CN103833565A - Preparation method for 3-N,N-dimethylamino ethyl acrylate - Google Patents
Preparation method for 3-N,N-dimethylamino ethyl acrylate Download PDFInfo
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- CN103833565A CN103833565A CN201310667831.XA CN201310667831A CN103833565A CN 103833565 A CN103833565 A CN 103833565A CN 201310667831 A CN201310667831 A CN 201310667831A CN 103833565 A CN103833565 A CN 103833565A
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- dimethylamino ethyl
- ethyl propenoate
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- ethyl acetate
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Abstract
The invention discloses a preparation method for 3-N,N-dimethylamino ethyl acrylate, and belongs to the technical field of fine chemical intermediates. 3-N,N-dimethylamino ethyl acrylate is obtained by using ethyl acetate, dimethylamine and carbon monoxide as raw materials and through a one-pot method comprising a step of reacting for 1-4 hours at a pressure of 10-60 bar under the effect of a catalyst A and a catalyst B while controlling a temperature at 30-70 DEG C. A process route in the method provided by the invention is simple and reasonable. 3-N,N-dimethylamino ethyl acrylate can be synthesized by the one-pot method, with a total yield higher than 95%. Utilization rate of the raw materials is high; production cost is low; the purity HPLC is higher than 99.8%; and the preparation method is suitable for large-scale continuous production.
Description
Technical field
The present invention relates to fine-chemical intermediate synthesis technical field, be specifically related to a kind of carbostyril family antibacterial drugs intermediate 3-
n,Nthe preparation method of-dimethylamino ethyl propenoate.
Background technology
3-
n,N-dimethylamino ethyl propenoate is the key intermediate of carbostyril family antibacterial drugs new synthetic process.Carbostyril family antibacterial drugs has that has a broad antifungal spectrum, anti-microbial activity are strong, convenient drug administration, toxic side effect are little, become without advantages such as cross resistances the complete synthesis antimicrobial drug that a unique class can be mentioned in the same breath with Beta-lactam medicine clinically with other microbiotic.Adopt 3-
n,Nthe new technology route of the synthetic main cyclic quinoline compound of-dimethylamino ethyl propenoate is short, has reduced raw material consumption, has improved Atom economy, reduced three waste discharge, overall yield of reaction significantly improves, reaction conditions gentleness, post-reaction treatment is simple, has good industrial prospect.
Up to the present, 3-
n,Nthe preparation method of-dimethylamino ethyl propenoate mainly reports in document abroad, and domestic report is less, is summed up and mainly contains following several method:
1) Recueil des Travaux Chimiques des Pays-BAS, 1966,85,929 have reported that DMF and oxyethyl group acetylene prepares 3-under the catalysis of boron trifluoride
n,Nthe method of-dimethylamino ethyl propenoate; 2) US5446192 has reported that methyl-sulfate and DMF make imino-complex, generates the imino-complex that dimethylamine replaces, then react to obtain Bredereck ' s reagent with potassium tert.-butoxide through reacting with dimethylamine, and last and acetic acid ethyl reaction is prepared 3-
n,Nthe method of-dimethylamino ethyl propenoate; 3) monopotassium salt that WO2000000460 generates with ethyl propenoate or diethyl malonate and KOH, then prepare 3-with the condensation reactant salt of methyl-sulfate and DMF
n,N-dimethylamino ethyl propenoate; 4) Journal of Heterocyclic Chemistry, 1987 provide by trifluoroacetic ethyl acetoacetate with
n,N-dimethyl formamide dimethyl acetal is prepared 3-under Catalyzed by p-Toluenesulfonic Acid
n,Nthe method of-dimethylamino ethyl propenoate; 5) by Pyruvic Acid Ethyl ester with
n,N-dimethyl formamide diethyl acetal reaction preparation 3-
n,Nthe method of-dimethylamino ethyl propenoate and method 3) mechanism is similar, and be reported in the same interim of same magazine; 6) ethyl propiolate with benzyldimethylamine under zinc bromide catalysis, react preparation 3-in acetonitrile solvent
n,N-dimethylamino ethyl propenoate (Tetrahedron Letters, 2004,46 (1), 69) or prepare 3-with dimethylamine direct addition
n,N-dimethylamino ethyl propenoate; 7) Synthetic Communications, 1982,12 (2), 939 have reported that cyanuric chloride reacts generation Gold ' s reagent with the DMF of six molecules, then under sodium alkoxide effect, prepare 3-with ethyl acetate
n,Nthe method of-dimethylamino ethyl propenoate; 8) EP388744, US5030747, take carbon monoxide as raw material, generate the sodium salt of formyl radical ethyl acetate, then react and make 3-with dimethylamine hydrochloride in autoclave with acetic acid ethyl reaction
n,N-dimethylamino ethyl propenoate; 9) in method 8) basis on, ethyl formate and ethyl acetate, under sodium Metal 99.5 or sodium hydride exist, generate the sodium salt of formyl radical ethyl acetate, then react and make 3-with dimethylamine hydrochloride through aldol condensation
n,N-dimethylamino ethyl propenoate.
Method 1) productive rate only have 25 %, long reaction time, raw material oxyethyl group acetylene, boron trifluoride be difficult to obtain and price higher; Method 2) in final step tert.-butoxy two (dimethylamino) methane and ethyl acetate need to be in high pressure vessel 170 ℃ react 20 hours (Chemische Berichte, 1971,104 (9), 2709), reaction raw materials methyl-sulfate and dimethylamine toxicity are large, severe reaction conditions, needs the strict proportioning of controlling, and Atom economy is poor; Method 3) in malonic ester monopotassium salt preparation process be difficult to control, and use hypertoxic methyl-sulfate, poor stability; Method 4) productive rate be 75%, but raw material sources difficulty and price are more expensive, by product is 3-dimethylamino-2-trifluoroacetyl group-2-ethyl propenoate, product postprocessing trouble; Method 5), method 6), method 7) shortcoming remain that raw material is not easy to obtain and productive rate is low; Method 8) two-step reaction makes target product, yield is high, Atom economy good, by product is ethanol and sodium-chlor, but the sodium salt of formyl radical ethyl acetate easily water suction degenerate, operation inconvenience; Method 9) and method 8) similar, only substitute carbon monoxide with ethyl formate and react.
Method 1 can be described from above-mentioned prior art) to method 7) all there is in varying degrees raw material sources difficulty, expensive, processing condition are harsh, quantity of three wastes is large, productive rate is low and be unsuitable for the problems such as industrial production; Method 8 and method 9) be two-step reaction, the sodium salt of intermediate formyl radical ethyl acetate easily water suction degenerates, and is unfavorable for production operation.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the present invention is to provide a kind of 3-
n,Nthe chemical preparation process of-dimethylamino ethyl propenoate.The method can realize by " one kettle way ", has solved that prior art Raw source is difficult, expensive, processing condition are harsh, quantity of three wastes is large, productive rate is low, cost is high, be unsuitable for the problems such as industrial production.
Described a kind of 3-
n,Nthe preparation method of-dimethylamino ethyl propenoate, it is characterized in that take ethyl acetate, dimethylamine and carbon monoxide as raw material, under the effect of catalyst A and catalyst B, control temperature is 30-70 ℃, pressure is that 10-60bar reacts 1-4 hour in organic solvent, obtains 3-by " one kettle way "
n,N-dimethylamino ethyl propenoate, its reaction equation is as follows:
Described a kind of 3-
n,Nthe preparation method of-dimethylamino ethyl propenoate, is characterized in that described catalyst A is sodium ethylate, sodium tert-butoxide or sodium hydride.
Described a kind of 3-
n,Nthe preparation method of-dimethylamino ethyl propenoate, is characterized in that described catalyst B is one or more mixtures in ethanol, diethyl carbonate, ethyl formate, DMF, triethyl orthoformate.
Described a kind of 3-
n,Nthe preparation method of-dimethylamino ethyl propenoate, is characterized in that described dimethylamine and the molar feed ratio of ethyl acetate are 1-2:1.
Described a kind of 3-
n,Nthe preparation method of-dimethylamino ethyl propenoate, is characterized in that described catalyst A and the molar feed ratio of ethyl acetate are 1.05-2:1.
Described a kind of 3-
n,Nthe preparation method of-dimethylamino ethyl propenoate, is characterized in that described catalyst B and the molar feed ratio of ethyl acetate are 0.05-0.5:1.
Described a kind of 3-
n,Nthe preparation method of-dimethylamino ethyl propenoate, is characterized in that described organic solvent is one or more mixtures in ethanol, toluene, methylene dichloride, chloroform, tetrahydrofuran (THF).
By adopting above-mentioned technology, compared with prior art, beneficial effect of the present invention is as follows:
1) the present invention, under catalyst A and catalyst B acting in conjunction, take ethyl acetate, dimethylamine and carbon monoxide as raw material, prepares 3-by " one kettle way "
n,N-dimethylamino ethyl propenoate, simple to operate in production process, greatly reduce labour intensity;
2) the invention solves that prior art Raw source is difficult, expensive, processing condition are harsh, quantity of three wastes is large, productive rate is low, cost is high, be unsuitable for the problems such as industrial production, its total recovery is up to more than 95%, raw material availability is high, low and the purity HPLC > 99.8% of production cost, applicable heavy industrialization is produced continuously.
Embodiment
Below in conjunction with concrete case study on implementation, the present invention is further described.Be construed as; the preparation method of the invention process case is only for the present invention is described, rather than limitation of the present invention, and protection scope of the present invention is not limited in this; under design prerequisite of the present invention, preparation method's of the present invention simple modifications is all belonged to the scope of protection of present invention.
Embodiment 1
By ethyl acetate (88.1g, 1mol), sodium ethylate (74.9g, 1.1mol), ethyl formate (7.4g, 0.1mol) and the ethanolic soln 250mL of dimethylamine (49.6g, 1.1mol) add in autoclave, pass into CO, control pressure is 20bar and is warming up to 50 ℃ of reaction 2.5h, CO pressure no longer declines, and is cooled to room temperature, filters, filtrate is reclaimed solvent, the cut 136.3g of 80-83 ℃/5mmHg, yield 95.2%, HPLC content 99.9% are collected in resistates underpressure distillation.
In the present embodiment, with sodium tert-butoxide or sodium hydride instead of ethanol sodium; With in ethanol, diethyl carbonate, DMF, triethyl orthoformate one or more mixing substitute ethyl formate; The mixing instead of ethanol of one or more for organic solvent in toluene, methylene dichloride, chloroform, tetrahydrofuran (THF), all can obtain above-mentioned effect.
Embodiment 2
By ethyl acetate (88.1g, 1mol), sodium ethylate (74.9g, 1.1mol), ethyl formate (7.4g, 0.1mol) and the dichloromethane solution 250mL of dimethylamine (49.6g, 1.1mol) add in autoclave, pass into CO, control pressure is 30bar and is warming up to 40 ℃ of reaction 4h, CO pressure no longer declines, and is cooled to room temperature, filters, filtrate is reclaimed solvent, the cut 136.2g of 80-83 ℃/5mmHg, yield 95.1%, HPLC content 99.9% are collected in resistates underpressure distillation.
Embodiment 3
By ethyl acetate (88.1g, 1mol), sodium ethylate (81.7g, 1.2mol), ethyl formate (7.4g, 0.1mol) and the tetrahydrofuran solution 250mL of dimethylamine (54.1g, 1.2mol) add in autoclave, pass into CO, control pressure is 30bar and is warming up to 40 ℃ of reaction 3h, CO pressure no longer declines, and is cooled to room temperature, filters, filtrate is reclaimed solvent, the cut 136.0g of 80-83 ℃/5mmHg, yield 95%, HPLC content 99.9% are collected in resistates underpressure distillation.
Embodiment 4
By ethyl acetate (88.1g, 1mol), sodium ethylate (81.7g, 1.2mol) and dimethylamine (49.6g, ethanolic soln 250mL 1.1mol) adds in autoclave, pass into CO, control pressure be 30bar and be warming up to 50 ℃ reaction 4h, CO pressure no longer declines, be cooled to room temperature, filter, filtrate is reclaimed solvent, and the cut 136.0g of 80-83 ℃/5mmHg is collected in resistates underpressure distillation, yield 95%, HPLC content 99.9%.
Embodiment 5
By ethyl acetate (88.1g, 1mol), sodium ethylate (74.9g, 1.1mol), diethyl carbonate (11.8g, 0.1mol) and the toluene solution 300mL of dimethylamine (49.6g, 1.1mol) add in autoclave, pass into CO, control pressure is 20bar and is warming up to 65 ℃ of reaction 3h, CO pressure no longer declines, and is cooled to room temperature, filters, filtrate is reclaimed solvent, the cut 136.9g of 80-83 ℃/5mmHg, yield 95.6%, HPLC content 99.8% are collected in resistates underpressure distillation.
Embodiment 6
By ethyl acetate (88.1g, 1mol), sodium tert-butoxide (105.7g, 1.1mol), triethyl orthoformate (14.8g, 0.1mol) and the toluene solution 300mL of dimethylamine (49.6g, 1.1mol) add in autoclave, pass into CO, control pressure is 20bar and is warming up to 65 ℃ of reaction 3h, CO pressure no longer declines, and is cooled to room temperature, filters, filtrate is reclaimed solvent, the cut 137.3g of 80-83 ℃/5mmHg, yield 95.9%, HPLC content 99.8% are collected in resistates underpressure distillation.
Embodiment 7
By ethyl acetate (88.1g, 1mol), sodium hydride (50g, 1.25mol), triethyl orthoformate (7.4g, 0.05mol) and the toluene solution 240mL of dimethylamine (54.1g, 1.2mol) add in autoclave, pass into CO, control pressure is 30bar and is warming up to 50 ℃ of reaction 2h, CO pressure no longer declines, and is cooled to room temperature, filters, filtrate is reclaimed solvent, the cut 136.6g of 80-83 ℃/5mmHg, yield 95.4%, HPLC content 99.9% are collected in resistates underpressure distillation.
Claims (6)
1. a 3-
n,Nthe preparation method of-dimethylamino ethyl propenoate, it is characterized in that take ethyl acetate, dimethylamine and carbon monoxide as raw material, under the effect of catalyst A and catalyst B, control temperature is 30-70 ℃, pressure is that 10-60bar reacts 1-4 hour in organic solvent, obtains 3-by " one kettle way "
n,N-dimethylamino ethyl propenoate, its reaction equation is as follows:
A kind of 3-as claimed in claim 1
n,Nthe preparation method of-dimethylamino ethyl propenoate, is characterized in that described catalyst A is sodium ethylate, sodium tert-butoxide or sodium hydride.
2. a kind of 3-as claimed in claim 1
n,Nthe preparation method of-dimethylamino ethyl propenoate, is characterized in that described catalyst B is one or more mixtures in ethanol, diethyl carbonate, ethyl formate, DMF, triethyl orthoformate.
3. a kind of 3-as claimed in claim 1
n,Nthe preparation method of-dimethylamino ethyl propenoate, is characterized in that described dimethylamine and the molar feed ratio of ethyl acetate are 1-2:1.
4. a kind of 3-as claimed in claim 1
n,Nthe preparation method of-dimethylamino ethyl propenoate, is characterized in that described catalyst A and the molar feed ratio of ethyl acetate are 1.05-2:1.
5. a kind of 3-as claimed in claim 1
n,Nthe preparation method of-dimethylamino ethyl propenoate, is characterized in that described catalyst B and the molar feed ratio of ethyl acetate are 0.05-0.5:1.
6. a kind of 3-as claimed in claim 1
n,Nthe preparation method of-dimethylamino ethyl propenoate, is characterized in that described organic solvent is one or more mixtures in ethanol, toluene, methylene dichloride, chloroform, tetrahydrofuran (THF).
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105367431A (en) * | 2014-08-12 | 2016-03-02 | 吉林普瑞特生物科技有限公司 | 3-N,N-dimethylamino ethyl acrylate preparation method |
| CN105646257A (en) * | 2014-11-12 | 2016-06-08 | 南京卓业医药技术有限公司 | N,N-dimethylamino ethyl acrylate preparation method |
| CN105693535A (en) * | 2016-02-26 | 2016-06-22 | 中国科学院长春应用化学研究所 | Preparation method of 3-N,N-dimethylamino ethyl acrylate |
| CN105732410A (en) * | 2016-04-05 | 2016-07-06 | 苏州开元民生科技股份有限公司 | Synthesizing method of 3-N,N-dimethylamino ethyl acrylate |
| CN106008241A (en) * | 2016-06-13 | 2016-10-12 | 江西博晟医药科技有限公司 | Synthesis method for N,N-dimethylaminoethyl acrylate |
| CN109553543A (en) * | 2017-12-29 | 2019-04-02 | 浙江本立科技股份有限公司 | A kind of synthetic method of N, N- dimethylamino ethyl acrylate |
| CN114369033A (en) * | 2022-01-17 | 2022-04-19 | 江苏飞宇医药科技股份有限公司 | Green preparation method of N, N-dimethylamino ethyl acrylate |
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|---|---|---|---|---|
| US4772711A (en) * | 1985-08-30 | 1988-09-20 | Dynamit Nobel Ag | Method for the preparation of 3-aminoacrylic acid esters |
| US5030747A (en) * | 1989-03-23 | 1991-07-09 | Bayer Aktiengesellschaft | Process for the preparation of μ-amino-acrylic acid esters |
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2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4772711A (en) * | 1985-08-30 | 1988-09-20 | Dynamit Nobel Ag | Method for the preparation of 3-aminoacrylic acid esters |
| US5030747A (en) * | 1989-03-23 | 1991-07-09 | Bayer Aktiengesellschaft | Process for the preparation of μ-amino-acrylic acid esters |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105367431A (en) * | 2014-08-12 | 2016-03-02 | 吉林普瑞特生物科技有限公司 | 3-N,N-dimethylamino ethyl acrylate preparation method |
| CN105367431B (en) * | 2014-08-12 | 2017-07-14 | 吉林普瑞特生物科技有限公司 | 3 N of one kind, the preparation method of N dimethylamino ethyl acrylates |
| CN105646257A (en) * | 2014-11-12 | 2016-06-08 | 南京卓业医药技术有限公司 | N,N-dimethylamino ethyl acrylate preparation method |
| CN105693535A (en) * | 2016-02-26 | 2016-06-22 | 中国科学院长春应用化学研究所 | Preparation method of 3-N,N-dimethylamino ethyl acrylate |
| CN105693535B (en) * | 2016-02-26 | 2018-05-11 | 中国科学院长春应用化学研究所 | The preparation method of 3-N, N- dimethylamino ethyl acrylate |
| CN105732410A (en) * | 2016-04-05 | 2016-07-06 | 苏州开元民生科技股份有限公司 | Synthesizing method of 3-N,N-dimethylamino ethyl acrylate |
| CN105732410B (en) * | 2016-04-05 | 2018-06-26 | 苏州开元民生科技股份有限公司 | A kind of 3-N, the synthetic method of TMSDMA N dimethylamine base ethyl acrylate |
| CN106008241A (en) * | 2016-06-13 | 2016-10-12 | 江西博晟医药科技有限公司 | Synthesis method for N,N-dimethylaminoethyl acrylate |
| CN109553543A (en) * | 2017-12-29 | 2019-04-02 | 浙江本立科技股份有限公司 | A kind of synthetic method of N, N- dimethylamino ethyl acrylate |
| CN109553543B (en) * | 2017-12-29 | 2021-11-16 | 浙江本立科技股份有限公司 | Synthesis method of N, N-dimethylamino ethyl acrylate |
| CN114369033A (en) * | 2022-01-17 | 2022-04-19 | 江苏飞宇医药科技股份有限公司 | Green preparation method of N, N-dimethylamino ethyl acrylate |
| CN114369033B (en) * | 2022-01-17 | 2023-01-31 | 江苏飞宇医药科技股份有限公司 | Green preparation method of N, N-dimethylamino ethyl acrylate |
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