CN107614478B - Process for producing 1-cyclopropylethylamine or acid addition salt thereof - Google Patents
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/33—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C211/34—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton
- C07C211/35—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton containing only non-condensed rings
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Abstract
The present invention relates to a process for producing 1-cyclopropylethylamine or an acid addition salt thereof. The present invention provides a method for producing high-purity 1-cyclopropylethylamine or an acid addition salt thereof, which comprises: cyclopropyl methyl ketone, ammonia and hydrogen are reacted in alcohols and/or ethers in the presence of a nickel catalyst supported on an inorganic oxide.
Description
Technical Field
The present invention relates to a method for producing 1-cyclopropylethylamine or an acid addition salt thereof, which is useful as an intermediate for medicines or agricultural chemicals.
Background
As a method for producing aliphatic amines having a cycloalkyl group such as 1-cyclopropylethylamine, for example, a method for producing 1-cyclopropylethylamine by reacting cyclopropylmethyl ketone (also known as cyclopropylethanone, acetylcyclopropane or cyclopropylmethyl ketone) with ammonia in the presence of a raney nickel catalyst has been known (non-patent document 1), but the method for activating raney nickel is complicated, may be spontaneous combustion, and the yield is insufficient. Further, a method for producing 1-cyclopentylethylamine from cyclopentylmethyl ketone by using the Leuckart reaction is known (non-patent document 2), but this method is a reaction at a high temperature, and has many wastes, which are problems in industrial production.
As a reduction method using a nickel catalyst supported on an inorganic oxide, for example, patent document 1 describes a method for producing a corresponding amine from a (3-oxobutyl) benzene compound. However, no example is known of its use for the reduction of cyclopropylmethyl ketone.
Documents of the prior art
Patent document
Patent document 1 Japanese patent laid-open No. Sho 63-258444
Non-patent document
Non-patent document 1, Zhurnal organic heskoi Khimii (1976),12,8,1827-
Non-patent document 2 Journal of the American Chemical Society (1954),76,4564-
Disclosure of Invention
Problems to be solved by the invention
1-cyclopropylethylamine or an acid addition salt thereof is useful as an intermediate for producing medicinal and agricultural chemicals, and there has been a demand for a method for producing the same more economically by an industrially simple, efficient and environmentally friendly method. Although a process for obtaining 1-cyclopropylethylamine using a raney nickel catalyst is known, raney nickel generally requires an activation pretreatment using a base, and if dried, it is liable to catch fire, so that the process is not satisfactory as an industrial process.
In addition, cyclopropyl groups are susceptible to ring opening by transition metal complexes, as is generally known. Therefore, the following problems are present: when a compound having a cyclopropyl group is reacted in the presence of a transition metal complex, a ring-opened by-product is produced, and the separation of the by-product from the target substance is not easy.
The purpose of the present invention is to provide a method for producing high-purity 1-cyclopropylethylamine or an acid addition salt thereof by a simple, efficient and environmentally friendly method.
Means for solving the problems
The present inventors have conducted studies to solve the above problems, and as a result, have found that 1-cyclopropylethylamine can be produced under a certain condition with high purity, thereby completing the present invention.
That is, the present invention relates to a method for producing 1-cyclopropylethylamine by reacting cyclopropylmethyl ketone, ammonia and hydrogen in the presence of a nickel catalyst supported on an inorganic oxide in alcohols and/or ethers, and further relates to a method for producing an acid addition salt of 1-cyclopropylethylamine by reacting 1-cyclopropylethylamine produced by the method with an acid in a solvent.
Effects of the invention
The method of the present invention enables the production of high-purity 1-cyclopropylethylamine and acid addition salts thereof in a simple, efficient and environmentally friendly manner.
Detailed Description
1-Cyclopropylethylamine can be produced by reacting cyclopropylmethyl ketone and ammonia in the presence of a nickel catalyst supported on an inorganic oxide as described below. Further, 1-cyclopropylethylamine has optical isomers (R isomer and S isomer), and both of the isomers and isomer mixtures are included in the present invention.
As ammonia, an ammonia alcohol solution, an aqueous ammonia solution, liquid ammonia, or ammonia gas can be suitably used. Examples of the alcohol in the alcohol-alcohol solution include methanol, ethanol, propanol, isopropanol, and butanol. When an ammonia alcohol solution is used, it can also be used as a solvent.
Ammonia is used in an amount of usually 1 to 10 times by mole, preferably 1 to 2 times by mole, based on 1 mole of cyclopropylmethyl ketone. However, depending on the reaction conditions, amounts outside this range may be used.
As the catalyst, a nickel catalyst supported on an inorganic oxide is used. Examples of the inorganic oxide include diatomaceous earth, silica, alumina, magnesia, calcia, titania, zirconia, niobia, and lanthana. Among them, diatomaceous earth, silica or alumina is preferable, and diatomaceous earth is more preferable.
The nickel catalyst supported on the inorganic oxide may be produced by a generally known method, preferably a precipitation method or an impregnation method, or may be a commercially available product, and the content of nickel in the catalyst is not particularly limited. Examples of commercially available products include stabilized nickel catalyst N-103 (supported on diatomaceous earth and having a nickel content of 52.5% by weight) manufactured by Nikkai chemical Co., Ltd, stabilized nickel SN-750 (supported on diatomaceous earth and having a nickel content of 47% by weight) manufactured by Sakai chemical industry Co., Ltd, and the like.
The nickel catalyst supported on the inorganic oxide is used in an amount of usually 1 to 50 wt%, preferably 5 to 20 wt%, in terms of nickel content, based on 100 wt% of cyclopropylmethyl ketone. However, depending on the reaction conditions, amounts outside this range may be used.
It is generally preferable to use 1 to 10 times by mole of hydrogen gas based on 1 mole of cyclopropylmethyl ketone. The pressure is usually selected from the range of 0.1 to 10MPa, but in order to efficiently carry out the reaction and obtain the target product with high purity and high yield on an industrial scale, it is preferable to react with hydrogen gas while keeping the pressure constant within the range of 1 to 10 MPa. However, depending on the reaction conditions, amounts and pressures outside these ranges may be used.
In the present invention, alcohols and/or ethers are used as the solvent used for producing 1-cyclopropylethylamine, and alcohols are preferably used. The alcohol is preferably an alcohol having 1 to 6 carbon atoms, and examples thereof include methanol, ethanol, propanol, isopropanol, and butanol. The ethers are preferably ethers having 1 to 6 carbon atoms, and examples thereof include diethyl ether, diisopropyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and ethylene glycol dimethyl ether. In addition, a solvent other than the above-mentioned solvents may be used within a range not affecting the reaction.
The solvent used in the production of 1-cyclopropylethylamine is used in an amount of usually 1 to 20 times (V/W), preferably 3 to 15 times (V/W) the amount of cyclopropylmethyl ketone. However, depending on the reaction conditions, amounts outside this range may be used.
The reaction temperature is usually about 80 to 200 ℃, preferably about 100 to 130 ℃, and the reaction time is usually about 1 to 12 hours, preferably about 1 to 6 hours.
An acid addition salt of 1-cyclopropylethylamine can be produced by reacting 1-cyclopropylethylamine with an acid in a solvent. The 1-cyclopropylethylamine obtained by the aforementioned reaction can be subjected to the main reaction without isolation or purification.
Examples of the acid addition salt of 1-cyclopropylethylamine produced in the main reaction include salts with inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid.
Examples of the acid include hydrogen chloride, hydrochloric acid, sulfuric acid, and acetic acid. The amount of the acid is usually 0.5 to 5 mol, preferably 0.5 to 1.5 mol, based on 1 mol of 1-cyclopropylethylamine. However, depending on the reaction conditions, amounts outside this range may be used.
In the present invention, the solvent used for producing an acid addition salt of 1-cyclopropylethylamine is preferably 1 or 2 or more selected from aromatic hydrocarbons, ketones, alcohols and a mixed solvent thereof, and particularly preferably alcohols and/or aromatic hydrocarbons. Examples of the aromatic hydrocarbons include benzene, toluene, xylene, chlorobenzene, and the like. Examples of the ketones include acetone and butanone. The alcohol is preferably an alcohol having 1 to 6 carbon atoms, and examples thereof include methanol, ethanol, propanol, isopropanol, and butanol.
The solvent used for the production of the acid addition salt of 1-cyclopropylethylamine is usually used in an amount of 1 to 20 times (V/W), preferably 3 to 15 times (V/W) the amount of 1-cyclopropylethylamine. However, depending on the reaction conditions, amounts outside this range may be used.
The reaction temperature is usually 0 to 100 ℃, preferably 10 to 50 ℃, and the reaction time is usually 1 to 10 hours, preferably 1 to 3 hours.
Next, some preferred embodiments of the present invention will be described, but the present invention is not limited thereto.
【1】 A method for producing 1-cyclopropylethylamine or an acid addition salt thereof, which comprises: cyclopropyl methyl ketone, ammonia and hydrogen are reacted in alcohols and/or ethers in the presence of a nickel catalyst supported on an inorganic oxide.
【2】 The method of [ 1 ], comprising:
(i) a 1 st step of reacting cyclopropylmethyl ketone, ammonia and hydrogen in the presence of a nickel catalyst supported on an inorganic oxide in an alcohol and/or an ether to obtain 1-cyclopropylethylamine, and
(ii) a 2 nd step of reacting 1-cyclopropylethylamine with an acid in a solvent to obtain an acid addition salt of 1-cyclopropylethylamine.
【3】 The method according to [ 1 ] or [ 2 ], wherein the inorganic oxide is diatomaceous earth, silica or alumina.
【4】 The method according to [ 3 ], wherein the inorganic oxide is diatomaceous earth.
【5】 The method according to any one of [ 1 ] to [ 3 ], wherein the nickel catalyst supported on the inorganic oxide is present in an amount of 1 to 50 wt% in terms of the content of nickel relative to cyclopropylmethyl ketone.
【6】 The method as described in [ 1 ], which is carried out in alcohols.
【7】 The method according to any one of [ 1 ] to [ 6 ], wherein the reaction is carried out with hydrogen under a pressure of 0.1 to 10 MPa.
【8】 The method as described in [ 7 ], wherein the reaction with hydrogen is carried out while keeping the pressure constant within a range of 1 to 10 MPa.
【9】 The method according to any one of [ 1 ] to [ 8 ], wherein the acid addition salt of 1-cyclopropylethylamine is a hydrochloride, sulfate or acetate salt.
【10】 The method according to [ 2 ], wherein an aromatic hydrocarbon and/or an alcohol is used as the solvent in the step 2.
Examples
The following examples are described in order to further specifically explain the present invention, but the present invention is not limited to these examples. The abbreviations in each table have the following meanings.
CPMK: cyclopropyl methyl ketone
CPEA: 1-Cyclopropylethylamine
AP: 2-aminopentane (Split ring as by-product)
The GC-PA% in each table represents the percentage of Peak area (Peak area%) obtained by Gas Chromatography (GC) analysis, and the measurement conditions are as follows.
Column, DB-1, manufactured by J & W, having an inner diameter of 320 μm, a film thickness of 1.00 μm and a length of 30m
Helium as carrier gas, LGV 23 cm/sec
Oven at 50 ℃ for 12 minutes, heating from 50 ℃ to 250 ℃ at 40 ℃/minute and holding at 250 ℃ for 3 minutes.
The sample inlet is 250 ℃, the split ratio is 100:1, and the split flow is 123 mL/min
Detector FID at 250 deg.C, hydrogen flow rate of 40.0 mL/min, air flow rate of 450 mL/min, injection volume of 3.0 μ L
Example 1
20g (purity 99%, 238mmol) of cyclopropylmethyl ketone, 63.6g (262mmol) of a 7% methanolic ammonia solution and 1.96g (17.0mmol) of a stabilized nickel catalyst N-103 (manufactured by Nikkaido Seisaku Co., Ltd.) were placed in a 500ml autoclave, and the inside of the reaction vessel was replaced with hydrogen gas 2 times. After the replacement, the reaction vessel was charged with hydrogen gas to 2.5MPa and stirred at 120 ℃ for 3 hours. The reaction mixture was cooled to 20 ℃ and then the inside of the reaction vessel was brought to normal pressure, and insoluble matter was filtered off. The reaction progress rate of the obtained solution was confirmed by gas chromatography (here, "reaction progress rate" means GC-PA% of the CPEA.
Example 2
10g (purity 99%, 119mmol) of cyclopropylmethyl ketone, 31.8g (131mmol) of a 7% methanolic ammonia solution and 0.98g (8.5mmol) of a stabilized nickel catalyst N-103 (manufactured by Nikkaido Seisaku Co., Ltd.) were placed in a 200ml autoclave, and the inside of the reaction vessel was replaced with hydrogen gas 2 times. After the replacement, the reaction vessel was charged with hydrogen gas to 2.5MPa and stirred at 100 ℃ for 3 hours. The reaction mixture was cooled to 20 ℃ and then the inside of the reaction vessel was brought to normal pressure, and insoluble matter was filtered off. The reaction progress rate of the obtained solution was confirmed by gas chromatography.
Example 3
10g (purity 99%, 119mmol) of cyclopropylmethyl ketone, 31.8g (131mmol) of a 7% methanolic ammonia solution and 0.98g (8.5mmol) of a stabilized nickel catalyst N-103 (manufactured by Nikkaido Seisaku Co., Ltd.) were placed in a 200ml autoclave, and the inside of the reaction vessel was replaced with hydrogen gas 2 times. After the replacement, the reaction vessel was charged with hydrogen gas to 3.5MPa and stirred at 120 ℃ for 3 hours. The reaction mixture was cooled to 20 ℃ and then the inside of the reaction vessel was brought to normal pressure, and insoluble matter was filtered off. The reaction progress rate of the obtained solution was confirmed by gas chromatography.
Example 4
10g (purity 99%, 119mmol) of cyclopropylmethyl ketone, 31.8g (131mmol) of a 7% methanolic ammonia solution and 1.96g (17mmol) of a stabilized nickel catalyst N-103 (manufactured by Nikkaido Kagaku Co., Ltd.) were placed in a 200ml autoclave, and the inside of the reaction vessel was replaced with hydrogen gas 2 times. After the replacement, the reaction vessel was charged with hydrogen gas to 2.5MPa and stirred at 120 ℃ for 3 hours. The reaction mixture was cooled to 20 ℃ and then the inside of the reaction vessel was brought to normal pressure, and insoluble matter was filtered off. The reaction progress rate of the obtained solution was confirmed by gas chromatography.
In examples 1 to 4, GC-PA% of the starting compound CPMK and the target compound CPEA are shown in Table 1.
Table 1
Comparative example 1
10g (purity 99%, 119mmol) of cyclopropylmethyl ketone, 31.8g (131mmol) of a 7% methanolic ammonia solution and 1g (0.94mmol) of 10% palladium on carbon were placed in a 200ml autoclave, and the inside of the reaction vessel was replaced with hydrogen gas 2 times. After the replacement, the reaction vessel was charged with hydrogen gas to 2.5MPa and stirred at 120 ℃ for 3 hours. The reaction mixture was cooled to 20 ℃ and then the inside of the reaction vessel was brought to normal pressure, and insoluble matter was filtered off. The reaction progress rate of the obtained solution was confirmed by gas chromatography.
Comparative example 2
10g (purity 99%, 119mmol) of cyclopropylmethyl ketone, 31.8g (131mmol) of a 7% methanolic ammonia solution and 1g (15.3mmol) of zinc were charged into a 200ml autoclave, and the inside of the reaction vessel was replaced with hydrogen gas 2 times. After the replacement, the reaction vessel was charged with hydrogen gas to 2.5MPa and stirred at 120 ℃ for 3 hours. The reaction mixture was cooled to 20 ℃ and then the inside of the reaction vessel was brought to normal pressure, and insoluble matter was filtered off. The reaction progress rate of the obtained solution was confirmed by gas chromatography.
In examples 1, comparative examples 1 and 2, GC-PA% of the starting compound CPMK, the target compound CPEA and the by-product AP are shown in Table 2. The case of "-" in the column of CPEA or AP means that it cannot be detected by GC.
Table 2
Comparative example 3
20g (purity 99%, 238mmol) of cyclopropylmethyl ketone, 15.9g (262mmol) of a 28% aqueous ammonia solution, 62.6g (3478mmol) of water and 7.84g (68.2mmol) of the stabilized nickel catalyst N-103 (manufactured by Nissan Kagaku Kogyo Co., Ltd.) were placed in a 500ml autoclave, and the inside of the reaction vessel was replaced with hydrogen gas 2 times. After the replacement, the reaction vessel was charged with hydrogen gas to 2.0MPa and stirred at 120 ℃ for 6 hours. The reaction mixture was cooled to 20 ℃ and then the inside of the reaction vessel was brought to normal pressure, and insoluble matter was filtered off. The reaction progress rate of the obtained solution was confirmed by gas chromatography.
Comparative example 4
20g (purity 99%, 238mmol) of cyclopropylmethyl ketone, 15.9g (262mmol) of a 28% aqueous ammonia solution, 64.0g (694.6mmol) of toluene and 7.84g (68.2mmol) of the stabilized nickel catalyst N-103 (manufactured by Nissan Kagaku Co., Ltd.) were placed in a 500ml autoclave, and the inside of the reaction vessel was replaced with hydrogen gas 2 times. After the replacement, the reaction vessel was charged with hydrogen gas to 2.0MPa and stirred at 120 ℃ for 6 hours. The reaction mixture was cooled to 20 ℃ and then the inside of the reactor was brought to normal pressure, and insoluble matter was filtered off. The reaction progress rate of the obtained solution was confirmed by gas chromatography.
In examples 1, 3 and 4, GC-PA% of CPMK as a starting compound and GC-PA% of CPEA as a target compound are shown in Table 3.
No. 3 table
Example 5
The reaction was carried out in the same manner as in example 1 except that the stabilized nickel catalyst N-103 (manufactured by Nissan catalytic chemical Co., Ltd.) which had been used for 1 time in the reaction was used, and the reaction progress rate was confirmed by gas chromatography.
Example 6
The reaction was carried out in the same manner as in example 1 except that N-103 (manufactured by Nikkaido catalyst Co., Ltd.) was used as a stabilized nickel catalyst and used for 2 times, and the reaction progress rate was confirmed by gas chromatography.
In examples 1, 5 and 6, GC-PA% of the starting compound CPMK and the target compound CPEA are shown in Table 4.
4 th table
Example 7
To a methanol solution of 1-cyclopropylethylamine obtained in example 1, 13.0g (367mmol) of hydrogen chloride gas was introduced, and the mixture was stirred at room temperature for 1 hour, followed by addition of 103.8g (1127mmol) of toluene. The reaction mixture was distilled at 95 ℃ under normal pressure to remove methanol, and then cooled to room temperature to precipitate crystals. The crystals were filtered and dried to give 26.8g of hydrochloride of 1-cyclopropylethylamine (purity 90.6%, yield 84.0%, melting point 183.5 ℃ C.).
1H NMR (solvent: CDCl)3/500MHz):δ(ppm)＝8.46(s,2H),2.62(m,1H),1.51(d,3H),1.13(m,1H),0.64(m,3H),0.31(m,1H).
Example 8
120g (purity 99%, 1427mmol) of cyclopropylmethyl ketone, 161.4g of methanol and 11.32g (102.2mmol) of stabilized nickel catalyst N-103B (manufactured by Nikkaido catalyst Co., Ltd.) were charged in a 900ml autoclave, and ammonia (26.73g, 1569mmol) was introduced from a gas cylinder into the reaction vessel. The reaction vessel was then purged 2 times with hydrogen. After the replacement, the reaction vessel was charged with hydrogen gas to 1.5MPa and stirred at 80 ℃. After the pressure in the reaction vessel was reduced, hydrogen gas was again continuously charged to 2.0MPa, and the reaction vessel was stirred at 80 ℃ for 8 hours while maintaining the pressure in the reaction vessel at 2.0 MPa. The reaction mixture was cooled to 20 ℃ and then the inside of the reaction vessel was brought to normal pressure, and while stirring and washing with 189.8g of methanol, insoluble matter was filtered off. The reaction progress rate of the obtained solution was confirmed by gas chromatography.
For example 8, GC-PA% of the starting compound CPMK and the target substance CPEA are shown in Table 5.
5 th table
Example 9
To a methanol solution of 1-cyclopropylethylamine obtained in example 8, 57.2g (1569mmol) of hydrogen chloride gas was introduced, and the mixture was stirred at room temperature for 1 hour, followed by addition of 624.2g (6774.9mmol) of toluene. The reaction mixture was distilled at 105 ℃ under normal pressure to remove methanol, and then cooled to room temperature to precipitate crystals. The crystals were filtered and then dried, whereby 158.6g of 1-cyclopropylethylamine hydrochloride was obtained (purity 99.8%, yield 91.4%, melting point 183.5 ℃ C.).
1H NMR (solvent: CDCl)3/500MHz):δ(ppm)＝8.46(s,2H),2.62(m,1H),1.51(d,3H),1.13(m,1H),0.64(m,3H),0.31(m,1H).
Industrial applicability
According to the present invention, 1-cyclopropylethylamine or an acid addition salt thereof can be produced in high purity under industrially advantageous conditions using cyclopropylmethyl ketone as a raw material.
Further, the specification, claims, drawings and abstract of Japanese patent application No. 2015-117588, which was filed on 10.6.2015, are all incorporated into the present specification as the disclosure of the present specification.
Claims (9)
1. A method for producing 1-cyclopropylethylamine or an acid addition salt thereof, which comprises: cyclopropyl methyl ketone, ammonia and hydrogen are reacted in alcohols and/or ethers in the presence of a nickel catalyst supported on an inorganic oxide.
2. The method of claim 1, comprising:
(i) a 1 st step of reacting cyclopropylmethyl ketone, ammonia and hydrogen in the presence of a nickel catalyst supported on an inorganic oxide in an alcohol and/or an ether to obtain 1-cyclopropylethylamine, and
(ii) a 2 nd step of reacting 1-cyclopropylethylamine with an acid in a solvent to obtain an acid addition salt of 1-cyclopropylethylamine.
3. The method of claim 1, wherein the inorganic oxide is diatomaceous earth, silica, or alumina.
4. The method of claim 3 wherein the inorganic oxide is diatomaceous earth.
5. The process according to claim 1, wherein the nickel catalyst supported on the inorganic oxide is contained in an amount of 1 to 50% by weight in terms of the content of nickel relative to cyclopropylmethyl ketone.
6. The process of claim 1, wherein the reaction is carried out in an alcohol.
7. The method of claim 1, wherein the reaction is carried out with hydrogen at a pressure of 0.1 to 10 MPa.
8. The method according to claim 7, wherein the reaction with hydrogen is carried out while keeping the pressure constant within the range of 1 to 10 MPa.
9. The method of claim 1, wherein the acid addition salt of 1-cyclopropylethylamine is the hydrochloride, sulfate or acetate salt.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015117588A JP2018123059A (en) | 2015-06-10 | 2015-06-10 | Method for producing 1-cyclopropyl ethyl amine or salt thereof |
| JP2015-117588 | 2015-06-10 | ||
| PCT/JP2016/066918 WO2016199763A1 (en) | 2015-06-10 | 2016-06-07 | Method for producing 1-cyclopropylethylamine or acid addition salt thereof |
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| CN107614478A CN107614478A (en) | 2018-01-19 |
| CN107614478B true CN107614478B (en) | 2020-04-28 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63258444A (en) * | 1987-04-15 | 1988-10-25 | Chisso Corp | Production of (3-aminobutyl)benzenes |
| JPH07196586A (en) * | 1993-12-28 | 1995-08-01 | Kuraray Co Ltd | Production of aliphatic diamine |
| US5986141A (en) * | 1998-09-29 | 1999-11-16 | Eastman Chemical Company | Process for the production of cyclopropanemethylamine |
| CN103204811A (en) * | 2006-12-15 | 2013-07-17 | 石原产业株式会社 | Process For Production Of Anthranilamide Compound |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7074805B2 (en) * | 2002-02-20 | 2006-07-11 | Abbott Laboratories | Fused azabicyclic compounds that inhibit vanilloid receptor subtype 1 (VR1) receptor |
| TWI435863B (en) * | 2006-03-20 | 2014-05-01 | Nihon Nohyaku Co Ltd | N-2-(hetero) arylethylcarboxamide derivative and pest controlling |
| NL2000613C2 (en) * | 2006-05-11 | 2007-11-20 | Pfizer Prod Inc | Triazole pyrazine derivatives. |
-
2015
- 2015-06-10 JP JP2015117588A patent/JP2018123059A/en active Pending
-
2016
- 2016-06-07 WO PCT/JP2016/066918 patent/WO2016199763A1/en active Application Filing
- 2016-06-07 CN CN201680031657.1A patent/CN107614478B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63258444A (en) * | 1987-04-15 | 1988-10-25 | Chisso Corp | Production of (3-aminobutyl)benzenes |
| JPH07196586A (en) * | 1993-12-28 | 1995-08-01 | Kuraray Co Ltd | Production of aliphatic diamine |
| US5986141A (en) * | 1998-09-29 | 1999-11-16 | Eastman Chemical Company | Process for the production of cyclopropanemethylamine |
| CN103204811A (en) * | 2006-12-15 | 2013-07-17 | 石原产业株式会社 | Process For Production Of Anthranilamide Compound |
Non-Patent Citations (1)
| Title |
|---|
| "ПОЛУЧЕНИЕ (ЦИКЛОПРОПИЛ МЕТИЛ)АМИНОВ ВОССТАНОВИТЕЛЬНЫМ АМИНИРОВАНИЕМ КЕТОНОВ";ADROV, P. M. et al.;《Zhurnal Organicheskoi Khimii》;19761231;第12卷(第8期);第1828页 * |
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| CN107614478A (en) | 2018-01-19 |
| JP2018123059A (en) | 2018-08-09 |
| WO2016199763A1 (en) | 2016-12-15 |
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