CN103880697A - N-dimethoxyethyl-m-aminoacetanilide synthesis process - Google Patents
N-dimethoxyethyl-m-aminoacetanilide synthesis process Download PDFInfo
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- CN103880697A CN103880697A CN201210556031.6A CN201210556031A CN103880697A CN 103880697 A CN103880697 A CN 103880697A CN 201210556031 A CN201210556031 A CN 201210556031A CN 103880697 A CN103880697 A CN 103880697A
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- monomethyl ether
- chloroethanol
- mass ratio
- reaction
- ethylene glycol
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 11
- VNWISEKSEFLISC-UHFFFAOYSA-N N-(3-aminophenyl)-N-(2,2-dimethoxyethyl)acetamide Chemical compound COC(CN(C1=CC(=CC=C1)N)C(C)=O)OC VNWISEKSEFLISC-UHFFFAOYSA-N 0.000 title abstract 2
- QWELSYQNDFTISP-UHFFFAOYSA-N 1-chloro-1-methoxyethane Chemical compound COC(C)Cl QWELSYQNDFTISP-UHFFFAOYSA-N 0.000 claims abstract description 48
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 19
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000017550 sodium carbonate Nutrition 0.000 claims abstract description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 15
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- -1 glycyl aminoaniline hydrochloride Chemical compound 0.000 claims description 20
- 239000012044 organic layer Substances 0.000 claims description 17
- 238000010792 warming Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 8
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 4
- 238000002955 isolation Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006467 substitution reaction Methods 0.000 abstract description 5
- 238000005660 chlorination reaction Methods 0.000 abstract description 2
- DJRCDWICTCWTQF-UHFFFAOYSA-N N-(3-aminophenyl)acetohydrazide Chemical compound NC=1C=C(N(N)C(C)=O)C=CC1 DJRCDWICTCWTQF-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000009413 insulation Methods 0.000 description 10
- 238000005204 segregation Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HAHSSWKSMRLGHG-UHFFFAOYSA-N 2-methoxyethyl benzenesulfonate Chemical compound COCCOS(=O)(=O)C1=CC=CC=C1 HAHSSWKSMRLGHG-UHFFFAOYSA-N 0.000 description 1
- KOSOMZGYXGBFSF-UHFFFAOYSA-N CC1=CC(CC2)C2C1 Chemical compound CC1=CC(CC2)C2C1 KOSOMZGYXGBFSF-UHFFFAOYSA-N 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses an N-dimethoxyethyl-m-aminoacetanilide synthesis process, wherein ethylene glycol monomethyl ether and thionyl chloride are subjected to a chlorination reaction to prepare chloroethanol monomethyl ether, and an m-amino acetyl aminoaniline hydrochlorate, soda ash and tetrabutyl ammonium bromide are added to carry out a double substitution reaction to obtain the target product. According to the invention, p-toluene sulfonyl chloride with high price in the traditional process is replaced by thionyl chloride so as to reduce the cost; the reaction conditions are mild, and particularly the pressure in the reactor is substantially reduced so as to reduce the risk of the reaction; and the period of the double substitution reaction is substantially reduced and is shortened to 24 h from the traditional 60 h, and the purity and the yield of the product are improved.
Description
Technical field
The present invention relates to a kind of synthesis technique of dispersed dye intermediate, particularly a kind of synthesis technique of N-dimethoxy-ethyl-3-acetylaminoaniline, belongs to chemical industry preparation field.
Background technology
N-dimethoxy-ethyl-3-acetylaminoaniline is a kind of intermediate of important synthetic dispersed dye, and its chemical formula is:
Maximum synthetic route that at present domestic synthetic this product adopts is; take ethylene glycol monomethyl ether and Tosyl chloride as raw material; through acylation reaction generating glycol monomethyl ether tosylate, then ethylene glycol monomethyl ether benzene sulfonate again and a glycyl aminoaniline hydrochloride process is monosubstituted and two substitution reactions generate target products.Reaction formula is as follows:
This technique is more stable, but reaction time is long, reaches 60 hours, and cost is high, and products therefrom purity and yield are all generally not high simultaneously.The present invention is exactly for this situation, has proposed new synthesis route, has overcome the problem that above-mentioned technique occurs.
Summary of the invention
The present invention, in order to overcome the problems such as in above-mentioned technique, product yield is low, purity is not high, reaction time is long, raw materials cost height, has proposed a kind of synthesis technique of new N-dimethoxy-ethyl-3-acetylaminoaniline.
In order to solve above-mentioned technical problem, technical scheme of the present invention is summarized as follows: a kind of synthesis technique of N-dimethoxy-ethyl-3-acetylaminoaniline, comprises the following steps:
The first step, ethylene glycol monomethyl ether and catalyzer DMF are dropped in reactor, the mass ratio of ethylene glycol monomethyl ether and DMF is 1:(0.01 ~ 0.05), the cooling lower slow dropping sulfur oxychloride of ice bath, the mass ratio of sulfur oxychloride and ethylene glycol monomethyl ether is (2 ~ 3): 1, after dripping, be warming up to 40 ~ 50 ℃ of reaction 4 ~ 8h;
After second step, reaction finish, be cooled to room temperature and slowly add water, separate organic layer, water layer is used extracted with diethyl ether again, merges organic layer, and after water and alkaline solution washing, normal pressure reclaims ether, obtains chloroethanol monomethyl ether;
Under the 3rd step, stirring, gradation adds soda ash and chloroethanol monomethyl ether, then glycyl aminoaniline hydrochloride between dropping into, the mass ratio of soda ash and a glycyl aminoaniline hydrochloride is (2 ~ 3): 4, the mass ratio of a glycyl aminoaniline hydrochloride and chloroethanol monomethyl ether is 4:(13 ~ 18);
The 4th step, in the 3rd step solution, add Tetrabutyl amonium bromide, wherein the mass ratio of Tetrabutyl amonium bromide and a glycyl aminoaniline hydrochloride is (0.005 ~ 0.01): 1, be warming up to 100 ~ 120 ℃ of reactions, 3h HPLC follows the trail of, if chloroethanol monomethyl ether reacts the complete remaining chloroethanol monomethyl ether of adding, continue reaction;
After the 5th step, reaction finish, be cooled to more than 90 ℃, reclaim remaining chloroethanol monomethyl ether, be then down to room temperature, add water isolation, filter, obtain product N-dimethoxy-ethyl-3-acetylaminoaniline.
The present invention is compared with the prior art, and significant advantage is: (1), Tosyl chloride higher relative price in traditional technology is replaced to sulfur oxychloride, reduce cost; (2), the gentleness that becomes of reaction conditions, especially reactor pressure reduces greatly, has reduced the danger of reaction; (3) cycle of two substitution reactions dwindles greatly, from traditional 60h, shortens to 24h; (4) purity of product and yield all increase.
Embodiment
Carrying out process in detail with specific embodiment below adopts new process to close N-dimethoxy-ethyl-3-acetylaminoaniline.
Concrete reactions steps is as follows:
1, chlorination: mass ratio is 1:(0.01 ~ 0.05) ethylene glycol monomethyl ether and catalyzer DMF, drop in the four-hole boiling flask of 2L; The cooling lower slow dropping sulfur oxychloride of ice bath, the mass ratio of sulfur oxychloride and ethylene glycol monomethyl ether is (2 ~ 3): 1, after dripping, be warming up to 40 ~ 50 ℃ of reaction 4 ~ 8h.After being cooled to room temperature, slowly add water, separate organic layer, water layer is used extracted with diethyl ether again, merges organic layer, and respectively with sodium hydroxide solution and water washing, normal pressure reclaims ether, obtains light yellow transparent liquid.
2, two substitution reactions: be (2 ~ 3) by the mass ratio of a glycyl aminoaniline hydrochloride 40g and soda ash sodium bicarbonate 20-30g(sodium bicarbonate and a glycyl aminoaniline hydrochloride: 4) drop in the autoclave of 500ml.The mass ratio that adds catalyzer Tetrabutyl amonium bromide 0.2-0.4g(Tetrabutyl amonium bromide and a glycyl aminoaniline hydrochloride is (0.005 ~ 0.01): 1) and the mass ratio of chloroethanol monomethyl ether 130 ~ 180g(chloroethanol monomethyl ether and a glycyl aminoaniline hydrochloride be (13 ~ 18): 4).Heating, 100 ~ 120 ℃ of insulations, depending on HPLC.If chloroethanol monomethyl ether reacts the complete remaining chloroethanol monomethyl ether of adding, continue reaction; After reaction finishes, be cooled to more than 90 ℃, reclaim remaining chloroethanol monomethyl ether, be then down to room temperature, add water isolation, filter, obtain product N-dimethoxy-ethyl-3-acetylaminoaniline.
Embodiment 1
The catalyzer DMF of the ethylene glycol monomethyl ether of 300g and 3g is dropped in the four-hole boiling flask of 2L.The sulfur oxychloride of the cooling lower slow dropping 600g of ice bath, is warming up to 40 ℃ of reaction 4h after dripping.Be cooled to the water that slowly adds 300ml after room temperature, separate organic layer (organic layer is chloroethanol monomethyl ether) herein, water layer is used ether (150ml × 3) extraction again, merges organic layer, respectively with 10% sodium hydroxide and water washing, normal pressure reclaims ether, treat that temperature rises to 90 ℃, start to stop reclaiming ether, obtain chloroethanol monomethyl ether, gained intermediate chloroethanol monomethyl ether purity 93%, yield 83.8%.
The soda ash of glycyl aminoaniline hydrochloride and 20g between 40g is dropped in autoclave.Add the catalyzer Tetrabutyl amonium bromide of 0.2g and the chloroethanol monomethyl ether of 130g.Heating, at 100 ℃ of insulation 12h, adds chloroethanol monomethyl ether and the 10g soda ash of 40g, is warming up to 100 ℃, insulation 12h.After finishing, reaction is cooled to more than 90 ℃, the chloroethanol monomethyl ether that rising temperature reclamation unreacted is complete, and recovered temperature is no more than 100 ℃.Treat to steam without chloroethanol monomethyl ether, start cooling, be cooled to and after 70 ℃, add the water of 300ml slowly to drip segregation, want guarantee system, then naturally to lower the temperature at least more than half an hour at 70 ℃ when segregation, filtration washing obtains finished product, purity 93.4%, yield 92.1%.
Embodiment 2
The catalyzer DMF of the ethylene glycol monomethyl ether of 300g and 9g is dropped in the four-hole boiling flask of 2L.The sulfur oxychloride of the cooling lower slow dropping 700g of ice bath, is warming up to 45 ℃ of reaction 6h after dripping.Be cooled to the water that slowly adds 300ml after room temperature, separate organic layer, water layer is used ether (150ml × 3) extraction again, merges organic layer, respectively with 10% sodium hydroxide and water washing, normal pressure reclaims ether, treat that temperature rises to 90 ℃, start to stop reclaiming ether, obtain chloroethanol monomethyl ether, gained intermediate chloroethanol monomethyl ether purity 92.4%, yield 84.5%
The soda ash of glycyl aminoaniline hydrochloride and 25g between 40g is dropped in autoclave.Add the catalyzer Tetrabutyl amonium bromide of 0.4g and the chloroethanol monomethyl ether of 150g.Heating, at 100 ℃ of insulation 12h, adds chloroethanol monomethyl ether and the 15g soda ash of 40g, is warming up to 110 ℃, insulation 12h.After finishing, reaction is cooled to more than 90 ℃, the chloroethanol monomethyl ether that rising temperature reclamation unreacted is complete, and recovered temperature is no more than 100 ℃.Treat to steam without chloroethanol monomethyl ether, start cooling, be cooled to and after 70 ℃, add the water of 300ml slowly to drip segregation, want guarantee system, then naturally to lower the temperature at least more than half an hour at 70 ℃ when segregation, filtration washing obtains finished product, purity 93.8%, yield 90.6%.
Embodiment 3
The catalyzer DMF of the ethylene glycol monomethyl ether of 300g and 15g is dropped in the four-hole boiling flask of 2L.The sulfur oxychloride of the cooling lower slow dropping 700g of ice bath, is warming up to 50 ℃ of reaction 6h after dripping.Be cooled to the water that slowly adds 300ml after room temperature, separate organic layer, water layer is used ether (150ml × 3) extraction again, merges organic layer, respectively with 10% sodium hydroxide and water washing, normal pressure reclaims ether, treat that temperature rises to 90 ℃, start to stop reclaiming ether, obtain chloroethanol monomethyl ether, gained intermediate chloroethanol monomethyl ether purity 92.8%, yield 88.6%
The soda ash of glycyl aminoaniline hydrochloride and 30g between 40g is dropped in autoclave.Add the catalyzer Tetrabutyl amonium bromide of 0.3g and the chloroethanol monomethyl ether of 180g.Heating, at 100 ℃ of insulation 12h, adds chloroethanol monomethyl ether and the 20g soda ash of 80g, is warming up to 120 ℃, insulation 12h.After finishing, reaction is cooled to more than 90 ℃, the chloroethanol monomethyl ether that rising temperature reclamation unreacted is complete, and recovered temperature is no more than 100 ℃.Treat to steam without chloroethanol monomethyl ether, start cooling, be cooled to and after 70 ℃, add the water of 300ml slowly to drip segregation, want guarantee system, then naturally to lower the temperature at least more than half an hour at 70 ℃ when segregation, filtration washing obtains finished product, purity 94.2%, yield 93.1%.
Embodiment 4
The catalyzer DMF of the ethylene glycol monomethyl ether of 300g and 9g is dropped in the four-hole boiling flask of 2L.The sulfur oxychloride of the cooling lower slow dropping 900g of ice bath, is warming up to 50 ℃ of reaction 8h after dripping.Be cooled to the water that slowly adds 300ml after room temperature, separate organic layer, water layer is used ether (150ml × 3) extraction again, merges organic layer, respectively with 10% sodium hydroxide and water washing, normal pressure reclaims ether, treat that temperature rises to 90 ℃, start to stop reclaiming ether, obtain chloroethanol monomethyl ether, gained intermediate chloroethanol monomethyl ether purity 93.1%, yield 86.8%
The soda ash of glycyl aminoaniline hydrochloride and 25g between 40g is dropped in autoclave.Add the catalyzer Tetrabutyl amonium bromide of 0.4g and the chloroethanol monomethyl ether of 150g.Heating, at 100 ℃ of insulation 12h, adds chloroethanol monomethyl ether and the 15g soda ash of 60g, is warming up to 120 ℃, insulation 12h.After finishing, reaction is cooled to more than 90 ℃, the chloroethanol monomethyl ether that rising temperature reclamation unreacted is complete, and recovered temperature is no more than 100 ℃.Treat to steam without chloroethanol monomethyl ether, start cooling, be cooled to and after 70 ℃, add the water of 300ml slowly to drip segregation, want guarantee system, then naturally to lower the temperature at least more than half an hour at 70 ℃ when segregation, filtration washing obtains finished product, purity 93.6%, yield 92.7%.
Optimised process is: mass ratio is 1:(0.01 ~ 0.03) ethylene glycol monomethyl ether and catalyzer DMF, drop in the four-hole boiling flask of 2L; The cooling lower slow dropping sulfur oxychloride of ice bath, the mass ratio of sulfur oxychloride and ethylene glycol monomethyl ether is (2.33 ~ 3): 1, after dripping, be warming up to 40 ~ 50 ℃ of reaction 4h.Be cooled to the water that slowly adds 300ml after room temperature, separate organic layer, water layer is used ether (150ml × 3) extraction again, merge organic layer, respectively with 10% sodium hydroxide and water washing, normal pressure reclaims ether, treat that temperature rises to more than 90 ℃, start to stop reclaiming ether, obtain chloroethanol monomethyl ether.
The mass ratio of soda ash and a glycyl aminoaniline hydrochloride is (2 ~ 3): 4 drop in the autoclave of 500ml.The mass ratio that adds catalyzer Tetrabutyl amonium bromide and a glycyl aminoaniline hydrochloride is (0.005 ~ 0.01): 1 and the mass ratio of chloroethanol monomethyl ether and a glycyl aminoaniline hydrochloride be (3.25 ~ 4.5): 1.Heating, 100 ~ 120 ℃ of insulations, depending on HPLC.If chloroethanol monomethyl ether reacts the complete remaining chloroethanol monomethyl ether of adding, continue reaction; After reaction finishes, be cooled to more than 90 ℃, reclaim remaining chloroethanol monomethyl ether, be then down to room temperature, add water isolation, filter, obtain product N-dimethoxy-ethyl-3-acetylaminoaniline.
Claims (3)
1. a synthesis technique for N-dimethoxy-ethyl-3-acetylaminoaniline, is characterized in that described technique comprises the following steps:
The first step, ethylene glycol monomethyl ether and catalyzer DMF are dropped in reactor, the mass ratio of ethylene glycol monomethyl ether and DMF is 1:(0.01 ~ 0.05), the cooling lower slow dropping sulfur oxychloride of ice bath, the mass ratio of sulfur oxychloride and ethylene glycol monomethyl ether is (2 ~ 3): 1, after dripping, be warming up to 40 ~ 50 ℃ of reactions;
After second step, reaction finish, be cooled to room temperature and slowly add water, separate organic layer, water layer is used extracted with diethyl ether again, merges organic layer, and after water and alkaline solution washing, normal pressure reclaims ether, obtains chloroethanol monomethyl ether;
Under the 3rd step, stirring, gradation adds soda ash and chloroethanol monomethyl ether, then glycyl aminoaniline hydrochloride between dropping into, the mass ratio of soda ash and a glycyl aminoaniline hydrochloride is (2 ~ 3): 4, the mass ratio of a glycyl aminoaniline hydrochloride and chloroethanol monomethyl ether is 4:(13 ~ 18);
The 4th step, in the 3rd step solution, add Tetrabutyl amonium bromide, wherein the mass ratio of Tetrabutyl amonium bromide and a glycyl aminoaniline hydrochloride is (0.005 ~ 0.01): 1, be warming up to 100 ~ 120 ℃ of reactions, 3h HPLC follows the trail of, if chloroethanol monomethyl ether reacts the complete remaining chloroethanol monomethyl ether of adding, continue reaction;
After the 5th step, reaction finish, be cooled to more than 90 ℃, reclaim remaining chloroethanol monomethyl ether, be then down to room temperature, add water isolation, filter, obtain product N-dimethoxy-ethyl-3-acetylaminoaniline.
2. the synthesis technique of N-dimethoxy-ethyl-3-acetylaminoaniline according to claim 1, is characterized in that the reaction times described in the first step is 4 ~ 8h.
3. the synthesis technique of N-dimethoxy-ethyl-3-acetylaminoaniline according to claim 1, it is characterized in that preferred 1:(0.01 ~ 0.03 of mass ratio of the ethylene glycol monomethyl ether described in the first step and DMF), the mass ratio of sulfur oxychloride and ethylene glycol monomethyl ether is (2.33 ~ 3) preferably: 1.
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| CN201210556031.6A CN103880697A (en) | 2012-12-20 | 2012-12-20 | N-dimethoxyethyl-m-aminoacetanilide synthesis process |
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| CN201210556031.6A CN103880697A (en) | 2012-12-20 | 2012-12-20 | N-dimethoxyethyl-m-aminoacetanilide synthesis process |
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- 2012-12-20 CN CN201210556031.6A patent/CN103880697A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 向海艳 等: "3-（N，N-二甲氧基乙基）氨基乙酰苯胺合成工艺优化研究", 《精细化工中间体》 * |
| 钱武: "C.I.分散蓝257与其中间体的合成", 《化工技术与开发》 * |
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Application publication date: 20140625 |