Query Query
Results
Date
25 reactions in Reaxys
2017-10-14 23h:49m:21s (EST)
O O
1. Query HO
O
Search as: As drawn, No salts, No mixtures, No isotopes, No charges, No radicals
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O HO
O
N
O
O
O
O
HO
Rx-ID: 39765357 View in Reaxys 1/25 Yield
Conditions & References
61 %
13 :100mL round bottom flask was added sesamol (4.1g, 30mmol)And DMF (24 mL) were completely dissolved and then cooled at 0 ° C under ice-cooling,POCl3 (16 mL) was slowly added dropwise.Drop finished,The reaction temperature was raised to 100 ° C,And the reaction was continued at this temperature for 1 hour.After cooling,The reaction mixture was poured into 250 mL of saturated sodium acetate solution,Heated to 100 ° C for 45 minutes,After cooling,The addition of dichloromethane (100 mL x 3 times)Organic saturated brine (100 mL x 3 times)Dried over anhydrous sodium sulfate,The solvent was removed by filtration under reduced pressure,100-200 mesh silica gel column chromatography,Ethyl acetate and petroleum ether mixed solvent (1:20)To give 3.0 g of the compound represented by the formula IIm,Yield 61percent. Stage 1: With trichlorophosphate, Time= 1h, T= 0 - 100 °C Stage 2: With sodium acetate, Time= 0.75h, T= 100 °C Patent; Institute of Chemistry, Chinese Academy of Sciences; Wang, Meixiang; Wang, Dexian; He, Ling; (26 pag.); CN104788462; (2017); (B) Chinese View in Reaxys
11 %
Stage 1: With trichlorophosphate, T= 0 - 100 °C , Vilsmeier-Haack Formylation Stage 2: With sodium acetate, T= 100 °C Zhang, Bingyu; Lv, Chao; Li, Weibo; Cui, Zhiming; Chen, Dongdong; Cao, Fangjun; Miao, Fang; Zhou, Le; Chemical and Pharmaceutical Bulletin; vol. 63; nb. 4; (2015); p. 255 - 262 View in Reaxys O HO
O
O
O O
HO
O
Rx-ID: 11213602 View in Reaxys 2/25 Yield 64 %
Conditions & References With triethylamine, magnesium chloride in acetonitrile, Time= 12h, T= 125 °C , Sealed tube Sun, Peng; Gao, Shang; Yang, Chi; Guo, Songjin; Lin, Aijun; Yao, Hequan; Organic Letters; vol. 18; nb. 24; (2016); p. 6464 - 6467 View in Reaxys
45 %
With triethylamine, magnesium chloride in tetrahydrofuran, Inert atmosphere, Reflux, regioselective reaction Akselsen, yvind W.; Skattebol, Lars; Hansen, Trond Vidar; Tetrahedron Letters; vol. 50; nb. 46; (2009); p. 6339 6341 View in Reaxys
36 %
With triethylamine, magnesium chloride in tetrahydrofuran, Time= 2h, Heating Juhasz, Laszlo; Docsa, Tibor; Brunyaszki, Attila; Gergely, Pal; Antus, Sandor; Bioorganic and Medicinal Chemistry; vol. 15; nb. 12; (2007); p. 4048 - 4056 View in Reaxys
26 %
With triethylamine, magnesium chloride in acetonitrile, Time= 6h, Reflux, Inert atmosphere Fowler, Katherine J.; Ellis, Jillian L.; Morrow, Gary W.; Synthetic Communications; vol. 43; nb. 12; (2013); p. 1676 - 1682 View in Reaxys
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O HO
N
O N
O
O
N N
HO
O
Rx-ID: 4616206 View in Reaxys 3/25 Yield
Conditions & References
65 %
With trifluoroacetic acid in dichloromethane, Heating, Duff formylation Bailly, Fabrice; Queffelec, Clemence; Mbemba, Gladys; Mouscadet, Jean-Francois; Cotelle, Philippe; Bioorganic and Medicinal Chemistry Letters; vol. 15; nb. 22; (2005); p. 5053 - 5056 View in Reaxys
56 %
With trifluoroacetic acid, Time= 4h, Heating Saito, Naoki; Tashiro, Kyoichi; Maru, Yukie; Yamaguchi, Kentaro; Kubo, Akinori; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 1; (1997); p. 53 - 70 View in Reaxys
54 %
With trifluoroacetic acid, Time= 3h, Reflux, Inert atmosphere, Duff Aldehyde Synthesis Guo, Wengang; Wu, Bo; Zhou, Xin; Chen, Ping; Wang, Xu; Zhou, Yong-Gui; Liu, Yan; Li, Can; Angewandte Chemie - International Edition; vol. 54; nb. 15; (2015); p. 4522 - 4526; Angew. Chem.; vol. 127; nb. 15; (2015); p. 4605 - 4609,5 View in Reaxys
53 %
A solution of sesamol (12.5 g, 90.44 mmol) and hexamethylenetetramine(15.2 g, 108 mmol) in trifluoroacetic acid (50 mL) was heated under reflux for 4 h. The mixture was added to water (100 mL), extracted with CH2Cl2,and washed with water and brine. The organic phase was dried over sodiumsulfate and concentrated in vacuo.The resulting oil was purified by column chromatography with n-hexane-ethyl acetate (7:1) to afford compound 15 as white solid (7.94 g, 53percent). 1H NMR(300 MHz, CDCl3) δ: 11.78 (s, 1H), 9.62 (s, 1H), 6.86 (s, 1H), 6.46 (s, 1H), 6.02 (s, 2H). With trifluoroacetic acid, Time= 4h, Reflux, Inert atmosphere, Duff Aldehyde Synthesis Jin, Yifeng; Khadka, Daulat Bikram; Yang, Su Hui; Zhao, Chao; Cho, Won-Jea; Tetrahedron Letters; vol. 55; nb. 7; (2014); p. 1366 - 1369 View in Reaxys
45 %
With trifluoroacetic acid, Time= 2h, Heating Gagey, Nathalie; Neveu, Pierre; Benbrahim, Chouaha; Goetz, Bernard; Aujard, Isabelle; Baudin, Jean-Bernard; Jullien, Ludovic; Journal of the American Chemical Society; vol. 129; nb. 32; (2007); p. 9986 - 9998 View in Reaxys
45 %
With trifluoroacetic acid, Time= 2h, Reflux Gagey, Nathalie; Emond, Matthieu; Neveu, Pierre; Benbrahim, Chouaha; Goetz, Bernard; Aujard, Isabelle; Baudin, Jean-Bernard; Jullien, Ludovic; Organic Letters; vol. 10; nb. 12; (2008); p. 2341 - 2344 View in Reaxys O O HO
O
Rx-ID: 5451175 View in Reaxys 4/25 Yield 84 %
Conditions & References 1 :General procedure: All the compounds disclosed in formula 1, are prepared by employing the similar method containing different substitutions at Rl, R2, R3 and R4 positions, as described for the preparation of compound A. The details of reaction conditions are depicted in the table given below-; Step 1; Synthesis of 2-hvdroxy. 4.5-dimethoxybenzaldehyde (Al): To solution of 3,4,5- trimethoxybenzaldehyde (5g, 25.5 mmol) in CH2C12 (125 ml) at 0 °C was added BBr3 (6.39 g, 25.5 mmol). The resulting dark mixture was stirred at 0°C for 10 hrs after completion of the reaction checked by TLC H20 (100 mL) was then added and the mixture was stirred for 10 min and the aqueous phase was extracted by CH2C12. The organic phase was dried over Na2S0 ) and evaporated under reduced pressure. The
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resulting residue was purified by silica gel (CH C12) afforded the 2- hydroxy 4,5dimethoxybenzaldehyde Al (4.3g) in 87percent yield isolated yellow solid: lH NMR (500 MHz, CDC13) 511.33 (s, 1H), 9.63 (s, 1H), 6.83 (s, 1H), 6.40 (s, 1H), 3.87 (s, 3H), 3.81 (s, 3H) ppm. Mass: ESI [M + Na]+: 225.06; Elemental anal, calcd. for C9H10O4; C: 59.34, H: 5.53, O: 35.13; found C: 59.14, H: 5.13, O: 34.90. With boron tribromide in dichloromethane, Time= 10h, T= 20 °C , Inert atmosphere Patent; COUNCIL OF SCIENTIFIC and INDUSTRIAL RESEARCH; VISHWAKARMA, Ram Asrey; SAWANT, Sanghapal Damodhar; SINGH, Parvinder Pal; DAR, Abid Hamid; SHARMA, Parduman Raj; SAXENA, Ajit Kumar; NARGOTRA, Amit; KOLLURU, Anjaneya Aravind Kumar; MUDUDUDDLA, Ramesh; QAZI, Asif Khurshid; HUSSAIN, Aashiq; CHANAURIA, Nayan; WO2013/140417; (2013); (A1) English View in Reaxys 84 %
1 : Synthesis of Compound A Step 1 Synthesis of 2-hydroxy, 4,5-dimethoxybenzaldehyde (A1) General procedure: Synthesis of Compound A Step 1 Synthesis of 2-hydroxy-4,5-dimethoxybenzaldehyde (A1) To solution of 2,4,5-trimethoxybenzaldehyde (5 g, 25.5 mmol) in CH2Cl2 (125 ml) at 0° C. was added BBr3 (6.39 g, 25.5 mmol). The resulting dark mixture was stirred at 0° C. for 10 hrs after completion of the reaction checked by TLC H2O (100 mL) was then added and the mixture was stirred for 10 min and the aqueous phase was extracted by CH2Cl2. The organic phase was dried over Na2SO4, and evaporated under reduced pressure. The resulting residue was purified by silica gel (CH2Cl2) afforded the 2-hydroxy-4,5-dimethoxybenzaldehyde A1 (4.3 g) in 87percent yield isolated yellow solid. With boron tribromide in dichloromethane, Time= 10h, T= 20 °C , Inert atmosphere Patent; Vishwakarma, Ram Asrey; Sawant, Sanghapal Damodhar; Singh, Parvinder Pal; Dar, Abid Hamid; Sharma, Parduman Raj; Saxena, Ajit Kumar; Nargotra, Amit; Kolluru, Anjaneya Aravind Kumar; Mudududdla, Ramesh; Qazi, Asif Khurshid; Hussain, Aashiq; Chanauria, Nayan; US2015/51173; (2015); (A1) English View in Reaxys
35%
R.38 : Reference Example 38 Reference Example 38 To a mixture of sesamol (8.28 g), ethyl orthoformate (53.58 g) and benzene (120 ml), powdered anhydrous aluminum chloride (12.0 g) was added, followed by stirring at room temperature for 1 hour. The mixture was then poured into 5percent hydrochloric acid (180 ml) and stirred at room temperature for 30 minutes. After the insoluble substance was filtered off, the filtrate was extracted with ether. The ether layer was washed with water and dried (MgSO4), after which the solvent was evaporated off. The residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1:8, v/v) to yield 2-hydroxy-4,5-methylenedioxybenzaldehyde (3.48 g, 35percent) having a melting point of 128°-129° C. Patent; Takeda Chemical Industries, Ltd.; US5716944; (1998); (A1) English View in Reaxys Suginome,H.; Bulletin of the Chemical Society of Japan; vol. 39; (1966); p. 1525 - 1529 View in Reaxys van Heerden,F.R. et al.; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); (1978); p. 137 - 145 View in Reaxys Fukui; Nakayama; Bulletin of the Chemical Society of Japan; vol. 35; (1962); p. 1321 View in Reaxys 119.1 Patent; PHARMACIA CORPORATION; WO2004/87686; (2004); (A2) English View in Reaxys Patent; PHARMACIA CORPORATION; WO2004/87687; (2004); (A1) English View in Reaxys
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O
O
O
O
O
HO
O
Rx-ID: 40920967 View in Reaxys 5/25 Yield
Conditions & References Reaction Steps: 3 1.1: nitric acid / water / 0.5 h / 20 °C 2.1: iron(II) sulfate; ammonium hydroxide / water / 0.17 h / |Heating 3.1: sodium nitrite; sulfuric acid / water / 5 °C 3.2: 8 h / 100 °C With ammonium hydroxide, sulfuric acid, nitric acid, iron(II) sulfate, sodium nitrite in water, 3.2: |Sandmeyer Reaction De Melos, Jorge Luiz R.; Torres-Santos, Eduardo Caio; Faiões, Viviane Dos S.; De Nigris Del Cistia, Catarina; Sant'Anna, Carlos Maurício R.; Rodrigues-Santos, Cláudio Eduardo; Echevarria, Aurea; European Journal of Medicinal Chemistry; vol. 103; (2015); p. 409 - 417 View in Reaxys
O
O
N
O
O
O
O
HO
O
O
Rx-ID: 40920979 View in Reaxys 6/25 Yield
Conditions & References Reaction Steps: 2 1.1: iron(II) sulfate; ammonium hydroxide / water / 0.17 h / |Heating 2.1: sodium nitrite; sulfuric acid / water / 5 °C 2.2: 8 h / 100 °C With ammonium hydroxide, sulfuric acid, iron(II) sulfate, sodium nitrite in water, 2.2: |Sandmeyer Reaction De Melos, Jorge Luiz R.; Torres-Santos, Eduardo Caio; Faiões, Viviane Dos S.; De Nigris Del Cistia, Catarina; Sant'Anna, Carlos Maurício R.; Rodrigues-Santos, Cláudio Eduardo; Echevarria, Aurea; European Journal of Medicinal Chemistry; vol. 103; (2015); p. 409 - 417 View in Reaxys
O
O
O H 2N
O
O
O
HO
Rx-ID: 40920990 View in Reaxys 7/25 Yield
Conditions & References
58 %
Stage 1: With sulfuric acid, sodium nitrite in water, T= 5 °C Stage 2: With water, copper(II) sulfate, Time= 8h, T= 100 °C , Sandmeyer Reaction De Melos, Jorge Luiz R.; Torres-Santos, Eduardo Caio; Faiões, Viviane Dos S.; De Nigris Del Cistia, Catarina; Sant'Anna, Carlos Maurício R.; Rodrigues-Santos, Cláudio Eduardo; Echevarria, Aurea; European Journal of Medicinal Chemistry; vol. 103; (2015); p. 409 - 417 View in Reaxys O
HO
O O
Cl
O Cl
O HO
O
Rx-ID: 10494775 View in Reaxys 8/25 Yield 91 %
Conditions & References 6-Hydroxybenzo[d][1,3]dioxole-5-carbaldehyde (13). With tin(IV) chloride in dichloromethane, Time= 3h, T= 0 - 20 °C
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Beekman, Andrew M.; Barrow, Russell A.; Journal of Organic Chemistry; vol. 79; nb. 3; (2014); p. 1017 - 1024 View in Reaxys 46 %
With tin(IV) chloride in dichloromethane, Time= 3h, T= 20 °C Cueva, Juan Pablo; Giorgioni, Gianfabio; Grubbs, Russell A.; Chemel, Benjamin R.; Watts, Val J.; Nichols, David E.; Journal of Medicinal Chemistry; vol. 49; nb. 23; (2006); p. 6848 - 6857 View in Reaxys
40 %
With tin(ll) chloride in dichloromethane, Time= 3h, T= 20 °C Fadeyi, Olugbeminiyi O.; Nathan Daniels; DeGuire, Sean M.; Lindsley, Craig W.; Tetrahedron Letters; vol. 50; nb. 25; (2009); p. 3084 - 3087 View in Reaxys
38 - 46 %
1 :Example 1 6-Hydroxybenzo[1,3]dioxole-5-carbaldehyde (2a). Sesamol (1a) (16.95 g, 1.23 mol) was dissolved in 350 ml CH2Cl2 in a two necked round bottom flask connected to a condenser. SnCl4 (35.4 ml, 3.07 mmol) was added and the solution was stirred at 0° C. Cl2CHOCH3 (11.7 ml, 1.29 mol) was added dropwise, and the solution was warmed to room temperature. The dark bluish mixture was cooled, and poured into a flask containing 500 ml of ice and water. The water layer was discarded, and the organic phase was filtered through Celite. The filtrates were washed with 2 M HCl (3*200 ml), and then with brine (1*100 ml). The solution was dried over MgSO4, filtered, and the solvent evaporated. The dark brown solids were then dissolved in ethanol, stirred with charcoal and filtered through Celite. Solvent was evaporated and the product was recrystallized from methanol to give 7.74 g (38percent yield): mp 119° C. This Example was repeated on a larger scale. Sesamol (50.98 g, 369 mmol) was dissolved in 600 mL of CH2Cl2 followed by 52 mL (448 mmol) of SnCl4 and the solution was cooled to 0° C. Cl2CHOCH3 (35 mL, 387.5 mmol) was added dropwise as the reaction mixture warmed to room temperature, and was then stirred for 3 h. The mixture was poured over ice, the water layer was separated and extracted once with CH2Cl2 (30 mL). The organic extracts were combined, washed with 2M HCl (5*100 mL), and brine (50 mL), and then passed through a small column packed with MgSO4, which removed color. The solvent was evaporated to yield 28 g (46percent yield): mp 119° C.; 1H-NMR (CDCl3) δ 9.63 (s, 1, CHO); 6.87 (s, 1, ArH); 6.47 (s, 1, ArH); 6.02 (s, 2, ArOCH2O); 1.54 (s, 1, ArOH); low resolution CIMS: m/z (rel. intensity) 167 (MH+, 100). Anal. Calcd. for C8H6O4: C, 57.84; H, 3.64. Found: C, 57.65; H, 3.76. With tin(IV) chloride in dichloromethane, T= 0 - 20 °C , Product distribution / selectivity Patent; PURDUE RESEARCH FOUNDATION; US2009/30025; (2009); (A1) English View in Reaxys O
HO
O O
O HO
O
Rx-ID: 1728435 View in Reaxys 9/25 Yield
Conditions & References Vilsmeier reaction Ohishi; Mukai; Nagahara; Yajima; Kajikawa; Chemical and Pharmaceutical Bulletin; vol. 37; nb. 9; (1989); p. 2398 - 2405 View in Reaxys Reaction Steps: 2 1.1: sodium hydride / tetrahydrofuran / 1 h / Cooling with ice 1.2: 3 h / 20 °C / Cooling with ice 2.1: tin(IV) chloride / dichloromethane / 2 h / 0 °C With tin(IV) chloride, sodium hydride in tetrahydrofuran, dichloromethane, 2.1: Friedel-Crafts type formylation
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Cueva, Juan Pablo; Chemel, Benjamin R.; Juncosa Jr., Jose I.; Lill, Markus A.; Watts, Val J.; Nichols, David E.; European Journal of Medicinal Chemistry; vol. 48; (2012); p. 97 - 107 View in Reaxys O
Cl
O
O
Cl
O
O
O
O
O
HO
Rx-ID: 32585192 View in Reaxys 10/25 Yield
Conditions & References
93.2 %
4.2.3. 6-Hydroxybenzo[1,3]dioxole-5-carboxaldehyde (10) In a two-neck flask, 40 g of 9 (0.222 mol) were dissolved in 500 mL CH2Cl2 and the solution cooled to 0 °C. Through a dropping funnel, 52 mL (0.444 mol) of SnCl4 were added dropwise, followed by slow addition of 22 mL (0.244 mol) of Cl2CHOCH3, causing the formation of a precipitate. The reaction was stirred for 2 h and was then poured over ice. The mixture was partitioned and the organic layer was washed with of 2M HCl (3 .x. 20 mL), and then with water (2 .x. 50 mL). The organic solution was dried over Na2SO4, filtered, and the solvent removed by rotary evaporation to afford a solid, which was triturated under cold MeOH, filtered, and dried to yield 34.38 g (93.2percent) of 10 as a tan solid: mp 120-121 °C (Lit [28]. mp 125-126). 1H NMR (CDCl3): δ 9.63 (s, 1H, CHO), 6.87 (s, 1H, ArH), 6.47 (s, 1, ArH), 6.02 (s, 2H, ArOCH2O), 1.54 (s, 1H, ArOH). CIMS: m/z 167 (M + H+, 100). Anal. (C8H6O4) C, H. With tin(IV) chloride in dichloromethane, Time= 2h, T= 0 °C , Friedel-Crafts type formylation Cueva, Juan Pablo; Chemel, Benjamin R.; Juncosa Jr., Jose I.; Lill, Markus A.; Watts, Val J.; Nichols, David E.; European Journal of Medicinal Chemistry; vol. 48; (2012); p. 97 - 107 View in Reaxys
O HO
O
H
O
O
H
O H
O
O
HO
H
O
O O
O
O O
O O
O
O racemate
racemate
Rx-ID: 33309727 View in Reaxys 11/25 Yield
Conditions & References Reaction Steps: 4 1: potassium carbonate / acetone / 5 h / Reflux; Inert atmosphere 2: 1.5 h / 180 °C / Inert atmosphere; Neat (no solvent) 3: potassium tert-butylate / dimethyl sulfoxide / 1.5 h / 100 °C / Inert atmosphere 4: oxygen; 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxy / benzene / 4 h / 70 °C With potassium tert-butylate, oxygen, potassium carbonate, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxy in dimethyl sulfoxide, acetone, benzene, 2: Claisen rearrangement Constantin, Mihaela-Anca; Conrad, Juergen; Merisor, Elena; Koschorreck, Katja; Urlacher, Vlada B.; Beifuss, Uwe; Journal of Organic Chemistry; vol. 77; nb. 10; (2012); p. 4528 - 4543 View in Reaxys
O E
O
O HO
O
H
O
H
O
HO
O
H
O
O O
O
O
H O
O
O O O
racemate
racemate
Rx-ID: 33309733 View in Reaxys 12/25 Yield 18 %Spectr.
Conditions & References With oxygen, 4-methoxy-2,2,6,6-tetramethylpiperidin-1-oxyl radical in benzene, Time= 4h, T= 70 °C , optical yield given as percent de
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Constantin, Mihaela-Anca; Conrad, Juergen; Merisor, Elena; Koschorreck, Katja; Urlacher, Vlada B.; Beifuss, Uwe; Journal of Organic Chemistry; vol. 77; nb. 10; (2012); p. 4528 - 4543 View in Reaxys
O
O
O
H
O
O
H
O H
O
O
HO
H
O
O O
O
O O
O O
O
O racemate
racemate
Rx-ID: 33309740 View in Reaxys 13/25 Yield
Conditions & References Reaction Steps: 3 1: 1.5 h / 180 °C / Inert atmosphere; Neat (no solvent) 2: potassium tert-butylate / dimethyl sulfoxide / 1.5 h / 100 °C / Inert atmosphere 3: oxygen; 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxy / benzene / 4 h / 70 °C With potassium tert-butylate, oxygen, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxy in dimethyl sulfoxide, benzene, 1: Claisen rearrangement Constantin, Mihaela-Anca; Conrad, Juergen; Merisor, Elena; Koschorreck, Katja; Urlacher, Vlada B.; Beifuss, Uwe; Journal of Organic Chemistry; vol. 77; nb. 10; (2012); p. 4528 - 4543 View in Reaxys
O
H
O
HO
O
H
O
O O
O
O
H
O
HO
H
O
O
O
O
O
O O O
racemate
racemate
Rx-ID: 33309746 View in Reaxys 14/25 Yield
Conditions & References Reaction Steps: 2 1: potassium tert-butylate / dimethyl sulfoxide / 1.5 h / 100 °C / Inert atmosphere 2: oxygen; 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxy / benzene / 4 h / 70 °C With potassium tert-butylate, oxygen, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxy in dimethyl sulfoxide, benzene Constantin, Mihaela-Anca; Conrad, Juergen; Merisor, Elena; Koschorreck, Katja; Urlacher, Vlada B.; Beifuss, Uwe; Journal of Organic Chemistry; vol. 77; nb. 10; (2012); p. 4528 - 4543 View in Reaxys O HO
–
C 2N
O
O
Zn 2+ O
HO
O
Rx-ID: 28856304 View in Reaxys 15/25 Yield
Conditions & References Stage 1: With hydrogenchloride, zinc(II) chloride in diethyl ether, T= 20 °C , Gattermann aldehyde synthesis Stage 2: in diethyl ether, Time= 0.5h, Heating, Acidic aq. solution, Gattermann aldehyde synthesis Riveiro, Maria E.; Maes, Dominick; Vazquez, Ramiro; Vermeulen, Monica; Mangelinckx, Sven; Jacobs, Jan; Debenedetti, Silvia; Shayo, Carina; De Kimpe, Norbert; Davio, Carlos; Bioorganic and Medicinal Chemistry; vol. 17; nb. 18; (2009); p. 6547 - 6559 View in Reaxys
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O HO
O
O
(v2)
N
Zn
N
O
O
HO
Rx-ID: 9869028 View in Reaxys 16/25 Yield
Conditions & References
76 %
Stage 1: With hydrogenchloride, sodium chloride, zinc(II) chloride in diethyl ether, Time= 0.5h, T= 20 °C , Gattermann formylation Stage 2: With sulfuric acid in water, Time= 0.5h, T= 100 °C Maes, Dominick; Vervisch, Stijn; Debenedetti, Silvia; Davio, Carlos; Mangelinckx, Sven; Giubellina, Nicola; De Kimpe, Norbert; Tetrahedron; vol. 61; nb. 9; (2005); p. 2505 - 2511 View in Reaxys
O
Br O
–O
Na +
O
HO
O
HO
O O
O
O
O
HO
O
O
O
Br
O
O
O
HO
HO
O O
O O
Rx-ID: 9881434 View in Reaxys 17/25 Yield
Conditions & References
52 %, 18 %, 3 %, 3 %
HO
With copper dichloride in methanol, N,N-dimethyl-formamide, Time= 32h, T= 100 °C Maes, Dominick; Vervisch, Stijn; Debenedetti, Silvia; Davio, Carlos; Mangelinckx, Sven; Giubellina, Nicola; De Kimpe, Norbert; Tetrahedron; vol. 61; nb. 9; (2005); p. 2505 - 2511 View in Reaxys
O
O
O
O
O
O O
HO
O
Rx-ID: 23745193 View in Reaxys 18/25 Yield 70.9 %
Conditions & References 6 :To an eggplant type flask (100 mL), sesamol (1.38 g, 10.0 mmol, 1.0 equivalent) and ether (40 mL) were added and dissolved. Triethyl orthoformate (10 mL, 7.6 mmol, 7.6 equivalents) was added to the solution. To the resulting yellow solution, aluminum chloride (2.0 g, 15 mmol, 1.5 equivalents) was added portionwise at 0C. The mixture color was changed from light red to green, and further, from dark green to dark blue. After 5 minutes, the mixture was cooled to 0C, and a 5percent hydrochloric acid solution (10 mL) was added. The resulting product was slightly soluble, and the separation thereof was difficult. The separation was carried out by adding distilled water (1 0mL) and ethyl acetate (40 mL). The aqueous layer was further extracted with ethyl acetate (40 mL). The collected organic layer was washed with saturated brine (10 mL), dried over sodium sulfate (approximately 5 g), and concentrated and solidified by an evaporator to obtain a dark red solid (1.6 g). From the resulting dark red solid, 506.6 mg thereof was taken and purified by silica gel chromatography [2.5 (diameter) *8.0 cm, 20 g; n-hexane:ethyl acetate (3:1)] to obtain 4,5-methylenedioxysalicylaldehyde (363.9 mg, yield = 70.9percent) in Fraction Nos. 2-4 as light brown needle crystals. Melting point: 125-126C TLC: Rf = 0.63 (n-hexane/ethyl acetate = 2:1) 1H-NMR (CDCl , δ ppm): 6.02 (s, 6H, Me ), 6.47 (s, 1H), 6.86 (s, 1H), 9.62 (s, 1H, CHO) 3 2 IR (KBr cm-1): 3076, 1646, 1614, 1506, 1482, 1424, 1388, 1314, 1270, 1230, 1162, 1086, 1036, 934, 872, 854, 786, 774, 722, 710, 514 With AlCl3, aluminium chloride in diethyl ether, Time= 0.0833333h, T= 0 °C Patent; Kureha Chemical Industry Co., Ltd.; EP1357118; (2003); (A1) English View in Reaxys
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O O
O
O
O
O
O
HO
Rx-ID: 17370660 View in Reaxys 19/25 Yield
Conditions & References Reaction Steps: 2 1: 10percent aq. KOH / methanol / 2.5 h / Ambient temperature 2: 56 percent / CF3COOH / 4 h / Heating With potassium hydroxide, trifluoroacetic acid in methanol Saito, Naoki; Tashiro, Kyoichi; Maru, Yukie; Yamaguchi, Kentaro; Kubo, Akinori; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 1; (1997); p. 53 - 70 View in Reaxys O
O
O
O
hydrogen sulfide remaining ammonium polysulfide
O
O
HO
Rx-ID: 17371124 View in Reaxys 20/25 Yield
Conditions & References Reaction Steps: 3 1: m-CPBA / CH2Cl2 / 4 h / Heating 2: 10percent aq. KOH / methanol / 2.5 h / Ambient temperature 3: 56 percent / CF3COOH / 4 h / Heating With potassium hydroxide, 3-chloro-benzenecarboperoxoic acid, trifluoroacetic acid in methanol, dichloromethane Saito, Naoki; Tashiro, Kyoichi; Maru, Yukie; Yamaguchi, Kentaro; Kubo, Akinori; Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999); nb. 1; (1997); p. 53 - 70 View in Reaxys O
O
O
N
O
Z
O
O
O
HO
Rx-ID: 2661811 View in Reaxys 21/25 Yield
Conditions & References
40 %
With aluminium trichloride, acetyl chloride in dichloromethane, Time= 0.5h, T= -30 °C Kelkar, Shriniwas L.; Phadke, Chetan P.; Marina, Sister; Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry; vol. 23; nb. 5; (1984); p. 458 - 459 View in Reaxys
E O
HO
O
HO
O OH
O
O
H O
O
O
O
O O
O
O
H HO
O
O O O racemate
O
OH
O
OH O
O O
O racemate
racemate
Rx-ID: 1576674 View in Reaxys 22/25
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Yield
Conditions & References
169 mg, 63 With lithium perchlorate, anodic oxidation mg, 39 mg, Nishiyama; Eto; Terada; et al.; Chemical and Pharmaceutical Bulletin; vol. 31; nb. 8; (1983); p. 2834 - 2844 3 mg View in Reaxys
E O
HO
O
HO
O
O
O
O
O
OH O
O
H O
O
OH
O
O
O
O
H HO
O
O O
O
O
O
O HO
racemate
racemate
O
racemate
Rx-ID: 1576673 View in Reaxys 23/25 Yield
Conditions & References
15 %, 11 anodic oxidation %, 1 %, 44 Iguchi, Masanobu; Nishiyama, Atsuko; Eto, Hideo; Yamamura,Shosuke; Chemistry Letters; (1981); p. 939 - 942 % View in Reaxys
E O O
HO
O
O
O
O
O
OH O
O
H O
O
OH
O
O
O
O
H HO
O
O O
O
O
O
O HO
racemate
racemate
O
racemate
Rx-ID: 1747212 View in Reaxys 24/25 Yield 44 %, 15 %, 11 %, 1 %
Conditions & References in methanol, anodic oxidation Iguchi, Masanobu; Nishiyama, Atsuko; Eto, Hideo; Yamamura,Shosuke; Chemistry Letters; (1981); p. 939 - 942 View in Reaxys O O
diazotized 2-amino-4,5-methylenedioxy-benzaldehyde HO
O
Rx-ID: 5451176 View in Reaxys 25/25 Yield
Conditions & References With copper(II) sulfate Campbell et al.; Journal of Organic Chemistry; vol. 16; (1951); p. 1736,1740 View in Reaxys Arnold; Bordwell; Journal of the American Chemical Society; vol. 64; (1942); p. 2983,2985 View in Reaxys
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