Ethyl trifluoroacetate [C4H5F3O2] by Asch

Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

Query Query F

1. Query

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Date

91 reactions in Reaxys

2018-07-17 15h:55m:12s (UTC)

O F O

Search as: Product, As drawn, No mixtures ) AND (IDE.RN='383-63-1') AND (IDE.INCHI='STSCVKRWJPWALQ-UHFFFAOYSA-N') NOT (RX.RXRN=1761411))

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

F O

Rx-ID: 3752874 View in Reaxys 1/91 Yield

Conditions & References With [Ru(acetylacetonate)3], dihydrogen peroxide, oxygen in dichloromethane, Time= 3h, T= 110 °C , p= 3750.3Torr , other alkanes, Product distribution Diversi, Pietro; Ingrosso, Giovanni; Lucherini, Antonio; Sagramora, Laura; Salvadori, Eleonora; Gazzetta Chimica Italiana; vol. 123; nb. 3; (1993); p. 179 - 180 View in Reaxys With ammonium iodate, potassium chloride, T= 180 - 200 °C Schwartz, Nichole A.; Boaz, Nicholas C.; Kalman, Steven E.; Zhuang, Thompson; Goldberg, Jonathan M.; Fu, Ross; Nielsen, Robert J.; Goddard, William A.; Groves, John T.; Gunnoe, T. Brent; ACS Catalysis; vol. 8; nb. 4; (2018); p. 3138 3149 View in Reaxys

O O

Rx-ID: 38183385 View in Reaxys 2/91 Yield

Conditions & References

0.13 mmol, 30 %, 0.06 mmol

With ammonium iodate, potassium chloride, Time= 1h, T= 180 °C , p= 15526.6Torr , Sealed tube Fortman, George C.; Boaz, Nicholas C.; Munz, Dominik; Konnick, Michael M.; Periana, Roy A.; Groves, John T.; Brent Gunnoe; Journal of the American Chemical Society; vol. 136; nb. 23; (2014); p. 8393 - 8401 View in Reaxys With ammonium iodate, potassium chloride, T= 140 °C Schwartz, Nichole A.; Boaz, Nicholas C.; Kalman, Steven E.; Zhuang, Thompson; Goldberg, Jonathan M.; Fu, Ross; Nielsen, Robert J.; Goddard, William A.; Groves, John T.; Gunnoe, T. Brent; ACS Catalysis; vol. 8; nb. 4; (2018); p. 3138 3149 View in Reaxys

F I

O O

O F

F O

F O O F

Rx-ID: 48052493 View in Reaxys 3/91 Yield

Conditions & References With ammonium iodate, potassium chloride, Time= 0.333333h, T= 180 °C , p= 5171.62Torr , Inert atmosphere, Temperature Schwartz, Nichole A.; Boaz, Nicholas C.; Kalman, Steven E.; Zhuang, Thompson; Goldberg, Jonathan M.; Fu, Ross; Nielsen, Robert J.; Goddard, William A.; Groves, John T.; Gunnoe, T. Brent; ACS Catalysis; vol. 8; nb. 4; (2018); p. 3138 3149 View in Reaxys F

F O

Rx-ID: 779590 View in Reaxys 4/91 Yield 100 %

Conditions & References Time= 24h, Heating, others alcohols, Product distribution

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

Hagen, Arnulf P.; Miller, Tammy S.; Bynum, Richard L.; Kapila Ved P.; Journal of Organic Chemistry; vol. 47; nb. 7; (1982); p. 1345 - 1347 View in Reaxys 100 %

Time= 24h, Heating Hagen, Arnulf P.; Miller, Tammy S.; Bynum, Richard L.; Kapila Ved P.; Journal of Organic Chemistry; vol. 47; nb. 7; (1982); p. 1345 - 1347 View in Reaxys

100 %

4 With 4-hydroxyacetophenone oxime, Time= 2h, T= 69.84 °C , p= 760.051Torr , Inert atmosphere, Sealed tube Quartarone, Giuseppe; Rancan, Elia; Ronchin, Lucio; Vavasori, Andrea; Applied Catalysis A: General; vol. 472; (2014); p. 167 - 177 View in Reaxys

99.2 %

3 :23] Example 3 2000L reactor, with a diameter of 200mm, A height of 15 meters of the distillation tower, It is divided into 7meter extraction section, 8-meter distillation section, and 20m2 enamel condenser. Using concentrated sulfuric acid as a catalyst. [0 024] under cooling conditions, To 1000kg of trifluoroacetic acid in advance slowly add 150kg concentrated sulfuric acid, Mixed evenly after the trifluoroacetic acid chestnut into the high slot The To the reaction dad to add 400Kg trifluoroacetic acid, 80kg concentrated sulfuric acid, 161.5kg anhydrous ethanol, And then heated to reflux for 30 minutes, to be the distillation column after the stability of the components, Start from the top of the extraction section to 120kg / h speed by adding trifluoroacetic acid, Plus trifluoroacetic acid at the same time, began to the reactor to 40kg / h speed plus ethanol, After 10 minutes of full reflux, Tower top temperature stable at 61 ° C, Began to 125kg / h rate of extraction of ethyl trifluoroacetateAfter 10 hours to stop the feed and recovery, After the reactor is cooled, Kettle material placed in the layered treatment, The organic layer in the reactor was thoroughly calculated and the pure ethyl trifluoroacetate was obtained. The total yield of the reaction was 99.2percent Pure ethyl trifluoroacetate content of 99.94percent. With sulfuric acid, Time= 0.666667h, T= 61 °C , Reflux Patent; Nantong BaoKai Chemical Co., Ltd.; Li, Huaxin; Yan, Zonggang; Ge, Fanlong; Wu, Shengjun; (6 pag.); CN106431908; (2017); (A) Chinese View in Reaxys

84.3 %

With sulfuric acid, Time= 3h, Heating Yuan, Chengye; Li, Jinfeng; Zhang, Wenchi; Journal of Fluorine Chemistry; vol. 127; nb. 1; (2006); p. 44 - 47 View in Reaxys With sulfuric acid Bergman; Journal of Organic Chemistry; vol. 23; (1958); p. 476 View in Reaxys

415 g

5 : Example 5 200 g of the catalyst D72 resin was charged in a 1000 ml single-necked flask,360 g trifluoroacetic acid,Stirring heated to 50 ° C,300 g of anhydrous ethanol was added dropwise,The temperature was kept at 50 ° C and dropping was completed.Stirred for 20 minutes,The mixture was heated to reflux and separated from water and ethanol (60 g)Distillation was initiated and the product was collected and the mixture of ethanol and water was brought to a stable gas phase temperature of 65 ° C without distillate stoppingheating. 510 g of crude was collected. Distillation of crude, containing 15percent alcohol, the first to add 20percent of the weight of the water washing once, the separation of the lower 95percent of the crude, according to this method can be washed twice 99.6percent purity ethyl trifluoroacetate, then The product slowly heated to 60 dehydration, water was less than 0.1percent of the product 415g. With D72 resin, Time= 0.333333h, T= 50 °C , Reflux, Temperature Patent; Nanjing Qi is Chemical Co., Ltd.; Che, Hong; Xi, Yanan; Wang, Chengxiu; Zhong, Qijun; (5 pag.); CN104710308; (2016); (B) Chinese View in Reaxys

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

Br O

Rx-ID: 44306111 View in Reaxys 5/91 Yield

Conditions & References

90 %Spectr. General procedure C for the halogen exchange reaction using (PPh3)3CuF General procedure: A reaction vial was charged with the corresponding bromodifluoderivative 1a-i, 5h-j (0.1 mmol, 1 equiv.), (PPh3)3CuF (0.14 mmol, 1.4 equiv., 122 mg) and dry DMF (0.3 mL) under an atmosphere of argon. The reaction was stirred at 100 °C for 2.5 h.The reaction was cooled down and α,α,α-trifluorotoluene (3 equiv., 37 mL) was added as internal standard and the yield was calculated by 19F NMR spectroscopy. With C54H45CuFP3 in N,N-dimethyl-formamide, Time= 2.5h, T= 100 °C , Inert atmosphere, Solvent, Temperature Bermejo Góme, Antonio; González, Miguel A. Cortés; Lübcke, Marvin; Johansson, Magnus J.; Schou, Magnus; Szabó, Kálmán J.; Journal of Fluorine Chemistry; vol. 194; (2017); p. 51 - 57 View in Reaxys

Cl OH

Br F

Rx-ID: 45551784 View in Reaxys 6/91 Yield

Conditions & References

21.7 g

7 : Preparation of ethyl trifluoroacetate At room temperature and pressure,Trifluorodibromoethane (40 g, 0.14 mol),Anhydrous ethanol (40 g, 0.87 mol) in dichloromethane (130 g, 1.4 mol)Adding to a reactor equipped with a condenser tube,Open the ozone generator,Ozone flow rate 8g / h.After 3 hours, the reaction solution was washed with water, saturated sodium bisulfite, saturated sodium bicarbonate, and 20 g of ethanol was added to the organic layer to continue the reactionTo the completion of the conversion of raw materials, and then again with water, saturated sodium bisulfite, saturated sodium bicarbonate, saturated brine, organic layerDried over anhydrous magnesium sulfate to give the crude product of ethyl trifluoroacetate, and the resulting crude product was transferred to a distillation column for distillation and collected 60° C to 62 ° C, and finally 21.7 g of ethyl trifluoroacetate and a molar yield of 95.0percent. With ozone in dichloromethane, Time= 3h, T= 20 °C , p= 760.051Torr Patent; LIANYUANGANG JINKANG PHARMACEUTICAL TECHNOLOGY CO., LTD.; CHENG, YONGZHI; WANG, HAI; JI, LI; (11 pag.); CN104628559; (2017); (B) Chinese View in Reaxys

F OH

F O

Rx-ID: 44434202 View in Reaxys 7/91 Yield 97.86 %

Conditions & References 4 : Example 4 The reactor was a three-necked flask having a volume of 250 ml,With stirring,thermometer,Airway and rectification column,The rectification column is connected to a condenser and a HCl absorption device.88 g of ethanol was added to the reactor,After the temperature had risen to 35 ° C, trifluoroacetyl chloride gas was introduced,The trifluoroacetyl chloride was fed at a feed rate of 2 g / min.After reaction at 35 ° C for 60 min,The ethanolic liquid was started to drop,The dropping rate of ethanol was 0.31 g / min,The temperature was gradually increased to 58 ° C,Distillation of ethyl trifluoroacetate was carried out by reactive distillation,The hydrogen chloride gas was absorbed by the HCl absorption device,Generation by-product hydrochloric acid.Reaction distillation for 160min to obtain distillation products 425.7g,Chromatographic analysis of the purity of ethyl trifluoroacetate was 97.93percentThe yield was 97.86percent. , Time= 1h, T= 35 - 58 °C , Temperature Patent; Sinochem Lantian Co., Ltd.; Li, Hua; Xu, Weiguo; Jiang, Qiang; Dai, Jialiang; Yang, Wangsong; (7 pag.); CN103864615; (2016); (B) Chinese View in Reaxys

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

1 :The reactor was a three-necked flask in a volume of 250 ml equipped with a stirrer, a thermometer, an airway, a dropping funnel and a distillation column, and the distillation column was connected to a condenser and a HCl absorber. The condensate recovers the unreacted complete trifluoroacetyl chloride in the exhaust gas, and then absorbs the hydrogen chloride gas through the absorption device, by-product hydrochloric acid. 80.0 g of ethyl acetate and ethanol mixed waste (in which the ethanol content of 44.8percent, ethyl acetate content of 54.2percent), rose to 40 after the introduction of trifluoroacetyl chloride gas, to maintain the rate of trifluoroacetyl chloride For 2.0 g / min. After 20 min of ventilation, the mixture was added dropwise with ethyl acetate and ethanol. The dropping speed was 1.3 g / min, and the temperature was gradually raised to 60 ° C,The reaction distillation was carried out to distill off the resulting ethyl trifluoroacetate and ethyl acetate. Reaction distillation 180min, a total of 465.2g distillation products,Chromatographic analysis of ethyl trifluoroacetate content of 68.9percent,The ethyl acetate content was 30.1percent. 15.2 g of unreacted trifluoroacetyl chloride was collected in the condenser. With hydrogenchloride in water, ethyl acetate, Time= 0.333333h, T= 40 - 60 °C , Temperature Patent; hejiang chemical science and Technology Co., Ltd.; Zhejiang Lantian Environmental Protection Hi-tech Co., Ltd; SINOCHEM LANTIAN CO., LTD.; Jiang, Qiang; Xu, Weiguo; Li, Hua; Hong, Jian; Miao, Shuibin; Ma, Xiaohong; Wu, Huaming; (7 pag.); CN104672091; (2016); (B) Chinese View in Reaxys F

HO F O

F Cl

O O

O F

O O

Rx-ID: 39635284 View in Reaxys 8/91 Yield

Conditions & References With potassium metaperiodate, potassium chloride, Time= 1h, T= 200 °C , p= 15526.6Torr , High pressure, Reagent/catalyst Kalman, Steven E.; Munz, Dominik; Fortman, George C.; Boaz, Nicholas C.; Groves, John T.; Gunnoe, T. Brent; Dalton Transactions; vol. 44; nb. 12; (2015); p. 5294 - 5298 View in Reaxys

F 3

–O

O O

Tl3+

F O O

Rx-ID: 37498841 View in Reaxys 9/91 Yield

Conditions & References With trifluoroacetic acid, Time= 3h, T= 180 °C , Overall yield = 75 percent Hashiguchi, Brian G.; Konnick, Michael M.; Bischof, Steven M.; Gustafson, Samantha J.; Devarajan, Deepa; Gunsalus, Niles; Ess, Daniel H.; Periana, Roy A.; Science; vol. 343; nb. 6176; (2014); p. 1232 - 1237 View in Reaxys

F 4

O F

Pb4+

O–

F O

O O

F O O F

Rx-ID: 38457337 View in Reaxys 10/91 Yield

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

1361.193W01 / TSRI Case 1560.1 PCT / FLA0129P Table 2. Reaction of Tl and Pb Oxidants with Methane, Ethane, and/or Propane. Standard Conditions: 0.25 M T1(TFA)3 or Pb(TFA)4 in 2 ml TFAH, gas pressure (MeH = 500 psig, EtH = 500 psig, or PrH = 125 psig), 180 °C 3 h. Cone (M) = (mol oxidant)/(L solvent added). Product Selectivity = [Individual Liquid Product]/ [Total Liquid Products]xl00. Yield based o 1H-NMR = [Oxidant]/[Total Liquid Products]xl00, [Product] = (mol Product)/(L solvent added). ^Pressure = 800 psig and T = 190 °C.†Total pressure = 500 psig. ^un with 2 M H20 present. Run with 15 psi 02 present. "Reactions were run at 150 °C. ^Products were a mixture of EtTF Et(MSA), EG(TFA)2, and EG(MSA)2. We focused primarily on trifluoroacetic acid (HTFA) as the reaction medium, but also observed efficient reactivity in other non-superacidic solvents such as methane sulfonic acid (MSA, entry 10), (HO Ac, entry 11), and TFAH/H20 mixtures (entry 7). Importantly, in contrast to the reported reactions with (bpym)Pt11 or Hgn in superacid media, no evidence for C-C cleavage or other side products were observed with the higher alkanes, ethane and propane. , Time= 3h, T= 180 °C , p= 26618.1Torr , Temperature, Overall yield = 90 percentSpectr. Patent; THE SCRIPS RESEARCH INSTITUTE; PERIANA, Roy; HASHIGUCHI, Brian G.; KONNICK, Michael M.; BISCHOF, Steven M.; WO2014/130987; (2014); (A1) English View in Reaxys

Bi3+

F (v0)

F O

–

F O

Rx-ID: 38457338 View in Reaxys 11/91 Yield

Conditions & References The Bi(TFA)3 greatly changes the selectivity of the oxidation of ethane with H202, it is important to also understand the differences in rate between the background and catalyzed reaction. However, to observe this requires lowering the reaction temperature from 180 °C to 80 °C. Under these reaction conditions, even after 1 hour, the catalyzed reaction achieves 75percent yield and the uncatalyzed reaction is <5percent yield. 25 mM Bi(TFA)3, 500 mM H202 EtH - EtTFA 500 psig 80 °C, 1 h, HTFA / TFAA(to balance water) Table 3 provides experimental results obtained by use of the Bi / H202 system. Table 3. Oxidation of ethane with H?02_catalvzed by Bi(TFA)3. Standard conditions: 25 mM Bi(TFA)3, 500 mM H202, 500 psig EtH, 1.75 ml HTFA, 0.22 ml TFAA (removes water from 50percent H202 solution). With sodium perborate, trifluoroacetic anhydride, Time= 1h, T= 180 °C , p= 26618.1Torr , Catalytic behavior, Temperature, Reagent/catalyst Patent; THE SCRIPS RESEARCH INSTITUTE; PERIANA, Roy; HASHIGUCHI, Brian G.; KONNICK, Michael M.; BISCHOF, Steven M.; WO2014/130987; (2014); (A1) English View in Reaxys

Bi3+

F (v0)

O–

F O

Rx-ID: 38457339 View in Reaxys 12/91 Yield

Conditions & References The Bi(TFA)3 greatly changes the selectivity of the oxidation of ethane with H202, it is important to also understand the differences in rate between the background and catalyzed reaction. However, to observe this requires lowering the reaction temperature from 180 °C to 80 °C. Under these reaction conditions, even after 1 hour, the catalyzed reaction achieves 75percent yield and the uncatalyzed reaction is <5percent yield. 25 mM Bi(TFA)3, 500 mM H202 EtH - EtTFA 500 psig 80 °C, 1 h, HTFA / TFAA(to balance water) Table 3 provides experimental results obtained by use of the Bi / H202 system. Table 3. Oxidation of ethane with H?02_catalvzed by Bi(TFA)3. Standard conditions: 25 mM Bi(TFA)3, 500 mM H202, 500 psig EtH, 1.75 ml HTFA, 0.22 ml TFAA (removes water from 50percent H202 solution). With dihydrogen peroxide, trifluoroacetic anhydride, Time= 1h, T= 80 °C , p= 26618.1Torr , Catalytic behavior Patent; THE SCRIPS RESEARCH INSTITUTE; PERIANA, Roy; HASHIGUCHI, Brian G.; KONNICK, Michael M.; BISCHOF, Steven M.; WO2014/130987; (2014); (A1) English View in Reaxys

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

F F

O F

F O

O O

F O

Rx-ID: 38457340 View in Reaxys 13/91 Yield

Conditions & References Heating a 100 mM solution of C6F5-Iin(TFA)2 at 150°C for 3 hrs in 100 mM TFAA/HTFA under 500 psi of methane or ethane (125 psi for PrH) was shown by the 1H-NMR of the crude reaction mixtures to generate the respective trifluoroacetate (TFA) mono-esters and 1 ,2-TFA-diesters (for EtH and PrH) as shown in Eq. 9: R-H + C6F5-l'"(TFA)2 R-TFA + C6F5-l' + HTFA TFAA HTFA (R = Me, Et, Pr, Ph) gq 9 1361.193W01 / TSRI Case 1560.1 PCT / FLA0129P Table 4. Conversions of Unactivated Hydrocarbons with Iodine, Selenium, and Tellurium Reagents The reactions are highly selective and no hydrocarbon derived products are observed besides the respective mono- and 1,2-di-esters (Table 5). 19F-NMR analysis of the solutions post-reaction showed that C6F5-Ini(TFA)2 is converted to C6F5-I1, as the reaction proceeds with no intermediate iodine species observed. With iodic acid, Time= 3h, T= 150 °C , p= 25858.1Torr , Reagent/catalyst, Temperature Patent; THE SCRIPS RESEARCH INSTITUTE; PERIANA, Roy; HASHIGUCHI, Brian G.; KONNICK, Michael M.; BISCHOF, Steven M.; WO2014/130987; (2014); (A1) English View in Reaxys F F

HO F

F O

F F

O O

Rx-ID: 38457341 View in Reaxys 14/91 Yield

Conditions & References Heating a 100 mM solution of C6F5-Iin(TFA)2 at 150°C for 3 hrs in 100 mM TFAA/HTFA under 500 psi of methane or ethane (125 psi for PrH) was shown by the 1H-NMR of the crude reaction mixtures to generate the respective trifluoroacetate (TFA) mono-esters and 1 ,2-TFA-diesters (for EtH and PrH) as shown in Eq. 9: R-H + C6F5-l'"(TFA)2 R-TFA + C6F5-l' + HTFA TFAA HTFA (R = Me, Et, Pr, Ph) gq 9 1361.193W01 / TSRI Case 1560.1 PCT / FLA0129P Table 4. Conversions of Unactivated Hydrocarbons with Iodine, Selenium, and Tellurium Reagents The reactions are highly selective and no hydrocarbon derived products are observed besides the respective mono- and 1,2-di-esters (Table 5). 19F-NMR analysis of the solutions post-reaction showed that C6F5-Ini(TFA)2 is converted to C6F5-I1, as the reaction proceeds with no intermediate iodine species observed. With oxygen, iodic acid, Time= 3h, T= 150 °C , p= 25858.1Torr Patent; THE SCRIPS RESEARCH INSTITUTE; PERIANA, Roy; HASHIGUCHI, Brian G.; KONNICK, Michael M.; BISCHOF, Steven M.; WO2014/130987; (2014); (A1) English View in Reaxys F F

O F

F O

O F

Rx-ID: 38457342 View in Reaxys 15/91

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

Yield

Conditions & References Heating a 100 mM solution of C6F5-Iin(TFA)2 at 150°C for 3 hrs in 100 mM TFAA/HTFA under 500 psi of methane or ethane (125 psi for PrH) was shown by the 1H-NMR of the crude reaction mixtures to generate the respective trifluoroacetate (TFA) mono-esters and 1 ,2-TFA-diesters (for EtH and PrH) as shown in Eq. 9: R-H + C6F5-l'"(TFA)2 R-TFA + C6F5-l' + HTFA TFAA HTFA (R = Me, Et, Pr, Ph) gq 9 1361.193W01 / TSRI Case 1560.1 PCT / FLA0129P Table 4. Conversions of Unactivated Hydrocarbons with Iodine, Selenium, and Tellurium Reagents The reactions are highly selective and no hydrocarbon derived products are observed besides the respective mono- and 1,2-di-esters (Table 5). 19F-NMR analysis of the solutions post-reaction showed that C6F5-Ini(TFA)2 is converted to C6F5-I1, as the reaction proceeds with no intermediate iodine species observed. With iodic acid, Time= 3h, T= 150 °C , p= 25858.1Torr Patent; THE SCRIPS RESEARCH INSTITUTE; PERIANA, Roy; HASHIGUCHI, Brian G.; KONNICK, Michael M.; BISCHOF, Steven M.; WO2014/130987; (2014); (A1) English View in Reaxys F F O F

O I

F F

O O

Rx-ID: 38457344 View in Reaxys 16/91 Yield

Conditions & References Heating a 100 mM solution of C6F5-Iin(TFA)2 at 150°C for 3 hrs in 100 mM TFAA/HTFA under 500 psi of methane or ethane (125 psi for PrH) was shown by the 1H-NMR of the crude reaction mixtures to generate the respective trifluoroacetate (TFA) mono-esters and 1 ,2-TFA-diesters (for EtH and PrH) as shown in Eq. 9: R-H + C6F5-l'"(TFA)2 R-TFA + C6F5-l' + HTFA TFAA HTFA (R = Me, Et, Pr, Ph) gq 9 1361.193W01 / TSRI Case 1560.1 PCT / FLA0129P Table 4. Conversions of Unactivated Hydrocarbons with Iodine, Selenium, and Tellurium Reagents The reactions are highly selective and no hydrocarbon derived products are observed besides the respective mono- and 1,2-di-esters (Table 5). 19F-NMR analysis of the solutions post-reaction showed that C6F5-Ini(TFA)2 is converted to C6F5-I1, as the reaction proceeds with no intermediate iodine species observed. With trifluoroacetic anhydride, Time= 3h, T= 150 °C , p= 25858.1Torr Patent; THE SCRIPS RESEARCH INSTITUTE; PERIANA, Roy; HASHIGUCHI, Brian G.; KONNICK, Michael M.; BISCHOF, Steven M.; WO2014/130987; (2014); (A1) English View in Reaxys F F F

F F

O O

O F

F O

F F

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

O O

Rx-ID: 38457348 View in Reaxys 17/91 Yield 72 %Spectr., 8 %Spectr.

Conditions & References The reactions are highly selective and no hydrocarbon derived products are observed besides the respective mono- and 1,2-diesters (Table 5). 19F-NMR analysis of the solutions post-reaction showed that C6F5-Ini(TFA)2 is converted to C6F5-I1, as the reaction proceeds with no intermediate iodine species observed. With trifluoroacetic anhydride, Time= 3h, T= 150 °C , p= 25858.1Torr Patent; THE SCRIPS RESEARCH INSTITUTE; PERIANA, Roy; HASHIGUCHI, Brian G.; KONNICK, Michael M.; BISCHOF, Steven M.; WO2014/130987; (2014); (A1) English View in Reaxys F F F

F F

O O

F F

Rx-ID: 38457349 View in Reaxys 18/91 Yield

Conditions & References

73 %Spectr. The reactions are highly selective and no hydrocarbon derived products are observed besides the respective mono- and 1,2-diesters (Table 5). 19F-NMR analysis of the solutions post-reaction showed that C6F5-Ini(TFA)2 is converted to C6F5-I1, as the reaction proceeds with no intermediate iodine species observed. With trifluoroacetic anhydride, Time= 3h, T= 150 °C , p= 25858.1Torr Patent; THE SCRIPS RESEARCH INSTITUTE; PERIANA, Roy; HASHIGUCHI, Brian G.; KONNICK, Michael M.; BISCHOF, Steven M.; WO2014/130987; (2014); (A1) English View in Reaxys F F F F

(v2)– O

(v3)

O – (v2) OO– Tl3+ O(v3)

F HO

O (v3)

(v6)

(v2)

F O

O O

F F

O F

Rx-ID: 38457351 View in Reaxys 19/91 Yield

Conditions & References Contrary to the predictions discussed above, we have surprisingly discovered that soft oxidizing electrophiles Tlin(TFA)3 and PbIV(TFA)4, among others, can rapidly functionalize methane, ethane and propane separately or as mixtures, in high selectivity and concentrations, to the corresponding trifluoroacetate esters of methanol (MeTFA), ethanol (EtTFA), ethylene glycol (EG(TFA)2), isopropanol (iPrTFA), and 1 ,2-propylene glycol (PG(TFA)2) (Table 2: entries 1-6, 8, 9, 12-15). Table 2 shows data relating to the reaction of lead and thallium based soft oxidizing electrophiles with methane, ethane, and/or propane. 1361.193W01 / TSRI Case 1560.1 PCT / FLA0129P Table 2. Reaction of Tl and Pb Oxidants with Methane, Ethane, and/or Propane. Standard Conditions: 0.25 M T1(TFA)3 or Pb(TFA)4 in 2 ml TFAH, gas pressure (MeH = 500 psig, EtH = 500 psig, or PrH = 125 psig), 180 °C 3 h. Cone (M) = (mol oxidant)/(L solvent added). Product Selectivity = [Individual Liquid Product]/ [Total Liquid Products]xl00. Yield based o 1H-NMR = [Oxidant]/[Total Liquid Products]xl00, [Product] = (mol Product)/(L solvent added). ^Pressure = 800 psig and T = 190 °C.†Total pressure = 500 psig. ^un with 2 M H20 present. Run with 15 psi 02 present. "Reactions were run at 150 °C. ^Products were a mixture of EtTF Et(MSA), EG(TFA)2, and EG(MSA)2. We focused primarily on trifluoroacetic acid (HTFA) as the reaction medium, but also observed efficient reactivity in other non-superacidic solvents such as methane sulfonic acid (MSA, entry 10), (HO Ac, entry 11), and TFAH/H20 mixtures (entry 7). Importantly, in

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

contrast to the reported reactions with (bpym)Pt11 or Hgn in superacid media, no evidence for C-C cleavage or other side products were observed with the higher alkanes, ethane and propane. With oxygen, Time= 3h, T= 180 °C , p= 26618.1Torr , Kinetics, Temperature, Concentration, Overall yield = 76 percentSpectr. Patent; THE SCRIPS RESEARCH INSTITUTE; PERIANA, Roy; HASHIGUCHI, Brian G.; KONNICK, Michael M.; BISCHOF, Steven M.; WO2014/130987; (2014); (A1) English View in Reaxys F

O F

F F

O F F

O F

Rx-ID: 42093427 View in Reaxys 20/91 Yield

Conditions & References

73 %

With trifluoroacetic acid, trifluoroacetic anhydride, T= 150 °C , Inert atmosphere Konnick, Michael M.; Hashiguchi, Brian G.; Devarajan, Deepa; Boaz, Nicholas C.; Gunnoe, T. Brent; Groves, John T.; Gunsalus, Niles; Ess, Daniel H.; Periana, Roy A.; Angewandte Chemie - International Edition; vol. 53; nb. 39; (2014); p. 10490 - 10494; Angew. Chem.; vol. 126; nb. 39; (2014); p. 10658 - 10662,5 View in Reaxys

N O

Rx-ID: 37685120 View in Reaxys 21/91 Yield

Conditions & References Ethyl Trifluoroacetate Sulfonimidate 1 (30 mg, 105 μmol, 1.1 equiv), dissolved in CCl4 (0.5 mL), was added to an NMR tube followed by TFA (7.1 μL,10.9 mg, 95.2 μmol). The tube was shaken and analyzed by NMR to observe that the reaction was complete. The mixture was filtered through a Pasteur pipet fitted with glass wool and 2-cm of silica gel to remove the byproduct sulfonamide 2. The filter was rinsed with additional CCl4 (0.25 mL) into a separate NMR tube. CDCl3 (0.25mL) and a drop of TMS were added for NMR analysis. Only ethyl trifluoroacetate was observed. in tetrachloromethane Maricich, Tom J.; Allan, Matthew J.; Kislin, Brett S.; Chen, Andrea I-T.; Meng, Fan-Chun; Bradford, Christine; Kuan, Nai-Chia; Wood, Jeremy; Aisagbonhi, Omonigho; Poste, Alethea; Wride, Dustin; Kim, Sylvia; Santos, Therese; Fimbres, Michael; Choi, Dianne; Elia, Haydi; Kaladjian, Joseph; Abou-Zahr, Ali; Mejia, Arturo; Synthesis (Germany); vol. 45; nb. 24; (2013); p. 3361 - 3368; Art.No: SS-2013-M0543-OP View in Reaxys F

F O

Rx-ID: 33106478 View in Reaxys 22/91 Yield 99 %

Conditions & References 3 :Ethyl difluoroacetate (60 g, 0.484 mol) is brought together with trifluoroacetic acid (56 g, 0.484 mol, 1 equivalent) in a glass reactor surmounted by a distillation column.The reaction medium is brought to the temperature of 85° C. at atmospheric pres-

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

sure.Ethyl trifluoroacetate is distilled off while keeping the temperature of the distillation top at 63° C.A fraction of 69 g of ethyl trifluoroacetate is obtained.All of the ethyl difluoroacetate was consumed (DC=100percent) and the difluoroacetic acid obtained at the distillation bottom has a purity of 99.5percent by weight.The yield (RY) is greater than 99percent. , T= 85 °C , Product distribution / selectivity Patent; RHODIA OPERATIONS; US2012/123159; (2012); (A1) English View in Reaxys O O

F O

O F

Rx-ID: 29169114 View in Reaxys 23/91 Yield

Conditions & References

95 %

in chloroform, Time= 20h, T= 25 °C Li, Wei; Li, Jianchang; Wu, Yuchuan; Fuller, Nathan; Markus, Michelle A.; Journal of Organic Chemistry; vol. 75; nb. 4; (2010); p. 1077 - 1086 View in Reaxys F

O O

F F

F F O F O

O O F O

Rx-ID: 29169115 View in Reaxys 24/91 Yield 92 %

Conditions & References in chloroform, Time= 1h, T= 20 °C Li, Wei; Li, Jianchang; Wu, Yuchuan; Fuller, Nathan; Markus, Michelle A.; Journal of Organic Chemistry; vol. 75; nb. 4; (2010); p. 1077 - 1086 View in Reaxys

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

O F O S

O F O

N O

Rx-ID: 29695396 View in Reaxys 25/91 Yield

Conditions & References With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione, Olah’s reagent in dichloromethane, T= 0 - 40 °C Hugenberg, Verena; Haufe, Guenter; Journal of Fluorine Chemistry; vol. 131; nb. 9; (2010); p. 942 - 950 View in Reaxys O F O S

Br O

N O

Rx-ID: 29695397 View in Reaxys 26/91 Yield

Conditions & References With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione, Olah’s reagent in dichloromethane, T= 0 - 45 °C Hugenberg, Verena; Haufe, Guenter; Journal of Fluorine Chemistry; vol. 131; nb. 9; (2010); p. 942 - 950 View in Reaxys O

Rx-ID: 29695402 View in Reaxys 27/91 Yield

O F

Rx-ID: 29695403 View in Reaxys 28/91 Yield

Conditions & References With N-chloro-succinimide, Olah’s reagent in dichloromethane, T= 0 - 45 °C Hugenberg, Verena; Haufe, Guenter; Journal of Fluorine Chemistry; vol. 131; nb. 9; (2010); p. 942 - 950 View in Reaxys

12/31

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

O S

Rx-ID: 29695404 View in Reaxys 29/91 Yield

O S

O F

F O

Rx-ID: 29695405 View in Reaxys 30/91 Yield

O S

Rx-ID: 29695406 View in Reaxys 31/91 Yield

O S

O F F

O O

F O

Br O

O F

Rx-ID: 29695407 View in Reaxys 32/91 Yield

13/31

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

O C

F O

H O

Rx-ID: 30123340 View in Reaxys 33/91 Yield

Conditions & References With rhodium(III) chloride, oxygen, copper(II) trifluoroacetate, sodium chloride in water, T= 80 °C , p= 45004.5Torr , Autoclave, Inert atmosphere Chepaikin; Bezruchenko; Menchikova; Moiseeva; Gekhman; Kinetics and Catalysis; vol. 51; nb. 5; (2010); p. 666 - 671 View in Reaxys F

O C

H O

F OH

Rx-ID: 30123341 View in Reaxys 34/91 Yield

O C

H O

F O

Rx-ID: 30123344 View in Reaxys 35/91 Yield

F O

Rx-ID: 30540673 View in Reaxys 36/91 Yield

Conditions & References With carbon monoxide, rhodium(III) trichloride hydrate, water, oxygen, sodium chloride, copper(II) oxide, Time= 2h, T= 80 °C , Autoclave Chepaikin; Bezruchenko; Menchikova; Moiseeva; Gekhman; Petroleum Chemistry; vol. 50; nb. 5; (2010); p. 332 - 337 View in Reaxys

14/31

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

H O

Rx-ID: 30540675 View in Reaxys 37/91 Yield

Conditions & References With carbon monoxide, rhodium(III) trichloride hydrate, water, oxygen, sodium chloride, copper(II) oxide, Time= 2h, T= 80 °C , Inert atmosphere, Autoclave Chepaikin; Bezruchenko; Menchikova; Moiseeva; Gekhman; Petroleum Chemistry; vol. 50; nb. 5; (2010); p. 332 - 337 View in Reaxys F

H O

F O

Rx-ID: 30540676 View in Reaxys 38/91 Yield

HO F

H O

O O

F O

O F

Rx-ID: 30540677 View in Reaxys 39/91 Yield

Conditions & References With [2,2]bipyridinyl, sodium tetrachloropalladate(II), carbon monoxide, water, oxygen, copper(II) oxide, Time= 2h, T= 80 °C , Inert atmosphere, Autoclave Chepaikin; Bezruchenko; Menchikova; Moiseeva; Gekhman; Petroleum Chemistry; vol. 50; nb. 5; (2010); p. 332 - 337 View in Reaxys F

F 2H

O F

H O

F O

Rx-ID: 30540681 View in Reaxys 40/91 Yield

Conditions & References With carbon monoxide, rhodium(III) trichloride hydrate, water-d2, oxygen, sodium chloride, copper(II) oxide, Autoclave Chepaikin; Bezruchenko; Menchikova; Moiseeva; Gekhman; Petroleum Chemistry; vol. 50; nb. 5; (2010); p. 332 - 337 View in Reaxys

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

F O

HO F

Rx-ID: 30540683 View in Reaxys 41/91 Yield

H O

O F

F O

Rx-ID: 30540686 View in Reaxys 42/91 Yield

O F

O P

F O

NH O

O OH

Rx-ID: 29044545 View in Reaxys 43/91 Yield 86.2 %

Conditions & References in toluene, T= 20 °C , optical yield given as percent de Metlushka, Kirill E.; Kashemirov, Boris A.; Zheltukhin, Viktor F.; Sadkova, Dilyara N.; Buechner, Bernd; Hess, Christian; Kataeva, Olga N.; McKenna, Charles E.; Alfonsov, Vladimir A.; Chemistry - A European Journal; vol. 15; nb. 27; (2009); p. 6718 - 6722

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

View in Reaxys

O F

F O

O F

O OH

Rx-ID: 29044547 View in Reaxys 44/91 Yield

Conditions & References

90.3 %

in toluene, T= 20 °C , optical yield given as percent de Metlushka, Kirill E.; Kashemirov, Boris A.; Zheltukhin, Viktor F.; Sadkova, Dilyara N.; Buechner, Bernd; Hess, Christian; Kataeva, Olga N.; McKenna, Charles E.; Alfonsov, Vladimir A.; Chemistry - A European Journal; vol. 15; nb. 27; (2009); p. 6718 - 6722 View in Reaxys

O P

F P

F O

Rx-ID: 29044554 View in Reaxys 45/91 Yield 76 %

Conditions & References in toluene, T= 20 °C , optical yield given as percent de

17/31

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

Metlushka, Kirill E.; Kashemirov, Boris A.; Zheltukhin, Viktor F.; Sadkova, Dilyara N.; Buechner, Bernd; Hess, Christian; Kataeva, Olga N.; McKenna, Charles E.; Alfonsov, Vladimir A.; Chemistry - A European Journal; vol. 15; nb. 27; (2009); p. 6718 - 6722 View in Reaxys

O F

HO O

O F O

O O

F O O F

Rx-ID: 9310530 View in Reaxys 46/91 Yield 38 % Spectr., 62 % Spectr.

Conditions & References in trifluoroacetic acid, T= -20 °C , Product distribution, Further Variations: Solvents Krasutsky, Pavel A.; Kolomitsyn, Igor V.; Botov, Evgenij M.; Carlson, Robert M.; Semenova, Irina G.; Fokin, Andrey A.; Tetrahedron Letters; vol. 43; nb. 48; (2002); p. 8687 - 8691 View in Reaxys F

O F O

Rx-ID: 6970935 View in Reaxys 47/91 Yield 21.7%

Conditions & References 7 : EXAMPLE 7 EXAMPLE 7 47.1 g (0.147 mol) of CF3 CBr3 together with 103 g (2.23 mol) of ethanol are charged to a conventional reactor fitted with a turbine-type stirrer, a condenser, a temperature monitor and a dip tube serving as gas inlet. 0.3 g of AIBN is then added, corresponding to 1.24 mol percent relative to the haloethane. The reaction medium is heated at 65° C. with stirring and with air sparging (7 l/h). After reaction for 13 h 30 min, a conversion of the CF3 CBr3 of 21.7percent and a yield of ethyl trifluoroacetate of 17percent, relative to the haloethane, are obtained. Patent; Elf Atochem S.A.; US5619023; (1997); (A) English View in Reaxys Majid,A.; Shreeve,J.M.; Journal of Organic Chemistry; vol. 38; nb. 23; (1973); p. 4028 - 4031 View in Reaxys Larock,R.C.; Journal of Organic Chemistry; vol. 39; (1974); p. 3721 - 3727 View in Reaxys Dyatkin,B.L. et al.; Journal of Organometallic Chemistry; vol. 57; (1973); p. 423 - 433 View in Reaxys Corey; Koenig; Journal of the American Chemical Society; vol. 84; (1962); p. 4904,4907 View in Reaxys Barnes et al.; Canadian Journal of Chemistry; vol. 50; (1972); p. 2175,2176-2178 View in Reaxys Belen'kii et al.; Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation); (1968); p. 1541; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; (1968); p. 1631; ; vol. 70; nb. 3218h; (1969) View in Reaxys Golovanov et al.; J. Gen. Chem. USSR (Engl. Transl.); vol. 43; (1973); p. 2666,2644,2646 View in Reaxys Ishikawa et al.; Nippon Kagaku Kaishi; (1975); p. 1541,1543 View in Reaxys Patent; Coll; Luis; DE1966974; (1969); ; vol. 85; nb. 5203 View in Reaxys Larock; Journal of Organic Chemistry; vol. 39; (1974); p. 834 View in Reaxys Nordlander; Deadman; Tetrahedron Letters; (1967); p. 4409,4411 View in Reaxys 17 : Preparation of Trifluoromethyl cyclopropylethynyl ketone, Compound XV STR44 Synthesis (a)

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

EXAMPLE 17 Preparation of Trifluoromethyl cyclopropylethynyl ketone, Compound XV STR44 Synthesis (a) To a solution of n-butyllithium in hexanes (2.5M, 1600ml) at 0° C. under nitrogen was added THF (1600ml). The mixture was cooled to -10° C. and neat 5-chloro-1-pentyne (201 gm) was added dropwise over 30 minutes while keeping the internal temperature between 0-5° C. The batch was aged at 0° C. for 3-4 hours, while the progress of the cyclization step was monitored by HPLC [Inertsil Phenyl column, CH3CN, water, phosphoric acid; gradient elution from 40:60:0.1 to 50:50:0.1 in 15 min, flow=1.0 ml/min, UV detection at 195 nm]. The reaction was considered complete when the level of starting material was below 0.5 A percent. Once the cyclization step was complete, the reaction was cooled to -50° C. To the resulting thin slurry was added neat ethyl trifluoroacetate (260 ml) over 30 minutes. Patent; Dupont Pharmaceuticals Company; US6147210; (2000); (A) English View in Reaxys 33 : Production of 3,6'-di-N-benzyloxycarbonyl-3"-N-trifluoroacetylkanamycin A EXAMPLE 33 Production of 3,6'-di-N-benzyloxycarbonyl-3"-N-trifluoroacetylkanamycin A A solution of 504 mg of 3,6'-di-N-benzyloxycarbonylkanamycin A (see Example 1) in 4 ml of dimethylsulfoxide was admixed with 220 mg of ethyl trifluoroacetate, and the admixture obtained was allowed to stand overnight at ambient temperature. Patent; Zaidan Hojin Biseibutsu Kagaku Kenkyu Kai; US4297485; (1981); (A) English View in Reaxys 35 : Production of 3,6'-di-N-benzyloxycarbonyl-3"-N-trifluoroacetylkanamycin A EXAMPLE 35 Production of 3,6'-di-N-benzyloxycarbonyl-3"-N-trifluoroacetylkanamycin A A solution of 10 mg of 3,6'-di-N-benzyloxycarbonylkanamycin A in 0.3 ml of hexamethylphosphoric triamide was admixed with 7 mg of ethyl trifluoroacetate, and the admixture obtained was allowed to stand overnight at ambient temperature. The reaction solution was admixed with a small volume of trifluoroacetic acid and then poured into a large volume of ethyl ether. Patent; Zaidan Hojin Biseibutsu Kagaku Kenkyu Kai; US4297485; (1981); (A) English View in Reaxys 36 : Production of 3,6'-di-N-benzyloxycarbonyl-3"-N-trifluoroacetylkanamycin A EXAMPLE 36 Production of 3,6'-di-N-benzyloxycarbonyl-3"-N-trifluoroacetylkanamycin A A suspension of 10 mg of 3,6'-di-N-benzyloxycarbonylkanamycin A in 0.3 ml of dimethylformamide was admixed with 7 mg of ethyl trifluoroacetate, and the admixture obtained was allowed to stand overnight at ambient temperature. The homogeneous reaction solution thus obtained was admixed with a small volume of trifluoroacetic acid and then poured into a large volume of ethyl ether. Patent; Zaidan Hojin Biseibutsu Kagaku Kenkyu Kai; US4297485; (1981); (A) English View in Reaxys

F F

O F

F F

Rx-ID: 4986977 View in Reaxys 48/91 Yield

Conditions & References With 18-crown-6 ether, <Me4N>OEt, strontium bromide, T= 25 °C , solvent isotope effects, other Ba and Sr salts, Rate constant, Mechanism Cacciapaglia, Roberta; Di Stefano, Stefano; Kelderman, Erik; Mandolini, Luigi; Spadola, Francesco; Journal of Organic Chemistry; vol. 63; nb. 19; (1998); p. 6476 - 6479 View in Reaxys

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

F F

H N

O O

Rx-ID: 4986978 View in Reaxys 49/91 Yield

Conditions & References With 18-crown-6 ether, barium thiocyanate, <Me4N>OEt, T= 25 °C , kinetic isotope effect, Rate constant Cacciapaglia, Roberta; Di Stefano, Stefano; Kelderman, Erik; Mandolini, Luigi; Spadola, Francesco; Journal of Organic Chemistry; vol. 63; nb. 19; (1998); p. 6476 - 6479 View in Reaxys F

F F

F O

Rx-ID: 5067651 View in Reaxys 50/91 Yield

Conditions & References

0.80 mmol, 0.15 mmol

With tetraethyllead(IV), Time= 24h, T= 90 °C , p= 51714.8Torr , Oxidation, Further byproducts given Hogan, Terrence; Sen, Ayusman; Journal of the American Chemical Society; vol. 119; nb. 11; (1997); p. 2642 - 2646 View in Reaxys

0.68 mmol, 0.33 mmol

With ethene, dihydrogen peroxide in water, Time= 24h, T= 90 °C , p= 51714.8Torr , Oxidation, Further byproducts given Hogan, Terrence; Sen, Ayusman; Journal of the American Chemical Society; vol. 119; nb. 11; (1997); p. 2642 - 2646 View in Reaxys

F O F

Rx-ID: 4340585 View in Reaxys 51/91 Yield

Conditions & References

61 %

T= -196.1 - 19.9 °C Wasiak, J.; Helinski, J.; Dabkowski, W.; Skrzypczynski, Z.; Michalski, J.; Polish Journal of Chemistry; vol. 69; nb. 7; (1995); p. 1027 - 1032 View in Reaxys

O O

O HO

F O

Rx-ID: 1848098 View in Reaxys 52/91

20/31

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

Yield

Conditions & References in various solvent(s), Time= 0.5h, T= -20 °C , Mechanism Ferrer, Marta; Sanchez-Baeza, Francisco; Casas, Josefina; Messeguer, Angel; Tetrahedron Letters; vol. 35; nb. 18; (1994); p. 2981 - 2984 View in Reaxys

O O

O P

O F

O O

F F

Rx-ID: 3076533 View in Reaxys 53/91 Yield

Conditions & References in sulfolane, T= 195 °C , other 2-acyloxyalkylphosphonates; entropy of activation, Rate constant, Thermodynamic data, Mechanism Jongh, Connie P. de; Modro, Tomasz A.; Journal of the Chemical Society, Chemical Communications; nb. 14; (1992); p. 1003 - 1004 View in Reaxys

O P

O F

O O

O F F F

Rx-ID: 3098749 View in Reaxys 54/91 Yield

Conditions & References in sulfolane, T= 195 °C , Rate constant Jongh, Connie P. de; Modro, Tomasz A.; Journal of the Chemical Society, Chemical Communications; nb. 14; (1992); p. 1003 - 1004 View in Reaxys

O O P O O O O F F

O O

O P

O F

O O

Rx-ID: 3099763 View in Reaxys 55/91

21/31

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

Yield

HO F O

F O

O O

Rx-ID: 3752875 View in Reaxys 56/91 Yield

Conditions & References With cobalt(III), Time= 1h, T= 180 °C , p= 30400Torr , also with O2-cobalt(II); other alkane, Product distribution, Mechanism Stolarov, Igor P.; Vargaftik, Michael N.; Shishkin, Dmitry I.; Moiseev, Ilya I.; Journal of the Chemical Society, Chemical Communications; nb. 14; (1991); p. 938 - 939 View in Reaxys

(v5) (v5) O (v5) O

(v5)

(v10)

(v5)

(v5) (v5) O (v5) (v3)

(v10)

(v5)

(v5) (v5)

(v5)

Fe +

(v5)

O O

(v5) (v5)

Rx-ID: 26846475 View in Reaxys 57/91 Yield

Conditions & References

100 %

in trifluoroacetic acid, byproducts: CH3CH2OH Kenny, T. P. E.; Knipe, A. C.; Watts, W. E.; Journal of Organometallic Chemistry; vol. 413; nb. 1-3; (1991); p. 257 - 261 ; (from Gmelin) View in Reaxys

Na +

O F

O– F

F O

NaF, CO2

Rx-ID: 8281784 View in Reaxys 58/91 Yield

Conditions & References Time= 0.666667h, T= 225 - 260 °C , p= 0.01Torr , Product distribution, Mechanism Pellerite, Mark J.; Journal of Fluorine Chemistry; vol. 49; nb. 1; (1990); p. 43 - 66 View in Reaxys

22/31

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

O O

F O

O OH

CO2

HO O

Rx-ID: 8426394 View in Reaxys 59/91 Yield

Conditions & References T= 70 - 90 °C , Rate constant, Thermodynamic data Rakhimov, A. I.; Chapurkin, V. V.; Val'dman, A. I.; Val'dman, D. I.; Saloutin, V. I.; et al.; Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation); vol. 39; nb. 7.2; (1990); p. 1496 - 1499; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; nb. 7; (1990); p. 1647 - 1650 View in Reaxys F F N F

N N

O F

O N

Rx-ID: 3955081 View in Reaxys 60/91 Yield

Conditions & References With piperidine, T= 25 °C , further bases, Rate constant, Mechanism Iley, Jim; Ruecroft, Graham; Carvalho, Emilia; Rosa, Eduarda; Journal of Chemical Research, Miniprint; nb. 6; (1989); p. 1264 - 1273 View in Reaxys F F N F

F O

N N

N O

Rx-ID: 3955082 View in Reaxys 61/91 Yield

Conditions & References With morpholine, T= 25 °C , Rate constant, Mechanism Iley, Jim; Ruecroft, Graham; Carvalho, Emilia; Rosa, Eduarda; Journal of Chemical Research, Miniprint; nb. 6; (1989); p. 1264 - 1273 View in Reaxys O N OH

F F

23/31

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

O F

Rx-ID: 3955083 View in Reaxys 62/91 Yield

O S

O F

Rx-ID: 3812892 View in Reaxys 63/91 Yield

Conditions & References

100 %, 100 %

T= 0 °C Forbus, T. R.; Taylor, S. L.; Martin, J. C.; Journal of Organic Chemistry; vol. 52; nb. 19; (1987); p. 4156 - 4159 View in Reaxys F

O OH O

Rx-ID: 1865464 View in Reaxys 64/91 Yield 5 % Chromat., 5 % Chromat.

Conditions & References With rhodium(III) chloride, Time= 2h, T= 100 °C , Product distribution Akhrem, I. S.; Vartanyan, R. S.; Afanas'eva, L. V.; Vol'pin, M. E.; Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation); vol. 32; (1983); p. 1217 - 1220; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; nb. 6; (1983); p. 1346 - 1350 View in Reaxys

F O

Rx-ID: 2005609 View in Reaxys 65/91 Yield 82 %

Conditions & References With ethyl iodide, bis-[(trifluoroacetoxy)iodo]benzene in chloroform, Time= 2h Gallos, John; Varvoglis, Anastasios; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); (1983); p. 1999 - 2002 View in Reaxys

H P

F O

Rx-ID: 2024687 View in Reaxys 66/91 Yield

Conditions & References With trifluoroacetic acid, Time= 2h, T= 25 °C

24/31

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

Konovalova, I. V.; Ofitserov, E. N.; Mironov, V. F.; Kostyuk, V. I.; Pudovik, A. N.; J. Gen. Chem. USSR (Engl. Transl.); vol. 53; nb. 9; (1983); p. 1945 - 1950,1754 - 1758 View in Reaxys F F F F

O I

I O

O F

I O

Rx-ID: 2855087 View in Reaxys 67/91 Yield

Conditions & References With para-xylene in chloroform, Time= 2h Gallos, John; Varvoglis, Anastasios; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); (1983); p. 1999 - 2002 View in Reaxys

O O

H P

Rx-ID: 3752976 View in Reaxys 68/91 Yield

Conditions & References Time= 2h, T= 25 °C Konovalova, I. V.; Ofitserov, E. N.; Mironov, V. F.; Kostyuk, V. I.; Pudovik, A. N.; J. Gen. Chem. USSR (Engl. Transl.); vol. 53; nb. 9; (1983); p. 1945 - 1950,1754 - 1758 View in Reaxys

F OH

F O

O F

O F F

Rx-ID: 1871502 View in Reaxys 69/91 Yield

Conditions & References With triethylamine Fokin, A. V.; Studnev, Yu. N.; Ragulin, L. I.; Krotovich, I. N.; Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation); vol. 31; (1982); p. 1696 - 1698; Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya; nb. 8; (1982); p. 1906 - 1907 View in Reaxys

O Cl

O O

O Cl

Rx-ID: 3752762 View in Reaxys 70/91 Yield 52 %

Conditions & References Time= 24h, T= 90 °C Downie, Ian M.; Wynne, Neil; Harrison, Stephen; Tetrahedron; vol. 38; nb. 10; (1982); p. 1457 - 1458 View in Reaxys

25/31

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

Cl F

PH (v5)

Rx-ID: 3752838 View in Reaxys 71/91 Yield

Conditions & References

72.1 %, 84.3 %

Time= 1h, T= 100 °C , sealed ampule Gazizov, T. Kh.; Belyalov, R. U.; Pudovik, A. N.; J. Gen. Chem. USSR (Engl. Transl.); vol. 52; nb. 12; (1982); p. 2724 2728,2402 - 2405 View in Reaxys F

F O

Rx-ID: 3752879 View in Reaxys 72/91 Yield

Conditions & References Time= 24h, Heating, other ethers, Product distribution Hagen, Arnulf P.; Miller, Tammy S.; Bynum, Richard L.; Kapila Ved P.; Journal of Organic Chemistry; vol. 47; nb. 7; (1982); p. 1345 - 1347 View in Reaxys

O O

P O

O F

F O

O O

P O

Rx-ID: 3754875 View in Reaxys 73/91 Yield

Conditions & References

39 %, 53 %, Gazizov, T. Kh.; Belyalov, R. U.; Pudovik, A. N.; J. Gen. Chem. USSR (Engl. Transl.); vol. 52; nb. 3; (1982); p. 487 - 491,428 34.9 %, 38 - 430 % View in Reaxys F (v3) (v3)

O O

Os 2(v4)

(v3) + O 2 Na O (v3)

S O

F F

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

(v3)

(v6)

H Os

(v4)

(v3)

O O

(v3)

(v3) (v3)

–H

2C – O (v6) 2+ Os CH 2(v4) O (v3) O

(v3)

F F

O (v3)

Rx-ID: 27020746 View in Reaxys 74/91 Yield

Conditions & References

54 %

in further solvent(s), to suspn. of Os complex in tetraglyme transferred in vac. CF3COOH (molar ratio 1:1), mixt. stirred at room temp. for 2 h, 2 equiv FSO3C2H5 distd. into react. vessel, mixt. stirred at room temp. for 5 min; mixt. of product and CF3COOCH3 distd. into -196°C cold trap, redistd. into -56°C trap, fractionated on vac. line (in -23°Ctrap) Carter, Willie J.; Kelland, John W.; Okrasinski, Stanley J.; Warner, Keith E.; Norton, Jack R.; Inorganic Chemistry; vol. 21; (1982); p. 3955 - 3960 ; (from Gmelin) View in Reaxys F O

O F N

N O

O F

Rx-ID: 2592065 View in Reaxys 75/91 Yield

Conditions & References

93 %

With trifluoroacetic anhydride in trifluoroacetic acid, Time= 72h, T= 56 °C Nordlander, J. Eric; Catalane, David B.; Kotian, Kirtivan D.; Stevens, Randall M.; Haky, Jerome E.; Journal of Organic Chemistry; vol. 46; (1981); p. 778 - 782 View in Reaxys With trifluoroacetic acid, trifluoroacetic anhydride, Time= 72h, T= 56 °C , various excess of trifluoroacetic anhydride, Product distribution Nordlander, J. Eric; Catalane, David B.; Kotian, Kirtivan D.; Stevens, Randall M.; Haky, Jerome E.; Journal of Organic Chemistry; vol. 46; (1981); p. 778 - 782 View in Reaxys F

F N

O F

Rx-ID: 2594751 View in Reaxys 76/91 Yield

Conditions & References With trifluoroacetic anhydride in trifluoroacetic acid, Time= 72h, T= 56 °C Nordlander, J. Eric; Catalane, David B.; Kotian, Kirtivan D.; Stevens, Randall M.; Haky, Jerome E.; Journal of Organic Chemistry; vol. 46; (1981); p. 778 - 782 View in Reaxys

O O

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

F F

O O

F F

F O

Rx-ID: 2597424 View in Reaxys 77/91 Yield

Conditions & References With trifluoroacetic anhydride in trifluoroacetic acid, Time= 75h, T= 56 °C , Title compound not separated from byproducts Nordlander, J. Eric; Catalane, David B.; Kotian, Kirtivan D.; Stevens, Randall M.; Haky, Jerome E.; Journal of Organic Chemistry; vol. 46; (1981); p. 778 - 782 View in Reaxys F O

F N

F O

Rx-ID: 2597621 View in Reaxys 78/91 Yield

Conditions & References

93 %

F O

O F

Rx-ID: 3770385 View in Reaxys 79/91 Yield

Conditions & References With trifluoroacetic acid in chloroform-d1, Time= 0.25h, in a standard NMR tube Nordlander, J. Eric; Catalane, David B.; Kotian, Kirtivan D.; Stevens, Randall M.; Haky, Jerome E.; Journal of Organic Chemistry; vol. 46; (1981); p. 778 - 782 View in Reaxys

F F

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

F F

O O

F F

F O

Rx-ID: 3771632 View in Reaxys 80/91 Yield

Conditions & References in trifluoroacetic acid, 0 deg C, 30 min, then reflux 70 h, Title compound not separated from byproducts Nordlander, J. Eric; Catalane, David B.; Kotian, Kirtivan D.; Stevens, Randall M.; Haky, Jerome E.; Journal of Organic Chemistry; vol. 46; (1981); p. 778 - 782 View in Reaxys F

O F

F O F F

Rx-ID: 3771712 View in Reaxys 81/91 Yield

Conditions & References Time= 0.0833333h, ice bath Nordlander, J. Eric; Catalane, David B.; Kotian, Kirtivan D.; Stevens, Randall M.; Haky, Jerome E.; Journal of Organic Chemistry; vol. 46; (1981); p. 778 - 782 View in Reaxys F

Rx-ID: 26727229 View in Reaxys 82/91 Yield

Conditions & References

>99, >99

at 10°C Foss, V. L.; Semenenko, N. M.; Sorokin, N. M.; Lutsenko, I. F.; Journal of Organometallic Chemistry; vol. 78; (1974); p. 107 - 113 ; (from Gmelin) View in Reaxys

>99, >99

at 10°C vol. Sb: Org.Comp.2; 1.2.1.1.9.1, page 28 - 30 ; (from Gmelin) View in Reaxys F

Rx-ID: 26753323 View in Reaxys 83/91 Yield >99, >99

Conditions & References at 10°C

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

Foss, V. L.; Semenenko, N. M.; Sorokin, N. M.; Lutsenko, I. F.; Journal of Organometallic Chemistry; vol. 78; (1974); p. 107 - 113 ; (from Gmelin) View in Reaxys >99, >99

at 10°C vol. Sb: Org.Comp.2; 1.2.1.1.9.1, page 28 - 30 ; (from Gmelin) View in Reaxys O

Rx-ID: 881262 View in Reaxys 84/91 Yield

Conditions & References Ginsburg,V.A.; Vasil'eva,M.N.; J. Gen. Chem. USSR (Engl. Transl.); vol. 37; (1967); p. 2493 - 2497,2371 - 2374 View in Reaxys F

Na +

O F

O–

Rx-ID: 193477 View in Reaxys 85/91 Yield

Conditions & References With sulfuric acid Campbell et al.; Journal of the American Chemical Society; vol. 72; (1950); p. 4380,4382 View in Reaxys F

F N

F OH

F N

F O

F F F

Rx-ID: 409445 View in Reaxys 86/91 Yield

Conditions & References With hydrogenchloride Norton; Journal of the American Chemical Society; vol. 72; (1950); p. 3527 View in Reaxys F

F OH

F N

O F

F F F

Rx-ID: 5465419 View in Reaxys 87/91 Yield

Conditions & References Norton; Journal of the American Chemical Society; vol. 72; (1950); p. 3527 View in Reaxys

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Ethyl trifluoroacetate [CF3COOEt; CF3CO2Et; EtOTFA]

fluorine

copper wire F

O F

F O

Rx-ID: 6970937 View in Reaxys 88/91 Yield

Conditions & References T= 100 °C , Umsetzen der Reaktionsprodukte mit absol.Aethanol bei -80grad,zuletzt bei Siedetemperatur Miller; Prober; Journal of the American Chemical Society; vol. 70; (1948); p. 2602 View in Reaxys

OH 2

O F

Hg 2+

mercury (II)-oxide

O–

Rx-ID: 8279853 View in Reaxys 89/91 Yield

Conditions & References unter Zutritt von Feuchtigkeit Swarts; Bulletin des Societes Chimiques Belges; vol. 48; (1939); p. 180 View in Reaxys F

F OH

O F

Rx-ID: 787690 View in Reaxys 90/91 Yield

Conditions & References Swarts; Bulletin de la Classe des Sciences, Academie Royale de Belgique; vol. <5>8; (1922); p. 346; Bulletin des Societes Chimiques Belges; vol. 32; (1923); p. 104; Chem. Zentralbl.; vol. 94; nb. I; (1923); p. 66 View in Reaxys F OH

trifluoroacetate_of sodium

F O

Rx-ID: 6970936 View in Reaxys 91/91 Yield

Conditions & References With sulfuric acid Swarts; Bulletin de la Classe des Sciences, Academie Royale de Belgique; vol. <5>8; (1922); p. 346; Bulletin des Societes Chimiques Belges; vol. 32; (1923); p. 104; Chem. Zentralbl.; vol. 94; nb. I; (1923); p. 66 View in Reaxys

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