CN105272896A - Preparation method of ((2S)-2-aziridinyl) benzhydrol - Google Patents
Preparation method of ((2S)-2-aziridinyl) benzhydrol Download PDFInfo
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- CN105272896A CN105272896A CN201510674826.0A CN201510674826A CN105272896A CN 105272896 A CN105272896 A CN 105272896A CN 201510674826 A CN201510674826 A CN 201510674826A CN 105272896 A CN105272896 A CN 105272896A
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- aziridino
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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
- C07D203/08—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
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Abstract
The invention discloses a preparation method of ((2S)-2-aziridinyl) benzhydrol. According to the preparation method, 2-triphenylmethylamine-methyl-3-hydroxypropanoate is taken as a raw material, the initial raw material reacts with triethylamine and methyl sulfonyl chloride, an intermediate product 2-((2S)-N-triphenylmethyl-2-aziridinyl) methyl acetate is obtained, the intermediate product reacts with a Grignard reagent, N-triphenylmethyl aziridinyl benzhydrol is produced and subjected to acidic hydrolysis, and a target product ((2S)-2-aziridinyl) benzhydrol is produced. The synthetic steps are simple and short, the synthetic method is simple, reaction conditions are easy to realize, the preparation method is suitable for industrial production, and synthesized ((2S)-2-aziridinyl) benzhydrol has good catalytic effect and is worthy of popularization.
Description
Technical field
The invention belongs to organic chemical synthesis technical field, be specifically related to the preparation method of one ((2S)-2-'-aziridino) diphenyl-carbinol.
Background technology
((2S)-2-'-aziridino) diphenyl-carbinol is a kind of catalyzer of Friedel-Crafts reaction.Be mainly used in the alkylated reaction and Diels-Alder reaction etc. between catalyzing N-methylpyrrole or N-skatole and α, beta-unsaturated aldehyde.The synthetic method of ((2S)-2-'-aziridino) diphenyl-carbinol is complicated at present, and cost is high, is not suitable for suitability for industrialized production.
Summary of the invention
For making up the deficiencies in the prior art, the invention provides a kind of excellent catalytic effect, cost is low, is applicable to the preparation method of industrialized ((2S)-2-'-aziridino) diphenyl-carbinol.
The present invention is achieved through the following technical solutions:
A kind of preparation method of ((2S)-2-'-aziridino) diphenyl-carbinol, its special character is: comprise the following steps:
(1) 2-((2S)-N-trityl-2-'-aziridino) preparation of methyl acetate: with 2-triphenyl methylamino-3-hydroxy methyl propionate for raw material, at room temperature be dissolved in THF, add triethylamine again, then slowly toward wherein dripping Methanesulfonyl chloride, after dropwising, mixture temperature is maintained room temperature and is about 30min, then slowly temperature is risen to 65-70 DEG C, after refluxing 35-50 hour at this temperature, be down to room temperature, through aftertreatment, obtain 2-((2S)-N-trityl-2-'-aziridino) methyl acetate;
(2) preparation of N-trityl '-aziridino diphenyl-carbinol: by 2-((2S)-N-trityl-2-'-aziridino) methyl acetate is dissolved in THF, and slowly join in Grignard reagent, react and add saturated (NH after 1.5 hours
4)
2sO
4termination reaction, namely obtains N-trityl '-aziridino diphenyl-carbinol through aftertreatment;
(3) preparation of ((2S)-2-'-aziridino) diphenyl-carbinol: N-trityl '-aziridino diphenyl-carbinol is dissolved in methyl alcohol-tetrahydrofuran (THF) mixed solvent, after being cooled to 0 DEG C, toward the sulfuric acid wherein dripping 6mL/L, after dropwising, at room temperature stir and spend the night, the white precipitate produced in mixture removes through extracted with diethyl ether, slowly drips 20%NaOH solution until produce white precipitate in aqueous phase, white depositions chloroform extraction, uses Na
2sO
4drying, and after precipitation, obtain target product ((2S)-2-'-aziridino) diphenyl-carbinol.
Synthetic route is as follows:
The preparation method of ((2S)-2-'-aziridino) of the present invention diphenyl-carbinol, the mol ratio of step (1) Raw 2-triphenyl methylamino-3-hydroxy methyl propionate and triethylamine is 1:2-3, be preferably 1:2.2, the mol ratio of raw material 2-triphenyl methylamino-3-hydroxy methyl propionate and Methanesulfonyl chloride is 1:1-1.5, is preferably 1:1.01.
The preparation method of ((2S)-2-'-aziridino) of the present invention diphenyl-carbinol, process in step (1) after mixture backflow cooling comprises: mixture is added ethyl acetate again except after desolventizing, respectively wash 3 times, organic extraction with 10% citric acid solution and aqueous soda solution, use anhydrous MgSO
4dry removing ethyl acetate equal solvent.
The preparation method of ((2S)-2-'-aziridino) of the present invention diphenyl-carbinol; described in step (2), Grignard reagent is PhMgBr; its preparation method is as follows: in ether, add magnesium chips; magnesium chips and 2-((2S)-N-trityl-2-'-aziridino) mol ratio of methyl acetate is 3-4:1; be preferably 3.4:1; again toward wherein slowly dripping the bromobenzene with the mole number such as magnesium chips; heating 1-2 hour; obtain Grignard reagent PhMgBr; more than operation is all carried out under Ar gas shield, and all glass waress all pass through strict drying.
Further, the preparation method of ((2S)-2-'-aziridino) of the present invention diphenyl-carbinol, Grignard reagent and 2-((2S described in step (2))-N-trityl-2-'-aziridino) mol ratio of methyl acetate is 3-4:1.
Further, the preparation method of ((2S)-2-'-aziridino) of the present invention diphenyl-carbinol, in step (3), in methyl alcohol-tetrahydrofuran (THF) mixed solvent, the mol ratio of methyl alcohol and tetrahydrofuran (THF) is 1:1.
The invention has the beneficial effects as follows: the present invention synthesizes ((2S)-2-'-aziridino) diphenyl-carbinols with 2-triphenyl methylamino-3-hydroxy methyl propionate for raw material passes through three steps, synthetic method is simple, reaction conditions easily realizes, be applicable to suitability for industrialized production, ((2S)-2-'-aziridino) the diphenyl-carbinol excellent catalytic effect synthesized, is worthy to be popularized.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.
Embodiment 1
(1) 2-((2S)-N-trityl-2-'-aziridino) preparation of methyl acetate: with 2-triphenyl methylamino-3-hydroxy methyl propionate for raw material, at room temperature be dissolved in THF, add triethylamine that is suitable and raw material 2 times of mole numbers again, then slowly toward wherein dripping the Methanesulfonyl chloride with the mole number such as raw material, after dropwising, mixture temperature is maintained room temperature and is about 30min, then slowly temperature is risen to 65 DEG C, after refluxing 35 hours at this temperature, be down to room temperature, mixture is added ethyl acetate again except after desolventizing, 3 times are respectively washed with 10% citric acid solution and aqueous soda solution, organic extraction, use anhydrous MgSO
4dry removing ethyl acetate equal solvent, obtains 2-((2S)-N-trityl-2-'-aziridino) methyl acetate,
(2) preparation of N-trityl '-aziridino diphenyl-carbinol: first prepare Grignard reagent PhMgBr, magnesium chips is added in ether, magnesium chips and 2-((2S)-N-trityl-2-'-aziridino) mol ratio of methyl acetate is 3:1, again toward wherein slowly dripping the bromobenzene with the mole number such as magnesium chips, heat 1 hour, obtain Grignard reagent PhMgBr, the operation preparing Grignard reagent is all carried out under Ar gas shield, and all glass waress all pass through strict drying; By 2-((2S)-N-trityl-2-'-aziridino) methyl acetate is dissolved in THF, slowly join in Grignard reagent, Grignard reagent and 2-((2S)-N-trityl-2-'-aziridino) mol ratio of methyl acetate is 3:1, reacts and adds saturated (NH after 1.5 hours
4)
2sO
4termination reaction, namely obtains N-trityl '-aziridino diphenyl-carbinol through aftertreatment;
(3) preparation of ((2S)-2-'-aziridino) diphenyl-carbinol: N-trityl '-aziridino diphenyl-carbinol is dissolved in methyl alcohol-tetrahydrofuran (THF) mixed solvent, in methyl alcohol-tetrahydrofuran (THF) mixed solvent, the mol ratio of methyl alcohol and tetrahydrofuran (THF) is 1:1, after being cooled to 0 DEG C, toward the sulfuric acid wherein dripping 6mL/L, after dropwising, at room temperature stir and spend the night, the white precipitate produced in mixture removes through extracted with diethyl ether, 20%NaOH solution is slowly dripped until produce white precipitate in aqueous phase, white depositions chloroform extraction, uses Na
2sO
4drying, and after precipitation, obtain target product ((2S)-2-'-aziridino) diphenyl-carbinol.
Embodiment 2
(1) 2-((2S)-N-trityl-2-'-aziridino) preparation of methyl acetate: with 2-triphenyl methylamino-3-hydroxy methyl propionate for raw material, at room temperature be dissolved in THF, add triethylamine that is suitable and raw material 2.2 times of mole numbers again, then slowly toward wherein dripping quite and the Methanesulfonyl chloride of raw material 1.01 times of mole numbers, after dropwising, mixture temperature is maintained room temperature and is about 30min, then slowly temperature is risen to 66 DEG C, after refluxing 40 hours at this temperature, be down to room temperature, mixture is added ethyl acetate again except after desolventizing, 3 times are respectively washed with 10% citric acid solution and aqueous soda solution, organic extraction, use anhydrous MgSO
4dry removing ethyl acetate equal solvent, obtains 2-((2S)-N-trityl-2-'-aziridino) methyl acetate,
(2) preparation of N-trityl '-aziridino diphenyl-carbinol: first prepare Grignard reagent PhMgBr, magnesium chips is added in ether, magnesium chips and 2-((2S)-N-trityl-2-'-aziridino) mol ratio of methyl acetate is 3.4:1, again toward wherein slowly dripping the bromobenzene with the mole number such as magnesium chips, heat 1 hour, obtain Grignard reagent PhMgBr, the operation preparing Grignard reagent is all carried out under Ar gas shield, and all glass waress all pass through strict drying; By 2-((2S)-N-trityl-2-'-aziridino) methyl acetate is dissolved in THF, slowly join in Grignard reagent, Grignard reagent and 2-((2S)-N-trityl-2-'-aziridino) mol ratio of methyl acetate is 3.5:1, reacts and adds saturated (NH after 1.5 hours
4)
2sO
4termination reaction, namely obtains N-trityl '-aziridino diphenyl-carbinol through aftertreatment;
(3) preparation of ((2S)-2-'-aziridino) diphenyl-carbinol: N-trityl '-aziridino diphenyl-carbinol is dissolved in methyl alcohol-tetrahydrofuran (THF) mixed solvent, in methyl alcohol-tetrahydrofuran (THF) mixed solvent, the mol ratio of methyl alcohol and tetrahydrofuran (THF) is 1:1, after being cooled to 0 DEG C, toward the sulfuric acid wherein dripping 6mL/L, after dropwising, at room temperature stir and spend the night, the white precipitate produced in mixture removes through extracted with diethyl ether, 20%NaOH solution is slowly dripped until produce white precipitate in aqueous phase, white depositions chloroform extraction, uses Na
2sO
4drying, and after precipitation, obtain target product ((2S)-2-'-aziridino) diphenyl-carbinol.
Embodiment 3
(1) 2-((2S)-N-trityl-2-'-aziridino) preparation of methyl acetate: with 2-triphenyl methylamino-3-hydroxy methyl propionate for raw material, at room temperature be dissolved in THF, add the triethylamine being equivalent to raw material 3 times of mole numbers again, then slowly toward wherein dripping the Methanesulfonyl chloride being equivalent to raw material 1.5 times of mole numbers, after dropwising, mixture temperature is maintained room temperature and is about 30min, then slowly temperature is risen to 70 DEG C, after refluxing 50 hours at this temperature, be down to room temperature, mixture is added ethyl acetate again except after desolventizing, 3 times are respectively washed with 10% citric acid solution and aqueous soda solution, organic extraction, use anhydrous MgSO
4dry removing ethyl acetate equal solvent, obtains 2-((2S)-N-trityl-2-'-aziridino) methyl acetate,
(2) preparation of N-trityl '-aziridino diphenyl-carbinol: first prepare Grignard reagent PhMgBr, magnesium chips is added in ether, magnesium chips and 2-((2S)-N-trityl-2-'-aziridino) mol ratio of methyl acetate is 4:1, again toward wherein slowly dripping the bromobenzene with the mole number such as magnesium chips, heat 1 hour, obtain Grignard reagent PhMgBr, the operation preparing Grignard reagent is all carried out under Ar gas shield, and all glass waress all pass through strict drying; By 2-((2S)-N-trityl-2-'-aziridino) methyl acetate is dissolved in THF, slowly join in Grignard reagent, Grignard reagent and 2-((2S)-N-trityl-2-'-aziridino) mol ratio of methyl acetate is 4:1, reacts and adds saturated (NH after 1.5 hours
4)
2sO
4termination reaction, namely obtains N-trityl '-aziridino diphenyl-carbinol through aftertreatment;
(3) preparation of ((2S)-2-'-aziridino) diphenyl-carbinol: N-trityl '-aziridino diphenyl-carbinol is dissolved in methyl alcohol-tetrahydrofuran (THF) mixed solvent, in methyl alcohol-tetrahydrofuran (THF) mixed solvent, the mol ratio of methyl alcohol and tetrahydrofuran (THF) is 1:1, after being cooled to 0 DEG C, toward the sulfuric acid wherein dripping 6mL/L, after dropwising, at room temperature stir and spend the night, the white precipitate produced in mixture removes through extracted with diethyl ether, 20%NaOH solution is slowly dripped until produce white precipitate in aqueous phase, white depositions chloroform extraction, uses Na
2sO
4drying, and after precipitation, obtain target product ((2S)-2-'-aziridino) diphenyl-carbinol.
Claims (9)
1. the preparation method of ((2S)-2-'-aziridino) diphenyl-carbinol, is characterized in that: comprise the following steps:
(1) 2-((2S)-N-trityl-2-'-aziridino) preparation of methyl acetate: with 2-triphenyl methylamino-3-hydroxy methyl propionate for raw material, at room temperature be dissolved in THF, add triethylamine again, then slowly toward wherein dripping Methanesulfonyl chloride, after dropwising, mixture temperature is maintained room temperature and is about 30min, then slowly temperature is risen to 65-70 DEG C, after refluxing 35-50 hour at this temperature, be down to room temperature, through aftertreatment, obtain 2-((2S)-N-trityl-2-'-aziridino) methyl acetate;
(2) preparation of N-trityl '-aziridino diphenyl-carbinol: by 2-((2S)-N-trityl-2-'-aziridino) methyl acetate is dissolved in THF, and slowly join in Grignard reagent, react and add saturated (NH after 1.5 hours
4) 2SO
4termination reaction, namely obtains N-trityl '-aziridino diphenyl-carbinol through aftertreatment;
(3) preparation of ((2S)-2-'-aziridino) diphenyl-carbinol: N-trityl '-aziridino diphenyl-carbinol is dissolved in methyl alcohol-tetrahydrofuran (THF) mixed solvent, after being cooled to 0 DEG C, toward the sulfuric acid wherein dripping 6mL/L, after dropwising, at room temperature stir and spend the night, the white precipitate produced in mixture removes through extracted with diethyl ether, 20%NaOH solution is slowly dripped until produce white precipitate in aqueous phase, white depositions chloroform extraction, dry with Na2SO4, and after precipitation, obtain target product ((2S)-2-'-aziridino) diphenyl-carbinol.
2. the preparation method of ((2S)-2-'-aziridino) diphenyl-carbinol according to claim 1, it is characterized in that: the mol ratio of step (1) Raw 2-triphenyl methylamino-3-hydroxy methyl propionate and triethylamine is 1:2-3, the mol ratio of raw material 2-triphenyl methylamino-3-hydroxy methyl propionate and Methanesulfonyl chloride is 1:1-1.5.
3. the preparation method of ((2S)-2-'-aziridino) diphenyl-carbinol according to claim 1 and 2, it is characterized in that: the process in step (1) after mixture backflow cooling comprises: mixture is added ethyl acetate again except after desolventizing, 3 times are respectively washed with 10% citric acid solution and aqueous soda solution, organic extraction, uses anhydrous MgSO
4dry removing ethyl acetate equal solvent.
4. the preparation method of ((2S)-2-'-aziridino) diphenyl-carbinol according to claim 1, it is characterized in that: described in step (2), Grignard reagent is PhMgBr, its preparation method is as follows: in ether, add magnesium chips, magnesium chips and 2-((2S)-N-trityl-2-'-aziridino) mol ratio of methyl acetate is 3-4:1, again toward wherein slowly dripping the bromobenzene with the mole number such as magnesium chips, heating 1-2 hour, obtains Grignard reagent PhMgBr.
5. the preparation method of ((2S)-2-'-aziridino) diphenyl-carbinol according to claim 4, is characterized in that: the operation preparing Grignard reagent is all carried out under Ar gas shield, and all glass waress all pass through strict drying.
6. the preparation method of ((the 2S)-2-'-aziridino) diphenyl-carbinol according to claim 1,4 or 5, is characterized in that: described Grignard reagent and 2-((2S)-N-trityl-2-'-aziridino) mol ratio of methyl acetate is 3-4:1.
7. the preparation method of ((2S)-2-'-aziridino) diphenyl-carbinol according to claim 1, is characterized in that: in step (3), in methyl alcohol-tetrahydrofuran (THF) mixed solvent, the mol ratio of methyl alcohol and tetrahydrofuran (THF) is 1:1.
8. the preparation method of ((2S)-2-'-aziridino) diphenyl-carbinol according to claim 1 and 2, it is characterized in that: the mol ratio of step (1) Raw 2-triphenyl methylamino-3-hydroxy methyl propionate and triethylamine is 1:2.2, the mol ratio of raw material 2-triphenyl methylamino-3-hydroxy methyl propionate and Methanesulfonyl chloride is 1:1.01.
9. the preparation method of ((the 2S)-2-'-aziridino) diphenyl-carbinol according to claim 1 or 4, is characterized in that: magnesium chips and 2-((2S in step (2))-N-trityl-2-'-aziridino) mol ratio of methyl acetate is 3.4:1.
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2015
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