CN101735118B - Process method for synthesizing tertiary butyl sulfinyl amine by using silicohydride as protective reagent - Google Patents
Process method for synthesizing tertiary butyl sulfinyl amine by using silicohydride as protective reagent Download PDFInfo
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- CN101735118B CN101735118B CN2009103128504A CN200910312850A CN101735118B CN 101735118 B CN101735118 B CN 101735118B CN 2009103128504 A CN2009103128504 A CN 2009103128504A CN 200910312850 A CN200910312850 A CN 200910312850A CN 101735118 B CN101735118 B CN 101735118B
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Abstract
The invention relates to synthesis of organic compounds, in particular to a process method for synthesizing tertiary butyl sulfinyl amine by using silicohydride as a protective reagent, which comprises the following steps: (a) synthesis of N-tertiary butyl dimethyl silicone-lithium amide; (b) synthesis of (S or R)-N-tertiary butyl dimethyl silicone-tertiary butyl sulfinyl amine; (c) and synthesis of (S or R)-tertiary butyl sulfinyl amine: adding the (S or R)-N-tertiary butyl dimethyl silicone-tertiary butyl sulfinyl amine in step (b) into a dilute acid water solution, stirring for 5-8 hours at room temperature, separating and purifying to obtain the tertiary butyl sulfinyl amine. Compared with similar process methods, the process method for synthesizing tertiary butyl sulfinyl amine by using silicohydride as the protective reagent has the distinguishing characteristics that the reaction conditions of the invention are mild; the invention avoids the ultralow temperature condition of -78 DEG C, is easy to operate, has stable technical stability and is environment-friendly; and the product has the advantages of high yield and good purity, and can easily realize the amplification of the industrial production.
Description
One, technical field
The present invention relates to a kind of compound method of organic cpds, particularly the process method of synthesizing tertiary butyl sulfinyl amine.
Two, background technology:
The Chiral Amine compounds has important use to be worth in medicine and natural product are synthetic; Therefore; Received the attention of many medicine scholars and synthetic chemistry man in recent years, and tertiary butyl sulfinyl amine is a kind of novel chipal compounds of Ellman 1997 design synthetic, it in numerous asymmetric catalysis synthesis as one type of chiral auxiliary reagent; Show good inducing action [reference: Ellman, J.A.; Owens, T.D.:Tang, T.P.Acc.Chem.Res., 2002,35,984.] realized preferably synthesizing of high reactivity Chiral Amine compounds.
Existing document Organic Syntheses, 2005,82,157. synthetic routes are following:
At-78～-72 ℃, ammonia and lithium equivalence ratio are under 29: 1 the condition, to process Lithamide; With a large amount of liquefied ammonia is solvent; Splash into the tetrahydrofuran solution of the 0.4 normal tertiary butyl-sulfinic acid sulfo-tert-butyl ester to it, insulated and stirred reaction 1 hour slowly rises to the liquefied ammonia in the room temperature volatilization system subsequently.Entire reaction course will be carried out under argon shield.After the liquefied ammonia volatilization finishes, with ice-water bath system temperature is reduced to about 0 ℃, after the adding 0.012 normal trash ice cancellation reaction, conventional aftertreatment obtains tertiary butyl sulfinyl amine bullion, through obtaining product, yield 75% after the normal hexane making beating in system.This synthetic route needs the deep cooling low-temp reaction, and has used a large amount of liquefied ammonia to help dissolve Lithamide as solvent.These disadvantageous reaction characteristicses have increased tertiary butyl sulfinyl amine industrial equipment and running cost, and the use of a large amount of liquefied ammonia has brought pollution to environment.Therefore seek and a kind ofly can avoid deep cooling low temperature, environment amenable, the synthesis technique that is fit to suitability for industrialized production is very important.
Three, summary of the invention
The objective of the invention is to overcome above-mentioned not enough problem, a kind of process method of using silane for protection reagent synthesizing tertiary butyl sulfinyl amine is provided, technology stability is good, and is easy and simple to handle, and productive rate is high, and is environmentally friendly, is easy to suitability for industrialized production.
The present invention for realizing the technical scheme that above-mentioned purpose adopted is: a kind of process method of using silane for protection reagent synthesizing tertiary butyl sulfinyl amine, synthetic route as shown in the formula:
Concrete steps are:
A) N-tertiary butyl dimethyl-silicon Lithamide is synthetic: with the TERT-BUTYL DIMETHYL CHLORO SILANE is starting raw material; With the Skellysolve A is solvent, under-40 ℃～-15 ℃ conditions, with the liquefied ammonia effect, generates tertiary butyl dimethylamino base silane; After separation and purification; In tetrahydrofuran solvent, add n-Butyl Lithium under controlled temperature-40 ℃～-15 ℃ of conditions, synthetic N-tertiary butyl dimethyl-silicon-Lithamide;
B) (S or R)-N-tertiary butyl dimethyl-silicon-tertiary butyl sulfinyl amine is synthetic: under-40 ℃～-15 ℃ temperature condition, (S or R)-tertiary butyl-sulfinic acid sulfo-tert-butyl ester is joined in the tetrahydrofuran solution of the N-tertiary butyl dimethyl-silicon-Lithamide that a) goes on foot; Add the insulated and stirred reaction 0.5～1 hour that finishes; Add the excessive lithium reagent of ammonium chloride cancellation then, separation and purification obtains (S or R)-N-tertiary butyl dimethyl-silicon-tertiary butyl sulfinyl amine;
C) synthesizing of (S or R)-tertiary butyl sulfinyl amine: with b) (S or the R)-N-tertiary butyl dimethyl-silicon-tertiary butyl sulfinyl amine in step joins in the dilute acid solution, stirs under the room temperature 5～8 hours, obtains tertiary butyl sulfinyl amine after the separation and purification.
Tertiary butyl dimethylamino base silane and n-Butyl Lithium in molar ratio 1.2～1.4: 1 in said a) N-tertiary butyl dimethyl-silicon-Lithamide synthetic.
Said b) the synthetic middle N-tertiary butyl dimethyl-silicon-Lithamide and (S or R)-tertiary butyl-sulfinic acid sulfo-tert-butyl ester mol ratio 1: 0.3～0.5 of (S or R)-N-tertiary butyl dimethyl-silicon-tertiary butyl sulfinyl amine.
Said c) used diluted acid is a hydrochloric acid in (S or R)-tertiary butyl sulfinyl amine synthetic, and pH value is 3-5.
Said entire reaction is reacted under protections such as rare gas element such as argon gas, nitrogen.
The present invention uses silane to compare with similar process method for the process method of protection reagent synthesizing tertiary butyl sulfinyl amine to have outstanding feature: reaction conditions of the present invention is gentle; Avoid very low temperature-78 ℃ condition, easy handling, and technology stability is good; Environmentally friendly; The product yield that makes is high, and purity is good, is easy to realize the suitability for industrialized production amplification.
Four, embodiment:
Through embodiment the present invention is detailed below; But the present invention is not limited to following embodiment.
Embodiment 1:
A kind of process method of using silane for protection reagent synthesizing tertiary butyl sulfinyl amine, synthetic route as shown in the formula:
Concrete steps are:
A) N-tertiary butyl dimethyl-silicon-Lithamide is synthetic: under the argon shield, in the 500mL reaction flask that the liquefied ammonia access tube is housed, add the 75.6g TERT-BUTYL DIMETHYL CHLORO SILANE, the 150.0g Skellysolve A; System temperature is reduced to-40 ℃, feed liquefied ammonia, it is muddy that clarifying reaction liquid becomes immediately, stops logical ammonia behind the 0.5h; Remove cryostat, system is slowly heated up, system temperature filters to room temperature; Filtrating concentrates, and promptly gets tertiary butyl dimethylamino base silane 59.8g, yield: 91%; Under the argon shield; With 59.8g tertiary butyl dimethylamino base silane, the 250mL THF is packed in the 1L reaction flask that has the constant voltage feed hopper, is cooled to-40 ℃; Drip 2.5M n-Butyl Lithium 153mL; After the insulation reaction 1.0 hours, obtain the tetrahydrofuran solution of N-tertiary butyl dimethyl-silicon Lithamide, directly be used for next step under the argon shield and synthesize;
B) (S or R)-N-tertiary butyl dimethyl-silicon tertiary butyl sulfinyl amine is synthetic: take by weighing 35.4g (S or R)-tertiary butyl-sulfinic acid sulfo-tert-butyl ester; 70.8g THF; Be configured to the tetrahydrofuran solution of (S or R)-tertiary butyl-sulfinic acid sulfo-tert-butyl ester; Pack in the 250mL constant pressure funnel, under-40 ℃ of argon shields, obtain in the tetrahydrofuran solution of N-tertiary butyl dimethyl-silicon Lithamide in slowly splashing into it a); Drip complete insulated and stirred 0.5 hour, and added the excessive lithium reagent of 17.5g ammonium chloride cancellation.Stirred 0.5 hour, system slowly is warming up to room temperature, filters, and filtrating concentrates, and gets 40.3g (S or R)-N-tertiary butyl dimethyl-silicon-tertiary butyl sulfinyl amine, yield 94%;
C) (S or R)-tertiary butyl sulfinyl amine is synthetic: with b) in gained (S or R)-N-tertiary butyl dimethyl-silicon-tertiary butyl sulfinyl amine join in the aqueous hydrochloric acid of 100mLPH value 5, stir 8h under the room temperature, with 300mL ethyl acetate extraction 3 times; Merge above-mentioned organic layer; Add anhydrous magnesium sulfate drying, filter, concentrate and obtain (S or R)-tertiary butyl sulfinyl amine bullion; Add normal hexane 50mL making beating filtration and obtain the pure article 20.1g of (S or R)-tertiary butyl sulfinyl amine, yield 97%.GC＞99%, fusing point are 97 ~ 100 ℃, the structure determination of organic cpds:
1H NMR,
13C NMR is consistent with the standard spectrogram with IR.
Embodiment 2:
A kind of process method of using silane for protection reagent synthesizing tertiary butyl sulfinyl amine, concrete steps are:
A) N-tertiary butyl dimethyl-silicon-Lithamide is synthetic: under the argon shield, in the 500mL reaction flask that the liquefied ammonia access tube is housed, add the 75.6g TERT-BUTYL DIMETHYL CHLORO SILANE, the 100.0g Skellysolve A; System temperature is reduced to-25 ℃, feed liquefied ammonia, it is muddy that clarifying reaction liquid becomes immediately, stops logical ammonia behind the 1.0h; Remove cryostat, system is slowly heated up, system temperature filters to room temperature; Filtrating concentrates, and promptly gets tertiary butyl dimethylamino base silane 58.5g, yield: 89%; Under the argon shield; With 58.5g tertiary butyl dimethylamino base silane, the 200mL THF is packed in the 1L reaction flask that has the constant voltage feed hopper, is cooled to-25 ℃; Drip 2.5M n-Butyl Lithium 137.4mL; After the insulation reaction 1.0 hours, obtain the tetrahydrofuran solution of N-tertiary butyl dimethyl-silicon-Lithamide, directly be used for next step under the argon shield and synthesize.
B) (S or R)-N-tertiary butyl dimethyl-silicon tertiary butyl sulfinyl amine is synthetic: take by weighing 33.3g (S or R)-tertiary butyl-sulfinic acid sulfo-tert-butyl ester; 45.6g THF; Be configured to the tetrahydrofuran solution of (S or R)-tertiary butyl-sulfinic acid sulfo-tert-butyl ester; Pack in the 250mL constant pressure funnel, under-25 ℃ of argon shields, obtain in the tetrahydrofuran solution of N-tertiary butyl dimethyl-silicon-Lithamide in slowly splashing into it a); Drip complete insulated and stirred 0.5 hour, and added the excessive lithium reagent of 17.5g ammonium chloride cancellation.Stirred 0.5 hour, system slowly is warming up to room temperature, filters, and filtrating concentrates, and gets 37.5g N-tertiary butyl dimethyl-silicon tertiary butyl sulfinyl amine, yield 93%.
C) (S or R)-tertiary butyl sulfinyl amine is synthetic: with b) in gained N-tertiary butyl dimethyl-silicon-tertiary butyl sulfinyl amine join in the aqueous hydrochloric acid of 45mL pH value 4, stir 7h under the room temperature, with 180mL ethyl acetate extraction 3 times; Merge above-mentioned organic layer, add anhydrous magnesium sulfate drying, filter; Concentrate and obtain (S or R)-tertiary butyl sulfinyl amine bullion; Add normal hexane 50mL making beating filtration and obtain the pure article 18.5g of (S or R)-tertiary butyl sulfinyl amine, yield 96%, GC＞99%; Fusing point is 98～101 ℃, the structure determination of organic cpds:
1H NMR,
13C NMR is consistent with the standard spectrogram with IR.
Embodiment 3:
A kind of process method of using silane for protection reagent synthesizing tertiary butyl sulfinyl amine, concrete steps are:
A) N-tertiary butyl dimethyl-silicon Lithamide is synthetic: under the argon shield, in the 500mL reaction flask that the liquefied ammonia access tube is housed, add the 75.6g TERT-BUTYL DIMETHYL CHLORO SILANE, the 226.8g Skellysolve A; System temperature is reduced to-15 ℃, feed liquefied ammonia, it is muddy that clarifying reaction liquid becomes immediately, stops logical ammonia behind the 0.5h; Remove cryostat, system is slowly heated up, system temperature filters to room temperature; Filtrating concentrates, and promptly gets tertiary butyl dimethylamino base silane 57.8g, yield 88%; Under the argon shield; With 57.8g tertiary butyl dimethylamino base silane, the 300mL THF is packed in the 1L reaction flask that has the constant voltage feed hopper, is cooled to-15 ℃; Drip 2.5M n-Butyl Lithium 135.8mL; After the insulation reaction 0.5 hour, obtain the tetrahydrofuran solution of N-tertiary butyl dimethyl-silicon-Lithamide, directly be used for next step under the argon shield and synthesize.
B) (S or R)-N-tertiary butyl dimethyl-silicon-tertiary butyl sulfinyl amine is synthetic: take by weighing 32.9g (S or R)-tertiary butyl-sulfinic acid sulfo-tert-butyl ester; 32.9g THF; Be configured to the tetrahydrofuran solution of (S or R)-tertiary butyl-sulfinic acid sulfo-tert-butyl ester; Pack in the 250mL constant pressure funnel, under-15 ℃ of argon shields, obtain in the tetrahydrofuran solution of N-tertiary butyl dimethyl-silicon Lithamide in slowly splashing into it a); Drip complete insulated and stirred 0.5 hour, and added the excessive lithium reagent of 17.5g ammonium chloride cancellation.Stirred 1.0 hours, system slowly is warming up to room temperature, filters, and filtrating concentrates, and gets 36.6g N-tertiary butyl dimethyl-silicon-tertiary butyl sulfinyl amine, yield 92%.
C) gained 36.6g (S or R)-N-tertiary butyl dimethyl-silicon-tertiary butyl sulfinyl amine joins in the aqueous hydrochloric acid of 40mL pH value 3 synthesizing of (S or R)-tertiary butyl sulfinyl amine: with b); Stir 5h under the room temperature; With 150mL ethyl acetate extraction 3 times; Merge above-mentioned organic layer, add anhydrous magnesium sulfate drying.Filter, concentrate and obtain (S or R)-tertiary butyl sulfinyl amine bullion 18.1g, yield 96%.Add normal hexane 40mL making beating and filter the pure article of (S or R)-tertiary butyl sulfinyl amine that obtain.GC＞99%, fusing point are 97～99 ℃, the structure determination of organic cpds:
1H NMR,
13C NMR is consistent with the standard spectrogram with IR.
Claims (5)
1. one kind is used silane for protecting the process method of reagent synthesizing tertiary butyl sulfinyl amine, and it is characterized in that: concrete steps are:
A) N-tertiary butyl dimethyl-silicon-Lithamide is synthetic: with the TERT-BUTYL DIMETHYL CHLORO SILANE is starting raw material; With the Skellysolve A is solvent, under-40 ℃～-15 ℃ conditions, with the liquefied ammonia effect, generates tertiary butyl dimethylamino base silane; After separation and purification; In tetrahydrofuran solvent, add n-Butyl Lithium under controlled temperature-40 ℃～-15 ℃ of conditions, synthetic N-tertiary butyl dimethyl-silicon-Lithamide;
B) (S or R)-N-tertiary butyl dimethyl-silicon-tertiary butyl sulfinyl amine is synthetic: under-40 ℃～-15 ℃ temperature condition, (S or R)-tertiary butyl-sulfinic acid sulfo-tert-butyl ester is joined in the tetrahydrofuran solution of the N-tertiary butyl dimethyl-silicon-Lithamide that a) goes on foot; Add the insulated and stirred reaction 0.5～1 hour that finishes; Add the excessive lithium reagent of ammonium chloride cancellation then, separation and purification obtains (S or R)-N-tertiary butyl dimethyl-silicon-tertiary butyl sulfinyl amine;
C) synthesizing of (S or R)-tertiary butyl sulfinyl amine: with b) (S or the R)-N-tertiary butyl dimethyl-silicon-tertiary butyl sulfinyl amine in step joins in the dilute acid solution, stirs under the room temperature 5～8 hours, obtains tertiary butyl sulfinyl amine after the separation and purification.
2. a kind of process method of using silane for protection reagent synthesizing tertiary butyl sulfinyl amine according to claim 1; It is characterized in that: a) in N-tertiary butyl dimethyl-silicon-Lithamide synthetic, tertiary butyl dimethylamino base silane and n-Butyl Lithium in molar ratio 1.2～1.4: 1.
3. a kind of process method of using silane for protection reagent synthesizing tertiary butyl sulfinyl amine according to claim 1; It is characterized in that: b) in (S or R)-N-tertiary butyl dimethyl-silicon-tertiary butyl sulfinyl amine synthetic, N-tertiary butyl dimethyl-silicon-Lithamide and (S or R)-tertiary butyl-sulfinic acid sulfo-tert-butyl ester mol ratio 1: 0.3～0.5.
4. a kind of process method of using silane for protection reagent synthesizing tertiary butyl sulfinyl amine according to claim 1 is characterized in that: c) in (S or R)-tertiary butyl sulfinyl amine synthetic, used diluted acid is a hydrochloric acid, and the pH value is 3-5.
5. a kind of process method of using silane for protection reagent synthesizing tertiary butyl sulfinyl amine according to claim 1, it is characterized in that: entire reaction is reacted under protection of inert gas.
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| US9216953B2 (en) * | 2012-11-02 | 2015-12-22 | Guigen Li | Chiral 2-arylpropyl-2-sulfinamide and chiral N-2-arylpropyl-2-sulfinylimines and synthesis thereof |
| US20140275582A1 (en) * | 2013-03-14 | 2014-09-18 | Texas Tech University | Chiral 2-arylpropyl-2-sulfinamide and chiral n-2-arylpropyl-2-sulfinylimines and synthesis thereof |
| CN106478471B (en) * | 2016-10-11 | 2018-03-09 | 上海瀚鸿科技股份有限公司 | A kind of synthesis technique of chiral tertiary fourth sulfenamide |
| CN112279791A (en) * | 2020-12-30 | 2021-01-29 | 和鼎（南京）医药技术有限公司 | Method for preparing chiral tert-butyl sulfinamide |
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| CN101525308A (en) * | 2009-04-20 | 2009-09-09 | 上海立科化学科技有限公司 | Method for synthesizing chiral sulfenamide |
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Non-Patent Citations (3)
| Title |
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| Derek A. Cogan,et al..Catalytic Asymmetric Oxidation of tert-Butyl Disulfide. Synthesis of tert-Butanesulfinamides, tert-Butyl Sulfoxides, and tert-Butanesulfinimines.《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》.1998,第120卷(第32期),8011-8019. * |
| Guangcheng Liu, et al..Catalytic Asymmetric Synthesis of tert-Butanesulfinamide. Application to the Asymmetric Synthesis of Amines.《J. Am. Chem. Soc.》.1997,第119卷(第41期),9913-9914. * |
| 王凯铭.沸石催化的手性叔丁基亚磺酰亚胺和对甲苯磺酰亚胺的合成.《中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑》.2006,(第12期),B014-133. * |
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