1,3-Benzodioxol-5-ol (Sesamol) by Asch

Query Query HO

Results

Date

33 reactions in Reaxys

2017-10-14 23h:08m:31s (EST)

1. Query O

Search as: As drawn, No salts, No mixtures, No isotopes, No charges, No radicals

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O O

Rx-ID: 123313 View in Reaxys 1/33 Yield 95 %

Conditions & References Stage 1: With 3-chloro-benzenecarboperoxoic acid, Time= 0.0833333h, Dakin oxidation Stage 2: With sodium hydroxide, Time= 0.0833333h, Further stages. Da Silva, Emerson Teixeira; Camara, Celso Amorim; Antunes; Barreiro, Eliezer J.; Fraga, Carlos A. M.; Synthetic Communications; vol. 38; nb. 5; (2008); p. 784 - 788 View in Reaxys

89 %

With sulfuric acid, dihydrogen peroxide, boric acid in tetrahydrofuran, water, Time= 3.5h, T= 20 °C , Oxidation Roy, Amrita; Reddy; Mohanta, Pramod K.; Ila; Junjappa; Synthetic Communications; vol. 29; nb. 21; (1999); p. 3781 - 3791 View in Reaxys

78 %

With sulfuric acid, dihydrogen peroxide, boric acid, 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate, T= 0 °C , Dakin reaction Zambrano, Jorge L.; Dortab, Romano; Synlett; nb. 10; (2003); p. 1545 - 1546 View in Reaxys

77 %

Stage 1: With formic acid, dihydrogen peroxide in dichloromethane, water, Time= 18h, Heating Stage 2: With sodium hydroxide in dichloromethane, water, Time= 0.25h, T= 20 °C Bezerra-Netto, Heleno J.C.; Lacerda, Daniel I.; Miranda, Ana Luisa P.; Alves, Helio M.; Barreiro, Eliezer J.; Fraga, Carlos A.M.; Bioorganic and Medicinal Chemistry; vol. 14; nb. 23; (2006); p. 7924 - 7935 View in Reaxys

56 %

With Oxone, EDTA, sodium hydrogencarbonate in water, acetonitrile, Time= 1h, Oxidation Webb, Kevin S.; Ruszkay, Stephen J.; Tetrahedron; vol. 54; nb. 3-4; (1998); p. 401 - 410 View in Reaxys

35 %

With formic acid, dihydrogen peroxide, Time= 16h, T= 5 °C Devakumar, C.; Saxena, V. S.; Mukerjee, S. K.; Agricultural and Biological Chemistry; vol. 49; nb. 3; (1985); p. 725 - 730 View in Reaxys With peracetic acid, toluene-4-sulfonic acid, acetic acid, Erwaermen des Reaktionsgemisches mit aethanol. Kalilauge Boeeseken et al.; Recueil des Travaux Chimiques des Pays-Bas; vol. 55; (1936); p. 815,817 View in Reaxys Beroza; Journal of Agricultural and Food Chemistry; vol. 4; (1956); p. 49,51, 52 View in Reaxys Wilkinson; Biochemical Journal; vol. 63; (1956); p. 601,603 View in Reaxys With sulfuric acid, dihydrogen peroxide in methanol, Time= 48h, T= 20 °C Nam, Nguyen-Hai; Kim, Yong; You, Young-Jae; Hong, Dong-Ho; Kim, Hwan-Mook; Ahn, Byung-Zun; Bioorganic and medicinal chemistry letters; vol. 12; nb. 17; (2002); p. 2345 - 2348 View in Reaxys Stage 1: With 3-chloro-benzenecarboperoxoic acid, Baeyer-Villiger oxidation Stage 2: With sodium hydroxide Sa E Sant'Anna; Evangelista; Alves; Raslan; Chemistry of Natural Compounds; vol. 41; nb. 4; (2005); p. 385 387 View in Reaxys

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Reaction Steps: 2 1: 900 mg / m-chlorperbenzoic acid / CH2Cl2 / 2.5 h 2: methanolic KOH / methanol; tetrahydrofuran / 30 h / 10 °C With potassium hydroxide, 3-chloro-benzenecarboperoxoic acid in tetrahydrofuran, methanol, dichloromethane Rohatgi, B. K.; Khanna, R. N.; Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry; vol. 22; nb. 11; (1983); p. 1150 View in Reaxys Reaction Steps: 2 1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 1 h / 0 - 20 °C 2: potassium hydoxide / methanol; water / 0.03 h / 20 °C With 3-chloro-benzenecarboperoxoic acid, potassium hydoxide in methanol, dichloromethane, water Gangar, Mukesh; Chouhan, Mangilal; Goyal, Sandeep; Harikrishnan; Chandran; Ittuveetil, Avinash; Nair, Vipin A.; Tetrahedron Letters; vol. 57; nb. 52; (2016); p. 5931 - 5934 View in Reaxys 28.5 g

1.2 : Synthesis of 3,4-methylenedioxyphenol Mechanical stirrer,To a 2 L separable flask equipped with a condenser and equipped with a jacket was added methanol6.2 g of 98percent by weight sulfuric acid and 92.0 g of the initial retention of heliotropin produced in step 1 (GC purity of heliotropin 96.5 areapercent) were mixed and the temperature of the solution was raised to 45 ° C. It warmed up. Thereafter, 54.1 g of 60 wtpercent hydrogen peroxide water was added dropwise. The temperature of the solution was kept at 60 ° C., and aging was carried out for 1 hour from the end of the hydrogen peroxide dropwise addition. After ripening for 1 hour, 49.0 g of a 20 wtpercent sodium hydroxide aqueous solution containing 16.8 g of sodium 3,4-methylenedioxyphenoxide (sodium salt of sesamol) was added dropwise at a solution temperature of 60 ° C., and the solution was neutral Respectively. Thereafter, 37.2 g of a 20percent by weight sodium hydroxide aqueous solution was added dropwise and aged at 60 ° C. for 1 hour. The concentration of hydrogen peroxide after aging was 516 ppm, and the pH was 8.2. To the obtained solution, 9.2 g of 30percent by weight HCl was added and the temperature of the solution was cooled from 60 ° C. to 25 ° C. to precipitate an inorganic salt and a high-boiling component, followed by filtration under reduced pressure. As a result, 872.5 g of filtrate (including 73.9 g of sesamol, reactionThe reaction yield to heliotropin contained in the initial distillate used at times was 74.1percent) and 28.5 g of filtered matter was obtained. With dihydrogen peroxide, sodium hydroxide in methanol, water, Time= 2h, T= 45 - 60 °C , Reagent/catalyst Patent; UBE INDUSTRIES LIMITED; KIMURA, KEISUKE; OOMORI, KIYOSHI; KAIDA, SUZUE; NISHIMURA, KOSUKE; (29 pag.); JP2017/101020; (2017); (A) Japanese View in Reaxys

O O

Rx-ID: 1718747 View in Reaxys 2/33 Yield 82 %

Conditions & References With water, potassium hydoxide in methanol, Time= 1h, T= 50 °C Singh, Pragya; Faridi, Uzma; Srivastava, Suchita; Kumar, Jonnala Kotesh; Darokar, Mahender Pandurang; Luqman, Suaib; Shanker, Karuna; Chanotiya, Chandan Singh; Gupta, Atul; Gupta, Madan Mohan; Negi, Arvind Singh; Chemical and Pharmaceutical Bulletin; vol. 58; nb. 2; (2010); p. 242 - 246 View in Reaxys With potassium hydroxide in tetrahydrofuran, methanol, Time= 30h, T= 10 °C , Yield given Rohatgi, B. K.; Khanna, R. N.; Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry; vol. 22; nb. 11; (1983); p. 1150 View in Reaxys With potassium hydroxide in methanol, Time= 1h, Ambient temperature, Yield given Syper, Ludwik; Synthesis; nb. 3; (1989); p. 167 - 172 View in Reaxys

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With potassium hydroxide in methanol, Time= 2.5h, Ambient temperature, Yield given 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 With potassium hydroxide in methanol, water Chandrasekhar; Reddy, N. Ramakrishna; Rao, Y. Srinivasa; Tetrahedron; vol. 62; nb. 51; (2006); p. 12098 12107 View in Reaxys 16 g

With methanol, potassium hydroxide, T= 20 °C Duan, Xin-Fang; Zeng, Jing; Zhang, Zhan-Bin; Zi, Guo-Fu; Journal of Organic Chemistry; vol. 72; nb. 26; (2007); p. 10283 - 10286 View in Reaxys Synthesis of Benzo[d][1,3]dioxol-5-ol (8) To the stirred solution of benzo[d][1,3]dioxole-5-carbaldehyde 7 (1 g, 6.7 mmol, 1.0 equiv) in DCM was added mCPBA (1.72 g, 10.1 mmol, 1.5 equiv) and stirred for another hour at rt. After the full conversion of starting material (monitored by the TLC) the reaction mixture was extracted with DCM. It was dried over anhydrous sodium sulfate and the solvent was evaporated under the reduced pressure to give the crude product. The crude product was taken in MeOH and aq. KOH was added to the reaction mixture and stirred at rt. After the completion of the reaction, MeOH was evaporated under reduced pressure. The pH was adjusted to 4-5 by the addition of conc. HCl and the reaction mixture was extracted with ethyl acetate. It was dried over anhydrous sodium sulfate and the solvent was evaporated under the reduced pressure to give the crude product. The crude product was purified by column chromatography over silica gel (60-120 mesh) using petroleum ether/EtOAc (90:10) as the eluent to afford desired product. With potassium hydoxide in methanol, water, Time= 0.0333333h, T= 20 °C Gangar, Mukesh; Chouhan, Mangilal; Goyal, Sandeep; Harikrishnan; Chandran; Ittuveetil, Avinash; Nair, Vipin A.; Tetrahedron Letters; vol. 57; nb. 52; (2016); p. 5931 - 5934 View in Reaxys

O O

Rx-ID: 33647868 View in Reaxys 3/33 Yield

Conditions & References

88 %

With copper acetylacetonate, N,N′-bis(4-hydroxyl-2,6-dimethylphenyl)oxalamide, water in water, dimethyl sulfoxide, Time= 24h, T= 130 °C , Schlenk technique, Inert atmosphere Xia, Shanghua; Gan, Lu; Wang, Kailiang; Li, Zheng; Ma, Dawei; Journal of the American Chemical Society; vol. 138; nb. 41; (2016); p. 13493 - 13496 View in Reaxys

51 %

With Herrmann catalyst, C29H45Pt, caesium carbonate in water, N,N-dimethyl-formamide, Time= 0.5h, T= 130 °C , Inert atmosphere, Microwave irradiation Yu, Chao-Wu; Chen, Grace S.; Huang, Chen-Wei; Chern, Ji-Wang; Organic Letters; vol. 14; nb. 14; (2012); p. 3688 - 3691 View in Reaxys

O O

O HO

Rx-ID: 42209585 View in Reaxys 4/33

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Yield

Conditions & References

24 %Chromat., 30 %Chromat., 20 %Chromat.

General procedure: General procedure for aryl 3-methyl-2-butenoate esters. Solutions of esters (1–9; 0.106mmol) were prepared in different organic media (100mL). Photoirradiations of the esters were performed as follow: i) analytical scale: a 2mL aliquot of solution was placed in a stoppered 3mL quartz cell and degassed with argon for 20min; ii) preparative scale: a 65mL aliquot was placed in a stoppered 100mL Erlenmeyer quartz flask and degassed with argon for 30min. The quartz cell as well as the Erlenmeyer quartz flask were placed in a home made optical bench provided with the possibility to use two or four lamps. The solutions of the esters were stirred during the irradiation process. Irradiations with λexc=313nm were carried out with four phosphorous–coated lamps (HelioQuartz, each of 18 Watts) that give a nearly parallel beam at 313nm. Irradiations with λexc=254nm were carried with four germicide lamps (Philips, each of 20 Watts). in cyclohexane, T= 25 °C , Inert atmosphere, Irradiation, Wavelength Iguchi, Daniela; Erra-Balsells, Rosa; Bonesi, Sergio M.; Tetrahedron; vol. 72; nb. 16; (2016); p. 1903 - 1910 View in Reaxys

O O

Rx-ID: 43723355 View in Reaxys 5/33 Yield

Conditions & References

99 %

With copper acetylacetonate, N,N′-bis(4-hydroxyl-2,6-dimethylphenyl)oxalamide, potassium hydoxide in water, dimethyl sulfoxide, Time= 24h, T= 60 °C , Schlenk technique, Inert atmosphere Xia, Shanghua; Gan, Lu; Wang, Kailiang; Li, Zheng; Ma, Dawei; Journal of the American Chemical Society; vol. 138; nb. 41; (2016); p. 13493 - 13496 View in Reaxys

O O

Rx-ID: 43723513 View in Reaxys 6/33 Yield 99 %

Conditions & References With copper acetylacetonate, N,N′-bis(4-hydroxyl-2,6-dimethylphenyl)oxalamide, water in water, dimethyl sulfoxide, Time= 24h, T= 80 °C , Schlenk technique, Inert atmosphere Xia, Shanghua; Gan, Lu; Wang, Kailiang; Li, Zheng; Ma, Dawei; Journal of the American Chemical Society; vol. 138; nb. 41; (2016); p. 13493 - 13496 View in Reaxys

O O

Rx-ID: 44079718 View in Reaxys 7/33 Yield

Conditions & References Reaction Steps: 3 1.1: 1,8-diazabicyclo[5.4.0]undec-7-ene / N,N-dimethyl-formamide / 0.5 h / 20 °C 1.2: 4 h / 0 °C / |Reflux 2.1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 1 h / 0 - 20 °C 3.1: potassium hydoxide / methanol; water / 0.03 h / 20 °C With 1,8-diazabicyclo[5.4.0]undec-7-ene, 3-chloro-benzenecarboperoxoic acid, potassium hydoxide in methanol, dichloromethane, water, N,N-dimethyl-formamide Gangar, Mukesh; Chouhan, Mangilal; Goyal, Sandeep; Harikrishnan; Chandran; Ittuveetil, Avinash; Nair, Vipin A.; Tetrahedron Letters; vol. 57; nb. 52; (2016); p. 5931 - 5934 View in Reaxys

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O O

Rx-ID: 29512006 View in Reaxys 8/33 Yield

Conditions & References

95 %

With water, potassium hydroxide in methanol, Time= 2h, T= 50 °C Singh, Pragya; Faridi, Uzma; Srivastava, Suchita; Kumar, Jonnala Kotesh; Darokar, Mahender Pandurang; Luqman, Suaib; Shanker, Karuna; Chanotiya, Chandan Singh; Gupta, Atul; Gupta, Madan Mohan; Negi, Arvind Singh; Chemical and Pharmaceutical Bulletin; vol. 58; nb. 2; (2010); p. 242 - 246 View in Reaxys

95 %

General Procedure for Deacetylation of Esters Using PBNS in H2O General procedure: A mixture of ester (1 mmol) and PBNS (30 mg) in H2O(2 mL) was stirred at ambient temperature. After completion of the reaction as monitored by TLC, the insoluble catalyst was separated by filtration. Water was removed by rotary evaporation and the residue was extracted with ethyl acetate(310 mL). The organic layer was dried over anhydrous Na2SO4. After evaporation of the solvent, the products were purified by column chromatography. The product’s purity was checked by TLC, it showed single spot of the final product, and evaporation of the solvent gave the desired pure products in good yields. With water, Time= 1.25h, T= 20 °C Khazaei, Ardeshir; Saednia, Shahnaz; Roshani, Liela; Kazem-Rostami, Masoud; Zare, Abdolkarim; Letters in Organic Chemistry; vol. 11; nb. 3; (2014); p. 159 - 167 View in Reaxys

O O

Rx-ID: 37467513 View in Reaxys 9/33 Yield

Conditions & References

57 %

With air in tetrahydrofuran, Time= 0.0566667h, T= -25 °C , p= 12929Torr , Green chemistry He, Zhi; Jamison, Timothy F.; Angewandte Chemie - International Edition; vol. 53; nb. 13; (2014); p. 3353 - 3357; Angew. Chem.; vol. 126; nb. 13; (2014); p. 3421 - 3425,5 View in Reaxys OH

O O

Rx-ID: 34317777 View in Reaxys 10/33 Yield 53 %, 17 %

Conditions & References With potassium hydroxide in ethylene glycol, Reflux, Mechanism Chang, Junbiao; Wang, Shuyang; Shen, Zhenhua; Huang, Gang; Zhang, Yueteng; Zhao, Jing; Li, Changwei; Fan, Fangfang; Song, Chuanjun; Tetrahedron Letters; vol. 53; nb. 50; (2012); p. 6755 - 6757,3 View in Reaxys

O O

OH O

NH 2

O O

OH P

H 2N

Rx-ID: 25607727 View in Reaxys 11/33 Yield

Conditions & References 3 :In order to examine whether the sesamol, 3-aminopropane phosphoric acid diester is hydrolyzed by phosphatase present on the skin into sesamol and 3-aminopropane phosphoric acid, the following test was performed. The sesamol, 3-aminopropane phosphoric acid diester of Example 1 and phsophatase were added in phosphate buffer (pH

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7.4), followed by hydrolysis. As the phosphatase, alkaline phosphatase commercially available from Sigma- Aldrich Co. was used. The amount of 3-aminopropane phosphoric acid formed as the hydrolysis progressed was measured by HPLC (high- performance liquid chromatography), and the measurement results are shown in FIG. 1.As can be seen in FIG. 1, it was found that the sesamol, 3- aminopropane phosphoric acid diester can be hydrolyzed by phosphatase present on the skin into sesamol and 3-aminopropane phosphoric acid, so that it can simultaneously the activities of sesamol and 3-aminopropane phosphoric acid. With alkaline phosphatase, pH= 7.4, Aqueous phosphate buffer, Enzymatic reaction Patent; AMOREPACIFIC CORPORATION; WO2006/132479; (2006); (A1) English View in Reaxys 3 :EXPERIMENTAL EXAMPLE 3; In order to examine whether the sesamol, 3-aminopropane phosphoric acid diester is hydrolyzed by phosphatase present on the skin into sesamol and 3-aminopropane phosphoric acid, the following test was performed. The sesamol, 3-aminopropane phosphoric acid diester of Example 1 and phsophatase were added in phosphate buffer (pH 7.4), followed by hydrolysis. As the phosphatase, alkaline phosphatase commercially available from Sigma-Aldrich Co. was used. The amount of 3-aminopropane phosphoric acid formed as the hydrolysis progressed was measured by HPLC (high-performance liquid chromatography), and the measurement results are shown in FIG. 1.As can be seen in FIG. 1, it was found that the sesamol, 3-aminopropane phosphoric acid diester can be hydrolyzed by phosphatase present on the skin into sesamol and 3-aminopropane phosphoric acid, so that it can simultaneously the activities of sesamol and 3-aminopropane phosphoric acid. With water, alkaline phosphatase, pH= 7.4, Aqueous phosphate buffer, Product distribution / selectivity Patent; AMOREPACIFIC CORPORATION; US2009/131686; (2009); (A1) English View in Reaxys

O O

Rx-ID: 28774743 View in Reaxys 12/33 Yield

Conditions & References

82 %Chromat.

With hypophosphorous ether in water, acetonitrile, Time= 15h, Irradiation, Inert atmosphere Dichiarante, Valentina; Fagnoni, Maurizio; Albini, Angelo; Green Chemistry; vol. 11; nb. 7; (2009); p. 942 - 945 View in Reaxys

isooxyurea O

Rx-ID: 12139231 View in Reaxys 13/33 Yield

Conditions & References Reaction Steps: 2 1: m-chloroperoxybenzoic acid / CH2Cl2 / 18 h / Heating 2: potassium hydroxide / methanol; H2O With potassium hydroxide, 3-chloro-benzenecarboperoxoic acid in methanol, dichloromethane, water, 1: Baeyer-Villiger oxidation Chandrasekhar; Reddy, N. Ramakrishna; Rao, Y. Srinivasa; Tetrahedron; vol. 62; nb. 51; (2006); p. 12098 12107 View in Reaxys

O O

Rx-ID: 9780725 View in Reaxys 14/33 Yield 81 %

Conditions & References With titanium(III) chloride in acetonitrile, Time= 24h, T= 20 °C

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Semwal, Abha; Nayak, Sandip K.; Synthesis; nb. 1; (2005); p. 71 - 74; Art.No: Z16603SS View in Reaxys O O

O O

Rx-ID: 166782 View in Reaxys 15/33 Yield

Conditions & References With formic acid, dihydrogen peroxide, anschliessend Behandeln mit methanol. Kalilauge Sugawara; Nippon Nogei Kagaku Kaishi; vol. 33; (1959); p. 648,650; Chem. Zentralbl.; vol. 134; (1963); p. 20767 View in Reaxys 11 : EXAMPLE 11. Synthesis of 3,4-methylenedioxo-phenol A mixture of 17. 7G (100 MMOL) of 1- (1, 3BENZODIOXOL-5-YL)-1-PROPANONE, 26 ML of dichloromethane, 22.5 G (220MMOL) of 98percent acetic anhydride and 0. 42g (2MMOL) of monohydrated paratoluensulfonic acid are heated to 40°C, 14 G (140MOL) of hydrogen peroxide are then slowly added. Once the hydrogen peroxide is completed the mixture is heated to the reflux temperature, afterwards it is cooled and the phases are separated. The aqueous phase was treated with 50 ml of dichloromethane and with 37percent hydrochloric acid up to a pH value of about 1. The organic phase was washed twice with water and dried on anhydrous sodium sulphate. After filtration the organic phase is evaporated under vacuum at 30°C/24MBAR, thereby obtaining 4. 4g of a product which after crystallisation form CYCLOHEXANE/DICHLOROMETHANE has m. p. =63-65°C whose NMR and MS correspond to those of the desired product. Stage 1: With acetic anhydride, toluene-4-sulfonic acid in dichloromethane, T= 40 °C Stage 2: With dihydrogen peroxide in dichloromethane, water, Heating / reflux Stage 3: With hydrogenchloride in dichloromethane, water, pH= 1 Patent; ENDURA S.P.A.; WO2004/92106; (2004); (A2) English View in Reaxys 14 : EXAMPLE 14. Synthesis of 3,4-methylenedioxo-phenol A mixture of 17, 7G (100MOL) of 1- (1, 3-BENZODIOXOL-5-YI)-L-PROPANONE and 30 ml of DICHLOROMETHANE are heated to 40°C ; then a solution of 40, Og (122MMOL) of phtalimido-peroxy hexanoic acid (P. A. P. from Solvay) (title 84.7percent w/w) in 100 ml of dichloromethaneare added slowly. Once the addition is completed the mixture is heated to reflux for 10 hours. Then it is cooled and treated as described in example 11 with suitable amounts of reactants. 6.4 G of a product are obtained which after crystallisation from cyclohexane/dichloromethane has m. p. 64-65°C and whose NMR and MS analyses correspond to those of the desired products. Stage 1: in dichloromethane, Time= 10h, T= 40 °C , Heating / reflux Stage 2: With hydrogenchloride in dichloromethane, water, pH= 1, Heating / reflux Patent; ENDURA S.P.A.; WO2004/92106; (2004); (A2) English View in Reaxys 12 : EXAMPLE 12. Synthesis of 3,4-methylenedioxo-phenol A mixture of 17. 7G (100MMOI) of 1-(1,3-benzodioxol-5-yl)-1-propanone, 50 ml of DICHLOROMETHANE, 33. OG (220MOL) of 97percent phthalic anhydride and 0. 42g (2MMOL) of monohydrated P-TOLUENSULFONIC acid are heated to 40°C, then 14. Og (140MMOL) of 35percent hydrogen peroxide. Once said addition is completed the reaction mixture is heated under reflux for 6 hours. The reaction mixture is cooled and unreacted phthalic anhydride is filtered and the organic solution obtained is treated as reported in Example 11, utilising the same amounts of reactants. 4.3g of a product are obtained which, after crystallisation of CYCLOHEXANE/DICHLOROMETHANE, has m. p =63-65°C, whose NMR and MS analyses correspond to those of the desired compound. Stage 1: With phthalic anhydride, toluene-4-sulfonic acid in dichloromethane, T= 40 °C Stage 2: With dihydrogen peroxide in dichloromethane, water, Heating / reflux Stage 3: With hydrogenchloride in dichloromethane, water, pH= 1 Patent; ENDURA S.P.A.; WO2004/92106; (2004); (A2) English View in Reaxys 13 : EXAMPLE 13. Synthesis of 3,4-methylenedioxo-phenol

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A mixture of 17. 7g (100MOL) of 1- (1, 3-BENZODIOXOL-5-YL)-1-PROPANONE, 50 ml of dichloromethane, 21. 4G (218 MMOL) of maleic anhydride and 0. 42g (2MMOL) of monohydrated P-TOLUENSULFONIC acid are heated to 40°C, then 14. Og (140MOL) of 35percent hydrogen peroxide are slowly added. Once the addition is completed the mixture is heated under reflux for 6 hours, afterwards it is cooled and treated as described in example 11 with the same amounts of reactants. 6. 3g of a products are obtained which after crystallisation from cyclohexane/dichloromethane has a m. p. =63-65°C, whose NMR and MS analyses correspond to those of the desired product. Stage 1: With maleic anhydride, toluene-4-sulfonic acid in dichloromethane, T= 40 °C Stage 2: With dihydrogen peroxide in dichloromethane, water, Heating / reflux Stage 3: With hydrogenchloride in dichloromethane, water, pH= 1 Patent; ENDURA S.P.A.; WO2004/92106; (2004); (A2) English View in Reaxys

O O

Rx-ID: 5428742 View in Reaxys 16/33 Yield

Conditions & References Crosby,D.G.; Berthold,R.V.; Journal of Organic Chemistry; vol. 27; (1962); p. 3083 - 3085 View in Reaxys Minamikawa; Brossi; Tetrahedron Letters; (1978); p. 3085 View in Reaxys Ohno et al.; Bulletin of the Institute for Chemical Research, Kyoto University; vol. 38; (1960); p. 34,38; ; nb. 22275d; (1961) View in Reaxys Orphanos; Taurius; Canadian Journal of Chemistry; vol. 44; (1966); p. 1875,1877 View in Reaxys 7 Patent; ENDURA S.P.A.; WO2004/92106; (2004); (A2) English View in Reaxys ...he customary manner and 2-(1,3-benzodioxol-5-yl)-2-(1,3-dihydro-1,3-dioxoisoindol-5-yloxy)-N-(4-tert-butylphenylsulfonyl)acetamide, m.p. 215°, is obtained; potassium salt of the compound FAB 575, m.p. 171°. Analogously, by reaction of methyl benzo[1,3]dioxol-5-ylbromoacetate with ... 5-hydroxybenzofuran 4-hydroxy-2-methylindole 5-hydroxy-1,3-benzodioxol, Patent; Merck Patent Gesellschaft mit Beschrankter Haftung; US5821256; (1998); (A1) English View in Reaxys

(v2)

O O

Rx-ID: 9687716 View in Reaxys 17/33 Yield

Conditions & References With triethylamine in various solvent(s), T= 20 °C , Kinetics, Further Variations: Reagents Joshi; Naumov; Kapoor; Mukherjee; Hermann; Brede; Journal of Physical Organic Chemistry; vol. 17; nb. 8; (2004); p. 665 - 674 View in Reaxys

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O O

Rx-ID: 23141818 View in Reaxys 18/33 Yield

Conditions & References 1 : EXAMPLE 1 30 g of TS-1 catalyst, 150 g of methylisobutylketone, 150 g of acetone and 150 g (1.23 moles) of MDB, are charged into a reactor equipped with a stirrer, thermometer, condenser and heating/cooling jacket. The resulting suspension is heated to [60°C,] maintaining the mass under stirring. 84 g of H202 at [10percent] (0.25 moles) are then fed in about 4 hours, the temperature of the suspension being maintained at [60°C.] The suspension is left under stirring at [60°C] for an hour and the organic phase is subsequently analyzed after separation from the TS-1 catalyst. The following results are obtained from GLC analysis of the organic phase: MDB conversion = 15percent ; selectivity to 5-hydroxy-MDB = 62percent. With dihydrogen peroxide, titanium-silicalite catalyst (TS-1) in isobutyl methylketone, acetone, Time= 5h, T= 60 °C , Conversion of starting material Patent; BORREGAARD ITALIA S.P.A.; WO2004/14827; (2004); (A1) English View in Reaxys 4 : EXAMPLE 4 The same procedure is used as in Example 1, except that 33 g of n-hexane are charged instead of acetone. The following results are obtained from GLC analysis of the organic phase: MDB conversion = 10percent; selectivity to [5-HYDROXY-MDB] = 70percent. With dihydrogen peroxide, titanium-silicalite catalyst (TS-1) in hexane, isobutyl methylketone, Time= 5h, T= 60 °C , Conversion of starting material Patent; BORREGAARD ITALIA S.P.A.; WO2004/14827; (2004); (A1) English View in Reaxys 5 : EXAMPLE 5 The same procedure is used as in Example 1, except that 150 g of dimethyl carbonate are charged instead of the acetone/methylisobutylketone mixture. The following results are obtained from GLC analysis of the organic phase: MDB conversion = 13percent ; selectivity to 5-hydroxy-MDB = 52percent. With dihydrogen peroxide, titanium-silicalite catalyst (TS-1) in carbonic acid dimethyl ester, Time= 5h, T= 60 °C , Conversion of starting material Patent; BORREGAARD ITALIA S.P.A.; WO2004/14827; (2004); (A1) English View in Reaxys 6 : EXAMPLE 6 The same procedure is used as in Example 1, except that 150 g of acetonitrile are charged instead of the acetone/ methylisobutylketone mixture. The following results are obtained from GLC analysis of the organic phase: MDB conversion = 10percent; selectivity to 5-hydroxy-MDB = [45percent.] With dihydrogen peroxide, titanium-silicalite catalyst (TS-1) in acetonitrile, Time= 5h, T= 60 °C , Conversion of starting material Patent; BORREGAARD ITALIA S.P.A.; WO2004/14827; (2004); (A1) English View in Reaxys 7 : EXAMPLE 7 The same procedure is used as in Example 1, except that 300 g of terbutanol are charged instead of the acetone/ methylisobutylketone mixture. The following results are obtained from GLC analysis of the organic phase: MDB conversion = [15percent] ; selectivity to 5-hydroxy-MDB = 48percent. With dihydrogen peroxide, titanium-silicalite catalyst (TS-1) in tert-butyl alcohol, Time= 5h, T= 60 °C , Conversion of starting material Patent; BORREGAARD ITALIA S.P.A.; WO2004/14827; (2004); (A1) English View in Reaxys

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2 : EXAMPLE 2 EXAMPLE 2 The same procedure is used as in Example 1 except that only 300 g of acetone are charged instead of the acetone/methylisobutylketone mixture. The following results are obtained from GLC analysis of the organic phase: MDB conversion = 12percent ; selectivity to [5-HYDROXY-MDB] = [58percent.] With dihydrogen peroxide, titanium-silicalite catalyst (TS-1) in acetone, Time= 5h, T= 60 °C , Conversion of starting material Patent; BORREGAARD ITALIA S.P.A.; WO2004/14827; (2004); (A1) English View in Reaxys 3 : EXAMPLE 3 The same procedure is used as in Example 1, except that 70 g of H20 are charged instead of the mixture of solvents and 28 g of H202 at [30percent] (0.25 moles), are dosed. The following results are obtained from GLC analysis of the organic phase: MDB conversion = 10percent ; selectivity to 5-hydroxy-MDB = [25percent.] With dihydrogen peroxide, titanium-silicalite catalyst (TS-1), Time= 5h, T= 60 °C , Conversion of starting material Patent; BORREGAARD ITALIA S.P.A.; WO2004/14827; (2004); (A1) English View in Reaxys

O–

Na + O

Rx-ID: 23164364 View in Reaxys 19/33 Yield

Conditions & References

94.3 %

2A : Example 2A - Acid hydrolysis of sesamyl propanoate. 1200 ml of methanol and 3.4 G of 96percent sulphuric acid are added to the crude reaction product from example 1. The mixture is stirred at 40°C for 9 hours, then cooled and the solvent is evaporated under vacuum at 30°C/23 mbar. The remainder is re-dissolved in 500 ml of methylene chloride to which 790 mi of 2M sodium hydroxide are added. The mixture is then stirred for 10 minutes and the phases are separated. The aqueous phase is extracted with 50 mi of methylene chloride. The organic phase containing the ketone and the non-hydrolysed ester is recycled as described in the following example 3A. The aqueous phase containing the sodium sesamate is then added with 37percent HCI till to pH 8.5 to obtain sesamol in free form, which is then extracted with 50 mi of methylene chloride. The organic phase containing the sesamol is concentrated under vacuum at 30°C/23 mbar. The sesamol is distilled at 116°C/3-4 mbar; hydrolysis yield : 94.3percent. With hydrogenchloride in water, pH= 8.5 Patent; ENDURA S.P.A.; WO2004/92106; (2004); (A2) English View in Reaxys

O O

Rx-ID: 23164366 View in Reaxys 20/33 Yield 92.3 - 95.8 %

Conditions & References 2B; 3B; 4A : Example 2B Basic hydrolysis of sesamyl propanoate EXAMPLE 4A-Basic hydrolysis 2.32 G (8 mmoles) of hydrated tetrabutylammonium chloride are added to the previous organic phase and 664 G (2.7 moles) of 4M NAOH are added over 45 minutes while maintaining the temperature at 20-25°C. After stirring for 8 hours at room temperature the phases are separated. 100 ml of CH2CI2 are added to the aqueous phase which is added with 37percent HGI till to pH 8.5. The phases are separated. The organic phase containing the sesamol is concentrated under vacuum at 30°C/23 mbar. The SESAMOL is distilled AT 116°C/34 mbar to obtain 82 G of product. Yield with respect to converted product: 92.3percent. The distilled sesamol is crystallised in a 1/2 (V/V) mixture of toluene/cyclohexane. The solid obtained is filtered off and dried under vacuum at 40°C/23 MBAR. 79 G OF crystallised SESAMOL with A concentration of 99. 7percent w/w are obtained. 1325 ml of 4M sodium hydroxide and 3.6 G (13 MMOLES) of 98percent hydrated tetrabutylammonium chloride are added to the organic phase in methylene chloride obtained at the end of the reaction in example 1. After stirring for 8 hours at room temperature, the phases are separated. 200 ml of methylene chloride are added to the aqueous phase, which is added with 37percent HCI till to pH 8.5 to release the sesamol which passes into the organic phase. The organic

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phase is separated and the solvent is evaporated under vacuum at 30°C/23 mbar. The sesamol is distilled at 116°C/23 mbar; hydrolysis yield: 95.8percent.EXAMPLE 3B-Recycling of the product derived from basic hydrolysis Following hydrolysis in an alkaline environment as described in example 2B, the organic solution containing the unreacted ketone and the non-hydrolyzed ester is made up to the same quantity of ketone indicated in example 1, and reacted as in example 1. The hydrolysis reaction is carried out by the same operative method given in example 3B and using the same molar ratio of SESAMYL propanoate/NaOH, with no further addition of catalyst. After distillation sesamol is obtained with a hydrolysis yield equal to 94percent. Stage 1: With sodium hydroxide, tetrabutyl-ammonium chloride, water in dichloromethane, Time= 8 - 8.75h, T= 20 25 °C Stage 2: With hydrogenchloride in dichloromethane, water, pH= 8.5 Patent; ENDURA S.P.A.; WO2004/92106; (2004); (A2) English View in Reaxys

O O

Rx-ID: 22848061 View in Reaxys 21/33 Yield

Conditions & References

23 %Chromat.

Comparative Example 2 With hydrogen peroxide in water, Time= 2h, T= 50 °C , Acidic conditions Patent; DAICEL CHEMICAL INDUSTRIES, Ltd.; EP1167365; (2002); (A1) English View in Reaxys

Rx-ID: 22848104 View in Reaxys 22/33 Yield

Conditions & References

79 - 80 %

Example 1-2 With ethanol, sodium hydroxide, Time= 4.5h, T= 82 - 96 °C , Reflux; elimination of ethyl formate Patent; DAICEL CHEMICAL INDUSTRIES, Ltd.; EP1167365; (2002); (A1) English View in Reaxys

O O

Rx-ID: 8645133 View in Reaxys 23/33 Yield

Conditions & References

91 %

With carbon tetrabromide in methanol, Time= 5h, Heating, ether cleavage Yadav; Reddy, B. V. Subba; Chemistry Letters; nb. 5; (2000); p. 566 - 567 View in Reaxys

S O

O O

Rx-ID: 4936120 View in Reaxys 24/33

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Yield

Conditions & References

95 %

With magnesium in methanol, Time= 4h, Ambient temperature Sridhar, Madabhushi; Kumar, B. Ashok; Narender; Tetrahedron Letters; vol. 39; nb. 18; (1998); p. 2847 - 2850 View in Reaxys

88 %

With potassium fluoride on basic alumina, Time= 0.05h, microwave irradiation, Substitution Sabitha, Gowravaram; Abraham, Sunny; Reddy, B. V. Subba; Yadav; Synlett; nb. 11; (1999); p. 1745 - 1746 View in Reaxys

O O

Rx-ID: 5343039 View in Reaxys 25/33 Yield

Conditions & References With hydrogenchloride, Time= 1h, Elimination Watanabe, Makoto; Nishiyama, Masakazu; Koie, Yasuyuki; Tetrahedron Letters; vol. 40; nb. 50; (1999); p. 8837 8840 View in Reaxys

hydrogen sulfide remaining ammonium polysulfide O

Rx-ID: 17371122 View in Reaxys 26/33 Yield

Conditions & References Reaction Steps: 2 1: m-CPBA / CH2Cl2 / 4 h / Heating 2: 10percent aq. KOH / methanol / 2.5 h / Ambient temperature With potassium hydroxide, 3-chloro-benzenecarboperoxoic 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

alkali O

(+-)-2-ethyl-1-vinyloxy-hexane O

Rx-ID: 20379904 View in Reaxys 27/33 Yield

Conditions & References Reaction Steps: 2 1: 30percent aq. H2O2 / 2-NO2C6H4SeSeC6H4NO2-2 / CH2Cl2 / 45 h / Ambient temperature 2: KOH / methanol / 1 h / Ambient temperature With potassium hydroxide, dihydrogen peroxide, O,O'-dinitrodiphenyl diselenide in methanol, dichloromethane Syper, Ludwik; Synthesis; nb. 3; (1989); p. 167 - 172 View in Reaxys

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O O

Rx-ID: 2301641 View in Reaxys 28/33 Yield

Conditions & References Time= 2h, T= 180 °C , variation of time, temperature; sesamol enhances antioxidativ action of γ-tocopherol, Product distribution Fukuda, Yasuko; Nagata, Masayasu; Osawa, Toshihiko; Namiki, Mitsuo; Agricultural and Biological Chemistry; vol. 50; (1986); p. 857 - 862 View in Reaxys O

O O

Rx-ID: 1748629 View in Reaxys 29/33 Yield

Conditions & References

67 %, 8 %

With dihydrogen peroxide, sulfuric acid in methanol, Time= 24h, Ambient temperature Matsumoto, Masakatsu; Kobayashi, Hisako; Hotta, Yasushi; Journal of Organic Chemistry; vol. 49; nb. 24; (1984); p. 4740 - 4741 View in Reaxys O HO

O O

Rx-ID: 1749279 View in Reaxys 30/33 Yield

Conditions & References

8 %, 67 %

O O

Rx-ID: 2562618 View in Reaxys 31/33 Yield

Conditions & References

94 %

With 2-chloro-1,3,2-dithioborolane in dichloromethane, Time= 0.75h, T= -78 °C Williams, D.R.; Sakdarat, Santi; Tetrahedron Letters; vol. 24; nb. 37; (1983); p. 3965 - 3968 View in Reaxys

sesamolin O

Rx-ID: 5428743 View in Reaxys 32/33

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Yield

Conditions & References With mineral acids Adriani; ; vol. 56; p. 187; Chem. Zentralbl.; vol. 100; nb. I; (1929); p. 1012 View in Reaxys Malagnini; Armanni; Chemiker-Zeitung, Chemische Apparatur; vol. 5; (1907); p. 884,133 View in Reaxys Kreis; Chemiker-Zeitung, Chemische Apparatur; vol. 27; (1903); p. 1030; Chemiker-Zeitung, Chemische Apparatur; vol. 28; (1904); p. 957 View in Reaxys With hydrogenchloride Adriani; ; vol. 56; p. 187; Chem. Zentralbl.; vol. 100; nb. I; (1929); p. 1012 View in Reaxys Malagnini; Armanni; Chemiker-Zeitung, Chemische Apparatur; vol. 5; (1907); p. 884,133 View in Reaxys Kreis; Chemiker-Zeitung, Chemische Apparatur; vol. 27; (1903); p. 1030; Chemiker-Zeitung, Chemische Apparatur; vol. 28; (1904); p. 957 View in Reaxys

H 2N

O O

Rx-ID: 628646 View in Reaxys 33/33 Yield

Conditions & References Diazotization Malagnini; Armanni; ; vol. 5; (1907); p. 135 View in Reaxys

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