CN102320926A

CN102320926A - Preparation method of 3-butene-1-ol

Info

Publication number: CN102320926A
Application number: CN201110218254A
Authority: CN
Inventors: 朱义胜; 尚林峰; 梁辉
Original assignee: Shandong Boyuan Chemical Co Ltd
Current assignee: Shandong Baoyuan Pharmaceutical Co ltd
Priority date: 2011-08-01
Filing date: 2011-08-01
Publication date: 2012-01-18
Anticipated expiration: 2031-08-01
Also published as: CN102320926B

Abstract

The invention discloses a preparation method of 3-butene-1-ol. The preparation method comprises the following steps of: (1) stirring tetrahydrofuran, zinc powder and a 10% ammonium chloride solution in a reaction kettle for later use; (2) dropwise adding allyl bromide to the reaction liquid obtained in the step (1), and stirring for later use; (3) adding trioxymethylene to the reaction liquid obtained in the step (2) by five times, stirring for 10-12 hours, and finally cooling the reaction liquid to 20-25 DEG C for later use; (4) extracting the reaction liquid obtained in the step (3) three times with dichloromethane, then combining the dichloromethane layer, and washing the dichloromethane layer twice with 200 L of saturated sodium chloride solution; and (5) distilling under normal pressure to remove dichloromethane and tetrahydrofuran, and collecting the fraction at 112-114 DEG C to obtain 61 kg of 3-butene-1-ol. By the preparation method disclosed by the invention, the defects in the prior art are solved, thus a method which is convenient for industrial operation and has low manufacture cost is provided for the field.

Description

The preparation method of a kind of 3-butene-1-alcohol

Technical field

The present invention relates to the preparation method of a kind of 3-butene-1-alcohol.

Background technology

Because 3-butene-1-alcohol is to have the alkene of two keys and hydroxyl and the compound of alcohol, character is very active, has been widely used in a plurality of fields such as medicine, food, spices, refining of petroleum at present.Especially in recent years developed country is used for the synthetic report in field such as antitumour drug, and the purposes of 3-butene-1-alcohol and consumption are increased gradually, and in order to reduce user's cost, more research is all done by many countries in the preparation method, to adapt to the demand of this country.All there is some deficiency in the preparation method of the discloseder 3-butene-1-alcohol of country such as the U.S., China at present: the more difficult realization of industrialization of US4288374 disclosed method; Us pat.APPL, Pub1, disclosed method among the 20040171892.02.sep2004, its expensive raw material price; Green Chemistry.4 (4), 317-318; Use a large amount of potassiumiodides in 2002 disclosed methods, manufacturing cost is high, and productive rate is lower; CN10759529 disclosed method, productive rate and need be produced through catalysis under the high temperature of 300-450 degree about 60%, and high to operational requirement, production cost of products is high relatively.

Summary of the invention

The purpose of this invention is to provide the preparation method of a kind of 3-butene-1-alcohol, make it can solve the deficiency of prior art, thereby a kind of industriallization operation, method that cost of manufacture is low be convenient to is provided for this area.

The present invention realizes through following technical scheme for realizing above-mentioned purpose: the preparation method of a kind of 3-butene-1-alcohol, be made up of following step:

1. with 100 liters of THFs, zinc powder 100kg and 10% ammonium chloride solution are inserted in the reaction kettle for 500 liters, stir 40 minutes down at 30 ℃, and be subsequent use;

2. get the 143.96kg allyl bromide 98 and be added drop-wise in the step subsequent use reaction solution 1., stirred 40 minutes down at 30-35 ℃ then, subsequent use;

3. get trioxymethylene 30kg; Join in the step subsequent use reaction solution 2. for following minute 5 times at 30-35 ℃, add 6kg at every turn, the timed interval of per twice adding is 10 minutes; Stirring reaction is 2.5 hours then; Stirred 10-12 hour after being warming up to 50 ℃ again, at last reacting liquid temperature is reduced to 20-25 ℃, subsequent use;

4. with step reaction solution 3. with dichloromethane extraction three times, the consumption of methylene dichloride is divided into 300 liters, 200 liters and 150 liters for three times, combined dichloromethane layer then is with twice of 200 liters of washings of saturated nacl aqueous solution dichloromethane layer;

5. steaming vibrating dichloromethane and THF under the normal pressure are collected 112 ℃ of-114 ℃ of cuts and are obtained 3-butene-1-pure 61kg.

The mixing speed of step described in 1. is 100-150 rev/min.The allyl bromide 98 of step described in 2. joined in 2 hours in the step subsequent use reaction soln 1..

Preparing method of the present invention is different fully with the preparation method of existing various 3-butene-1s-alcohol.The production unit that the inventive method adopts is conventional normal pressure equipment; Facility investment is few, and each operation does not all need pyroreaction, and processing safety is high; Quality product is easy to control; Manufacturing cost is than the low 40-60% of existing method, is higher than 98.5% with the product purity of method manufacturing of the present invention, and productive rate is greater than 80%.

Embodiment

One of preferred version of preparation method of the present invention is:

1. with 100 liters of THFs, zinc powder 100kg (1538mol) and 10% ammonium chloride solution are inserted in the reaction kettle for 500 liters, and the rotating speed with 100-150 rev/min under 30 ℃ stirred 40 minutes, and is subsequent use;

2. get 143.96kg (1200mol) allyl bromide 98 and in 2 hours, be added drop-wise in the step subsequent use reaction solution 1., stirred 40 minutes at 30-35 ℃ of following 100-120 rev/min rotating speed then, subsequent use;

3. get trioxymethylene 30kg (330mol); Join in the step reaction solution 2. for following minute 5 times at 30-35 ℃, add 6kg at every turn, the timed interval of per twice adding is 10 minutes; Stirring reaction is 2.5 hours then; Stirred 10-12 hour after being warming up to 50 ℃ again, at last reacting liquid temperature is reduced to 20-25 ℃, subsequent use;

5. steaming vibrating dichloromethane and THF under the normal pressure are collected 112 ℃ of-114 ℃ of cuts and are obtained 3-butene-1-pure 61kg, and purity is 98.6% (GC), and yield is 87.5%.

Two of preferred version is:

1. with 90 liters of THFs, zinc powder 94.82kg (1450mol), 15% brometo de amonio solution is inserted in the reaction kettle for 450 liters, and the rotating speed with 100-150 rev/min under 25 ℃ stirred 30 minutes, and is subsequent use;

2. get chlorallylene 91.8kg (1200mol), in 1.5 hours, be added drop-wise in the step subsequent use reaction solution 1., the rotating speed with 100-120 rev/min stirred 30 minutes under 25-30 ℃ then, and is subsequent use;

3. with 35% formalin 85.7kg (1000mol), under 25-30 ℃, be added drop-wise in the step subsequent use reaction solution 2., the dropping time is 5 hours; After dripping, reacted 3 hours down, be warming up to 45 ℃ then at 25-30 ℃; Reacted 8 hours, and at last reacting liquid temperature was reduced to 20 ℃, subsequent use;

4. with step subsequent use reaction solution 3. with ether extraction three times, the consumption of ether is divided into 300 liters, 200 liters and 150 liters for three times, combined ether layer then is again with twice of 150 liters of washings of saturated nacl aqueous solution ether layer;

5. normal pressure boils off ether and THF down, collects 112 ℃ of-114 ℃ of cuts, obtains 3-butene-1-pure 59kg, and purity is 98.5% (GC), and yield is 80.6%.

Preparing method of the present invention also can be according to requirements such as following plurality of raw materials, ratios, and specific embodiments prepares 3-butene-1-pure product according to the present invention.

Trioxymethylene described in the preparation method of the present invention can substitute with Paraformaldehyde 96 or formaldehyde; Described allyl bromide 98 can use chlorallylene, allyl iodide to substitute.Aldehyde among the preparation method of the present invention and the preferred 1:1.2-1.5 of the mol ratio of allyl halide; Said ammonium chloride can be the aqueous solution of inorganic weak acid property ammonium classes such as brometo de amonio, ammonium sulfate, monoammonium sulfate also, and the concentration of aqueous solution of inorganic weak acid property ammonium class all can to saturated by 5%; The aqueous solution volume ratio of THF and inorganic weak acid property ammonium class is preferably 1:5, can certainly select 1:1-4,1:6-10 or 1:11-20; The zinc powder of selecting for use is generally the 100-200 order, the preferred 1:1.2-1.5 of the mol ratio of zinc powder and allyl halide.

Claims

1. the preparation method of 3-butene-1-alcohol is characterized in that: be made up of following step:

2. the preparation method of a kind of 3-butene-1 according to claim 1-alcohol is characterized in that: the mixing speed of step described in 1. is 100-150 rev/min.

3. the preparation method of a kind of 3-butene-1 according to claim 1-alcohol is characterized in that: the allyl bromide 98 of step described in 2. joined in 2 hours in the step subsequent use reaction soln 1..