CN107698462A - A kind of preparation method of the cyclopropylniitrile hydrochloride of 1 amino 1 - Google Patents
A kind of preparation method of the cyclopropylniitrile hydrochloride of 1 amino 1 Download PDFInfo
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- CN107698462A CN107698462A CN201710935505.0A CN201710935505A CN107698462A CN 107698462 A CN107698462 A CN 107698462A CN 201710935505 A CN201710935505 A CN 201710935505A CN 107698462 A CN107698462 A CN 107698462A
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- amino
- cyclopropylniitrile
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a kind of preparation method of the cyclopropylniitrile hydrochloride of 1 amino 1, belong to technical field of organic synthesis.Technical scheme main points are：It is initiation material using nitroacetonitrile, with 1 under base catalysis, the cyclopropylniitrile of 1 nitro 1 is made in the reaction of 2 dihalo- ethane, then obtains the cyclopropylniitrile hydrochloride of 1 amino 1 through nitro-reduction reaction.Reaction condition of the present invention is gentle, yield is higher, cost is cheap and is suitable to commercial application.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of preparation side of 1- amino -1- cyclopropylniitrile hydrochlorides
Method.
Background technology
1- amino -1- cyclopropylniitriles are a kind of important organic intermediates, and it can continue hydrolysis and obtain 1- amino -1- rings third
Acid, it is a kind of excellent new plant growth regulator.Contain cyclopropane moiety in numerous medicines, at present its disclosed synthesis
Method has：Nineteen ninety, Salaun, Jacques（Journal of Organic Chemistry, 1990, 55(14),
4276-81.）Report makees raw material with methacrylaldehyde, and aminopropionitrile hydrochloric acid is obtained through chlorination, cyanalation, ammonolysis, condensation, hydrolysis
Salt.Subsequent numerous patent PCT Int. Appl., 2005028429,2005074904,2006060810,2006060494,
2006102535th, 2008042968,2010056877,2012064642 and United States Patent (USP) US 20080293819 is reported with two
Benzophenone imines reacts with aminopropionitrile in dichloromethane, then phase transfer catalysis (PTC) in toluene be present with 1,2- Bromofumes
Reacted in the case of agent and benzophenone imino-acetonitrile is made, finally react to obtain ammonia in aqueous hydrochloric acid solution and ether two-phase system
Base propionitrile hydrochloride.Chinese patent in 2008（CN 101225057B）With article in 2009（Guangdong chemical industry, 2009,36 (6),
35-36.）It is same to use benzophenone imine to be reacted for raw material and aminopropionitrile by improving literature method, in alkalescence condition
It is lower to be reacted with 1,2- Bromofumes, the protection of benzophenone imine, deprotection are then gone using acid cation exchange resin solution
Sulfonic acid group reaction in amino and resin cation afterwards, product is immobilized into resin, and product and substrate are realized by filtering
Separation.2013, Shivaraj, Yellappa（Journal of the Korean Chemical Society, 57
(2), 241-245; 2013.）Report using cyclopropanone as raw material and obtain 1- amino -1- cyclopropylniitriles through some row reactions.2015
Year, document（Chemical Science, 6(9), 5164-5171; 2015.）The third two eyeballs of report make starting material and synthesize 1-
Amino -1- cyclopropylniitriles, but document refers to without specific steps, and yield is unknown.
The content of the invention
Present invention solves the technical problem that it there is provided a kind of preparation method of 1- amino -1- cyclopropylniitrile hydrochlorides, the party
Method is initiation material using nitroacetonitrile, is reacted under base catalysis with 1,2- dihalo-s ethane and 1- nitro -1- cyclopropylniitriles are made,
Again 1- amino -1- cyclopropylniitrile hydrochlorides are obtained through nitro-reduction reaction.
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, a kind of 1- amino -1- cyclopropylniitrile hydrochlorides
Preparation method, it is characterised in that concretely comprise the following steps：
（1）Nitroacetonitrile and 1,2- dihalo- ethane are added in reaction vessel, mixed system is cooled to -5-0 DEG C, is added portionwise
Alkali is reacted, and reaction adds mixture of ice and water washing after terminating, and anhydrous sodium sulfate drying obtains 1- nitro -1- cyclopropylniitriles, institute
It is 1,2- dichloroethanes or 1,2- Bromofume to state 1,2- dihalo-s ethane, and the alkali is sodium hydroxide or potassium hydroxide；
（2）1- nitro -1- cyclopropylniitriles and etoh solvent or methanol are added in reaction vessel, palladium carbon catalysis is added after nitrogen displacement
Agent, hydrogen being intermittently passed through at room temperature and is reacted, the use of palladium-carbon catalyst repetitive cycling is recovered by filtration in reaction after terminating, filtrate is dense
1- amino -1- cyclopropylniitrile solution is obtained after contracting, dry hydrogen chloride gas are passed through into 1- amino -1- cyclopropylniitrile solution then at 0 DEG C
White solid is produced, is filtrated to get 1- amino -1- cyclopropylniitrile hydrochlorides.
Further preferably, step（1）Described in nitroacetonitrile, 1,2- dihalo-s ethane and alkali molar ratio be 1:1:2-
4。
Further preferably, step（2）Described in Pd in palladium-carbon catalyst weight percentage be 10%, the palladium carbon catalysis
The dosage of agent is the 1%-5% of 1- nitro -1- cyclopropylniitrile weight.
The present invention has advantages below compared with prior art：Reaction condition of the present invention is gentle, yield is higher, cost is cheap
And it is suitable to commercial application.
Embodiment
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
Embodiment 1
The g of nitroacetonitrile 86 is added in reaction bulb（1.0 mol）With the g of glycol dibromide 186（1.0 mol）, by mixture
System is cooled to -5 DEG C, and the g of sodium hydroxide 160 is added portionwise（4.0 mol）Reacted, reaction adds mixture of ice and water after terminating
Washing, anhydrous sodium sulfate drying obtain the g of 1- nitro -1- cyclopropylniitriles 103, yield 91.9%, gas phase purity 99.2%.
The g of 1- nitro -1- cyclopropylniitriles 112 is added in reaction bulb（1.0 mol）With the mL of methanol 1120, after nitrogen displacement plus
The weight percentage for entering palladium is 10% palladium-carbon catalyst 1.12g, is intermittently passed through hydrogen at room temperature and is reacted, reaction terminates
After the use of palladium-carbon catalyst repetitive cycling is recovered by filtration, filtrate is concentrated into original 1/3, by concentrate be cooled to 0 DEG C it is slowly logical
Enter dry hydrogen chloride gas and separate out a large amount of white solids, be filtrated to get the g of 1- amino -1- cyclopropylniitriles hydrochloride 107, yield
90.6%, purity 99.5%.
Embodiment 2
The g of nitroacetonitrile 86 is added in reaction bulb（1.0 mol）With the g of 1,2- dichloroethanes 99（1.0 mol）, by mixed system
0 DEG C is cooled to, the g of sodium hydroxide 80 is added portionwise（2.0 mol）To be reacted, reaction adds mixture of ice and water washing after terminating,
Anhydrous sodium sulfate drying obtains the g of 1- nitro -1- cyclopropylniitriles 108, yield 96.4%, gas phase purity 99.0%.
The g of 1- nitro -1- cyclopropylniitriles 112 is added in reaction bulb（1.0 mol）With the mL of methanol 560, after nitrogen displacement plus
The weight percentage for entering palladium is 10% palladium-carbon catalyst 5.6g, is intermittently passed through hydrogen at room temperature and is reacted, after reaction terminates
The use of palladium-carbon catalyst repetitive cycling is recovered by filtration, filtrate is concentrated into original 1/3, and concentrate is cooled into 0 DEG C is slowly introducing
Dry hydrogen chloride gas separate out a large amount of white solids, are filtrated to get the g of 1- amino -1- cyclopropylniitriles hydrochloride 107, yield 89.0%,
Purity 99.3%.
Embodiment 3
The g of nitroacetonitrile 86 is added in reaction bulb（1.0 mol）With the g of 1,2- dichloroethanes 99（1.0 mol）, by mixed system
- 5 DEG C are cooled to, the g of potassium hydroxide 224 is added portionwise（4.0 mol）Reacted, reaction adds mixture of ice and water after terminating and washed
Wash, anhydrous sodium sulfate drying obtains the g of 1- nitro -1- cyclopropylniitriles 103, yield 92.0%, gas phase purity 99.1%.
The g of 1- nitro -1- cyclopropylniitriles 112 is added in reaction bulb（1.0 mol）With the mL of ethanol 560, after nitrogen displacement plus
The weight percentage for entering palladium is 10% palladium-carbon catalyst 1.12g, is intermittently passed through hydrogen at room temperature and is reacted, reaction terminates
After the use of palladium-carbon catalyst repetitive cycling is recovered by filtration, filtrate is concentrated into original 1/3, by concentrate be cooled to 0 DEG C it is slowly logical
Enter dry hydrogen chloride gas and separate out a large amount of white solids, be filtrated to get the g of 1- amino -1- cyclopropylniitriles hydrochloride 108, yield
91.5%, purity 99.5%.
Embodiment 4
The g of nitroacetonitrile 86 is added in reaction bulb（1.0 mol）With the g of glycol dibromide 186（1.0 mol）, by mixture
System is cooled to -5 DEG C, and the g of potassium hydroxide 224 is added portionwise（4.0 mol）Reacted, reaction adds mixture of ice and water after terminating
Washing, anhydrous sodium sulfate drying obtain the g of 1- nitro -1- cyclopropylniitriles 109, yield 97.3%, gas phase purity 99.0%.
The g of 1- nitro -1- cyclopropylniitriles 112 is added in reaction bulb（1.0 mol）With the mL of methanol 560, after nitrogen displacement plus
The weight percentage for entering palladium is 10% palladium-carbon catalyst 1.12g, is intermittently passed through hydrogen at room temperature and is reacted, reaction terminates
After the use of palladium-carbon catalyst repetitive cycling is recovered by filtration, filtrate is concentrated into original 1/3, by concentrate be cooled to 0 DEG C it is slowly logical
Enter dry hydrogen chloride gas and separate out a large amount of white solids, be filtrated to get the g of 1- amino -1- cyclopropylniitriles hydrochloride 107, yield
90.6%, purity 99.5%.
Embodiment 5
The g of nitroacetonitrile 86 is added in reaction bulb（1.0 mol）With the g of 1,2- dichloroethanes 99（1.0 mol）, by mixed system
0 DEG C is cooled to, the g of potassium hydroxide 112 is added portionwise（2.0 mol）Reacted, reaction adds mixture of ice and water after terminating and washed
Wash, anhydrous sodium sulfate drying obtains the g of 1- nitro -1- cyclopropylniitriles 108, yield 96.4%, gas phase purity 99.0%.
The g of 1- nitro -1- cyclopropylniitriles 112 is added in reaction bulb（1.0 mol）With the mL of ethanol 1120, after nitrogen displacement plus
The weight percentage for entering palladium is 10% palladium-carbon catalyst 5.6g, is intermittently passed through hydrogen at room temperature and is reacted, after reaction terminates
The use of palladium-carbon catalyst repetitive cycling is recovered by filtration, filtrate is concentrated into original 1/3, and concentrate is cooled into 0 DEG C is slowly introducing
Dry hydrogen chloride gas separate out a large amount of white solids, are filtrated to get the g of 1- amino -1- cyclopropylniitriles hydrochloride 110, yield 93.2%,
Purity 99.5%.
Embodiment 6
The g of nitroacetonitrile 86 is added in reaction bulb（1.0 mol）With the g of 1,2- dichloroethanes 99（1.0 mol）, by mixed system
0 DEG C is cooled to, the g of potassium hydroxide 112 is added portionwise（2.0 mol）Reacted, reaction adds mixture of ice and water after terminating and washed
Wash, anhydrous sodium sulfate drying obtains the g of 1- nitro -1- cyclopropylniitriles 108, yield 96.4%, gas phase purity 99.0%.
The g of 1- nitro -1- cyclopropylniitriles 112 is added in reaction bulb（1.0 mol）With the mL of ethanol 1120, after nitrogen displacement plus
The weight percentage for entering palladium is 10% palladium-carbon catalyst 5.6g, is intermittently passed through hydrogen at room temperature and is reacted, after reaction terminates
The use of palladium-carbon catalyst repetitive cycling is recovered by filtration, filtrate is concentrated into original 1/3, and concentrate is cooled into 0 DEG C is slowly introducing
Dry hydrogen chloride gas separate out a large amount of white solids, are filtrated to get the g of 1- amino -1- cyclopropylniitriles hydrochloride 110, yield 93.2%,
Purity 99.5%.
Embodiment 7
The g of nitroacetonitrile 86 is added in reaction bulb（1.0 mol）With the g of glycol dibromide 186（1.0 mol）, by mixture
System is cooled to -5 DEG C, and the g of sodium hydroxide 80 is added portionwise（2.0 mol）Reacted, reaction adds mixture of ice and water after terminating and washed
Wash, anhydrous sodium sulfate drying obtains the g of 1- nitro -1- cyclopropylniitriles 103, yield 91.9%, gas phase purity 99.2%.
The g of 1- nitro -1- cyclopropylniitriles 112 is added in reaction bulb（1.0 mol）With the mL of methanol 1120, after nitrogen displacement plus
The weight percentage for entering palladium is 10% palladium-carbon catalyst 5.6g, is intermittently passed through hydrogen at room temperature and is reacted, after reaction terminates
The use of palladium-carbon catalyst repetitive cycling is recovered by filtration, filtrate is concentrated into original 1/3, and concentrate is cooled into 0 DEG C is slowly introducing
Dry hydrogen chloride gas separate out a large amount of white solids, are filtrated to get the g of 1- amino -1- cyclopropylniitriles hydrochloride 107, yield 90.6%,
Purity 99.0%.
Embodiment 8
The g of nitroacetonitrile 86 is added in reaction bulb（1.0 mol）With the g of 1,2- dichloroethanes 99（1.0 mol）, by mixed system
0 DEG C is cooled to, the g of sodium hydroxide 160 is added portionwise（4.0 mol）Reacted, reaction adds mixture of ice and water after terminating and washed
Wash, anhydrous sodium sulfate drying obtains the g of 1- nitro -1- cyclopropylniitriles 108, yield 96.4%, gas phase purity 99.5%.
The g of 1- nitro -1- cyclopropylniitriles 112 is added in reaction bulb（1.0 mol）With the mL of methanol 560, after nitrogen displacement plus
The weight percentage for entering palladium is 10% palladium-carbon catalyst 5.6g, is intermittently passed through hydrogen at room temperature and is reacted, after reaction terminates
The use of palladium-carbon catalyst repetitive cycling is recovered by filtration, filtrate is concentrated into original 1/3, and concentrate is cooled into 0 DEG C is slowly introducing
Dry hydrogen chloride gas separate out a large amount of white solids, are filtrated to get the g of 1- amino -1- cyclopropylniitriles hydrochloride 107, yield 89.0%,
Purity 99.6%.
Embodiment 9
The g of nitroacetonitrile 86 is added in reaction bulb（1.0 mol）With the g of glycol dibromide 186（1.0 mol）, by mixture
System is cooled to 0 DEG C, and the g of potassium hydroxide 112 is added portionwise（2.0 mol）Reacted, reaction adds mixture of ice and water after terminating and washed
Wash, anhydrous sodium sulfate drying obtains the g of 1- nitro -1- cyclopropylniitriles 102, yield 91.2%, gas phase purity 99.7%.
The g of 1- nitro -1- cyclopropylniitriles 112 is added in reaction bulb（1.0 mol）With the mL of methanol 1120, after nitrogen displacement plus
The weight percentage for entering palladium is 10% g of palladium-carbon catalyst 5.6, is intermittently passed through hydrogen at room temperature and is reacted, reaction terminates
After the use of palladium-carbon catalyst repetitive cycling is recovered by filtration, filtrate is concentrated into original 1/3, by concentrate be cooled to 0 DEG C it is slowly logical
Enter dry hydrogen chloride gas and separate out a large amount of white solids, be filtrated to get the g of 1- amino -1- cyclopropylniitriles hydrochloride 115, yield
97.4%, purity 99.0%.
Embodiment above describes the general principle of the present invention, main features and advantages, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, the original for simply illustrating the present invention described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (3)
1. a kind of preparation method of 1- amino -1- cyclopropylniitrile hydrochlorides, it is characterised in that concretely comprise the following steps：
（1）Nitroacetonitrile and 1,2- dihalo- ethane are added in reaction vessel, mixed system is cooled to -5-0 DEG C, is added portionwise
Alkali is reacted, and reaction adds mixture of ice and water washing after terminating, and anhydrous sodium sulfate drying obtains 1- nitro -1- cyclopropylniitriles, institute
It is 1,2- dichloroethanes or 1,2- Bromofume to state 1,2- dihalo-s ethane, and the alkali is sodium hydroxide or potassium hydroxide；
（2）1- nitro -1- cyclopropylniitriles and etoh solvent or methanol are added in reaction vessel, palladium carbon catalysis is added after nitrogen displacement
Agent, hydrogen being intermittently passed through at room temperature and is reacted, the use of palladium-carbon catalyst repetitive cycling is recovered by filtration in reaction after terminating, filtrate is dense
1- amino -1- cyclopropylniitrile solution is obtained after contracting, dry hydrogen chloride gas are passed through into 1- amino -1- cyclopropylniitrile solution then at 0 DEG C
White solid is produced, is filtrated to get 1- amino -1- cyclopropylniitrile hydrochlorides.
2. the preparation method of 1- amino -1- cyclopropylniitrile hydrochlorides according to claim 1, it is characterised in that：Step（1）In
The molar ratio of the nitroacetonitrile, 1,2- dihalo-s ethane and alkali is 1:1:2-4.
3. the preparation method of 1- amino -1- cyclopropylniitrile hydrochlorides according to claim 1, it is characterised in that：Step（2）In
The weight percentage of the Pd in palladium-carbon catalyst is 10%, and the dosage of the palladium-carbon catalyst is 1- nitro -1- cyclopropylniitrile weight
1%-5%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114989024A (en) * | 2021-11-17 | 2022-09-02 | 郑州尼采生物科技有限公司 | Synthesis method and application of 1-aminocyclopropane carboxylic acid compound |
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| CN101225057A (en) * | 2008-01-20 | 2008-07-23 | 浙江大学宁波理工学院 | Method for synthesizing 1-amido-1-naphthenic nitrile compound |
| CN102046576A (en) * | 2008-06-11 | 2011-05-04 | 奇斯药制品公司 | Process of preparing derivatives of 1-(2-halobiphenyl-4-yl)-cyclopropanecarboxylic acid |
| CN103864635A (en) * | 2014-03-27 | 2014-06-18 | 张家港威胜生物医药有限公司 | Simple synthesis process of 1-aminocyclopropane-1-carboxylic acid |
| CN106536489A (en) * | 2014-05-28 | 2017-03-22 | 葛兰素史密斯克莱知识产权发展有限公司 | Novel compounds |
-
2017
- 2017-10-10 CN CN201710935505.0A patent/CN107698462A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101225057A (en) * | 2008-01-20 | 2008-07-23 | 浙江大学宁波理工学院 | Method for synthesizing 1-amido-1-naphthenic nitrile compound |
| CN102046576A (en) * | 2008-06-11 | 2011-05-04 | 奇斯药制品公司 | Process of preparing derivatives of 1-(2-halobiphenyl-4-yl)-cyclopropanecarboxylic acid |
| CN103864635A (en) * | 2014-03-27 | 2014-06-18 | 张家港威胜生物医药有限公司 | Simple synthesis process of 1-aminocyclopropane-1-carboxylic acid |
| CN106536489A (en) * | 2014-05-28 | 2017-03-22 | 葛兰素史密斯克莱知识产权发展有限公司 | Novel compounds |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114989024A (en) * | 2021-11-17 | 2022-09-02 | 郑州尼采生物科技有限公司 | Synthesis method and application of 1-aminocyclopropane carboxylic acid compound |
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Application publication date: 20180216 |