Synthetic method of 1,2-o-diol compounds

A synthesis method and technology of vicinal diols, which are applied in the preparation of organic compounds, chemical instruments and methods, preparation of hydroxyl compounds, etc., can solve the problems of unfriendly environment, high price, low conversion rate, etc., and achieve environmental friendliness and convenient operation , the effect of mild system

Active Publication Date: 2021-11-23
HUAIHUA UNIV
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Problems solved by technology

Osmium tetroxide is expensive and highly toxic, not suitable for large-scale industrial production
The patent application publication number CN 101597211A discloses a synthesis method of 1,2-o-diol compounds. Although it avoids the use of osmium tetroxide as a catalyst, it uses a palladium compound as a catalyst, but the palladium catalyst is also a A heavy metal, expensive and unfriendly to the environment
In addition, solid-supported heteropolyacids are also used as catalysts, but they are heterogeneous reactions with defects such as low conversion rates and low product yields.

Method used

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preparation example Construction

[0015] Synthetic method of the present invention, comprises the following steps:

[0016] (1) Using terminal olefin as raw material, potassium persulfate compound salt as oxidant, inorganic salt as catalyst, water and ketone organic solvent mixed as reaction solvent, react at 30-100°C;

[0017] (2) After the reaction, add an inorganic base at 0-40°C to make the pH of the reaction system 10-14;

[0018] (3) Continue the reaction at 30-100°C. After the reaction, separate and purify to obtain 1,2-o-diol compounds.

[0019] In some embodiments, in step (1), the molar ratio of the raw material, the oxidant and the catalyst is 1: (1-5): (0.5-10); preferably, the molar ratio of the raw material, the oxidant and the catalyst is 1 :(1-3):(0.5-2).

[0020] In some embodiments, in step (1), the mass ratio of the reaction solvent to the olefin is 5-20:1.

[0021] In some embodiments, in step (1), the mass ratio of the water to the ketone organic solvent is (1-6):(1-2); the ketone organ...

Embodiment 1

[0029] In a 100L reactor, add 34kg of water, 16kg of acetone, 35kg of potassium persulfate compound salt (oxone, 0.0569Kmol), 3.4kg of sodium chloride (0.058Kmol) and 5kg of 1-hexene (0.059Kmol), and heat to 50 ℃, stirring and reacting for 18 hours, after the reaction was completed, lower the temperature to 25 ℃, add 20% sodium hydroxide aqueous solution to adjust the pH value to 12, heat to 50 ℃, and stir and react for 3 hours. After the reaction, cool down to room temperature, keep strong alkalinity, extract with dichloromethane to remove impurities, then adjust the pH value to 2 with 6mol / L hydrochloric acid, extract the product with ethyl acetate, and evaporate the solvent to obtain 1,2-hexanediol 6.24kg, 89% yield. MS(m / z): 117[M-H] _ ; 1 HNMR (400MHz, CDCl3): δ = 3.68 (brm, 2H), 3.44 (brt, J = 10.3Hz, 1H), 2.67 (s, 2H), 1.43-1.33 (br m, 6H), 0.91ppm (m, 3H); 13 C NMR (100MHz, CDCl 3 )δ14.1, 22.4, 27.9, 33.0, 66.2, 72.1.

Embodiment 2

[0031] In a 100L reactor, add water 50kg, 10kg acetone, 44kg potassium persulfate compound salt (oxone, 0.071Kmol), potassium chloride 6.3kg (0.11Kmol) and 1-butene 4kg (56.11, 0.071Kmol), heat to 30°C, stirred and reacted for 12 hours, after the reaction was completed, cooled to 25°C, added 20% potassium hydroxide aqueous solution to adjust the pH value to 12, heated to 40°C, stirred and reacted for 4 hours. After the reaction, cool down to room temperature, keep strong alkalinity, extract with dichloromethane to remove impurities, then adjust the pH value to 2 with 6mol / L hydrochloric acid, extract the product with ethyl acetate, and evaporate the solvent to obtain 1,2-butanediol 5.65kg, 88% yield. MS (m / z): 89 [M-H] _ ; 1 HNMR (400MHz, CDCl3): δ = 3.66 (brm, 2H), 3.45 (brt, J = 10.3Hz, 1H), 2.68 (s, 2H), 0.93ppm (m, 3H); 13 C NMR (100MHz, CDCl 3 ) δ10.1, 25.3, 66.3, 77.2.

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Abstract

The invention relates to a method for synthesizing 1,2-o-diol compounds. The synthesis method comprises the following steps: (1) using a terminal olefin as a raw material, potassium hydrogen persulfate compound salt as an oxidizing agent, an inorganic salt as a catalyst, mixing water and a ketone organic solvent as a reaction solvent, and reacting at 30-100° C.; (2) After the reaction, add an inorganic base at 0-40°C to make the pH of the reaction system 10-14; (3) continue the reaction at 30-100°C, after the reaction, separate and purify to obtain 1,2-o-diol class of compounds. The synthesis method has mild reaction system, cheap and easy-to-obtain raw materials, environment-friendly oxidant, good reaction selectivity and high conversion rate.

Description

technical field [0001] The invention relates to the field of organic chemical synthesis, in particular to a method for synthesizing 1,2-o-diol compounds. Background technique [0002] 1,2-O-diol compounds are important industrial raw materials, widely used in medicine, pesticides, cosmetics, spices, surfactants and other fields. In addition, 1,2-o-diols are important components of natural products and pharmacologically active molecules, and are also important intermediates in organic synthesis. [0003] Olefins are used as raw materials to prepare 1,2-o-diols, generally through two steps, first oxidizing olefins into epoxy compounds, and then further hydrolyzing them into diols under strong acid or alkali conditions. The traditional dihydroxylation of olefins is mainly realized by using osmium tetroxide as a catalyst (Branco, L.C.; Ferreira, F.C.; Santos, J.L.; Crespo, J.G.; Afonsoa, C.A.M., Sharpless Asymmetric Dihydroxylation of Olefins in Water-Surfactant Media with Recy...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C29/10C07C31/20
CPCC07C29/106C07C31/20C07C31/207C07C31/205
Inventor 向德轩杨建荣陈迪钊胡扬剑欧阳跃军李元祥汤艳林红卫宴小红刘莎莎肖柳
Owner HUAIHUA UNIV
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