CN101633622A - Method for preparing choline chloride - Google Patents
Method for preparing choline chloride Download PDFInfo
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- CN101633622A CN101633622A CN 200910304783 CN200910304783A CN101633622A CN 101633622 A CN101633622 A CN 101633622A CN 200910304783 CN200910304783 CN 200910304783 CN 200910304783 A CN200910304783 A CN 200910304783A CN 101633622 A CN101633622 A CN 101633622A
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- Prior art keywords
- choline chloride
- chloride
- mixture
- preparing
- methane sulfonate
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- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 title claims abstract description 66
- 235000019743 Choline chloride Nutrition 0.000 title claims abstract description 66
- 229960003178 choline chloride Drugs 0.000 title claims abstract description 66
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000005703 Trimethylamine hydrochloride Substances 0.000 claims abstract description 35
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010521 absorption reaction Methods 0.000 claims abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- 238000003756 stirring Methods 0.000 claims description 35
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 239000005457 ice water Substances 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 12
- 239000003463 adsorbent Substances 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000011720 vitamin B Substances 0.000 abstract description 4
- 235000019156 vitamin B Nutrition 0.000 abstract description 4
- 231100000086 high toxicity Toxicity 0.000 abstract description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 2
- 229930003270 Vitamin B Natural products 0.000 abstract 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 abstract 1
- 230000002860 competitive effect Effects 0.000 abstract 1
- 239000012043 crude product Substances 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 238000003760 magnetic stirring Methods 0.000 description 17
- 238000010992 reflux Methods 0.000 description 17
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 244000144977 poultry Species 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- GGRLKHMFMUXIOG-UHFFFAOYSA-M 2-acetyloxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC(=O)OCC[N+](C)(C)C GGRLKHMFMUXIOG-UHFFFAOYSA-M 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of a vitamin B, in particular to a method for preparing choline chloride, which mainly solves the problem that epoxy ethane which is taken as a raw material in the prior art is a gas under normal temperature, has the shortages of high toxicity, inflammability and explosivity, needs special conditions when being transported, stored and used and is easy to have potential safety hazards and also solves the technical problems of higher market price and preparation cost and the like of chlorohydrin which is taken as the raw material. The preparation method comprises the following steps: using 1, 2-ethanediol as the raw material; firstly, reacting the 1, 2-ethanediol with methylsulfonyl chloride in esterification reaction; and finally reacting the 1, 2-ethanediol with trimethylamine hydrochloride to generate a crude product which is separated through resin absorption so as to obtain competitive products.
Description
Technical field
The present invention relates to a kind of preparation method of vitamins B, especially relate to a kind of method for preparing choline chloride 60.
Background technology
In the development of modern animal husbandry, for herding and the poultry raised can be in the growth of growing period health, and after butchering, maturation has a better quality, in feeding process except the staple food of necessity, also to add some functional auxiliary materials, additive just, these additives can effectively improve the quality of the meat of being cultured.
In these additives, vitamins B is a wherein very important big class, and a kind of as vitamins B of choline chloride 60, very big usage quantity is also arranged on market, choline chloride 60 is the integral part of vagusstoff in the biological tissue, Yelkin TTS and lipid sphyngomyelin, can save amino acid, be the required important substance of livestock and poultry fish, can regulate the metabolism and the conversion of fat in animal body, can prevent in the liver precipitation and tissue degeneratiaon thereof donor as a kind of methyl, promote amino acid whose formation again, improve amino acid whose utilization ratio.
At present, the main preparation methods of choline chloride 60 has two kinds, and a kind of oxyethane and Trimethylamine 99 prepared in reaction of being to use forms, and another kind of method is to form with Trimethylamine 99 and chloroethanol prepared in reaction.Chinese patent discloses a kind of manufacture method (publication number: CN 107823IA) of choline chloride 60, its by hydrochloric acid and Trimethylamine 99 with 1: the proportioning of (1～1.01) (mole), under 30～40 ℃ temperature, be carried out to reactant salt, generate trimethylamine hydrochloride, and then with the proportioning of oxyethane with 1: 1.05 (mole), under 30～70 ℃ temperature, carry out addition reaction, make choline chloride 60, used oxyethane is for containing the aqueous solution of 8 (weight) % right and left rings ethyl oxide and 0.3～4.5 (weight) % ethylene glycol, this aqueous solution of ethylene oxide is before advancing people's reactive system, utilize the boiling-point difference of oxyethane and ethylene glycol, in advance evaporation separate remove ethylene glycol after, enter reactor with form with the oxyethane steam of water vapor; When hydrochloric acid and Trimethylamine 99 were carried out to reactant salt, pH value was controlled at 4.5～6.5, and trimethylamine hydrochloride is when carrying out addition reaction with the oxyethane steam of water vapor, and temperature of reaction is 60～70 ℃.But in this preparation method, because oxyethane is gas at normal temperatures, and has the shortcoming of high toxicity and inflammableness explosion hazard, transportation, storage and use also need special condition, have potential safety hazard easily.If adopt Trimethylamine 99 and chloroethanol prepared in reaction, though this method processing safety is better, the chloroethanol market value is higher, makes that this method cost is higher.
Summary of the invention
The technical issues that need to address of the present invention provide a kind of method for preparing choline chloride 60, it mainly is that the solution existing in prior technology is raw material with oxyethane, oxyethane is gas at normal temperatures, and shortcoming with high toxicity and inflammableness explosion hazard, transportation, storage and use also need special condition, have the problem of potential safety hazard easily; It is raw material that the present invention has also solved with the chloroethanol, and the chloroethanol market value is higher, the technical problem that preparation cost is more high.
Above-mentioned technical problem of the present invention is mainly solved by following technical proposals:
A kind of method for preparing choline chloride 60 of the present invention is characterized in that:
A. in reactor, add 1, toluene, sodium bicarbonate or saleratus and fully react, after the stirring mixture placed on the ice-water bath and lower the temperature;
B. in mixture, drip methylsulfonyl chloride, thereby fully react with mixture, dropwising the back fully stirs, until there not being bubble to produce, remove by filter insolubles, normal pressure steams and desolventizes toluene, resistates is carried out underpressure distillation collect 134～138 ℃/4mmHg cut, obtains the beta-hydroxy ethyl methane sulfonate;
Normal pressure steams to remove and refers to just can directly connect air under a normal atmospheric situation.Underpressure distillation refers to that at distillation pressure be 4mmHg.
C. add the beta-hydroxy ethyl methane sulfonate in reactor, the aqueous solution and the beta-hydroxy ethyl methane sulfonate that drip trimethylamine hydrochloride in reactor fully react, and dropwise the back and fully stir, and obtain the mixing solutions of product choline chloride 60 and methylsulfonic acid;
D. mixing solutions is removed methylsulfonic acid through the ionic absorption with macroporous adsorbent resin, obtain the aqueous solution of choline chloride 60, obtain product choline chloride 60 elaboration after the evaporating water.
The ionic macroporous adsorbent resin is a general designation, and the present invention mainly uses the anionite-exchange resin of alkalescence, for example: D201 macroporous strong basic styrene series anionite-exchange resin, 7170 strong-basicity styrene series anion exchange resins or the like.
Reaction equation of the present invention is:
Reactor is the three-necked bottle that reflux condensing tube, thermometer and magnetic stirring apparatus are housed, of the present invention respectively go on foot raw material be commercially available, wide material sources, in liberal supply, and low price, can effectively control production cost.Reaction conditions of the present invention gentleness and technology relatively is simple, and each step reaction is conventional operation, avoids using oxyethane, makes the security and the environmental protection aspect that produce obtain effective assurance.Ice-water bath forms mixture of ice and water for add ice cube in water, and by continuous interpolation ice cube, keeping in the ice-water bath is the mixture of ice and water all the time, and temperature is generally 0 ℃.
Drip not free restriction, generally control dropping process mixture temperature and be no more than 50 ℃ and get final product.
As preferably, the mass ratio of 1 and toluene is 1: 2～10 among the described step a, and the mass ratio of 1 and sodium bicarbonate or saleratus is 1: 1.35～1.63 or 1: 1.61～1.94.
As preferably, when described step b dripped methylsulfonyl chloride, the 1 in the mixture and the mass ratio of methylsulfonyl chloride were 1: 1.84～2.04.
As preferably, the mass ratio of beta-hydroxy ethyl methane sulfonate and trimethylamine hydrochloride, water is 1: 0.68～0.76: 2～3 among the described step c.
As preferably, the temperature of described mixture after cooling on the ice-water bath is 0～10 ℃.
As preferably, described when in mixture, dripping methylsulfonyl chloride, keep temperature of reaction at 0～10 ℃.
As preferably, described in mixture, the dropping after methylsulfonyl chloride finishes, the time of stirring is 3～4 hours.
As preferably, described is to finish under agitation condition when dripping trimethylamine hydrochloride, can make that reaction is more complete.
As preferably, after finishing, stirred 0.5～1.5 hour described dropping trimethylamine hydrochloride, and the temperature during stirring is 20～30 ℃.
Therefore, the present invention has the domestic various raw materials that obtain easily of employing, each goes on foot the reaction conditions gentleness, technology is simple, each step reaction is routine operation, the security of producing is guaranteed, and effectively avoided adopting expensive raw material, reduced the cost of product, making it large-scale application becomes and may wait characteristics.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1: a kind of method for preparing choline chloride 60 of this example the steps include:
A. add 1mol 1 62g in the 1000ml three-necked bottle of reflux condensing tube, thermometer and magnetic stirring apparatus is housed, toluene 300g and 1mol sodium bicarbonate 84g place on the ice-water bath under stirring, and reaction mixture is cooled to below 10 ℃;
B. in mixture, drip about 1mol methylsulfonyl chloride 115g, the dropping process keeps temperature of reaction to be no more than 10 ℃, dropwising the back continues to stir 4 hours, until there not being bubble to produce, remove by filter insolubles, normal pressure steams and desolventizes toluene, resistates carries out underpressure distillation and collects 134-138 ℃/4mmHg cut, promptly? does the hydroxyl ethyl methane sulfonate obtain 93.7g's? the hydroxyl ethyl methane sulfonate, yield 66.9%;
C. reflux condensing tube is being housed, in the 500ml three-necked bottle of thermometer and magnetic stirring apparatus, the beta-hydroxy ethyl methane sulfonate 140g that adds 1mol, under agitation condition, drip the trimethylamine hydrochloride aqueous solution, the trimethylamine hydrochloride aqueous solution is made into by 95.5g trimethylamine hydrochloride and 280g water, dropwised the back stirring at room 1 hour, obtain the mixing solutions of product choline chloride 60 and methylsulfonic acid, then mixing solutions is removed methylsulfonic acid through the ionic absorption with macroporous adsorbent resin, obtain the aqueous solution of choline chloride 60, obtain the about 128.6g of product choline chloride 60 elaboration after the evaporating water, yield 92.2%.
The fusing point of the choline chloride 60 elaboration that obtains is 302～305 ℃ (decomposition), and 1H-NMR (CDCl3): δ 3.29 (9H, s), 3.41-3.50 (2H, t), 3.95-4.01 (2H, t) .MS (EI), m/z 141 (M+H).
Embodiment 2: a kind of method for preparing choline chloride 60 of this example the steps include:
A. add 1mol 1 62g in the 1000ml three-necked bottle of reflux condensing tube, thermometer and magnetic stirring apparatus is housed, toluene 400g and 1.2mol sodium bicarbonate 100.5g place on the ice-water bath under stirring, and reaction mixture is cooled to below 10 ℃;
B. in mixture, drip about 1.05mol methylsulfonyl chloride 120g, the dropping process keeps temperature of reaction to be no more than 10 ℃, dropwising the back continues to stir 4 hours, until there not being bubble to produce, remove by filter insolubles, normal pressure steams and desolventizes toluene, resistates carries out underpressure distillation and collects 134-138 ℃/4mmHg cut, promptly? does the hydroxyl ethyl methane sulfonate obtain 98.5g's? the hydroxyl ethyl methane sulfonate, yield 70.4%;
C. reflux condensing tube is being housed, in the 500ml three-necked bottle of thermometer and magnetic stirring apparatus, the beta-hydroxy ethyl methane sulfonate 140g that adds 1mol, under agitation condition, drip the trimethylamine hydrochloride aqueous solution, the trimethylamine hydrochloride aqueous solution is made into by 95.5g trimethylamine hydrochloride and 280g water, dropwised the back stirring at room 1 hour, obtain the mixing solutions of product choline chloride 60 and methylsulfonic acid, then mixing solutions is removed methylsulfonic acid through the ionic absorption with macroporous adsorbent resin, obtain the aqueous solution of choline chloride 60, obtain the about 128.6g of product choline chloride 60 elaboration after the evaporating water, yield 92.2%.
The fusing point of the choline chloride 60 elaboration that obtains is 302～305 ℃ (decomposition), and 1H-NMR (CDCl3): δ 3.29 (9H, s), 3.41-3.50 (2H, t), 3.95-4.01 (2H, t) .MS (EI), m/z 141 (M+H).
Embodiment 3: a kind of method for preparing choline chloride 60 of this example the steps include:
A. add 1mol 1 62g in the 1000ml three-necked bottle of reflux condensing tube, thermometer and magnetic stirring apparatus is housed, toluene 130g and 1mol saleratus 100g place on the ice-water bath under stirring, and reaction mixture is cooled to below 10 ℃;
B. in mixture, drip about 1.05mol methylsulfonyl chloride 120g, the dropping process keeps temperature of reaction to be no more than 10 ℃, dropwising the back continues to stir 4 hours, until there not being bubble to produce, remove by filter insolubles, normal pressure steams and desolventizes toluene, resistates carries out underpressure distillation and collects 134-138 ℃/4mmHg cut, promptly? does the hydroxyl ethyl methane sulfonate obtain 94.3g's? the hydroxyl ethyl methane sulfonate, yield 67.4%;
C. reflux condensing tube is being housed, in the 500ml three-necked bottle of thermometer and magnetic stirring apparatus, the beta-hydroxy ethyl methane sulfonate 140g that adds 1mol, under agitation condition, drip the trimethylamine hydrochloride aqueous solution, the trimethylamine hydrochloride aqueous solution is made into by 95.5g trimethylamine hydrochloride and 280g water, dropwised the back stirring at room 1 hour, obtain the mixing solutions of product choline chloride 60 and methylsulfonic acid, then mixing solutions is removed methylsulfonic acid through the ionic absorption with macroporous adsorbent resin, obtain the aqueous solution of choline chloride 60, obtain the about 128.6g of product choline chloride 60 elaboration after the evaporating water, yield 92.2%.
The fusing point of the choline chloride 60 elaboration that obtains is 302～305 ℃ (decomposition), and 1H-NMR (CDCl3): δ 3.29 (9H, s), 3.41-3.50 (2H, t), 3.95-4.01 (2H, t) .MS (EI), m/z 141 (M+H).
Embodiment 4: a kind of method for preparing choline chloride 60 of this example the steps include:
A. add 1mol 1 62g in the 1000ml three-necked bottle of reflux condensing tube, thermometer and magnetic stirring apparatus is housed, toluene 500g and 1.2mol saleratus 120g place on the ice-water bath under stirring, and reaction mixture is cooled to below 10 ℃;
B. in mixture, drip about 1.05mol methylsulfonyl chloride 120g, the dropping process keeps temperature of reaction to be no more than 10 ℃, dropwising the back continues to stir 4 hours, until there not being bubble to produce, remove by filter insolubles, normal pressure steams and desolventizes toluene, resistates carries out underpressure distillation and collects 134-138 ℃/4mmHg cut, promptly? does the hydroxyl ethyl methane sulfonate obtain 97.8g's? the hydroxyl ethyl methane sulfonate, yield 69.9%;
C. reflux condensing tube is being housed, in the 500ml three-necked bottle of thermometer and magnetic stirring apparatus, the beta-hydroxy ethyl methane sulfonate 140g that adds 1mol, under agitation condition, drip the trimethylamine hydrochloride aqueous solution, the trimethylamine hydrochloride aqueous solution is made into by 95.5g trimethylamine hydrochloride and 280g water, dropwised the back stirring at room 1 hour, obtain the mixing solutions of product choline chloride 60 and methylsulfonic acid, then mixing solutions is removed methylsulfonic acid through the ionic absorption with macroporous adsorbent resin, obtain the aqueous solution of choline chloride 60, obtain the about 128.6g of product choline chloride 60 elaboration after the evaporating water, yield 92.2%.
The fusing point of the choline chloride 60 elaboration that obtains is 302～305 ℃ (decomposition), and 1H-NMR (CDCl3): δ 3.29 (9H, s), 3.41-3.50 (2H, t), 3.95-4.01 (2H, t) .MS (EI), m/z 141 (M+H).
Embodiment 5: a kind of method for preparing choline chloride 60 of this example the steps include:
A. add 1mol 1 62g in the 1000ml three-necked bottle of reflux condensing tube, thermometer and magnetic stirring apparatus is housed, toluene 620g and 1.1mol saleratus 110g place on the ice-water bath under stirring, and reaction mixture is cooled to below 10 ℃;
B. in mixture, drip about 1.05mol methylsulfonyl chloride 120g, the dropping process keeps temperature of reaction to be no more than 10 ℃, dropwising the back continues to stir 4 hours, until there not being bubble to produce, remove by filter insolubles, normal pressure steams and desolventizes toluene, resistates carries out underpressure distillation and collects 134-138 ℃/4mmHg cut, promptly? does the hydroxyl ethyl methane sulfonate obtain 97.1g's? the hydroxyl ethyl methane sulfonate, yield 69.4%;
C. reflux condensing tube is being housed, in the 500ml three-necked bottle of thermometer and magnetic stirring apparatus, the beta-hydroxy ethyl methane sulfonate 140g that adds 1mol, under agitation condition, drip the trimethylamine hydrochloride aqueous solution, the trimethylamine hydrochloride aqueous solution is made into by 95.5g trimethylamine hydrochloride and 280g water, dropwised the back stirring at room 1 hour, obtain the mixing solutions of product choline chloride 60 and methylsulfonic acid, then mixing solutions is removed methylsulfonic acid through the ionic absorption with macroporous adsorbent resin, obtain the aqueous solution of choline chloride 60, obtain the about 128.6g of product choline chloride 60 elaboration after the evaporating water, yield 92.2%.
The fusing point of the choline chloride 60 elaboration that obtains is 302～305 ℃ (decomposition), and 1H-NMR (CDCl3): δ 3.29 (9H, s), 3.41-3.50 (2H, t), 3.95-4.01 (2H, t) .MS (EI), m/z 141 (M+H).
Embodiment 6: a kind of method for preparing choline chloride 60 of this example the steps include:
A. add 1mol 1 62g in the 1000ml three-necked bottle of reflux condensing tube, thermometer and magnetic stirring apparatus is housed, toluene 500g and 1.2mol sodium bicarbonate 100.5g place on the ice-water bath under stirring, and reaction mixture is cooled to below 10 ℃;
B. in mixture, drip about 1.1mol methylsulfonyl chloride 126g, the dropping process keeps temperature of reaction to be no more than 10 ℃, dropwising the back continues to stir 4 hours, until there not being bubble to produce, remove by filter insolubles, normal pressure steams and desolventizes toluene, resistates carries out underpressure distillation and collects 134-138 ℃/4mmHg cut, promptly? does the hydroxyl ethyl methane sulfonate obtain 98.7g's? the hydroxyl ethyl methane sulfonate, yield 70.5%;
C. reflux condensing tube is being housed, in the 500ml three-necked bottle of thermometer and magnetic stirring apparatus, the beta-hydroxy ethyl methane sulfonate 140g that adds 1mol, under agitation condition, drip the trimethylamine hydrochloride aqueous solution, the trimethylamine hydrochloride aqueous solution is made into by 95.5g trimethylamine hydrochloride and 280g water, dropwised the back stirring at room 1 hour, obtain the mixing solutions of product choline chloride 60 and methylsulfonic acid, then mixing solutions is removed methylsulfonic acid through the ionic absorption with macroporous adsorbent resin, obtain the aqueous solution of choline chloride 60, obtain the about 128.6g of product choline chloride 60 elaboration after the evaporating water, yield 92.2%.
The fusing point of the choline chloride 60 elaboration that obtains is 302～305 ℃ (decomposition), and 1H-NMR (CDCl3): δ 3.29 (9H, s), 3.41-3.50 (2H, t), 3.95-4.01 (2H, t) .MS (EI), m/z 141 (M+H).
Embodiment 7: a kind of method for preparing choline chloride 60 of this example the steps include:
A. add 1mol 1 62g in the 1000ml three-necked bottle of reflux condensing tube, thermometer and magnetic stirring apparatus is housed, toluene 300g and 1mol sodium bicarbonate 84g place on the ice-water bath under stirring, and reaction mixture is cooled to below 10 ℃;
B. in mixture, drip about 1mol methylsulfonyl chloride 115g, the dropping process keeps temperature of reaction to be no more than 10 ℃, dropwising the back continues to stir 4 hours, until there not being bubble to produce, remove by filter insolubles, normal pressure steams and desolventizes toluene, resistates carries out underpressure distillation and collects 134-138 ℃/4mmHg cut, promptly? does the hydroxyl ethyl methane sulfonate obtain 93.7g's? the hydroxyl ethyl methane sulfonate, yield 66.9%;
C. reflux condensing tube is being housed, in the 500ml three-necked bottle of thermometer and magnetic stirring apparatus, the beta-hydroxy ethyl methane sulfonate 140g that adds 1mol, under agitation condition, drip the trimethylamine hydrochloride aqueous solution, the trimethylamine hydrochloride aqueous solution is made into by 106g trimethylamine hydrochloride and 350g water, dropwised the back stirring at room 1 hour, obtain the mixing solutions of product choline chloride 60 and methylsulfonic acid, then mixing solutions is removed methylsulfonic acid through the ionic absorption with macroporous adsorbent resin, obtain the aqueous solution of choline chloride 60, obtain the about 131.2g of product choline chloride 60 elaboration after the evaporating water, yield 94.1%.
The fusing point of the choline chloride 60 elaboration that obtains is 302～305 ℃ (decomposition), and 1H-NMR (CDCl3): δ 3.29 (9H, s), 3.41-3.50 (2H, t), 3.95-4.01 (2H, t) .MS (EI), m/z 141 (M+H).
Embodiment 8: a kind of method for preparing choline chloride 60 of this example the steps include:
A. add 1mol 1 62g in the 1000ml three-necked bottle of reflux condensing tube, thermometer and magnetic stirring apparatus is housed, toluene 300g and 1mol sodium bicarbonate 84g place on the ice-water bath under stirring, and reaction mixture is cooled to below 10 ℃;
B. in mixture, drip about 1mol methylsulfonyl chloride 115g, the dropping process keeps temperature of reaction to be no more than 10 ℃, dropwising the back continues to stir 4 hours, until there not being bubble to produce, remove by filter insolubles, normal pressure steams and desolventizes toluene, resistates carries out underpressure distillation and collects 134-138 ℃/4mmHg cut, promptly? does the hydroxyl ethyl methane sulfonate obtain 93.7g's? the hydroxyl ethyl methane sulfonate, yield 66.9%;
C. reflux condensing tube is being housed, in the 500ml three-necked bottle of thermometer and magnetic stirring apparatus, the beta-hydroxy ethyl methane sulfonate 140g that adds 1mol, under agitation condition, drip the trimethylamine hydrochloride aqueous solution, the trimethylamine hydrochloride aqueous solution is made into by 100g trimethylamine hydrochloride and 420g water, dropwised the back stirring at room 1 hour, obtain the mixing solutions of product choline chloride 60 and methylsulfonic acid, then mixing solutions is removed methylsulfonic acid through the ionic absorption with macroporous adsorbent resin, obtain the aqueous solution of choline chloride 60, obtain the about 129.7g of product choline chloride 60 elaboration after the evaporating water, yield 93.0%.
The fusing point of the choline chloride 60 elaboration that obtains is 302～305 ℃ (decomposition), and 1H-NMR (CDCl3): δ 3.29 (9H, s), 3.41-3.50 (2H, t), 3.95-4.01 (2H, t) .MS (EI), m/z 141 (M+H).
Claims (9)
1. method for preparing choline chloride 60 is characterized in that:
A. in reactor, add 1, toluene, sodium bicarbonate or saleratus and fully react, after the stirring mixture placed on the ice-water bath and lower the temperature;
B. in mixture, drip methylsulfonyl chloride, thereby fully react with mixture, dropwising the back fully stirs, until there not being bubble to produce, remove by filter insolubles, normal pressure steams and desolventizes toluene, resistates is carried out underpressure distillation collect 134～138 ℃/4mmHg cut, obtains the beta-hydroxy ethyl methane sulfonate;
C. add the beta-hydroxy ethyl methane sulfonate in reactor, the aqueous solution and the beta-hydroxy ethyl methane sulfonate that drip trimethylamine hydrochloride in reactor fully react, and dropwise the back and fully stir, and obtain the mixing solutions of product choline chloride 60 and methylsulfonic acid;
D. mixing solutions is removed methylsulfonic acid through the ionic absorption with macroporous adsorbent resin, obtain the aqueous solution of choline chloride 60, obtain product choline chloride 60 elaboration after the evaporating water.
2. a kind of method for preparing choline chloride 60 according to claim 1, it is characterized in that among the described step a 1, the mass ratio of 2-ethylene glycol and toluene is 1: 2～10, and the mass ratio of 1 and sodium bicarbonate or saleratus is 1: 1.35～1.63 or 1: 1.61～1.94.
3. a kind of method for preparing choline chloride 60 according to claim 1, when it is characterized in that described step b drips methylsulfonyl chloride, the 1 in the mixture and the mass ratio of methylsulfonyl chloride are 1: 1.84～2.04.
4. a kind of method for preparing choline chloride 60 according to claim 1 is characterized in that the mass ratio of beta-hydroxy ethyl methane sulfonate and trimethylamine hydrochloride among the described step c, water is 1: 0.68～0.76: 2～3.
5. a kind of method for preparing choline chloride 60 according to claim 1 is characterized in that the temperature of described mixture after cooling on the ice-water bath is 0～10 ℃.
6. a kind of method for preparing choline chloride 60 according to claim 1 is characterized in that describedly when dripping methylsulfonyl chloride in mixture, keeps temperature of reaction at 0～10 ℃.
7. a kind of method for preparing choline chloride 60 according to claim 1 is characterized in that described the dropping after methylsulfonyl chloride finishes in mixture, the time of stirring is 3～4 hours.
8. a kind of method for preparing choline chloride 60 according to claim 1 is characterized in that described is to finish under agitation condition when dripping trimethylamine hydrochloride.
9. a kind of method for preparing choline chloride 60 according to claim 1 is characterized in that stirring 0.5～1.5 hour after described dropping trimethylamine hydrochloride finishes, and the temperature during stirring is 20～30 ℃.
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Denomination of invention: A method for preparing choline chloride Effective date of registration: 20221014 Granted publication date: 20130313 Pledgee: Xiaoshan Branch of Agricultural Bank of China Ltd. Pledgor: HEALTHY (HANGZHOU) HUSBANDRY SCI-TECH CO.,LTD. Registration number: Y2022980018382 |