CN116621709B - Synthesis method of cyclopropylamine - Google Patents
Synthesis method of cyclopropylamine Download PDFInfo
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- CN116621709B CN116621709B CN202310904364.1A CN202310904364A CN116621709B CN 116621709 B CN116621709 B CN 116621709B CN 202310904364 A CN202310904364 A CN 202310904364A CN 116621709 B CN116621709 B CN 116621709B
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- chloroform
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- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000001308 synthesis method Methods 0.000 title description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005977 Ethylene Substances 0.000 claims abstract description 11
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 10
- 238000011049 filling Methods 0.000 claims abstract description 10
- 238000005576 amination reaction Methods 0.000 claims abstract description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 9
- 238000007789 sealing Methods 0.000 claims abstract description 9
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 9
- 239000011592 zinc chloride Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 9
- 239000007868 Raney catalyst Substances 0.000 claims description 7
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 7
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- -1 potassium alkoxide Chemical class 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000005913 hydroamination reaction Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
- 239000002699 waste material Substances 0.000 abstract description 11
- 239000000047 product Substances 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- ARQRPTNYUOLOGH-UHFFFAOYSA-N chcl3 chloroform Chemical compound ClC(Cl)Cl.ClC(Cl)Cl ARQRPTNYUOLOGH-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 238000005915 ammonolysis reaction Methods 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
- C07C45/43—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis of >CX2 groups, X being halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The application discloses a method for synthesizing cyclopropylamine, which relates to the technical field of organic synthesis and specifically comprises the following steps: adding an alcohol solution of chloroform and a catalyst I into a pressure container, sealing, filling ethylene into the pressure container, and carrying out a cyclization reaction at a constant temperature; cooling and deflating after the pressure of the pressure vessel is stable; zinc chloride and water are added into a pressure vessel, the pressure vessel is sealed and then is insulated for carbonylation reaction, and the temperature is reduced and the gas is discharged after the pressure of the pressure vessel is stable; adding a second catalyst into the pressure vessel, sealing, filling hydrogen and ammonia into the pressure vessel, preserving heat for catalytic hydrogenation amination reaction, cooling and deflating after the pressure in the pressure vessel is stable, filtering the reaction solution in the pressure vessel, rectifying the filtrate, collecting the fraction at 48-52 ℃, and drying the fraction to obtain cyclopropylamine. The method has the advantages of short process flow, high atom utilization rate of raw materials and auxiliary materials, high product yield, and less waste liquid and waste salt generated in the preparation process, thereby further saving the cost of the raw materials and the auxiliary materials and the cost of waste liquid treatment.
Description
Technical Field
The application relates to the technical field of organic synthesis, in particular to a synthesis method of cyclopropylamine.
Background
Cyclopropylamine is an important intermediate for medicine, pesticide and pesticide, and is mainly used for producing ciprofloxacin and is also used for synthesizing pesticide and plant protecting agent.
At present, the preparation process of cyclopropylamine mainly uses gamma-butyrolactone as a starting material, and prepares cyclopropylamine by a five-step method of ring opening, esterification, cyclization, ammonolysis and Hofmann degradation. Although the preparation method is mature and industrialized, the preparation method still has more problems, such as sulfoxide chloride or hydrogen chloride used in the ring-opening reaction, both of which have strong corrosiveness and high requirements on equipment materials; the consumption of solvent and catalyst for cyclization reaction and ammonolysis reaction is large, and the conversion rate of raw materials is low; the Hofmann degradation reaction produces a large amount of saline wastewater. In the whole, the above preparation method has poor atom utilization rate of raw materials and auxiliary materials, can generate more waste liquid, increases the treatment cost of the waste liquid, and further improves the yield of the product.
Disclosure of Invention
The technical problems to be solved by the application are as follows: aiming at the defects existing in the prior art, the method provides a method for synthesizing cyclopropylamine, which uses ethylene as an initial raw material to sequentially perform a cyclization reaction, a carbonylation reaction and a catalytic hydrogenation amination reaction to obtain a target product; the process flow is short, the atomic utilization rate of raw materials and auxiliary materials is high, the product yield is high, the amount of waste liquid and waste salt generated in the preparation process is small, and the cost of raw materials and auxiliary materials and the cost of waste liquid treatment are further saved.
In order to solve the technical problems, the technical scheme of the application is as follows:
a method for synthesizing cyclopropylamine, comprising the following steps:
(1) Adding an alcohol solution of chloroform and a catalyst I into a pressure container, sealing, filling ethylene into the pressure container, and carrying out a cyclization reaction at a constant temperature; cooling and deflating after the pressure in the pressure vessel is stable;
(2) Zinc chloride and water are added into a pressure vessel, the pressure vessel is sealed and then is insulated for carbonylation reaction, and the temperature is reduced and the gas is discharged after the pressure in the pressure vessel is stable;
(3) Adding a second catalyst into the pressure vessel, sealing, filling hydrogen and ammonia into the pressure vessel, preserving heat for catalytic hydrogenation amination reaction, cooling and deflating after the pressure in the pressure vessel is stable, filtering the reaction solution in the pressure vessel, rectifying the filtrate, collecting the fraction at 48-52 ℃, and drying the fraction to obtain cyclopropylamine.
In the above technical scheme, in the step (1), the first catalyst is one of hydroxide of alkali metal, potassium alkoxide or sodium alkoxide.
As a preferable mode of the above technical scheme, in the step (1), the alcohol in the alcoholic solution of chloroform includes one of methanol, ethanol and isopropanol; the mass ratio of the alcohol to the chloroform is (1-3): 1.
as a preferable mode of the above technical scheme, in the step (1), the molar ratio of the catalyst one, ethylene and chloroform is (1.1-1.31): (1.09-2.2): 1.
as a preferable mode of the technical scheme, in the step (1), the temperature of the cyclization reaction is 30-80 ℃, and the stirring speed is 200-400rpm.
As a preferable mode of the above technical scheme, in the step (2), the mass ratio of water to chloroform is 2:1, a step of; the mole ratio of zinc chloride to chloroform is (0.01-0.1): 1.
as a preferable mode of the above technical scheme, in the step (2), the temperature of the carbonylation reaction is 45-55 ℃ and the stirring rotation speed is 200-400rpm.
As the preferable technical scheme, in the step (3), the catalyst II is Raney nickel, and the mass ratio of Raney nickel to chloroform is (0.005-0.015): 1.
as a preferable mode of the technical scheme, in the step (3), the molar ratio of ammonia gas to chloroform is (1.1-1.7): 1, a step of; the pressure of the hydrogen gas is 1.5MPa.
As a preferable mode of the technical scheme, in the step (3), the temperature of the catalytic hydrogenation amination reaction is 30-90 ℃, and the stirring speed is 200-400rpm.
The chemical reaction formula related to the synthesis method provided by the application is as follows:
(1) Cyclization reaction
；
(2) Carbonylation reaction
；
(3) Catalytic hydroamination
。
Due to the adoption of the technical scheme, the application has the beneficial effects that:
according to the application, ethylene is used as a starting material, firstly, the ethylene and chloroform are subjected to cyclization reaction under a certain condition, then water is added into a reaction system, zinc chloride is added as a catalyst for carbonylation reaction, and the stability of a carbonylation product is effectively ensured by adding water; then ammonia gas and hydrogen gas are added, and catalytic hydrogenation amination reaction is carried out under the catalysis of Raney nickel, so that the target product is prepared. The method disclosed by the application has mild conditions, is not easy to cause side reaction, has high atom utilization rate of raw and auxiliary materials, and the obtained target product has high yield and purity, and generates less waste liquid and waste salt, thereby effectively reducing the cost of raw and auxiliary materials and the treatment cost of the waste liquid. The method has the advantages of simple operation steps and short process flow, and effectively reduces the operation cost and the equipment cost.
Drawings
FIG. 1 is a gas phase detection spectrum of cyclopropylamine produced in example 1;
FIG. 2 is a gas phase detection spectrum of a cyclopropylamine standard.
Detailed Description
The application is further illustrated below with reference to examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application.
The yields of cyclopropylamine in the examples below were calculated as follows:
cyclopropylamine yield (%) = [ (m) Cyclopropylamine /M Cyclopropylamine ）/（m Chloroform (chloroform) /M Chloroform (chloroform) ）]×100%；
Wherein m is Cyclopropylamine : mass, g of cyclopropylamine;
M cyclopropylamine : the molar molecular weight of cyclopropylamine, g/mol;
m chloroform (chloroform) : chloroform, g;
M chloroform (chloroform) : the molar weight of chloroform, g/mol.
Example 1
Adding 100.0g of ethanol, 50.0g of chloroform and 34.2g of sodium ethoxide into a pressure vessel, sealing the pressure vessel, then filling 18.8g of ethylene into the pressure vessel, maintaining the temperature at the stirring speed of 300rpm and the temperature of 55 ℃ for cyclization reaction until the pressure in the pressure vessel is stable (the pressure is not changed within half an hour), and cooling and deflating; opening a pressure container, adding 2.9g of zinc chloride and 100.0g of water into the pressure container, sealing the pressure container, maintaining the temperature at the stirring rotation speed of 300rpm and the temperature of 50 ℃ for carbonylation until the pressure in the pressure container is stable (the pressure is not changed within half an hour), and cooling and deflating; opening a pressure container, adding 0.5g of Raney nickel into the pressure container, filling 1.5MPa of hydrogen and 10.0g of ammonia, stirring at 300rpm, and preserving heat at 60 ℃ to perform catalytic hydrogenation amination reaction; when the pressure of the pressure vessel is reduced to a stable value (the pressure is not changed within half an hour), the temperature is reduced and the air is discharged; the pressure vessel was opened, raney nickel was removed by filtration of the reaction solution in the pressure vessel, the filtrate was distilled off to obtain a fraction at 48-52℃and the fraction was dried over anhydrous magnesium sulfate to obtain 21.72g of cyclopropylamine, the yield of which was 90.8%.
The gas phase detection spectrum of the product prepared in the embodiment is shown in fig. 1, and the gas phase detection spectrum of the cyclopropylamine standard is shown in fig. 2. As can be seen from fig. 1 and 2, the peak of the product obtained in example 1 is consistent with that of the cyclopropylamine standard, i.e., the product is cyclopropylamine.
Example 2
This embodiment differs from embodiment 1 in that: the feeding amount of sodium ethoxide is 31.4g, the feeding amount and reaction parameters of other materials are unchanged, and 21.47g of cyclopropylamine is obtained, and the yield of the cyclopropylamine is 89.8%.
Example 3
This embodiment differs from embodiment 1 in that: the feeding amount of sodium ethoxide is 37.1g, the feeding amount and reaction parameters of other materials are unchanged, 21.57g of cyclopropylamine is obtained, and the yield of cyclopropylamine is 90.2%.
Example 4
This embodiment differs from embodiment 1 in that: the ethylene charge was 12.9g, and the other materials were fed in unchanged amounts and reaction parameters to give 21.45g of cyclopropylamine with a yield of 89.71%.
Example 5
This embodiment differs from embodiment 1 in that: the ethylene charge was 24.7g, and the other materials were fed in unchanged amounts and reaction parameters to give 21.79g of cyclopropylamine with a cyclopropylamine yield of 91.1%.
Example 6
This embodiment differs from embodiment 1 in that: the zinc chloride feeding amount is 0.6g, the feeding amount and the reaction parameters of other materials are unchanged, and 21.44g of cyclopropylamine is obtained, and the cyclopropylamine yield is 89.7%.
Example 7
This embodiment differs from embodiment 1 in that: the zinc chloride feeding amount is 5.7g, the feeding amount and the reaction parameters of other materials are unchanged, and 21.82g of cyclopropylamine is obtained, and the cyclopropylamine yield is 91.3%.
Example 8
This embodiment differs from embodiment 1 in that: the filling amount of ammonia is 7.9g, the feeding amount and reaction parameters of other materials are unchanged, and 21.49g of cyclopropylamine is obtained, and the yield of the cyclopropylamine is 89.9%.
Example 9
This embodiment differs from embodiment 1 in that: the filling amount of ammonia gas is 12.1g, the feeding amount and reaction parameters of other materials are unchanged, and 21.84g of cyclopropylamine is obtained, and the yield of the cyclopropylamine is 91.3%.
Example 10
This embodiment differs from embodiment 1 in that: the cyclization reaction temperature is 30 ℃, the feeding amount and the reaction parameters of other materials are unchanged, 21.41g of cyclopropylamine is obtained, and the yield of the cyclopropylamine is 89.5%.
Example 11
This embodiment differs from embodiment 1 in that: the cyclization reaction temperature is 80 ℃, the feeding amount and the reaction parameters of other materials are unchanged, 21.86g of cyclopropylamine is obtained, and the yield of the cyclopropylamine is 91.4%.
Example 12
This embodiment differs from embodiment 1 in that: the catalytic hydrogenation amination reaction temperature is 30 ℃, the feeding amount and the reaction parameters of other materials are unchanged, 21.52g of cyclopropylamine is obtained, and the yield of the cyclopropylamine is 90.0%.
Example 13
This embodiment differs from embodiment 1 in that: the catalytic hydrogenation amination reaction temperature is 90 ℃, the feeding amount and the reaction parameters of other materials are unchanged, and 21.88g of cyclopropylamine is obtained, and the yield of the cyclopropylamine is 91.5%.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (8)
1. A method for synthesizing cyclopropylamine, comprising the steps of:
(1) Adding an alcohol solution of chloroform and a catalyst I into a pressure container, sealing, filling ethylene into the pressure container, preserving heat at 30-80 ℃ for cyclization reaction, and cooling and deflating after the pressure in the pressure container is stable; the catalyst I is one of hydroxide of alkali metal, potassium alkoxide or sodium alkoxide;
(2) Zinc chloride and water are added into a pressure vessel, the temperature is kept at 45-55 ℃ after sealing for carbonylation reaction, and the temperature is reduced and the gas is discharged after the pressure in the pressure vessel is stable;
(3) Adding Raney nickel into a pressure container, sealing, filling hydrogen and ammonia into the pressure container, preserving heat at 30-90 ℃ for catalytic hydrogenation amination reaction, cooling and deflating after the pressure in the pressure container is stable, filtering a reaction solution in the pressure container, rectifying filtrate, collecting a fraction at 48-52 ℃, and drying the fraction to obtain cyclopropylamine; the mass ratio of the Raney nickel to the chloroform is (0.005-0.015): 1, a step of; the pressure of the hydrogen gas is 1.5MPa.
2. The method for synthesizing cyclopropylamine according to claim 1, wherein in step (1), the alcohol in the alcoholic solution of chloroform is selected from one of methanol, ethanol and isopropanol; the mass ratio of the alcohol to the chloroform is (1-3): 1.
3. the method for synthesizing cyclopropylamine according to claim 1, wherein in step (1), the molar ratio of catalyst one, ethylene and chloroform is (1.1-1.31): (1.09-2.2): 1.
4. the method for synthesizing cyclopropylamine according to claim 1, wherein in step (1), the stirring speed of the cyclization reaction is 200-400rpm.
5. The method for synthesizing cyclopropylamine according to claim 1, wherein in step (2), the mass ratio of water to chloroform is 2:1, a step of; the mole ratio of zinc chloride to chloroform is (0.01-0.1): 1.
6. the method for synthesizing cyclopropylamine according to claim 1, wherein in step (2), the stirring speed of the carbonylation reaction is 200 to 400rpm.
7. The method for synthesizing cyclopropylamine according to claim 1, wherein in step (3), the molar ratio of ammonia gas to chloroform is (1.1-1.7): 1.
8. the method for synthesizing cyclopropylamine according to claim 1, wherein in step (3), the stirring speed of the catalytic hydroamination reaction is 200 to 400rpm.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114702391A (en) * | 2021-12-17 | 2022-07-05 | 青岛科技大学 | Method for preparing cyclopropylamine by performing Hofmann rearrangement by using hydrogen peroxide |
| CN114989018A (en) * | 2022-08-05 | 2022-09-02 | 山东国邦药业有限公司 | Synthetic method of cyclopropylamine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114702391A (en) * | 2021-12-17 | 2022-07-05 | 青岛科技大学 | Method for preparing cyclopropylamine by performing Hofmann rearrangement by using hydrogen peroxide |
| CN114989018A (en) * | 2022-08-05 | 2022-09-02 | 山东国邦药业有限公司 | Synthetic method of cyclopropylamine |
Non-Patent Citations (1)
| Title |
|---|
| The Generation of CF and an Investigation of the Products of Its Reaction with Alkenes;M. Rahman等;J. Am. Chem. Soc.;第108卷(第20期);第6296-6299页 * |
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