WO2016199763A1 - Procédé de production de 1-cyclopropyléthylamine ou sel d'addition d'acide de celui-ci - Google Patents

Procédé de production de 1-cyclopropyléthylamine ou sel d'addition d'acide de celui-ci Download PDF

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Publication number
WO2016199763A1
WO2016199763A1 PCT/JP2016/066918 JP2016066918W WO2016199763A1 WO 2016199763 A1 WO2016199763 A1 WO 2016199763A1 JP 2016066918 W JP2016066918 W JP 2016066918W WO 2016199763 A1 WO2016199763 A1 WO 2016199763A1
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Prior art keywords
cyclopropylethylamine
reaction
addition salt
acid addition
mmol
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PCT/JP2016/066918
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English (en)
Japanese (ja)
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竜也 日比野
健郷 木津
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石原産業株式会社
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Priority to CN201680031657.1A priority Critical patent/CN107614478B/zh
Publication of WO2016199763A1 publication Critical patent/WO2016199763A1/fr

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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a method for producing 1-cyclopropylethylamine or an acid addition salt thereof useful as an intermediate for pharmaceuticals or agricultural chemicals.
  • Non- Patent Document 1 a method for producing 1-cyclopropylethylamine by reacting cyclopropylmethylketone with ammonia in the presence of a Raney nickel catalyst (non- Patent Document 1) is known, but Raney nickel has a complicated activation method, may spontaneously ignite, and its yield is not sufficient.
  • Non-patent Document 2 a method for producing 1-cyclopentylethylamine from cyclopentylmethylketone using the Leukart reaction. However, this is a reaction at a high temperature, and there are many wastes. Had a problem in terms.
  • Patent Document 1 describes a method for producing a corresponding amine from (3-oxobutyl) benzenes.
  • an example used for reduction of cyclopropyl methyl ketone is not known.
  • 1-Cyclopropylethylamine or an acid addition salt thereof is useful as an intermediate for the production of pharmaceuticals and agricultural chemicals, and is required to be produced more economically by an industrially simple and efficient environmentally friendly method. It was.
  • a production method for obtaining 1-cyclopropylethylamine using a Raney nickel catalyst has already been known. However, Raney nickel usually requires a pretreatment to be activated with an alkali, and easily ignites when dried. It was not satisfactory as a manufacturing method. Further, it is generally known that a cyclopropyl group is easily opened by a transition metal complex.
  • An object of the present invention is to provide a method for producing highly pure 1-cyclopropylethylamine or an acid addition salt thereof in a simple and efficient manner by an environment-friendly technique.
  • the present inventors have obtained the knowledge that high-purity 1-cyclopropylethylamine can be produced under certain conditions, and have completed the present invention. That is, the present invention provides a process for producing 1-cyclopropylethylamine by reacting cyclopropylmethylketone, ammonia and hydrogen in alcohols and / or ethers in the presence of a nickel catalyst supported on an inorganic oxide. Further, the present invention 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.
  • high-purity 1-cyclopropylethylamine or an acid addition salt thereof can be produced simply and efficiently by an environmentally friendly technique.
  • 1-cyclopropylethylamine can be produced by reacting cyclopropylmethylketone and ammonia in the presence of a nickel catalyst supported on an inorganic oxide as follows.
  • 1-Cyclopropylethylamine has enantiomers (R-form and S-form), but includes both isomers and isomer mixtures.
  • ammonia alcohol solution As the ammonia, ammonia alcohol solution, aqueous ammonia solution, liquefied ammonia or ammonia gas can be used as appropriate.
  • the alcohol in the ammonia alcohol solution include methanol, ethanol, propanol, isopropanol, and butanol.
  • an ammonia alcohol solution When an ammonia alcohol solution is used, it can also be used as a solvent.
  • Ammonia can be used usually in an amount of 1 to 10 times mol, preferably 1 to 2 times mol for 1 mol of cyclopropyl methyl ketone. However, depending on the reaction conditions, an amount outside this range can be used.
  • a nickel catalyst supported on an inorganic oxide is used.
  • the inorganic oxide include diatomaceous earth, silica, alumina, silica alumina, magnesia, calcia, titania, zirconia, niobium oxide, and lanthanum oxide. Among them, diatomaceous earth, silica or alumina is desirable, and diatomaceous earth is more desirable.
  • a nickel catalyst prepared by a generally known method such as a precipitation method or an impregnation method can be used, a commercially available product may be used, and the nickel content in the catalyst is particularly limited.
  • Commercially available products include, for example, stabilized nickel catalyst N-103 (diatomaceous earth supported, nickel content 52.5% by weight) manufactured by JGC Catalysts & Chemicals, and stabilized nickel SN-750 (diatomaceous earth manufactured by Sakai Chemical Industry Co., Ltd.). Support, nickel content of 47% by weight).
  • the nickel catalyst supported on the inorganic oxide is usually used in an amount of 1 to 50% by weight, preferably 5 to 20% by weight, in terms of nickel content, with respect to 100% by weight of cyclopropyl methyl ketone. It can. However, depending on the reaction conditions, an amount outside this range can be used.
  • Hydrogen is usually preferably used in an amount of 1 to 10 times mol per mol of cyclopropyl methyl ketone.
  • the pressure can usually be selected from the range of 0.1 to 10 MPa. In order to perform the reaction efficiently and obtain the target product with high purity and high yield on an industrial scale, the pressure is in the range of 1 to 10 MPa. It is desirable to react with hydrogen while keeping the pressure constant within. However, depending on the reaction conditions, amounts and pressures outside this range can be used.
  • alcohols and / or ethers are used as a solvent used in producing 1-cyclopropylethylamine, but alcohols are preferably used.
  • alcohols having 1 to 6 carbon atoms are desirable, and examples thereof include methanol, ethanol, propanol, isopropanol, and butanol.
  • the ethers are preferably ethers having 1 to 6 carbon atoms, such as diethyl ether, diisopropyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether and the like.
  • the solvent used for producing 1-cyclopropylethylamine is usually used in an amount of 1 to 20 times (V / W), preferably 3 to 15 times (V / W) based on cyclopropyl methyl ketone. be able to. However, depending on the reaction conditions, an amount outside this range can be used.
  • the reaction temperature is usually about 80 to 200 ° C., preferably about 100 to 130 ° C.
  • the reaction time is usually about 1 to 12 hours, preferably about 1 to 6 hours.
  • the acid addition salt of 1-cyclopropylethylamine can be produced by reacting 1-cyclopropylethylamine with an acid in a solvent. This reaction may be carried out without isolating or producing 1-cyclopropylethylamine obtained by the above reaction.
  • Examples of the acid addition salt of 1-cyclopropylethylamine produced by this reaction include salts with inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid.
  • the acid examples include hydrogen chloride, hydrochloric acid, sulfuric acid, acetic acid and the like.
  • the acid is usually used in an amount of 0.5 to 5 mol, preferably 0.5 to 1.5 mol, per 1 mol of 1-cyclopropylethylamine. However, depending on the reaction conditions, an amount outside this range can be used.
  • the solvent used in producing the acid addition salt of 1-cyclopropylethylamine is one selected from the group consisting of aromatic hydrocarbons, ketones, alcohols, and mixed solvents thereof.
  • aromatic hydrocarbons include benzene, toluene, xylene, chlorobenzene and the like.
  • ketones include acetone and methyl ethyl ketone.
  • alcohols having 1 to 6 carbon atoms are desirable, and examples thereof include methanol, ethanol, propanol, isopropanol, and butanol.
  • the solvent used in preparing the acid addition salt of 1-cyclopropylethylamine is usually 1 to 20 times (V / W), preferably 3 to 15 times (V / W) based on 1-cyclopropylethylamine. / W) Can be used. However, depending on the reaction conditions, an amount outside this range can be used.
  • the reaction temperature is usually 0 to 100 ° C., preferably about 10 to 50 ° C.
  • the reaction time is usually about 1 to 10 hours, preferably about 1 to 3 hours.
  • Oven 50 °C for 12 minutes, 50 °C to 250 °C at 40 °C / min., 250 °C for 3 minutes
  • Inlet 250 °C, split ratio 100: 1, split flow 123 mL / min.
  • Detector FID at 250 °C, Hydrogen flow 40.0 mL / min., Air flow 450 mL / min.
  • Injection volume 3.0 ⁇ L
  • Example 1 500 ml autoclave containing 20 g of cyclopropyl methyl ketone (purity 99%, 238 mmol), 63.6 g (262 mmol) of 7% ammonia methanol solution and 1.96 g (17.0 mmol) of stabilized nickel catalyst N-103 (manufactured by JGC Catalysts & Chemicals)
  • the inside of the reaction vessel was replaced twice with hydrogen gas. After the replacement, the reaction vessel was filled with hydrogen gas to 2.5 MPa and stirred at 120 ° C. for 3 hours. After cooling the reaction mixture to 20 ° C., the inside of the reaction vessel was brought to normal pressure, and insoluble matters were filtered off.
  • the reaction progress rate of the obtained solution was confirmed by gas chromatography (here, “reaction progress rate” means GC-PA% of the above-mentioned CPEA).
  • Example 2 200 ml autoclave containing 10 g of cyclopropyl methyl ketone (purity 99%, 119 mmol), 31.8 g (131 mmol) of 7% ammonia methanol solution and 0.98 g (8.5 mmol) of stabilized nickel catalyst N-103 (manufactured by JGC Catalysts & Chemicals)
  • the inside of the reaction vessel was replaced twice with hydrogen gas. After the replacement, the reaction vessel was filled with hydrogen gas to 2.5 MPa and stirred at 100 ° C. for 3 hours. After cooling the reaction mixture to 20 ° C., the inside of the reaction vessel was brought to normal pressure, and insoluble matters were filtered off. The reaction progress rate of the obtained solution was confirmed by gas chromatography.
  • Example 3 200 ml autoclave containing 10 g of cyclopropyl methyl ketone (purity 99%, 119 mmol), 31.8 g (131 mmol) of 7% ammonia methanol solution and 0.98 g (8.5 mmol) of stabilized nickel catalyst N-103 (manufactured by JGC Catalysts & Chemicals)
  • the inside of the reaction vessel was replaced twice with hydrogen gas. After the replacement, the reaction vessel was filled with hydrogen gas to 3.5 MPa and stirred at 120 ° C. for 3 hours. After cooling the reaction mixture to 20 ° C., the inside of the reaction vessel was brought to normal pressure, and insoluble matters were filtered off. The reaction progress rate of the obtained solution was confirmed by gas chromatography.
  • Example 4 10 g of cyclopropyl methyl ketone (purity 99%, 119 mmol), 31.8 g (131 mmol) of 7% ammonia methanol solution and 1.96 g (17 mmol) of stabilized nickel catalyst N-103 (manufactured by JGC Catalysts & Chemicals) were added to a 200 ml autoclave. The inside of the reaction vessel was replaced twice with hydrogen gas. After the replacement, the reaction vessel was filled with hydrogen gas to 2.5 MPa and stirred at 120 ° C. for 3 hours. After cooling the reaction mixture to 20 ° C., the inside of the reaction vessel was brought to normal pressure, and insoluble matters were filtered off. The reaction progress rate of the obtained solution was confirmed by gas chromatography.
  • Comparative Example 1 10 g of cyclopropyl methyl ketone (purity 99%, 119 mmol), 31.8 g (131 mmol) of 7% ammonia methanol solution and 1 g (0.94 mmol) of 10% palladium on carbon were added to a 200 ml autoclave, and the inside of the reaction vessel was filled with hydrogen gas. Replaced twice. After the replacement, the reaction vessel was filled with hydrogen gas to 2.5 MPa and stirred at 120 ° C. for 3 hours. After cooling the reaction mixture to 20 ° C., the inside of the reaction vessel was brought to normal pressure, and insoluble matters were filtered off. The reaction progress rate of the obtained solution was confirmed by gas chromatography.
  • Comparative Example 2 10 g of cyclopropyl methyl ketone (purity 99%, 119 mmol), 31.8 g (131 mmol) of 7% ammonia methanol solution and 1 g (15.3 mmol) of zinc were added to a 200 ml autoclave, and the inside of the reaction vessel was replaced with hydrogen gas twice. . After the replacement, the reaction vessel was filled with hydrogen gas to 2.5 MPa and stirred at 120 ° C. for 3 hours. After cooling the reaction mixture to 20 ° C., the inside of the reaction vessel was brought to normal pressure, and insoluble matters were filtered off. The reaction progress rate of the obtained solution was confirmed by gas chromatography.
  • Example 1 Comparative Example 1 and Comparative Example 2, the raw material compound CPMK, the target product CPEA and the by-product AP GC-PA% are listed in Table 2, respectively.
  • the CPEA or AP column is “ ⁇ ”, it indicates that the GC could not be detected.
  • Comparative Example 3 20 g of cyclopropyl methyl ketone (purity 99%, 238 mmol), 15.9 g (262 mmol) of 28% aqueous ammonia solution, 62.6 g (3478 mmol) of water and 7.84 g of stabilized nickel catalyst N-103 (manufactured by JGC Catalysts & Chemicals) 68.2 mmol) was added to a 500 ml autoclave, and the inside of the reaction vessel was replaced twice with hydrogen gas. After the replacement, the reaction vessel was filled with hydrogen gas to 2.0 MPa and stirred at 120 ° C. for 6 hours. After cooling the reaction mixture to 20 ° C., the inside of the reaction vessel was brought to normal pressure, and insoluble matters were filtered off. The reaction progress rate of the obtained solution was confirmed by gas chromatography.
  • Example 5 The reaction was conducted in the same manner as in Example 1 except that the stabilized nickel catalyst N-103 (manufactured by JGC Catalysts & Chemicals Co., Ltd.) was already used for the reaction once, and the reaction progress rate was determined by gas chromatography. confirmed.
  • the stabilized nickel catalyst N-103 manufactured by JGC Catalysts & Chemicals Co., Ltd.
  • Example 6 The reaction was conducted in the same manner as in Example 1 except that the stabilized nickel catalyst N-103 (manufactured by JGC Catalysts & Chemicals Co., Ltd.) was used twice for the reaction, and the reaction progress rate was determined by gas chromatography. confirmed.
  • the stabilized nickel catalyst N-103 manufactured by JGC Catalysts & Chemicals Co., Ltd.
  • Example 1 For Example 1, Example 5 and Example 6, GC-PA% of CPMK as the raw material compound and CPEA as the target product are shown in Table 4, respectively.
  • Example 7 13.0 g (367 mmol) of hydrogen chloride gas was introduced into a methanol solution of 1-cyclopropylethylamine obtained according to Example 1, and after stirring at room temperature for 1 hour, 103.8 g (1127 mmol) of toluene was added. Methanol was distilled off from the reaction mixture at 95 ° C. under normal pressure, and then cooled to room temperature to precipitate crystals. The crystals were filtered and dried to obtain 26.8 g of 1-cyclopropylethylamine hydrochloride (purity 90.6%, yield 84.0%, melting point 183.5 ° C.).
  • Example 8 120 g of cyclopropyl methyl ketone (purity 99%, 1427 mmol), 161.4 g of methanol and 11.32 g (102.2 mmol) of stabilized nickel catalyst N-103B (manufactured by JGC Catalysts & Chemicals) were added to a 900 ml autoclave and ammonia (26. 73 g, 1569 mmol) was introduced into the reaction vessel from a gas cylinder. Thereafter, the inside of the reaction vessel was replaced twice with hydrogen gas. After the replacement, the reaction vessel was filled with hydrogen gas to 1.5 MPa and stirred at 80 ° C. When the pressure in the reaction vessel decreased, hydrogen gas was continuously charged to 2.0 MPa again, and stirred at 80 ° C.
  • reaction progress rate of the obtained solution was confirmed by gas chromatography.
  • Table 5 shows GC-PA% of CPMK as a raw material compound and CPEA as a target product for Example 8.
  • Example 9 Hydrogen chloride gas 57.2 g (1569 mmol) was introduced into a methanol solution of 1-cyclopropylethylamine obtained according to Example 8, and the mixture was stirred at room temperature for 1 hour, and then 624.2 g (6764.9 mmol) of toluene was added. . Methanol was distilled off from the reaction mixture under normal pressure at 105 ° C., and then cooled to room temperature to precipitate crystals. The crystals were filtered and dried to obtain 158.6 g of 1-cyclopropylethylamine hydrochloride (purity 99.8%, yield 91.4%, melting point 183.5 ° C.).
  • high-purity 1-cyclopropylethylamine or an acid addition salt thereof can be produced from cyclopropylmethylketone as a raw material under industrially advantageous conditions.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention se rapporte à un procédé de production de 1-cyclopropyléthylamine ou un sel d'addition d'acide de celui-ci. L'invention concerne un procédé de production de 1-cyclopropyléthylamine de haute pureté ou un sel d'addition d'acide de celui-ci, lequel procédé comprend la mise en réaction de cyclopropylméthylcétone, d'ammoniac, et d'hydrogène dasn des alcools et/ou des éthers en présence d'un catalyseur au nickel sur support en oxyde inorganique.
PCT/JP2016/066918 2015-06-10 2016-06-07 Procédé de production de 1-cyclopropyléthylamine ou sel d'addition d'acide de celui-ci WO2016199763A1 (fr)

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JP2015117588A JP2018123059A (ja) 2015-06-10 2015-06-10 １−シクロプロピルエチルアミン又はその塩の製造方法
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63258444A (ja) * 1987-04-15 1988-10-25 Chisso Corp （３−アミノブチル）ベンゼン類の製造方法
JPH07196586A (ja) * 1993-12-28 1995-08-01 Kuraray Co Ltd 脂肪族ジアミンの製造方法
US20030158198A1 (en) * 2002-02-20 2003-08-21 Chih-Hung Lee Fused azabicyclic compounds that inhibit vanilloid receptor subtype 1 (VR1) receptor
WO2007108483A1 (fr) * 2006-03-20 2007-09-27 Nihon Nohyaku Co., Ltd. Dérivé de n-2-(hétéro)aryléthylcarboxamide, et agent de maîtrise des nuisibles comprenant ledit dérivé
US20070265272A1 (en) * 2006-05-11 2007-11-15 Pfizer Inc. Triazolopyrazine derivatives

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5986141A (en) * 1998-09-29 1999-11-16 Eastman Chemical Company Process for the production of cyclopropanemethylamine
JP5507045B2 (ja) * 2006-12-15 2014-05-28 石原産業株式会社 アントラニルアミド系化合物の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63258444A (ja) * 1987-04-15 1988-10-25 Chisso Corp （３−アミノブチル）ベンゼン類の製造方法
JPH07196586A (ja) * 1993-12-28 1995-08-01 Kuraray Co Ltd 脂肪族ジアミンの製造方法
US20030158198A1 (en) * 2002-02-20 2003-08-21 Chih-Hung Lee Fused azabicyclic compounds that inhibit vanilloid receptor subtype 1 (VR1) receptor
WO2007108483A1 (fr) * 2006-03-20 2007-09-27 Nihon Nohyaku Co., Ltd. Dérivé de n-2-(hétéro)aryléthylcarboxamide, et agent de maîtrise des nuisibles comprenant ledit dérivé
US20070265272A1 (en) * 2006-05-11 2007-11-15 Pfizer Inc. Triazolopyrazine derivatives

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ADROV, P. M. ET AL., ZHURNAL ORGANICHESKOI KHIMII, vol. 12, no. 8, 1976, pages 1827 - 1828, ISSN: 0514-7492 *

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