CN108558714A - A kind of chirality optical voidness is to the preparation method of toluenesulfinamide - Google Patents
A kind of chirality optical voidness is to the preparation method of toluenesulfinamide Download PDFInfo
- Publication number
- CN108558714A CN108558714A CN201810449685.6A CN201810449685A CN108558714A CN 108558714 A CN108558714 A CN 108558714A CN 201810449685 A CN201810449685 A CN 201810449685A CN 108558714 A CN108558714 A CN 108558714A
- Authority
- CN
- China
- Prior art keywords
- toluenesulfinamide
- toluene
- preparation
- optical voidness
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/02—Sulfinic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/02—Sulfinic acids; Derivatives thereof
- C07C313/04—Sulfinic acids; Esters thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/02—Sulfinic acids; Derivatives thereof
- C07C313/06—Sulfinamides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Abstract
The invention discloses a kind of chiral optical voidnesses to the preparation method of toluenesulfinamide, chloride is carried out with sodium toluene sulfinate and chloride reagent to obtain to toluene sulphinyl chlorine, it is then obtained with hydrazine hydrate to toluene sulfenyl hydrazine, fractionation dissociation is carried out with tartaric acid resolving agent again, it is pure to toluenesulfinamide that mapping is obtained after zinc acetic acid cracking.Present invention process stabilization easy to operate, yield is high, and environmental-friendly, more existing technique, raw material is cheap and easy to get, significantly reduces existing chiral optical voidness to the production cost of toluenesulfinamide, is conducive to industrial-scale production.
Description
Technical field
The invention belongs to technical field of medicine synthesis, and in particular to a kind of preparation of the chirality optical voidness to toluenesulfinamide
Method.
Background technology
To toluenesulfinamide, the entitled p-toluenesulfinamide molecular formula of English are：C7H9NOS.Including R types and
Two kinds of configurations of S types, English name correspond to (R)-p-toluenesulfinamide and (S)-p- respectively
toluenesulfinamide.Since eighties of last century mid-term synthesizes for the first time, as chiral amine drug and its intermediate
One of crucial chiral source.Especially relatively broad academicly, it is a kind of important chemical as chiral auxiliary, is closed in chirality
At having great importance in being synthesized with chiral drug.Nowadays, there are amine groups in most of drug or pharmaceutical intermediate, is being permitted
In more reports, chiral optical voidness is to the flexible source that toluenesulfinamide is diastereomer in asymmetric syntheses.
(R)-wherein synthetic route is as follows is had been reported that toluenesulfinamide document to toluenesulfinamide and (S)-：
Route one：Its reaction equation is as follows：
With it is racemic to toluenesulfinamide synthesize N- p-tolysulfinyl amides, then with alpha -chymotrypsin into
Row deconsolidation process 24 hours, mixture obtain (R)-to toluenesulfinamide, then obtain (S)-N- to toluene Asia by HCl processing
Sulfonyl amide.
In the above-mentioned methods, N- p-tolysulfinyl amides are synthesized to toluenesulfinamide with racemic, then with α-
Chymotrypsin carries out deconsolidation process 24 hours.The method splits that the time is longer and not easy purification, alpha -chymotrypsin valence
Lattice are higher, are unfavorable for amplification production, and economic benefit is bad.
For (S)-to toluenesulfinamide document report, synthesis route is as follows：
It is generated to toluene sulphinyl chlorine by raw material and thionyl chloride of sodium toluene sulfinate, the intermediate and L- are thin to after
The reaction of lotus alcohol generates corresponding chiral ester, and (S)-is obtained to toluenesulfinamide, reaction equation finally by LiHMDS ammonolysis
It is as follows：
In the above-mentioned methods, LiHMDS higher prices used, solvent for use large percentage, and just for (S)-to toluene Asia
Sulfonamide is effective, is unfavorable for mass producing.
Invention content
For the above-mentioned deficiency of the prior art, the present invention provides a kind of stabilization easy to operate, high income, environmental-friendly, raw
Produce at low cost, preparation method of the suitable industrial-scale production chirality optics to toluenesulfinamide.
The present invention provides a kind of preparation method of chiral optical voidness to toluenesulfinamide.Its reaction equation is as follows：
The realization of technical scheme of the present invention, which is characterized in that including steps are as follows:
Synthesis of the first step to toluene sulphinyl chlorine.
Paratoluenesulfonic acid sodium salt is added in organic solvent, chloride reagent is added dropwise at 0 DEG C and obtains to toluene after the reaction was complete
Sulphinyl chlorine.Wherein reaction temperature is selected from 0 DEG C to 70 DEG C.
Synthesis of the second step to toluene sulfenyl hydrazine.
Toluene sulfenyl hydrazine will be obtained by the reaction to being added in hydrazine hydrate at 0 DEG C of toluene sulphinyl chlorine, wherein reaction temperature is selected
From 0 DEG C to 30 DEG C.
Third step to toluene sulfenyl hydrazine split at salt and be dissociated.
Toluene sulfenyl hydrazine will be added in organic solvent, in the solution of 30 DEG C of dropwise addition tartaric acids resolving agents, knot is added dropwise
Shu Huiliu 3 hours, slow cooling obtain chiral to toluene sulfenyl hydrazine complex salt.Wherein reaction temperature is selected from 0 DEG C to 66
℃.Dissociate to obtain chiral optical voidness again to toluene sulfenyl hydrazine.
Synthesis of the 4th step chirality optical voidness to toluenesulfinamide.
It will be chiral optically pure in toluene sulfenyl hydrazine addition acetic acid and dichloromethane, 40-45 DEG C is added portionwise zinc powder
It is reacted, then obtains chiral optically pure to toluenesulfinamide, wherein reaction temperature is selected from 20 DEG C to 45 DEG C.
Further, in the above-mentioned technical solutions, the first step reacts the chloride reagent selected from oxalyl chloride and protochloride
Sulfone.Sodium toluene sulfinate and the molar ratio of oxalyl chloride and thionyl chloride are：1:1.1-1.25:1.5-1.8.
Further, in the above-mentioned technical solutions, the first step reaction organic solvent is selected from toluene, methyl tertbutyl
Ether, dichloromethane and benzene.The mass ratio of sodium toluene sulfinate and toluene, methyl tertiary butyl ether(MTBE), dichloromethane and benzene is 1:
5-7:6-8:7-10:6-8。
Further, in the above-mentioned technical solutions, the derivative series resolving agent described in four-step reaction be selected from tartaric acid,
DBTA and DTTA.It is split respectively using 1 equivalent or 0.5 equivalent resolving agent when fractionation.
Wherein, DBTA is dibenzoyl tartaric acid (Dibenzoyl-L-tartaric acid) abbreviation；DTTA is two pairs of first
Base benzoyltartaric sour (Di-p-toluoyl-tartaric acid) is referred to as；Both resolving agents include its hydrate shape
Formula.
Further, in the above-mentioned technical solutions, the product E E that third walks>98%.
Further, in the above-mentioned technical solutions, the product that the 4th step obtains is recrystallized to give purity using butyl acetate>
99% and EE>99% or more sterling.
Invention advantageous effect：
Compared with previous synthetic method, the present invention has the advantages that：
1) synthetic route of the present invention is simple, and raw material, which is easy to get, to be avoided holding high using this inflammable raw materials of LiMSDS or biological enzyme are this
Your raw material greatly facilitates industrial amplification production and cost-effective.
2) present invention obtains, to toluene sulfenyl hydrazine, not only increasing alkalinity, also improving yield.Its product preferably purifies, instead
Answer mild condition.
3) present invention is improved in this way by splitting, and deep cooling is avoided to react, easy to operate, and atom utilization is high.It solvent and tears open
Point agent is recyclable applies mechanically, and largely improves the yield of product, and industrialization can be more suitble to amplify.
Specific implementation mode
Below by specific example, invention is further explained.
These embodiments are interpreted as being merely to illustrate the present invention rather than limit the scope of the invention.It is reading
After the content of the invention recorded, those skilled in the art can make various modifications or changes to the present invention, these equivalent changes
Change and modification equally falls into the scope of the claims in the present invention.
Test method without specific conditions in following embodiment of the present invention carries out usually according to normal condition.
Raw material or reagent used in following embodiment of the present invention are commercially available in addition to special instruction.
20-35 DEG C of room temperature mean value described in following embodiment of the present invention.Unless otherwise indicated, the reagent is not special
Explanation is to be used without further purification.All solvents are purchased from commercialization supplier, and just can be used without processing.Reaction
It is analyzed by TLC, GC, HPLC, the termination of reaction is judged by the consumption of starting material.
Embodiment 1
The first step：Synthesis to toluene sulphinyl chlorine.
(1) 267g toluene, 53.4g are put into toluenesulfinic acid with charging hopper in the 500mL four-hole bottles of dried and clean
Sodium and 0.1g n,N-Dimethylformamide, room temperature be added dropwise 57.5g thionyl chlorides, at 55-65 DEG C react 4 hours, sample GC or
HPLC is detected after derivative, and raw material is less than 0.3%, is concentrated under reduced pressure, and is replaced once with toluene 150g, is added 50g dilution with toluene and wait for
With.External standard yield 94%.
(2) the 500mL four-hole bottles of dried and clean charging hopper put into 267g benzene, 53.4g sodium toluene sulfinate and
57.5g thionyl chlorides are added dropwise in 0.1g n,N-Dimethylformamide, room temperature, and 4 hours are reacted at 55-65 DEG C, sample GC or derivative
HPLC is detected afterwards, and raw material is less than 0.3%, is concentrated under reduced pressure, and is replaced once with benzene 150g, and it is for use to add the dilution of 50g benzene.External standard is received
Rate 93%.
(3) 260g methyl tertiary butyl ether(MTBE)s, 44.5g are put into toluene in the 500mL four-hole bottles of dried and clean charging hopper
16.5g oxalyl chlorides are added dropwise at 0 DEG C for sulfinic acid sodium and 0.04g pyridines, after reacting 2 hours at 35-40 DEG C, then are added dropwise at 0 DEG C surplus
Remaining 20g oxalyl chlorides, after reacting 2 hours at 35-40 DEG C, HPLC is detected after sampling GC or derivative, and raw material is less than 0.3%, decompression
Concentration is replaced once with toluene 150g, it is for use to add 45g dilution with toluene.External standard yield 89%.
(4) 330g dichloromethane, 44.5g are put into toluene Asia sulphur in the 500mL four-hole bottles of dried and clean charging hopper
16.5g oxalyl chlorides are added dropwise at 0 DEG C for sour sodium and 0.04g pyridines, after reacting 2 hours at 35-40 DEG C, then are added dropwise at 0 DEG C remaining
20g oxalyl chlorides, after reacting 2 hours at 35-40 DEG C, HPLC is detected after sampling GC or derivative, and raw material is less than 0.3%, and decompression is dense
Contracting is replaced once with toluene 150g, it is for use to add 45g dilution with toluene.External standard yield 91%.
Second step：Synthesis to toluene sulfenyl hydrazine.
(1) 80% hydrazine hydrates of 50g and 85g water are put into clean 500mL four-hole bottles charging hopper, the first step is added dropwise
(3/4) in 45g dilution with toluene to toluene sulphinyl chlorine solution, and control temperature and be added dropwise at -5 DEG C to 15 DEG C, after completion of dropwise addition,
20-25 DEG C is reacted 2 hours, and sampling TLC detections are stood, subregion upper toluene, and lower layer's water phase centrifugation obtains 37g to toluene Asia sulphur
Hydrazides, yield 89%.Toluene sulfenyl hydrazine is preferably deliquesced, Cord blood is needed.
(2) 80% hydrazine hydrates of 70g and 104g water are put into clean 500mL four-hole bottles charging hopper, the first step is added dropwise
(2) 50g benzene is diluted to toluene sulphinyl chlorine solution in, and controls temperature and be added dropwise at -5 DEG C to 15 DEG C, after completion of dropwise addition, 20-
25 DEG C are reacted 2 hours, and sampling TLC detections are stood, subregion upper toluene, and lower layer's water phase centrifugation obtains 45g to toluene sulfenyl
Hydrazine, yield 91%.Toluene sulfenyl hydrazine is preferably deliquesced, Cord blood is needed.
Third walks：Salt dissociation is split into toluene sulfenyl hydrazine.
(1) 140g MTBE and 29g is added in clean 500mL four-hole bottles to toluene sulfenyl hydrazine, 32.9g is added dropwise
(0.5eq) D-DTTA is dissolved in the solution of 150g MTBE, and control dropping temperature is at 30-45 DEG C, and after being added dropwise, reflux heat preservation 3 is small
When, gradient slow cooling is to 5-10 DEG C, filtering, and cold MTBE elution, wet product is recrystallized with 140g MTBE, and filtering drying obtains
31.3g splits product, EE=98.6%, yield 33%.It is hydrolyzed again by 4N aqueous hydrochloric acid solutions, adjusts pH=3-4, MTBE
D-DTTA recoveries are extracted, water phase uses NaOH aqueous solutions to adjust pH=9-10 again, and it is right that 8.4g (R)-is obtained by extraction in dichloromethane
Toluene sulfenyl hydrazine, EE=99.1% dissociate yield 87.5%.
(2) 130mL 1,2- dichloroethanes and 29g are added in clean 500mL four-hole bottles to toluene sulfenyl hydrazine, drop
30.5g (0.5eq) L-DBTA is added to be dissolved in 120mL1, the solution of 2- dichloroethanes, control dropping temperature is dripped at 30-45 DEG C
Bi Hou, 63 DEG C keep the temperature 3 hours, and gradient slow cooling is to 15-20 DEG C, filtering, then are eluted with 10 DEG C of 1,2- dichloroethanes, product
Drying obtains 34.2g and splits product, EE=97.9%, yield 38%.It is hydrolyzed again by 4N aqueous hydrochloric acid solutions, adjusts pH
=3-4, MTBE extract D-DBTA recoveries, and water phase uses NaOH aqueous solutions to adjust pH=9-10 again, and dichloromethane is obtained by extraction
9.8g (S)-dissociates yield 89% to toluene sulfenyl hydrazine, EE=98.6%.
(3) 150g methanol, 3g water and 32g are added in clean 500mL four-hole bottles to toluene sulfenyl hydrazine, is added dropwise
28.2g (1eq) D-Tartaric acid are dissolved in the solution of 140g methanol, and control dropping temperature is at 30-45 DEG C, after being added dropwise,
65 DEG C keep the temperature 3 hours, and to 0-10 DEG C, filtering obtains wet product EE=76%, dissociated by NaOH water dissolutions gradient slow cooling
Afterwards, dichloromethane extraction, the product being concentrated to give once are split again by aforesaid operations, are obtained 18.6g and are split product, EE
=99.3%, yield 31%.It is hydrolyzed again by NaOH aqueous solutions, 8.3g (R)-is obtained by extraction to toluene Asia sulphur in dichloromethane
Hydrazides, EE=99.6% dissociate yield 83%.
(4) be added in clean 500mL four-hole bottles filtered in the 4th step (3) at salt mother liquor, be concentrated to dryness, be added few
Ethyl acetate mashing is measured, 42.1g solids are obtained by filtration, then be hydrolyzed by NaOH aqueous solutions, dichloromethane is obtained by extraction
20.1g adds 100g methanol, 1g water to toluene sulfenyl hydrazine, and 17.7g (1eq) L-Tartaric acid are added dropwise and are dissolved in 90g
The solution of methanol, control dropping temperature is at 30-45 DEG C, and after being added dropwise, 64 DEG C keep the temperature 3 hours, gradient slow cooling to 0-10
DEG C, filtering, then with the methanol elution of 0 DEG C of 10g, product drying obtains 23.8g fractionation products, yield 63%.Pass through NaOH again
Aqueous solution is hydrolyzed, and 10.7g (S)-is obtained by extraction to toluene sulfenyl hydrazine in dichloromethane, and EE=99.3% dissociates yield
85%.
4th step：The chiral optically pure synthesis to toluenesulfinamide.
(1) clean 500mL four-hole bottles be added 70g acetic acid, 51g (R)-to toluene sulfenyl hydrazine, 58.5g zinc powders and
160mL dichloromethane is slowly heated to 40-45 DEG C, reacts 9-11 hours, and sampling TLC, HPLC detection, raw material is less than 2%, mistake
Filter, filtrate are poured into 120mL water, and 75g dichloromethane is added every time and is extracted, and coextraction 3 times is enriched with organic phase, is added
30%NaOH adjusts pH=7-8, layering, and organic phase is washed 1 time with saturated sodium-chloride water solution 30g, and magnesium sulfate drying is filtered, filter
It being concentrated under reduced pressure at 25-30 DEG C of liquid and does not slip liquid, butyl acetate is replaced, and 251g butyl acetates are added and are recrystallized, cooling filtering,
32.1g (R)-is obtained to toluenesulfinamide, HPLC purity=99.3%, EE=99.1%, yield 69%, HNMR and document one
It causes.
(2) 70g acetic acid, 51g (S)-tertiary butyl sulfenyl hydrazine (methods 2 in third step is added in clean 500mL four-hole bottles
Obtained product), 60.5g zinc powders and 160mL dichloromethane, be slowly heated to 40-45 DEG C, react 9-11 hour, sample TLC,
HPLC is detected, and raw material is less than 2%, and filtering, filtrate is poured into water containing 120mL, and 75g dichloromethane is added every time and is extracted, altogether
Extraction 3 times is enriched with organic phase, and 30%NaOH is added and adjusts pH=7-8, layering, organic phase is washed with saturated sodium-chloride water solution 30g
1 time, magnesium sulfate drying filters, is concentrated under reduced pressure at 25-30 DEG C of filtrate and does not slip liquid, and butyl acetate is replaced, and 243g acetic acid fourths are added
Ester is recrystallized, and cooling filtering obtains 35.7g (S)-to toluenesulfinamide, HPLC purity=99.7%, EE=
99.6%, yield 77%, HNMR is consistent with document.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope of present disclosure, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of chirality optical voidness is to toluenesulfinamide to the preparation method of toluenesulfinamide, which is characterized in that including：1)
First chloride is carried out with chloride reagent and sodium toluene sulfinate in organic solvent to obtain to toluene sulphinyl chlorine；2) it instills
In hydrazine hydrate, obtain to toluene sulfenyl hydrazine；3) tartaric acid resolving agent is used to carry out splitting dissociation at salt；4) pass through zinc/acetic acid
Reduction obtains chiral optically pure to toluenesulfinamide.
2. according to chiral optical voidness in claim 1 to the preparation method of toluenesulfinamide, it is characterised in that：The chloride
Reagent is oxalyl chloride and thionyl chloride.
3. according to chiral optical voidness in claim 1 to the preparation method of toluenesulfinamide, it is characterised in that：It is described organic molten
Agent is selected from toluene, methyl tertiary butyl ether(MTBE), dichloromethane and benzene.
4. according to chiral optical voidness in claim 2 to the preparation method of toluenesulfinamide, it is characterised in that：To toluene Asia sulphur
Sour sodium is 1 with the molar ratio of oxalyl chloride and thionyl chloride:1.1-1.25:1.5-1.8.
5. according to chiral optical voidness in claim 3 to the preparation method of toluenesulfinamide, it is characterised in that：To toluene Asia sulphur
The mass ratio of sour sodium and toluene, methyl tertiary butyl ether(MTBE), dichloromethane and benzene is 1:5-7:6-8:7-10:6-8.
6. according to chiral optical voidness in claim 1 to the preparation method of toluenesulfinamide, it is characterised in that：It is used when fractionation
1 equivalent or 0.5 equivalent resolving agent are split respectively.
7. according to chiral optical voidness in claim 1 to the preparation method of toluenesulfinamide, it is characterised in that：Product uses vinegar
Acid butyl ester recrystallization further increases purity, and the wherein mass ratio of product and butyl acetate is 1：6.5-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810449685.6A CN108558714B (en) | 2018-05-11 | 2018-05-11 | Preparation method of chiral optical pure p-toluenesulfinamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810449685.6A CN108558714B (en) | 2018-05-11 | 2018-05-11 | Preparation method of chiral optical pure p-toluenesulfinamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108558714A true CN108558714A (en) | 2018-09-21 |
| CN108558714B CN108558714B (en) | 2020-10-16 |
Family
ID=63538294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810449685.6A Active CN108558714B (en) | 2018-05-11 | 2018-05-11 | Preparation method of chiral optical pure p-toluenesulfinamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108558714B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100044A (en) * | 2019-12-27 | 2020-05-05 | 鹤壁元昊化工有限公司 | Preparation method of alkyl zinc sulfinate series compounds |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1007503B (en) * | 1953-07-14 | 1957-05-02 | Bayer Ag | Process for the polymerization of monomeric vinyl compounds, preferably in the presence of polymer powders, in block, solution or in bead form |
| 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 |
-
2018
- 2018-05-11 CN CN201810449685.6A patent/CN108558714B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1007503B (en) * | 1953-07-14 | 1957-05-02 | Bayer Ag | Process for the polymerization of monomeric vinyl compounds, preferably in the presence of polymer powders, in block, solution or in bead form |
| 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 |
Non-Patent Citations (6)
| Title |
|---|
| AHMED CHELOUAN等: ""DMAP-Catalysed Sulfinylation of Diacetone-D-Glucose: Improved Method for the Synthesis of Enantiopure tert -Butyl Sulfoxides and tert-Butanesulfinamides"", 《EUR. J. ORG. CHEM.》 * |
| CHRISTOPHER K. SAVILE等: ""Subtilisin-Catalyzed Resolution of N-Acyl Arylsulfinamides"", 《J. AM. CHEM. SOC.》 * |
| 刘强等: "手性叔丁基亚磺酰胺的制备方法及其在药物合成中的应用", 《药学进展》 * |
| 孙晓霞: ""手性叔丁基亚磺酰胺的制备及其双亚胺的金属有机试剂不对称加成反应的研究"", 《中国科学院成都有机化学研究所博士学位论文》 * |
| 朱瑞恒: ""基于各种拆分方法的四氢异喹啉生物碱、手性亚磺酰胺和顺式哌虫啶的合成研究"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
| 桂厚瑛等: "叔丁基磺酰胺的合成", 《石油化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100044A (en) * | 2019-12-27 | 2020-05-05 | 鹤壁元昊化工有限公司 | Preparation method of alkyl zinc sulfinate series compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108558714B (en) | 2020-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110818610B (en) | Method for preparing melatonin | |
| CN108440349A (en) | A kind of chirality optical voidness is to the preparation method of toluenesulfinamide | |
| CN107235958A (en) | A kind of synthetic method for preparing PARP inhibitor Niraparib | |
| CN108558714A (en) | A kind of chirality optical voidness is to the preparation method of toluenesulfinamide | |
| CN111170892A (en) | Synthesis method of N-methyl (2S) -2-N-fluorenylmethoxycarbonylamino-aspartic acid (4-tert-butyl ester) | |
| JP2005206527A (en) | METHOD FOR PRODUCING OPTICALLY ACTIVE trans-4-AMINO-1-BENZYL-3-PYRROLIDINOL DERIVATIVE | |
| CN108484455A (en) | A kind of method of synthesis of chiral optical voidness to toluenesulfinamide | |
| CN108558715B (en) | Method for preparing enantiopure tert-butyl sulfenamide | |
| CN108467353B (en) | Preparation method of enantiopure tert-butyl sulfinamide | |
| AU2017333054B2 (en) | Method for preparing phenylalanine compound | |
| JP2011012032A (en) | Method for producing optically active 3-aminopiperidine and production intermediate | |
| CN106588921B (en) | A kind of synthetic method of the methyl formate of 7 azaindole 3 | |
| CN112645813B (en) | Preparation method of (R) -3-cyclohexene carboxylic acid | |
| CN111072660A (en) | Simple preparation method of rilibatan | |
| CN108409615B (en) | Method for synthesizing enantiopure tert-butyl sulfenamide | |
| CN111302996A (en) | Preparation method of high-chiral-purity chloromalastine fumarate | |
| CN106748816A (en) | A kind of synthetic method of the amino butanol of Du Lutewei key intermediates (R) 3 | |
| WO2021100730A1 (en) | Method for producing pyrrolidine compound | |
| CN112920005B (en) | Preparation method of (R) -3- (3-chloro-2-fluorobenzene) -4, 5-dihydroisoxazole-5-carboxylic acid | |
| CN104262201A (en) | Synthesis method of chiral optically-pure (S)-3-aminovaleric acid | |
| CN104892491B (en) | Method for synthesizing paroxetine chiral intermediate | |
| JP5397706B2 (en) | Method for producing high purity 1-benzyl-3-aminopyrrolidine | |
| WO2020132819A1 (en) | Method for preparing (1r,3s)-3-aminocyclopentanol hydrochloride | |
| CN103539794A (en) | Salifying method of lurasidone hydrochloride | |
| CN107698589A (en) | A kind of novel preparation method of Adprin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Hua Inventor after: Gao Feng Inventor after: Zeng Sailan Inventor before: Gao Feng Inventor before: Zeng Sailan |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200915 Address after: 201512 Shanghai city Jinshan District Qiushi Road No. 688 Building No. 4 room 201-205 Applicant after: SHANGHAI TIANYE CHEMICAL Co.,Ltd. Address before: 201512 Shanghai City, Jinshan District Jinshanwei town Qiushi Road No. 688 Building 1, unit 2, room 404 Applicant before: SHANGHAI TBBMED Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |