CN104447472A - Synthesis method of D)-2-benzyl-N,N-dimethyl-aziridinyl-1-sulfonamide - Google Patents
Synthesis method of D)-2-benzyl-N,N-dimethyl-aziridinyl-1-sulfonamide Download PDFInfo
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- CN104447472A CN104447472A CN201410618310.XA CN201410618310A CN104447472A CN 104447472 A CN104447472 A CN 104447472A CN 201410618310 A CN201410618310 A CN 201410618310A CN 104447472 A CN104447472 A CN 104447472A
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- benzyl
- dimethyl
- dimethyl ethylenimine
- sulphonamide
- phenylalaninol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
- C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D203/22—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
- C07D203/24—Sulfur atoms
Abstract
The invention relates to a synthesis method of D)-2-benzyl-N,N-dimethyl-aziridinyl-1-sulfonamide. The synthesis method comprises the following steps: (a) reducing D-phenylalanine to D-phenylalaninol; (b) esterifying and cyclizing D-phenylalaninol to form D)-2-benzyl-N,N-dimethyl-aziridine; and (c) enabling D)-2-benzyl-N,N-dimethyl-aziridine to react with dimethylamino sulfonyl chloride to generate D)-2-benzyl-N,N-dimethyl-aziridinyl-1-sulfonamide. Crystals are generated as long as D)-2-benzyl-N,N-dimethyl-aziridine is dropwise added into dimethylamino sulfonyl chloride and reacts with the dimethylamino sulfonyl chloride, and the crystals do not participate in the reaction anymore, thus no other impurities are generated, the forward reaction can be facilitated, the industrial production yield can be increased, and the production cycle can be shortened.
Description
Technical field
The present invention relates to a kind of synthesis D newly)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide method.
Background technology
D) its structure of-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide is:
,
Former industrial production adopts methylene dichloride as solvent, reacts 24 ~ 36 hours once at≤0 DEG C, takes a fancy to control and instead should cross filtering amine amine salt by former material≤0.2%, 30 DEG C of de-dry dichloromethanes of decompression, add ethyl acetate and carry out crystallization, obtain crude product, pass through washing, the sterling obtaining 99% washed by ethanol, product is dissolved in solution simultaneously, is unfavorable for forward reaction, and industrial production yield is low and the cycle is long, and the impurity produced in reaction is higher, be unfavorable for improving product purity.
Summary of the invention
The present invention relates to a kind of synthesis D newly)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide method, the content purity of its not only product is high, and improves industrial yield, shorten industrial time half the time, and the problem such as environmental protection.
The technical solution used in the present invention is: a kind of D) synthetic method of-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide, comprise following several step
A. D-phenylalanine becomes D-phenylalaninol through reduction:
D-phenylalanine 100 ± 5g, dioxane 800-850g, sodium borohydride 74 ± 5g are added zinc chloride 45 ± 5g after mixing, be warming up to 70 DEG C, treat that a large amount of bubble is released, be cooled to 30 DEG C, drip the aqueous sodium hydroxide solution cancellation of 30%, dropwise to releasing without gas, be warming up to 70 DEG C to stir 1 hour, cooling, add ethyl acetate 500-600g stratification, with 200-300g water washing organic layer, the de-dry solvent of decompression, adds the oven dry of 300-400g acetic acid ethyl dissolution cooling crystallization and obtains D-phenylalaninol; Reduction-type is as follows:
;
B.D-phenylalaninol forms (D)-2-benzyl-N, N-dimethyl ethylenimine through over-churning, cyclization:
By D-phenylalaninol 61 ± 5g, toluene 480-600g, vitriol oil 20-40g mixing temperature rising reflux, control in sampling, react qualified after, with 8% aqueous sodium hydroxide solution washing, add the sodium hydroxide solution of 40% again, continue temperature rising reflux, control in sampling, react qualified after, stratification, get organic layer first to reduce pressure toluene, upper rectifying tower rectifying goes out (D)-2-benzyl-N, N-dimethyl ethylenimine; Esterification, cyclization formula are as follows:
;
C. D)-2-benzyl-N, N-dimethyl ethylenimine and dimethylaminosulfonyl chloride react and generate D)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide:
Acid binding agent triethylamine 27.35 ± 2g, dimethylin SULPHURYL CHLORIDE 34.2 ± 2g are mixed, add methyl-tert fourth man ether 60-80g dissolved product, drip D adding at 60-80g normal heptane≤0 DEG C)-2-benzyl-N, N-dimethyl ethylenimine 30 ± 2g, in 12-36 hour control, sample qualified after, filter, obtain crude product, through water making beating, ethanol making beating, obtain D)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide, reaction formula is as follows:
。
Further, step a adopts EA extraction, and reducing pressure 60 DEG C to concentrate obtains crude product, obtains D-phenylalaninol, content 98% through ethyl acetate M:M=1:1 recrystallization
Further, in step B, the vitriol oil carries out high temperature of 120 DEG C esterification, be cooled to normal temperature after reaction terminates, first wash to water layer by the aqueous onium hydroxide solutions of 8%, then the sodium hydroxide solution adding 40% be warming up in 120 DEG C of cyclizations, react qualified after, stratification, product introduction toluene layer, toluene is deviate from decompression, eventually pass extracting rectifying and obtain (D)-2-benzyl-N, N-dimethyl ethylenimine.
Further, D prepared by step B)-2-benzyl-N, N-dimethyl ethylenimine nitrogen cryogenic collector, preservation.
Again further, methyl tertiary butyl ether in step C: the proportioning polarity of the solvent of normal heptane=1:1 or other similar ether and alkane is between 1-1.5.
Compared with prior art, advantage of the present invention is: adopt the proportioning polarity of solvent between 1-1.5, its effect is the insoluble product of dissolved impurity, and in the process of reaction, limit coronite separates out product, easily impels speed of response to accelerate, the reaction times is decreased than technique originally, reduce energy consumption, reduce reactions steps simultaneously, reduce operation difficulty degree, last and solvent is applied mechanically, and reaches suitability for industrialized production standard; D is dripped in dimethylaminosulfonyl chloride)-2-benzyl-N, N-dimethyl ethylenimine, product has reacted and has been crystallization and goes out, and in participation reaction, does not produce other impurity, is beneficial to forward reaction, improves industrial production yield low long with the shortening production cycle.
Specific embodiments
Be described further below in conjunction with enforcement, but become any restriction of the present invention not.
Embodiment one
A. D-phenylalanine becomes D-phenylalaninol through reduction:
D-phenylalanine 100 ± 5g, dioxane 800-850g, sodium borohydride 74 ± 5g are added zinc chloride 45 ± 5g after mixing, be warming up to 70 DEG C, treat that a large amount of bubble is released, be cooled to 30 DEG C, drip the aqueous sodium hydroxide solution cancellation of 30%, dropwise to releasing without gas, be warming up to 70 DEG C to stir 1 hour, cooling, adds ethyl acetate 500g stratification, with 200g water washing organic layer, EA extracts, reduce pressure 60 DEG C to concentrate and obtain crude product, add the oven dry of ethyl acetate M:M=1:1 dissolving-recrystallization cooling crystallization and obtain D-phenylalaninol, content 98%;
B.D-phenylalaninol forms (D)-2-benzyl-N, N-dimethyl ethylenimine through over-churning, cyclization:
By D-phenylalaninol 61 ± 5g, toluene 480g, vitriol oil 20g mixing temperature rising reflux, high temperature of 120 DEG C esterification, normal temperature is cooled to after reaction terminates, with 8% aqueous sodium hydroxide solution washing washing to water layer, then the sodium hydroxide solution adding 40% be warming up in 120 DEG C of cyclizations, stratification, product introduction toluene layer, toluene is deviate from decompression, upper rectifying tower rectifying goes out (D)-2-benzyl-N, N-dimethyl ethylenimine; D)-2-benzyl-N, N-dimethyl ethylenimine nitrogen cryogenic collector, preservation;
C. D)-2-benzyl-N, N-dimethyl ethylenimine and dimethylaminosulfonyl chloride react and generate D)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide:
By acid binding agent triethylamine 27.35 ± 2g, dimethylin SULPHURYL CHLORIDE 34.2 ± 2g mixes, add methyl-tert fourth man ether 60g dissolved product, adding 60g normal heptane, wherein methyl tertiary butyl ether: normal heptane=1:1 or replace with other similar ethers and alkane the proportioning polarity of solvent between 1-1.5, D is dripped at≤0 DEG C)-2-benzyl-N, N-dimethyl ethylenimine 30 ± 2g, control in 12 hours, sample qualified after, filter, obtain crude product, pulling an oar through water, ethanol is pulled an oar, obtain D)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide, content 98.6%, yield 56%.
Embodiment two
C. D)-2-benzyl-N, N-dimethyl ethylenimine and dimethylaminosulfonyl chloride react and generate D)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide:
By acid binding agent triethylamine 27.35 ± 2g, dimethylin SULPHURYL CHLORIDE 34.2 ± 2g mixes, add methyl-tert fourth man ether 70g dissolved product, adding 70g normal heptane, wherein methyl tertiary butyl ether: normal heptane=1:1 or replace with other similar ethers and alkane the proportioning polarity of solvent between 1-1.5, D is dripped at≤0 DEG C)-2-benzyl-N, N-dimethyl ethylenimine 30 ± 2g, control in 18 hours, sample qualified after, filter, obtain crude product, pulling an oar through water, ethanol is pulled an oar, obtain D)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide, content 99.5%, yield 58%.
Embodiment three
C. D)-2-benzyl-N, N-dimethyl ethylenimine and dimethylaminosulfonyl chloride react and generate D)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide:
By acid binding agent triethylamine 27.35 ± 2g, dimethylin SULPHURYL CHLORIDE 34.2 ± 2g mixes, add methyl-tert fourth man ether 80g dissolved product, adding 80g normal heptane, wherein methyl tertiary butyl ether: normal heptane=1:1 or replace with other similar ethers and alkane the proportioning polarity of solvent between 1-1.5, D is dripped at≤0 DEG C)-2-benzyl-N, N-dimethyl ethylenimine 30 ± 2g, control in 24 hours, sample qualified after, filter, obtain crude product, pulling an oar through water, ethanol is pulled an oar, obtain D)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide, content 99.4%, yield 64%.
Embodiment four
C. D)-2-benzyl-N, N-dimethyl ethylenimine and dimethylaminosulfonyl chloride react and generate D)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide:
By acid binding agent triethylamine 27.35 ± 2g, dimethylin SULPHURYL CHLORIDE 34.2 ± 2g mixes, add methyl-tert fourth man ether 80g dissolved product, adding 80g normal heptane, wherein methyl tertiary butyl ether: normal heptane=1:1 or replace with other similar ethers and alkane the proportioning polarity of solvent between 1-1.5, D is dripped at≤0 DEG C)-2-benzyl-N, N-dimethyl ethylenimine 30 ± 2g, control in 36 hours, sample qualified after, filter, obtain crude product, pulling an oar through water, ethanol is pulled an oar, obtain D)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide, content 98.7%, yield 65%
Above-mentionedly be embodied as preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; the change done under he any single does not deviate from spirit of the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (5)
1. a D)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide synthetic method, it is characterized in that, comprise following several step
A. D-phenylalanine becomes D-phenylalaninol through reduction:
D-phenylalanine 100 ± 5g, dioxane 800-850g, sodium borohydride 74 ± 5g are added zinc chloride 45 ± 5g after mixing, be warming up to 70 DEG C, treat that a large amount of bubble is released, be cooled to 30 DEG C, drip the aqueous sodium hydroxide solution cancellation of 30%, dropwise to releasing without gas, be warming up to 70 DEG C to stir 1 hour, cooling, add ethyl acetate 500-600g stratification, with 200-300g water washing organic layer, the de-dry solvent of decompression, adds the oven dry of 300-400g acetic acid ethyl dissolution cooling crystallization and obtains D-phenylalaninol; Reduction-type is as follows:
;
B.D-phenylalaninol forms (D)-2-benzyl-N, N-dimethyl ethylenimine through over-churning, cyclization:
By D-phenylalaninol 61 ± 5g, toluene 480-600g, vitriol oil 20-40g mixing temperature rising reflux, control in sampling, react qualified after, with 8% aqueous sodium hydroxide solution washing, add the sodium hydroxide solution of 40% again, continue temperature rising reflux, control in sampling, react qualified after, stratification, get organic layer first to reduce pressure toluene, upper rectifying tower rectifying goes out (D)-2-benzyl-N, N-dimethyl ethylenimine; Esterification, cyclization formula are as follows:
;
C. D)-2-benzyl-N, N-dimethyl ethylenimine and dimethylaminosulfonyl chloride react and generate D)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide:
Acid binding agent triethylamine 27.35 ± 2g, dimethylin SULPHURYL CHLORIDE 34.2 ± 2g are mixed, add methyl-tert fourth man ether 60-80g dissolved product, drip D adding at 60-80g normal heptane ，≤0 DEG C)-2-benzyl-N, N-dimethyl ethylenimine 30 ± 2g, in 12-36 hour control, sample qualified after, filter, obtain crude product, through water making beating, ethanol making beating, obtain D)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide; Reaction formula is as follows:
。
2. according to the D described in claim 1)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide synthetic method, is characterized in that: step a adopts EA extraction, and reducing pressure 60 DEG C to concentrate obtains crude product, D-phenylalaninol is obtained, content 98% through ethyl acetate M:M=1:1 recrystallization.
3. according to the D described in claim 1)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide synthetic method, it is characterized in that: in step B, the vitriol oil carries out high temperature of 120 DEG C esterification, normal temperature is cooled to after reaction terminates, first wash to water layer by the aqueous onium hydroxide solutions of 8%, 120 DEG C of cyclizations during the sodium hydroxide solution adding 40% is again warming up to, react qualified after, stratification, product introduction toluene layer, toluene is deviate from decompression, eventually passes extracting rectifying and obtains (D)-2-benzyl-N, N-dimethyl ethylenimine.
4. according to the D described in claim 1 or 3)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide synthetic method, it is characterized in that: D prepared by step B)-2-benzyl-N, N-dimethyl ethylenimine nitrogen cryogenic collector, preservation.
5. according to the D described in claim 1)-2-benzyl-N, N-dimethyl ethylenimine base-1-sulphonamide synthetic method, is characterized in that: methyl tertiary butyl ether in step C: the proportioning polarity of the solvent of normal heptane=1:1 or other similar ether and alkane is between 1-1.5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655466A (en) * | 2019-01-16 | 2020-01-07 | 安徽贝克联合制药有限公司 | Preparation method of benzphetamine hydrochloride |
| CN110668952A (en) * | 2019-01-16 | 2020-01-10 | 安徽贝克联合制药有限公司 | Preparation method of benzphetamine hydrochloride |
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| US20030153771A1 (en) * | 2001-09-27 | 2003-08-14 | Kolb Hartmuth C. | Large scale synthesis of optically pure aziridines |
| FR2881425A1 (en) * | 2005-02-01 | 2006-08-04 | Isochem Sa | Process for preparing amino-alcohols or alcohols from amino-acids, carboxylic acids or their esters, comprises reduction of carboxylic acid or ester groups to give alcohol group in the presence of a reducing agent |
| WO2012045007A1 (en) * | 2010-10-01 | 2012-04-05 | Gilead Sciences, Inc. | Method of preparation of (4 - {4 -acetylamino- 2 - [3- ( 2 - isopropyl - thiazol - 4 - ylmethyl) - 3 -methyl - ureido] - butyryl amino} -1 -benzyl- 5 -phenyl- pentyl) -carbamic acid thiazol - 5 - ylmethyl ester |
| CN102438982A (en) * | 2009-04-03 | 2012-05-02 | 吉里德科学公司 | Methods and intermediates for preparing pharmaceutical agents |
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| US20030153771A1 (en) * | 2001-09-27 | 2003-08-14 | Kolb Hartmuth C. | Large scale synthesis of optically pure aziridines |
| FR2881425A1 (en) * | 2005-02-01 | 2006-08-04 | Isochem Sa | Process for preparing amino-alcohols or alcohols from amino-acids, carboxylic acids or their esters, comprises reduction of carboxylic acid or ester groups to give alcohol group in the presence of a reducing agent |
| CN102438982A (en) * | 2009-04-03 | 2012-05-02 | 吉里德科学公司 | Methods and intermediates for preparing pharmaceutical agents |
| WO2012045007A1 (en) * | 2010-10-01 | 2012-04-05 | Gilead Sciences, Inc. | Method of preparation of (4 - {4 -acetylamino- 2 - [3- ( 2 - isopropyl - thiazol - 4 - ylmethyl) - 3 -methyl - ureido] - butyryl amino} -1 -benzyl- 5 -phenyl- pentyl) -carbamic acid thiazol - 5 - ylmethyl ester |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655466A (en) * | 2019-01-16 | 2020-01-07 | 安徽贝克联合制药有限公司 | Preparation method of benzphetamine hydrochloride |
| CN110668952A (en) * | 2019-01-16 | 2020-01-10 | 安徽贝克联合制药有限公司 | Preparation method of benzphetamine hydrochloride |
| CN110655466B (en) * | 2019-01-16 | 2023-02-24 | 安徽贝克制药股份有限公司 | Preparation method of benzphetamine hydrochloride |
| CN110668952B (en) * | 2019-01-16 | 2023-06-27 | 安徽贝克制药股份有限公司 | Preparation method of benzphetamine hydrochloride |
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