CN108794335A - A method of di-tert-butyl dicarbonate is synthesized using phase transfer catalysis process - Google Patents
A method of di-tert-butyl dicarbonate is synthesized using phase transfer catalysis process Download PDFInfo
- Publication number
- CN108794335A CN108794335A CN201810780760.7A CN201810780760A CN108794335A CN 108794335 A CN108794335 A CN 108794335A CN 201810780760 A CN201810780760 A CN 201810780760A CN 108794335 A CN108794335 A CN 108794335A
- Authority
- CN
- China
- Prior art keywords
- tert
- phase transfer
- butyl dicarbonate
- triphosgene
- butyl
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/02—Preparation of esters of carbonic or haloformic acids from phosgene or haloformates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods synthesizing di-tert-butyl dicarbonate using phase transfer catalysis process, belong to organic synthesis technology field.It is that raw material synthesizes di-tert-butyl dicarbonate under conditions of adding alkali, phase transfer catalyst with triphosgene, tert-butyl alcohol etc., it is raw material to avoid using dangerous phosgene, and reaction condition is mild, while substantially reducing the reaction time, there is larger application value.
Description
Technical field
The invention belongs to organic synthesis technology fields, are related to a kind of utilization phase transfer catalyst two dimethyl dicarbonates of synthesis
The new method of butyl ester.
Background technology
Di-tert-butyl dicarbonate is a kind of novel amino acid protective agent, it is than traditional protective agent (such as benzyl chloroformate
Etc. comparing) compared to safer, more economical, more efficient, more easy to control.It is widely used in medicine, protein and polypeptide synthesis, biology
In the synthesis of the multiple products such as chemistry.Di-tert-butyl dicarbonate has price low, and reactivity is good, post-processes the advantages that simple,
Byproduct of reaction is carbon dioxide and the tert-butyl alcohol, will not cause new pollution.
The preparation method of existing di-tert-butyl dicarbonate has:It is original with the metal sylvite or sodium salt of single-tert-butyl carbonate
Material reacts with aromatic series or aliphatic sulfonic acid chloride and generates the routes such as di-tert-butyl dicarbonate.The method produces di-tert-butyl dicarbonate,
The dosage of fragrance or aliphatic category sulfonic acid chloride is larger, and reaction yield is not high, purifying products difficult problem.
In addition, the flat 4-356445 of Japan Patent JP disclose a kind of synthetic method of di-tert-butyl dicarbonate, using tertiary fourth
Sodium alkoxide is raw material, and n-hexane is solvent, introduces C02Afterwards, it is catalyst that one or two azo cyclooctane (DABCO) of Isosorbide-5-Nitrae, which is added, introduces light
Solid/liquid/gas reactions, then through pickling, alkali cleaning desolventizing obtains product.This method catalyst is expensive, and industrialization future is undesirable.China
The method that patent 200610117788 discloses another synthesis di-tert-butyl dicarbonate, uses sodium tert-butoxide for raw material, with first
Benzene or heptane are solvent, introduce C02Afterwards, it after organic alkali catalyst and crown ether interfacial catalysis agent being added, is dissolved in liquid surpalite
Reaction is instilled in toluene.Pickling after reaction, after alkali cleaning washing, precipitation obtains di-tert-butyl dicarbonate product.The method use
Expensive crown ether catalyst, and it is complicated for operation, and wastewater flow rate is big, and industrialized production has larger difficulty.
The present invention synthesizes di-tert-butyl dicarbonate using phase transfer catalysis process, avoids metal base and CO2Use, behaviour
Work is more easy, and the present invention uses triphosgene instead and replaces phosgene, and reaction is safer, changes for the synthesis of di-tert-butyl dicarbonate
Into one important approach of offer.
Invention content
The present invention for insufficient present on, invent the technical solution that uses for:
It is a kind of using phase transfer catalysis process synthesize di-tert-butyl dicarbonate method and technology field, as steps described below into
Row:
(1) using the tert-butyl alcohol, triphosgene as raw material, addition auxiliary agent, phase transfer catalyst synthesize in batch tank reactor
Di-tert-butyl dicarbonate.
(2) it at -5 DEG C~10 DEG C, will be mixed in the tert-butyl alcohol-hexane solution and a certain amount of auxiliary agent input reaction kettle
Uniformly, and triphosgene-hexane solution is slowly added dropwise, heat preservation is added dropwise, and the reaction was continued, and sampling analysis, lye absorbs tail gas.
Reaction, which finishes, removes water-bath, and ice buck is washed till neutrality, and water pump pumps hydrogen chloride and extra phosgene in product.In above-mentioned reaction solution
Phase transfer catalyst is put into, aqueous slkali is slowly added dropwise in magnetic agitation, and temperature is controlled at 0 DEG C~10 DEG C, heat preservation.Be used in combination dilute hydrochloric acid,
Clear water washing reaction liquid to neutrality, liquid separation dries organic layer with anhydrous calcium chloride, and rotation removes partial solvent.In 0 DEG C of following crystallization 20
~40h, crystallization finish centrifugation, obtain di-tert-butyl dicarbonate, content 99% or so, yield 65~72%.
Carbonylation agent wherein described in step (1) is triphosgene, the molar ratio of triphosgene and the tert-butyl alcohol be (0.75~
3.0):1, preferred molar ratio is (1.50~3.0):1.
Auxiliary agent wherein described in step (1) is one kind in triethylamine, NNNN- tetramethylethylenediamines, pyridine.Its dosage is
The 0.5%~3% of the molal quantity of triphosgene, wherein preferred molar ratio are 1%~2%.
Alkali wherein described in step (2) is sodium hydroxide, potassium hydroxide etc., and concentration of aqueous solution is 15%~70%.It is excellent
Select a concentration of 30%~50%.
Wherein the reaction temperature is -5 DEG C~10 DEG C, and preferable reaction temperature is 0~8 DEG C.
Phase transfer catalyst wherein described in step (1) preferentially selects tetrabutylammonium bromide, tetraalkyl trimethyl ammonia chloride to press,
One kind in hexadecyltrimethylammonium chloride, phase transfer catalyst are that base amount is 1%~5% (wt.).
Present invention process is simple, easy to operate, applied widely, and production is flexible, high income.Use triphosgene replace phosgene as
Carbonylation agent safety higher.
Description of the drawings
Fig. 1 is the process flow chart of phase transfer catalysis process synthesis di-tert-butyl dicarbonate between the present invention.
Specific implementation mode
With reference to embodiment, the present invention will be described in detail, but the following examples are only the preferable embodiment of the present invention,
Scope of protection of the present invention is not limited thereto, technology model of any one skilled in the art in present disclosure
In enclosing, it is subject to equivalent substitute or change according to the technical scheme of the invention and its inventive conception, should all covers the guarantor in the present invention
Within the scope of shield.
Embodiment 1
(1) carbonylation:4g triethylamines and the 100g tert-butyl alcohols and 15ml n-hexanes are put into reaction kettle, stirring,
Ice-water bath keeps -5 DEG C of temperature.Triphosgene-hexane solution (0.84mol/L) 400min is slowly added dropwise after mixing, is added dropwise
Finishing heat preservation, the reaction was continued, absorbs tail gas every 3min sampling analyses, lye in insulating process.Reaction, which finishes, removes water-bath, ice
Buck is washed till neutrality, and water pump extracts 20min, pumps the hydrogen chloride in product and extra phosgene.
(2) 1.2g Macrogol 4000s are put into above-mentioned reaction solution, NaOH aqueous solutions (3mol/ is slowly added dropwise in magnetic agitation
L) 300min, temperature are controlled at 10 DEG C, keep the temperature 20min.It is used in combination dilute hydrochloric acid, clear water washing reaction liquid to neutrality, liquid separation, use is anhydrous
Calcium chloride dries organic layer, and rotation removes partial solvent.In 0 DEG C of following crystallization 20h, crystallization finishes centrifugation, obtains two dimethyl dicarbonates
Butyl ester 70g.Content 99%, yield 72%.
Embodiment 2
(1) carbonylation:Put into 3.2gN, N, N, N tetramethylethylenediamines and the 100g tert-butyl alcohols and 15ml n-hexanes in
In reaction kettle, stirring, ice-water bath keeps 3 DEG C of temperature.Triphosgene-hexane solution (0.68mol/ is slowly added dropwise after mixing
L) 400min, heat preservation is added dropwise, and the reaction was continued, absorbs tail gas every 3min sampling analyses, lye in insulating process.It has reacted
Finish and remove water-bath, ice buck is washed till neutrality, and water pump extracts 20min, pumps the hydrogen chloride in product and extra phosgene.
(2) 0.8g Macrogol 6000s are put into above-mentioned reaction solution, NaOH aqueous solutions are slowly added dropwise in magnetic agitation
(2.8mol/L) 300min, temperature are controlled at 15 DEG C, keep the temperature 20min.Dilute hydrochloric acid, clear water washing reaction liquid to neutrality is used in combination, point
Liquid dries organic layer with anhydrous calcium chloride, and rotation removes partial solvent.In 0 DEG C of following crystallization 25h, crystallization finishes centrifugation, obtains two
Dimethyl dicarbonate butyl ester 65g.Content 99%, yield 67%.
Embodiment 3
(1) carbonylation:2.8g pyridines and the 100g tert-butyl alcohols and 15ml n-hexanes are put into reaction kettle, stirring,
Ice-water bath keeps 0 DEG C of temperature.Triphosgene-hexane solution (0.60mol/L) 400min is slowly added dropwise after mixing, drips
The reaction was continued by Bi Baowen, absorbs tail gas every 3min sampling analyses, lye in insulating process.Reaction, which finishes, removes water-bath, ice alkali
It is washed to neutrality, water pump extracts 20min, pumps the hydrogen chloride in product and extra phosgene.
(2) 0.5g tetrabutylammonium chlorides are put into above-mentioned reaction solution, NaOH aqueous solutions are slowly added dropwise in magnetic agitation
(2.6mol/L) 300min, temperature are controlled at 15 DEG C, keep the temperature 20min.Dilute hydrochloric acid, clear water washing reaction liquid to neutrality is used in combination, point
Liquid dries organic layer with anhydrous calcium chloride, and rotation removes partial solvent.In 5 DEG C of following crystallization 26h, crystallization finishes centrifugation, obtains two
Dimethyl dicarbonate butyl ester 66g.Content 99%, yield 65%.
Embodiment 4
(1) carbonylation:2.5g diethylenetriamines and the 100g tert-butyl alcohols and 15ml n-hexanes are put into reaction kettle,
Stirring, ice-water bath keep 5 DEG C of temperature.Triphosgene-hexane solution (0.57mol/L) 400min is slowly added dropwise after mixing,
Heat preservation is added dropwise, and the reaction was continued, absorbs tail gas every 3min sampling analyses, lye in insulating process.Reaction, which finishes, removes water
Bath, ice buck are washed till neutrality, and water pump extracts 20min, pumps the hydrogen chloride in product and extra phosgene.
(2) it puts into 0.35g tetradecyltrimethylammonium chlorinations in above-mentioned reaction solution to press, NaOH water is slowly added dropwise in magnetic agitation
Solution (2.4mol/L) 300min, temperature are controlled at 30 DEG C, keep the temperature 20min.It is used in combination dilute hydrochloric acid, clear water washing reaction liquid into
Property, liquid separation dries organic layer with anhydrous calcium chloride, revolves and remove partial solvent.In 5 DEG C of following crystallization 28h, crystallization finishes centrifugation point
From obtaining di-tert-butyl dicarbonate 68g.Content 99%, yield 67%.
Embodiment 5
(1) carbonylation:The more diethylstilbestrol polyamines of 2.2g and the 100g tert-butyl alcohols and 15ml n-hexanes are put into reaction kettle,
Stirring, ice-water bath keep 5 DEG C of temperature.Triphosgene-hexane solution (0.52mol/L) 400min is slowly added dropwise after mixing,
Heat preservation is added dropwise, and the reaction was continued, absorbs tail gas every 3min sampling analyses, lye in insulating process.Reaction, which finishes, removes water
Bath, ice buck are washed till neutrality, and water pump extracts 20min, pumps the hydrogen chloride in product and extra phosgene.
(2) 0.32g hexadecyltrimethylammonium chlorides are put into above-mentioned reaction solution, it is water-soluble that KOH is slowly added dropwise in magnetic agitation
Liquid (2.0mol/L) 300min, temperature are controlled at 21 DEG C, keep the temperature 20min.Dilute hydrochloric acid, clear water washing reaction liquid to neutrality is used in combination,
Liquid separation dries organic layer with anhydrous calcium chloride, and rotation removes partial solvent.In 5 DEG C of following crystallization 32h, crystallization finishes centrifugation, obtains
Di-tert-butyl dicarbonate 63g.Content 99%, yield 61%.
Embodiment 6
(1) carbonylation:2g divinyls tetramine and the 100g tert-butyl alcohols and 15ml n-hexanes are put into reaction kettle, is stirred
It mixes, ice-water bath keeps 5 DEG C of temperature.Triphosgene-hexane solution (0.5mol/L) 400min is slowly added dropwise after mixing, is added dropwise
Finishing heat preservation, the reaction was continued, absorbs tail gas every 3min sampling analyses, lye in insulating process.Reaction, which finishes, removes water-bath, ice
Buck is washed till neutrality, and water pump extracts 20min, pumps the hydrogen chloride in product and extra phosgene.
(2) 0.3g benzyltrimethylammonium chlorides are put into above-mentioned reaction solution, KOH aqueous solutions are slowly added dropwise in magnetic agitation
(1.8mol/L) 300min, temperature are controlled at 10 DEG C -30 DEG C, keep the temperature 20min.It is used in combination dilute hydrochloric acid, clear water washing reaction liquid into
Property, liquid separation dries organic layer with anhydrous calcium chloride, revolves and remove partial solvent.In 5 DEG C of following crystallization 34h, crystallization finishes centrifugation point
From obtaining di-tert-butyl dicarbonate 68g.Content 99%, yield 70%.
Embodiment 7
(1) carbonylation:Input 1.6gN, N, N, N- tetraethylethylenediamines and the 100g tert-butyl alcohols and 15ml n-hexanes
In reaction kettle, stirring, ice-water bath keeps 8 DEG C of temperature.Triphosgene-hexane solution is slowly added dropwise after mixing
(0.42mol/L) 400min, heat preservation is added dropwise, and the reaction was continued, absorbs tail every 3min sampling analyses, lye in insulating process
Gas.Reaction, which finishes, removes water-bath, and ice buck is washed till neutrality, and water pump extracts 20min, pumps the hydrogen chloride in product and extra light
Gas.
(2) 0.28g tetrabutylammonium bromide is put into above-mentioned reaction solution, KOH aqueous solutions are slowly added dropwise in magnetic agitation
(1.5mol/L) 300min, temperature are controlled at 10 DEG C -30 DEG C, keep the temperature 20min.It is used in combination dilute hydrochloric acid, clear water washing reaction liquid into
Property, liquid separation dries organic layer with anhydrous calcium chloride, revolves and remove partial solvent.In 8 DEG C of following crystallization 36h, crystallization finishes centrifugation point
From obtaining di-tert-butyl dicarbonate 62g.Content 99%, yield 65%.
Embodiment 8
(1) carbonylation:1g DMF and the 100g tert-butyl alcohol and 15ml n-hexanes are put into reaction kettle, stirring, ice
Water-bath keeps 10 DEG C of temperature.Triphosgene-hexane solution (0.40mol/L) 400min is slowly added dropwise after mixing, drips
The reaction was continued by Bi Baowen, absorbs tail gas every 3min sampling analyses, lye in insulating process.Reaction, which finishes, removes water-bath, ice alkali
It is washed to neutrality, water pump extracts 20min, pumps the hydrogen chloride in product and extra phosgene.
(2) 0.26g benzyltrimethylammonium chlorides are put into above-mentioned reaction solution, KOH aqueous solutions are slowly added dropwise in magnetic agitation
(1mol/L) 300min, temperature are controlled at 23 DEG C, keep the temperature 20min.It is used in combination dilute hydrochloric acid, clear water washing reaction liquid to neutrality, liquid separation,
Organic layer is dried with anhydrous calcium chloride, rotation removes partial solvent.In 10 DEG C of following crystallization 40h, crystallization finishes centrifugation, obtains two carbon
Sour di tert butyl carbonate 68g.Content 99%, yield 70%.
Claims (7)
1. it is a kind of using phase transfer catalysis process synthesize di-tert-butyl dicarbonate method, it is characterised in that as steps described below into
Row:
(1) using the tert-butyl alcohol, triphosgene as raw material, addition auxiliary agent, phase transfer catalyst synthesize two carbon in batch tank reactor
Sour di tert butyl carbonate;
(2) equal by being mixed in the tert-butyl alcohol-hexane solution and a certain amount of auxiliary agent input reaction kettle at -5 DEG C~10 DEG C
It is even, and triphosgene-hexane solution is slowly added dropwise, heat preservation is added dropwise, and the reaction was continued, and sampling analysis, lye absorbs tail gas;Instead
It should finish and remove water-bath, ice buck is washed till neutrality, and water pump pumps hydrogen chloride and extra phosgene in product;It is thrown in above-mentioned reaction solution
Enter phase transfer catalyst, aqueous slkali is slowly added dropwise in magnetic agitation, and temperature is controlled at 0 DEG C~10 DEG C, heat preservation;Dilute hydrochloric acid, clear is used in combination
Water washing reaction solution to neutrality, liquid separation dries organic layer with anhydrous calcium chloride, and rotation removes partial solvent;In 0 DEG C of following crystallization 20~
40h, crystallization finish centrifugation, obtain di-tert-butyl dicarbonate, content 99% or so, yield 65~72%.
2. a kind of method synthesizing di-tert-butyl dicarbonate using phase transfer catalysis process according to claim 1, feature
It is the carbonylation agent described in wherein step (1) for triphosgene, the molar ratio of triphosgene and the tert-butyl alcohol is (0.75~3.0):
1。
3. a kind of method synthesizing di-tert-butyl dicarbonate using phase transfer catalysis process according to claim 1, feature
It is that wherein step (1) triphosgene and the molar ratio of the tert-butyl alcohol are (1.50~3.0):1.
4. a kind of method synthesizing di-tert-butyl dicarbonate using phase transfer catalysis process according to claim 1, feature
It is that the auxiliary agent described in wherein step (1) is one kind in triethylamine, NNNN- tetramethylethylenediamines, pyridine;Its dosage is three light
The 0.5%~3% of the molal quantity of gas.
5. a kind of method synthesizing di-tert-butyl dicarbonate using phase transfer catalysis process according to claim 1, feature
It is that the dosage of the auxiliary agent described in wherein step (1) is the 1%~2% of the molal quantity of triphosgene.
6. a kind of method synthesizing di-tert-butyl dicarbonate using phase transfer catalysis process according to claim 1, feature
It is that the alkali described in wherein step (2) is sodium hydroxide, potassium hydroxide etc., concentration of aqueous solution is 15%~70%;It is preferred that dense
Degree is 30%~50%.
7. a kind of method synthesizing di-tert-butyl dicarbonate using phase transfer catalysis process according to claim 1, feature
It is that the wherein described reaction temperature is -5 DEG C~10 DEG C, preferable reaction temperature is 0~8 DEG C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810780760.7A CN108794335A (en) | 2018-07-17 | 2018-07-17 | A method of di-tert-butyl dicarbonate is synthesized using phase transfer catalysis process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810780760.7A CN108794335A (en) | 2018-07-17 | 2018-07-17 | A method of di-tert-butyl dicarbonate is synthesized using phase transfer catalysis process |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108794335A true CN108794335A (en) | 2018-11-13 |
Family
ID=64076588
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810780760.7A Pending CN108794335A (en) | 2018-07-17 | 2018-07-17 | A method of di-tert-butyl dicarbonate is synthesized using phase transfer catalysis process |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108794335A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115057778A (en) * | 2022-07-28 | 2022-09-16 | 西安思科赛实业有限公司 | Novel method for synthesizing di-tert-butyl dicarbonate |
CN115322096A (en) * | 2022-09-14 | 2022-11-11 | 开封华瑞化工新材料股份有限公司 | Method for synthesizing di-tert-butyl dicarbonate by adopting phase transfer catalysis method |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5523481A (en) * | 1993-12-08 | 1996-06-04 | Bayer Aktiengesellschaft | Process for the preparation of dialkyl dicarbonates |
CN101235046A (en) * | 2007-01-29 | 2008-08-06 | 中国科学院上海药物研究所 | Novel vinblastine derivative, preparation method and use thereof, and medical composition containing the derivative |
CN102219690A (en) * | 2011-04-29 | 2011-10-19 | 浙江手心医药化学品有限公司 | Preparation method for dimethyl dicarbonate |
CN107188805A (en) * | 2016-03-14 | 2017-09-22 | 重庆长风生物科技有限公司 | A kind of continuous preparation technology of the carbonate of dimethyl two |
CN108084027A (en) * | 2016-11-23 | 2018-05-29 | 利尔化学股份有限公司 | The preparation method of sec-butyl chloroformate |
-
2018
- 2018-07-17 CN CN201810780760.7A patent/CN108794335A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5523481A (en) * | 1993-12-08 | 1996-06-04 | Bayer Aktiengesellschaft | Process for the preparation of dialkyl dicarbonates |
CN101235046A (en) * | 2007-01-29 | 2008-08-06 | 中国科学院上海药物研究所 | Novel vinblastine derivative, preparation method and use thereof, and medical composition containing the derivative |
CN102219690A (en) * | 2011-04-29 | 2011-10-19 | 浙江手心医药化学品有限公司 | Preparation method for dimethyl dicarbonate |
CN107188805A (en) * | 2016-03-14 | 2017-09-22 | 重庆长风生物科技有限公司 | A kind of continuous preparation technology of the carbonate of dimethyl two |
CN108084027A (en) * | 2016-11-23 | 2018-05-29 | 利尔化学股份有限公司 | The preparation method of sec-butyl chloroformate |
Non-Patent Citations (1)
Title |
---|
DANIEL PLUSQUELLER等: "A new synthesis of carboxylic and carbonic acid anhydrides using phase transfer reactions", 《TETRAHEDRON》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115057778A (en) * | 2022-07-28 | 2022-09-16 | 西安思科赛实业有限公司 | Novel method for synthesizing di-tert-butyl dicarbonate |
CN115322096A (en) * | 2022-09-14 | 2022-11-11 | 开封华瑞化工新材料股份有限公司 | Method for synthesizing di-tert-butyl dicarbonate by adopting phase transfer catalysis method |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPH0273051A (en) | Production of internal olefin sulfonate | |
CN100546972C (en) | The method for preparing the 4-amino-diphenyl-amine | |
CN108794335A (en) | A method of di-tert-butyl dicarbonate is synthesized using phase transfer catalysis process | |
CN107935921A (en) | A kind of preparation method of 2,3 dichloropyridine | |
CN111039771B (en) | Preparation method of 3,3, 3-trifluoropropionic acid | |
CN106748763B (en) | The method of two kettles joint phase-transfer Wittig reaction methyl benzoate | |
CN108191674A (en) | A kind of synthetic method of benzidine compound | |
CN102190648A (en) | Method for synthesizing cyclic carbonate by using carbon dioxide and epoxide | |
CN104262227B (en) | A method of preparing (S) -1- (2- chloracetyls) pyrrolidines -2- formonitrile HCNs | |
CN105924328B (en) | A kind of highly selective green hydrolysis technique for preparing benzyl alcohol | |
CN102766156B (en) | The preparation method of tetramethyl divinyl disilazane | |
CN102344346B (en) | Method for synthetizing tetrabromobisphenol A diallyl ether in water phase | |
CN104910032A (en) | Preparation method of anilino-acetate | |
CN101234955B (en) | Method for preparing 3-methoxyl-4-t-butyltoluene | |
CN107805201B (en) | Preparation method of methyl dihydrojasmonate | |
CN108424356A (en) | A kind of production method and production system of 2,4 dichloro phenol | |
CN106892849B (en) | A kind of preparation method of lauric acid methyl tin | |
CN101333161B (en) | Method for preparing alpha-chloro-fatty acid | |
CN104557551A (en) | Novel method for catalytically synthesizing benzyl salicylate via solid-liquid phase transfer | |
CN103242204B (en) | The method of purification phenylhydrazine-β-carboxylate compound | |
CN106565441A (en) | Synthesis method of 3,5-dichloro-2-pentanone | |
CN101318974B (en) | Process for synthesizing methyl tin chloride | |
CN206447796U (en) | A kind of production system of 2,4 chlorophenesic acid | |
CN114478264B (en) | Synthesis method of intermediate of bisamide pesticide | |
CN117756625B (en) | Preparation method of o-ethoxybenzoyl chloride |
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 | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181113 |
|
RJ01 | Rejection of invention patent application after publication |