CN102320926B - Preparation method of 3-butene-1-ol - Google Patents
Preparation method of 3-butene-1-ol Download PDFInfo
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- CN102320926B CN102320926B CN 201110218254 CN201110218254A CN102320926B CN 102320926 B CN102320926 B CN 102320926B CN 201110218254 CN201110218254 CN 201110218254 CN 201110218254 A CN201110218254 A CN 201110218254A CN 102320926 B CN102320926 B CN 102320926B
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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
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, now has been widely used in a plurality of fields such as medicine, food, spices, refining of petroleum.Especially in recent years developed country increases the purposes of 3-butene-1-alcohol and consumption for the synthetic report in fields such as antitumour drug 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 by catalysis under the high temperature of 300-450 degree about 60%, and to the operational requirement height, 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 deficiencies in the prior art, thereby provide a kind of industrialization operation, method that cost of manufacture is low be convenient to for this area.
The present invention is achieved through the following technical solutions for achieving the above object: the preparation method of a kind of 3-butene-1-alcohol, be made up of following step:
1. with 100 liters of tetrahydrofuran (THF)s, zinc powder 100kg and 10% ammonium chloride solution are inserted in the reactor for 500 liters, stir 40 minutes down at 30 ℃, and be standby;
2. get the 143.96kg allyl bromide 98 and be added drop-wise in the step standby reaction solution 1., stirred 40 minutes down at 30-35 ℃ then, standby;
3. get trioxymethylene 30kg, join in the step standby reaction solution 2. for following minute 5 times at 30-35 ℃, each 6kg that adds, 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, reacting liquid temperature is down to 20-25 ℃ at last, standby;
4. with dichloromethane extraction three times of step reaction solution 3., the consumption of methylene dichloride is divided into 300 liters, 200 liters and 150 liters for three times, and the combined dichloromethane layer washs dichloromethane layer twice for 200 liters with saturated nacl aqueous solution then;
5. steaming vibrating dichloromethane and tetrahydrofuran (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 standby reaction soln 1..
Preparation 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, each operation does not all need pyroreaction, the processing safety height, 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 tetrahydrofuran (THF)s, zinc powder 100kg(1538mol) and 10% ammonium chloride solution insert in the reactor for 500 liters, under 30 ℃, stirred 40 minutes with 100-150 rev/min rotating speed, standby;
2. get 143.96kg(1200mol) allyl bromide 98 was added drop-wise in 2 hours in the step standby reaction solution 1., stirred 40 minutes at 30-35 ℃ of following 100-120 rev/min rotating speed then, and is standby;
3. get trioxymethylene 30kg(330mol), join in the step reaction solution 2. for following minute 5 times at 30-35 ℃, each 6kg that adds, 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, reacting liquid temperature is down to 20-25 ℃ at last, standby;
4. with dichloromethane extraction three times of step reaction solution 3., the consumption of methylene dichloride is divided into 300 liters, 200 liters and 150 liters for three times, and the combined dichloromethane layer washs dichloromethane layer twice for 200 liters with saturated nacl aqueous solution then;
5. steaming vibrating dichloromethane and tetrahydrofuran (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), yield is 87.5%.
Two of preferred version is:
1. with 90 liters of tetrahydrofuran (THF)s, zinc powder 94.82kg(1450mol), 15% brometo de amonio solution is inserted in the reactor for 450 liters, and the rotating speed with 100-150 rev/min under 25 ℃ stirred 30 minutes, and is standby;
2. get chlorallylene 91.8kg(1200mol), in 1.5 hours, be added drop-wise in the step standby reaction solution 1., the rotating speed with 100-120 rev/min stirred 30 minutes under 25-30 ℃ then, and is standby;
3. with 35% formalin 85.7kg(1000mol), under 25-30 ℃, be added drop-wise in the step standby reaction solution 2., the dropping time is 5 hours, after dripping, reacted 3 hours down at 25-30 ℃, be warming up to 45 ℃ then, reacted 8 hours, and reacting liquid temperature was down to 20 ℃ at last, standby;
4. with step standby reaction solution ether extraction three times 3., the consumption of ether is divided into 300 liters, 200 liters and 150 liters for three times, and combined ether layer washs ether layer twice for 150 liters with saturated nacl aqueous solution more then;
5. boil off ether and tetrahydrofuran (THF) under the normal pressure, collect 112 ℃ of-114 ℃ of cuts, obtain 3-butene-1-pure 59kg, purity is 98.5%(GC), yield is 80.6%.
Preparation method of the present invention also can prepare 3-butene-1-pure product according to specific embodiments of the present invention according to requirements such as following plurality of raw materials, ratios.
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; Described ammonium chloride can be the aqueous solution of inorganic weak acid ammonium classes such as brometo de amonio, ammonium sulfate, monoammonium sulfate also, and the concentration of aqueous solution of inorganic weak acid ammonium class all can to saturated by 5%; The aqueous solution volume ratio of tetrahydrofuran (THF) and inorganic weak acid 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)
1. the preparation method of 3-butene-1-alcohol is characterized in that: be made up of following step:
1. with 100 liters of tetrahydrofuran (THF)s, zinc powder 100kg and 10% ammonium chloride solution are inserted in the reactor for 500 liters, stir 40 minutes down at 30 ℃, and be standby;
2. get the 143.96kg allyl bromide 98 and be added drop-wise in the step standby reaction solution 1., stirred 40 minutes down at 30-35 ℃ then, standby;
3. get trioxymethylene 30kg, join in the step standby reaction solution 2. for following minute 5 times at 30-35 ℃, each 6kg that adds, 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, reacting liquid temperature is down to 20-25 ℃ at last, standby;
4. with dichloromethane extraction three times of step reaction solution 3., the consumption of methylene dichloride is divided into 300 liters, 200 liters and 150 liters for three times, and the combined dichloromethane layer washs dichloromethane layer twice for 200 liters with saturated nacl aqueous solution then;
5. steaming vibrating dichloromethane and tetrahydrofuran (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 standby reaction soln 1..
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| CN 201110218254 CN102320926B (en) | 2011-08-01 | 2011-08-01 | Preparation method of 3-butene-1-ol |
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| CN 201110218254 CN102320926B (en) | 2011-08-01 | 2011-08-01 | Preparation method of 3-butene-1-ol |
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| CN102320926B true CN102320926B (en) | 2013-08-21 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4288374A (en) * | 1979-09-10 | 1981-09-08 | E. I. Du Pont De Nemours And Company | Synthesis of 3-buten-1-ol, 3,4-dichlorobutan-1-ol and 3-chlorotetrahydrofuran |
| CN101475445A (en) * | 2009-01-15 | 2009-07-08 | 西北师范大学 | Preparation of homoallylic alcohols |
| CN102060659A (en) * | 2010-11-12 | 2011-05-18 | 西北师范大学 | Method for preparing homoallylic alcohol |
-
2011
- 2011-08-01 CN CN 201110218254 patent/CN102320926B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4288374A (en) * | 1979-09-10 | 1981-09-08 | E. I. Du Pont De Nemours And Company | Synthesis of 3-buten-1-ol, 3,4-dichlorobutan-1-ol and 3-chlorotetrahydrofuran |
| CN101475445A (en) * | 2009-01-15 | 2009-07-08 | 西北师范大学 | Preparation of homoallylic alcohols |
| CN102060659A (en) * | 2010-11-12 | 2011-05-18 | 西北师范大学 | Method for preparing homoallylic alcohol |
Non-Patent Citations (6)
| Title |
|---|
| Brindaban C.Ranu etal..Facile and Efficient Synthesis of Homoallylic alcohols using allyl bromide and commercial zinc dust.《Tetrahedron Letters》.1995,第36卷(第27期),第4885-4888页. |
| Cathy Einhorn etal..Selective allylation of carbonyl compounds in aqueous media.《Journal of Organometallic Chemistry》.1987,第322卷第177-183页. |
| Facile and Efficient Synthesis of Homoallylic alcohols using allyl bromide and commercial zinc dust;Brindaban C.Ranu etal.;《Tetrahedron Letters》;19951231;第36卷(第27期);第4885-4888页 * |
| Selective allylation of carbonyl compounds in aqueous media;Cathy Einhorn etal.;《Journal of Organometallic Chemistry》;19871231;第322卷;第177-183页 * |
| 查正根等.水相Barbier-Grignard反应实验设计.《大学化学》.2009,第24卷(第4期),第40-42、55页. |
| 水相Barbier-Grignard反应实验设计;查正根等;《大学化学》;20090831;第24卷(第4期);第40-42、55页 * |
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Address after: Strong Street Jibei Economic Development Zone in Ji'nan City, Shandong province 251400 Applicant after: SHANDONG BOYUAN PHARMACEUTICAL Co.,Ltd. Address before: Strong Street Jibei Economic Development Zone in Ji'nan City, Shandong province 251400 Applicant before: SHANDONG BOYUAN CHEMICAL Co.,Ltd. |
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Address after: 251400 No. 12, Taixing East Street, Jibei Economic Development Zone, Jiyang District, Jinan City, Shandong Province Patentee after: Shandong Baoyuan Pharmaceutical Co.,Ltd. Address before: 251400 Qiangqiang street, Jibei Economic Development Zone, Jinan City, Shandong Province Patentee before: SHANDONG BOYUAN PHARMACEUTICAL Co.,Ltd. |