O2 with and without the presence of a known, constant volume of liquid acetic acid, in all cases at a temperature of 23 0C, and the reactor was weighed to determine the mass of the gas in the reactor with and without the acetic acid. Presence of an expanded volume of acetic acid in the reactor and <n="20"/>greater solubility of oxygen in the expanded acetic acid are consistent with the plot of

gas mass against pressure with and without acetic acid in Figure 1 , from which it is seen that at given pressures, the mass of the gas mixture added to the reactor was greater when acetic acid was present in the reactor than when acetic acid was not present.Example 1A stock catalyst solution containing cobalt (as cobalt acetate, 21 mM), manganese (as manganese acetate, 21 mM), and hydrogen bromide (21 mM) was prepared in 95percent aqueous acetic acid. Catalyst solution (5 g) and p-xylene (0.5 g) were added to the reactor followed by pressurization at room temperature with 80/20 by volume CO2/O2 to 3000 kPa, then further pressurized to 4930 kPa with CO2, such that the partial pressure of CO2 was 4330 kPa. The result was a 91/9 by volume CO2/O2 gas mixture with the concentration of Co, Mn, and HBr in the liquid mixture of 20 millimolar (mM) each. An oxidation reaction was conducted at 195 0C for 20 minutes with agitation, after which the reactor was cooled, depressured, opened, and product recovered by filtration. From the initial liquid level in the reactor and reactor volume corresponding to height of reaction product particles present on the thermocouple, the volume of the expanded liquid was calculated to correspond to an expansion ratio (Ve/V0) equal to 2.9. Oxidation of

acetic acid was estimated from the amount of carbon monoxide produced as reported as mole CO/mole p-xylene. Yields of terephthalic acid and intermediate oxidation products, expressed in mole percent based on feed, were determined by liquid chromatographic (LC) analysis of dry filter cake. The terephthalic acid recovered showed morphology similar to that observed in conventional preparations. Results are shown in Table 1. Example 2An oxidation was conducted in a manner similar to that described for Example1 except that the reactor was initially pressurized to 2310 kPa with 80/20 by volumeCO2/O2 and then further pressurized to 4930 kPa with CO2 providing a 93/7 CO2/O2 mixture, carbon dioxide partial pressure of 4585 kPa and an estimated Ve/Vo of about 3.2. Results are shown in Table 1. <n="21"/>Example 3An oxidation was conducted in a manner similar to that described for Example1 except that the reactor was initially pressurized to 3550 kPa with 80/20 by volumeCO2/O2 and then further pressurized to 4930 kPa with CO2 providing a 89/11 CO2/O2 mixture, carbon dioxide partial pressure of 4390 kPa and an estimated Ve/Vo of about 3. Results are shown in Table 1.Example 4An oxidation was conducted in a manner similar to that described for Example 1 except that the oxidation reaction was conducted for 10 minutes. Results are shown in Table 1.Example 5An oxidation was conducted in a manner similar to that described for Example 1 except that 2.5 g of catalyst stock solution and 2.5 g of 95percent acetic acid were used, which yielded 10 mM concentrations of Co, Mn, and HBr. Results are shown in Table 1.Comparative Runs A1-A8A series of eight comparative oxidation runs using the catalyst and p-xylene concentrations indicated in Example 1 was conducted without pressuring with CO2 using 95percent aqueous acetic acid as solvent and different 1/1/1 Co/MnBr catalyst concentrations of 5 to 35 mM. The total pressure was 3550 kPa using air as the oxidizing gas. Results from these runs including averaged data for baseline comparisons are reported in Table 1. <n="22"/>Table 1The amount of methyl bromide produced in Examples 1-5 was comparable to that produced in the comparative runs.Comparative Run B The oxidation reaction procedure of Example 5 was repeated except that the reactor was pressurized with air (80/20 by volume N2/O2) to 3550 kPa and then to 4930 kPa with nitrogen. The resulting gas mixture was 85/15 by volume N2/O2. The <n="24"/>resulting mole CO/mole pX, which reflected solvent burning, was 0.092, the total intermediates was 0.76 wtpercent, and the yield was 99.2 molepercent.Examples 10-16A series of oxidations was conducted similar to that described for Example 1 , except that the concentration of catalyst was varied, while the molar ratio of Co/Mn/Br catalyst components was fixed at 1/1/1. The results are shown in Table 3.Examples 17-20A series of oxidations was conducted in a manner similar to that described for Example 1 except the amount of water in the solvent (percent based on acetic acid) was varied. Ve/Vo was estimated to be about 2.9 in Examples 17 and 18, about 2.6 in Example 19 and about 2.0 in Example 20. Results are shown in Table 4.Examples 21-24A series of oxidations was conducted in a manner similar to that described for Example 1 at varying reaction temperatures. Also in these examples, 2 grams of a catalyst stock solution containing 21 mM concentrations of the Co/Mn/Br catalyst components were used with 2 grams of glacial (>99.5percent) acetic acid and 0.5 gram deionized water. The resulting catalyst concentration was 10 mM of each component and 10 wtpercent water. The results are shown in Table 5.

With oxygen; acetic acid; hydrogen bromide; anhydrous cobalt diacetate; Manganese (II) acetate

T=195°C; P=36978.7 Torr; 0.333333 h; Product distribution / selectivity; Hide Experimental Procedure

BP CORPORATION NORTH AMERICA INC.

Patent: WO2008/67112 A2, 2008 ; Location in patent: Page/Page column 22-23 ; Title/Abstract Full Text Show Details

17:

Examples 17-20A series of oxidations was conducted in a manner similar to that described for Example 1 except the amount of water in the solvent (percent based on acetic acid) was varied. Ve/Vo was estimated to be about 2.9 in Examples 17 and 18, about 2.6 in Example 19 and about 2.0 in Example 20. Results are shown in Table 4. A

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198

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Stage #1: With hydrogen bromide; oxygen; anhydrous cobalt diacetate; Manganese (II) acetate; benzoic acid in water

T=234.99°C; P=36961.4 Torr; 0.25 - 0.5 h; Stage #2: With hydrogen; 0.5 Pd/C in water

T=232.212 - 237.768°C; P=5171.62 Torr; 4 h; Product distribution / selectivity; Hide Experimental Procedure

BP Corporation North America Inc.

Patent: US2008/194866 A1, 2008 ; Location in patent: Page/Page column 4-6 ; Title/Abstract Full Text Show Details

4a; 4b; 5a; 5b:

A 2-liter reactor was charged with 442 g of benzoic acid and 443 g of water. Next, 0.67 g of cobalt(II) in the form of cobalt acetate, 1.86 g of manganese(II) in the form of manganese acetate, and 1.8 g of bromide ion in the form of 48percent HBr solution was added to the reactor. The reactor was pressurized (700 psig) with N2 purge, stirred, and heated to approximately the reaction temperature at 455° F. The paraxylene (pX) feedstock flow was initiated at 4.1 g/minute and the gas feed (0.45 standard cubic ft/minute) was changed to 21percent O2 to provide the oxidant. After 82 g of pX and about 20-30 g of additional water had been added, the feedstock addition was terminated, the gas low was changed to 8percent O2, and the stirring and heating was maintained for an additional 15 minutes to provide a 15-minute period of "post-oxidation".Table 2 below contains a summary of the oxidation conditions and the analytical results of the products. The "Total Product" was obtained by first drying the total reactor effluent to remove the water and obtain a representative sample of the aromatic components, analyzing the sample by liquid chromatography (LC), then calculating the component concentrations in the reactor at the water/benzoic acid concentrations used in the feedstock. The TA concentration in the reactor of 10.6percent for Example 2 is below the solubility of TA given in Example 1 (10.9percent at 455° F.) indicating that all of the TA formed was in solution and suitable for direct feeding to the purification step without additional process steps and equipment to dissolve TA solids.The off-gas from the reaction was continuously monitored for O2, CO, and CO2 content, thus providing the necessary information for burning calculations in Table 2.The analysis for organic impurities of a sample of the reactor off-gas taken midway through the pX addition period illustrates that the use of the benzoic acid/water solvent system virtually eliminated the formation of methyl bromide, methyl acetate, methane, and other components normally formed by the use of the conventional acetic acid solvent. The calculated total mols of COx/mol of pX fed was 0.34, which indicates that excessive burning of the solvent or feedstock did not occur even at the elevated temperatures of this reaction. Therefore, under the process conditions of this Example, benzoic acid was found to be relatively resistant to oxidation when a solvent containing 50percent water was used; Example 3 was conducted as indicated above for Example 2, except that the gas purge during the oxidation step was changed from 21percent O2 to pure N2 as soon as all of the pX feedstock had been added, thereby eliminating the post-oxidation step. The conditions and results from Example 3 are listed below in Table 2 and illustrate that a secondary oxidation step is not essential for high levels of pX conversion. The TA concentration in the reactor of 7.77percent for Example 3 is below the solubility of TA given in Example 1 (10.9percent at 455° F.) indicating that all of the TA formed was in solution and suitable for direct feeding to the purification step without additional process steps and equipment to dissolve TA solids. The formation of only 0.255 mol COx/mol pX illustrates the desirable burning resistance of the solvent and feedstock under these conditions; Examples 4 and 5 were conducted to demonstrate that hydrogenation of the 4-carboxybenzaldehyde (4-CBA) intermediate in the total reactor effluent from the oxidation step occurs in the presence of the benzoic acid, metals, and other oxidation impurities.To accomplish this, a sample of the dried oxidation total product (which includes the benzoic acid) from Examples 2 and 3, respectively, was charged to a 1 gallon reactor fitted with a basket to contain an aged commercial 0.5percent Pd/carbon hydrogenation catalyst. Water was then added to raise the level of the slurry to just below the catalyst basket. The mixed slurry was heated under N2 until the indicated temperature range (the same as used for the oxidation step, i.e., 450-460° F.) was reached. Hydrogen was next charged into the reactor to provide about 100 psi of hydrogen partial pressure. The catalyst basket was then lowered using external controls to contact the mixed liquid, and the hydrogenation was conducted for 4 hours.Following the 4-hour reaction period, the temperature was reduced, the reactor de-pressurized, and a total product was recovered. The composition of this total product, after removal of most of the water by drying, is shown below in Table 3. The total product contained no detectable 4-CBA, indicating that the hydrogenation catalyst was active for this reaction.The dried total product from hydrogenation was heated to about 300° F. and hot filtered, then washed with acetic acid to reduce the benzoic acid (simulating high temperature water washing). This treatment produced the "hot filtered cake" obtained from the corresponding total hydrogenated products in Table 3. Thus, Examples 4a and 4b were obtained from the product of Example 2 and Examples 5a and 5b were obtained from the product of Example 3. The results indicate that a TA product free of 4-CBA was obtained with this process.