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Method for synthesizing alcohol by olefin

A technology for synthesizing alcohols and olefins, applied in the chemical industry, can solve the problems of difficult post-treatment process, low yield of synthetic alcohol, high price, etc., and achieves high regioselectivity and stereoselectivity, mild reaction conditions, and high reaction yield. Effect

Inactive Publication Date: 2008-07-30
GUANGZHOU INST OF GEOCHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Among them, the borane reagent can selectively reduce the terminal olefin, and then oxidize it to generate the primary alcohol, but its toxicity is high, and the yield of the synthetic alcohol is very low; It has very high stereoselectivity and regioselectivity to olefins, but it is expensive and has harsh requirements on reaction conditions; the post-treatment process with diisobutyl aluminum hydride reagent is difficult, and large-scale preparation cannot be realized; in addition, with Transition metals are used as catalysts, because they are relatively expensive, which also makes it difficult to synthesize alcohols by hydroboration-oxidation on a large scale
There are also people who have reported the method of using titanium trichloride as a catalyst and using sodium borohydride as a reducing agent to synthesize alcohols from olefins, but because titanium trichloride is unstable, it needs to be stored in an aqueous solution of hydrochloric acid, so titanium trichloride is limited. The application of this kind of olefin synthetic alcohol method is difficult to popularize and apply on a large scale

Method used

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  • Method for synthesizing alcohol by olefin

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Experimental program
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Effect test

Embodiment 1

[0026] In a 500ml three-necked flask with electric stirring, add 2.84g (50mmol) potassium borohydride, 0.264g (1mmol) 18-crown-6, and 150ml tetrahydrofuran under stirring, cool to 5°C, and slowly add 10ml tetrahydrofuran Dissolved 0.113ml (1mmol) TiCl 1 , and then heated up to 30° C., and reacted for 0.5 hour to obtain a titanium composite. Then 7.76ml (50mmol) of 1,7-octadiene was added to the above reaction system, and the reaction was continued for 4 hours to obtain an organoboron compound. Then the above reaction system was cooled to 5°C, 60ml of 6mol / L sodium methoxide and 120ml of hydrogen peroxide (30% mass, concentration about 8.8mol / L) were added, then the temperature was raised to 65°C, reacted for 0.5 hours, and then extracted 3 times with diethyl ether, 50ml each time, concentrated to obtain the crude product, the molar ratio of 7-octen-1-ol in the crude product: 7-octen-2-ol was detected by GC under the conditions of initial temperature 80°C and heating rate 10°C...

Embodiment 2

[0028] In a 500ml three-necked flask with electric stirring, add 2.84g (50mmol) of potassium borohydride, 0.792g (3mmol) of 18-crown-6 under stirring, add 150ml of tetrahydrofuran, cool to 5°C, slowly add 10ml of 0.339(3mmol)TiCl dissolved in tetrahydrofuran 1 , heated to 20°C, reacted for 0.5 hours to obtain a titanium complex, then added 5.3ml (50mmol) 1,4-pentadiene to the reaction solution, and continued to react for 3 hours to obtain an organoboron compound; then cool the above system to 5°C, add 120ml of 3mol / L sodium hydroxide and 120ml of hydrogen peroxide (30% mass, concentration about 8.8mol / L, heat up to 65°C, react for 0.5 hours, extract with ether 3 times, 50ml each time, concentrate, and distill under reduced pressure 3.58 g of 3-penten-1-ol, a fraction at 134-136°C, was collected, with a yield of 73.0%.

Embodiment 3

[0030] In a 500ml three-necked flask with electric stirring, add 3.12g (55mmol) of potassium borohydride, 0.264g (1mmol) of 18-crown-6, and 150ml of tetrahydrofuran under stirring, cool to 5°C, and slowly add 10ml of 0.113ml (1mmol) TiCl dissolved in tetrahydrofuran 1 , heated to 35°C, reacted for 0.5 hours to obtain a titanium complex, then added 7.85ml (50mmol) 1-octene to the reaction solution, and continued the reaction for 3 hours to obtain an organoboron compound; then cooled the above system to 5°C , add 60ml of 6mol / L sodium methoxide and 120ml of hydrogen peroxide (30% mass, concentration about 8.8mol / L), heat up to 65°C, react for 0.5 hours, extract with ether 3 times, 50ml each time, concentrate and collect under reduced pressure to obtain 52~ 54°C / 6mm-Hg fraction 1-octanol 6.28g, 2-octanol was not detected by GC, yield 93%.

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Abstract

This invention discloses alkene synthesizing alcohol method, it includes following procedures under function of phase-transfer catalyst 18-crown ether-6, titanium tetrachloride and borohydride react and generate titanium compound in solution. Then the titanium is used as catalyst, alkene and borohydride react with each other to generate organic boron compounds. The organic boron compounds are oxidized by alkaline liquor and oxydol, and then corresponding alcohol is got after extraction, concentration and decompressing distillation. This invention has higher regioselectivity and stereoselectivity, the main product alcohol is agree with inverse markovnikovs rule. Material price used is low, reaction condition is wild, reaction yield is high, and it can be large scale applied in industrial generation.

Description

technical field [0001] The invention relates to the field of chemical industry, in particular to a method for synthesizing alcohol from olefins. Background technique [0002] Unsaturated olefin synthesis alcohol usually adopts methods such as hydroboration-oxidation, such as borane-hydrogen peroxide (B_H,-H 2 o 2 ), 9-borabicyclo[3.3.1]nonane-hydrogen peroxide (9-BBN-H 2 o 2 ), diisobutylaluminum hydride-oxygen (DIBAH-O 2 ), and reagents such as lithium aluminum hydride and sodium borohydride under the catalysis of transition metals such as titanium. Among them, the borane reagent can selectively reduce the terminal olefin, and then oxidize it to generate the primary alcohol, but its toxicity is high, and the yield of the synthetic alcohol is very low; It has very high stereoselectivity and regioselectivity to olefins, but it is expensive and has harsh requirements on reaction conditions; the post-treatment process with diisobutyl aluminum hydride reagent is difficult, ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C29/04
Inventor 哈成勇王广军高红云沈敏敏
Owner GUANGZHOU INST OF GEOCHEMISTRY - CHINESE ACAD OF SCI