JPH04117348A - Production of aliphatic primary amine - Google Patents

Abstract

PURPOSE:To obtain the subject compound in high purity and yield without using ammonia by the catalytic hydrogenation of an aliphatic nitrile by hydrogenating the nitrile in a 1-3C aliphatic alcohol in the presence of a mixture of a cobalt-manganese catalyst and a nickel-based catalyst. CONSTITUTION:The objective aliphatic primary amine can be produced in high purity and yield without using ammonia by the catalytic hydrogenation of an aliphatic nitrile in a 1-3C aliphatic alcohol at about 80-200 deg.C (preferably about 90-150 deg.C) under a pressure of about 10-100kg/cm<2>G in the presence of a mixed catalyst consisting of (A) a cobalt-manganese catalyst, e.g. a manganese-modified Raney cobalt catalyst (Co-Al-Mn) or its developed product and (B) a nickel- based catalyst, e.g. a Raney cobalt catalyst (Ni-Al) or its developed product at a weight ratio A/B of about 5/1 to 1/5, preferably about 3/2 to 2/3.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing an aliphatic primary amine, and more specifically, to a method for producing an aliphatic primary amine, and more specifically, a method for producing an aliphatic nitrile without using ammonia. The present invention relates to a method for producing a highly pure aliphatic primary amine in good yield.

[Prior Art] A method for producing a corresponding aliphatic primary amine by catalytic hydrogenation of an aliphatic nitrile is known, and an applicable metal catalyst (cobalt, nickel, rhodium, palladium,
Various proposals have been made regarding Iffl (ruthenium, platinum, etc.). For example, (1) U.S. Pat. A method is proposed in which alkylene bis-oxypropionitrile is hydrogenated using a catalyst such as nickel or cobalt in a solvent such as dioxane to obtain 1,3-diaminopropane.

(2) U.S. Pat. No. 3,372,195 discloses that various nitriles, including aliphatic nitriles and cyanoethylated glycols, are hydrogenated with a ruthenium catalyst in the presence of ammonia to produce corresponding primary It has been shown that it is converted to an amine.

(3) JP-A-55-122744 discloses the hydrogenation of aliphatic nitriles, alkylene oxynitrile, alkylene aminonitrile, etc. using a cobalt or ruthenium catalyst in a mixed solvent of ether/water to obtain the corresponding primary amines. is manufactured.

[4] H. Greenfield has investigated the hydrogenation of butyronide 1-nor using various catalysts such as nickel, cobalt, platinum, palladium, rhodium, and rubidium. According to this study, the yield of butylamine when hydrogenated using a nickel catalyst was 91% when the solvent was alkaline methanol, 96.5% when using ammonia/methanol, and 81% when using only a methanol solution. [Ind, Eng, ChemProd, Res
, Dev, 6, 142 (1967)].

[Problems to be Solved by the Invention] As is clear from the above-mentioned aspects, the presence of ammonia contributes to high reaction rate and high yield when hydrogenating aliphatic nitriles to produce primary amines. It was thought to be meaningful in obtaining the desired object. However, in a system where hydrogen and ammonia coexist, such as in this reaction, the partial pressure of ammonia cannot be ignored, so the required equipment is pressure resistant and large in scale, making it unsuitable for producing the target product in small quantities. I'll go. Furthermore, the characteristic odor of ammonia not only complicates equipment maintenance;
Environmentally, the location conditions are extremely limited.

The present inventors hydrogenated aliphatic nitriles without using ammonia to produce the corresponding aliphatic primary amines in good yields and with high N! As a result of intensive studies on the method for obtaining polyhydric acid, it was discovered that the specified objective could be achieved by selecting and applying a specific solvent and catalyst system, and based on this knowledge, the present invention was completed.

[Means for Solving the Problems] The method for producing an aliphatic primary amine according to the present invention includes a method for producing an aliphatic primary amine having 1 to 3 carbon atoms when producing an aliphatic primary amine by catalytically hydrogenating an aliphatic nitrile. It is characterized in that hydrogenation is carried out in an aliphatic alcohol in the presence of a mixed catalyst of a cobalt-manganese catalyst and a nickel catalyst.

The aliphatic nitriles used as raw materials in the present invention include:
The following compounds are exemplified.

(1) Aliphatic nitrile (-ship stock ■) R1(CN)n (1) [In the formula, R
1 represents an alkyl group or an alkylene group having 1 to 22 carbon atoms. n is an integer of 1 or 2. ] Specifically, the following compounds are exemplified.

Malonitrile, suberonitrile, geltalonitrile, adiponitrile, pimelonitrile, suberonitrile, azelaonitrile, sepaconitrile, nonane-1,9-dinitrile, decane-1,10-nitrile, undecane-1,11-dinitrile, dodecane-1,12-dinitrile , tridecane-1,13-nitrile, tetradecane-1,14-dinitrile, pentadecane-
1,15-dinitrile, hexadecane-1,16-dinitrile, heptadecane-1,17-dinitrile, octadecane-1,18-nitrile, nonadecane-1,19-dinitrile, icosane-1,20-nitrile, heneicosane- 1,21-dinitrile, tocosan-1
, 22-nitrile, etc.

(2) Alkylene oxynitrile (-Fleet ■〉A(R-
0-R3)+nCN (If) [where R2, R
3 is the same or different and represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms, and A represents hydrogen or a nitrile group. m is an integer from 1 to 3. ] Examples of odorants include the following compounds.

CHjCH2C)h-0-CH2CHz -CNNC-
CH2CHz CHI -0-CH2CH2-0-CH
2CH2CH2-CNNC-CtbCH2-0-CHz
CH2CHz-0-CHzCH2-CNNC-CH2C
H2-O-CtbCH(CH3)-0-CToCHz-
CNNC-C1bCHz-0-(CHx)4-0-CH
2CH2-CNNC-Ctb CH2-0-CItzC
tb CH(CH3)-0-CHzCH2-CN[NC
-C1bCHz-0-CH(CM,z)-12(CJ)
2C(0-CH2CH2-CN)Ctb-0-CHzC
H2-CNNC-CtbCH2-0-CH2)3CH(
CL)-0-CHzC day 2-CNNC-CToCHz-
0-CHa)r-0-CToCHz-CNNC-CH2
CH2-07CH2)6-0-CH2CH2-CNNC
-CH2CH2-0-CHz)ta -0-CH2CH
2-CN(3) Alkylenoaminonitrile (-Fleet ■)
A (R2-NR4-R3)m CN (iii)
[In the formula, R4 represents hydrogen or a lower alkyl group having 1 to 4 carbon atoms, and R2, R3, A and m have the same meanings as in Ichifunezo. ] Specifically, the following compounds are exemplified.

CH2CH2CHJ-NH-CH2CH2-CNCH3
CHz-N(CHj)-CH,CCH2-CNNC-C
H2CH2-NH-CyuCtL2-NH-CH2CH2
-CM The aliphatic alcohol having 1 to 3 carbon atoms functions as a reaction solvent in the reaction, and examples of the aliphatic alcohol include methanol, ethanol, n-propanol, and impropanol.

The amount of aliphatic alcohol to be applied is about 5 to 50 parts by weight, preferably 10 to 3 parts by weight, per 100 parts by weight of the aliphatic nitrile.
It is approximately 0 parts by weight. When the amount is less than 5 parts by weight, the reaction rate decreases and the amount of by-products increases. On the other hand, if it is used in an amount exceeding 50 parts by weight, productivity decreases, and both are unfavorable under industrial manufacturing conditions.

Cobalt-manganese catalyst is a general term for catalysts containing cobalt and manganese, specifically manganese-modified Raney cobalt catalyst (CO-/', J7-Mn).
and their developments are exemplified.

In this case, the weight ratio of manganese to cobalt is usually about 3 to 20%.

In addition, as a nickel-based catalyst, Raney cobalt catalyst (N
i-A#) and their expansions are exemplified.

Cobalt-manganese catalyst (A) and nickel catalyst* (B)
) G17) Mixing ratio (A/B) 4. t is about 5/1 to 115, preferably about 3/2 to 2/3 on a weight basis.

Each of the above catalysts is usually supported on a carrier such as carbon, silica, alumina, diatomaceous earth, silica-alumina, etc.
Contains about 0 to 60% metal.

Such a mixed catalyst is applied in an amount of about 1 to 5 parts by weight per 100 parts by weight of the aliphatic nitrile. When the amount is less than 1 part by weight, the reaction rate is low, and even if it is used in excess of 5 parts by weight, no significant difference is observed, which is economically disadvantageous.

Furthermore, when carrying out the hydrogenation reaction, an effective amount of an alkali metal compound, for example, per 100 parts by weight of aliphatic alcohol,
When about 0.1 to 1 part by weight is added, the reaction rate increases,
By-product generation is suppressed.

Examples of such alkali metal compounds include simple alkali metals such as lithium, sodium, and potassium, alkali metal alcolades, hydroxides, carbonates, and bicarbonates of the alkali metals.

The method for producing a primary amine according to the present invention will be specifically illustrated below.

A predetermined amount of aliphatic nitrile, aliphatic alcohol, and a mixed catalyst were placed in a predetermined electromagnetic stirring autoclave, and 80
Heating to about ~200'C, preferably about 90 to 150°C, and introducing hydrogen while stirring, about 10 to 100 kg
The reaction is continued under a pressure of /CIAG until hydrogen absorption stops. After the reaction is completed, the reaction mixture is cooled and the reactant is filtered to recover the catalyst. The recovered catalyst can be reused after being washed.

Meanwhile, the filtrate is distilled to recover the solvent. The obtained product can be purified by distillation.

The manufacturing method according to the present invention can be applied not only by a batch method but also by a continuous method.

[Example] The present invention will be described in detail below with reference to Examples.

Example 1 Suberonitrile 809, methanol 16g, potassium methoxide 0.0 in a 0.5i electromagnetic stirring autoclave
53 and mankan-modified cobalt-based development catalyst (product name: Raney Cobalt 0FT-60J, Yoken Fine Chemical ■
>1.2g and nickel development catalyst (product name: Raney Nickel NDHT-90J, manufactured by Yoken Fine Chemical ■)
Prepare 1.29, 115±5°C150Kg/cff
Hydrogenation was carried out for 5 hours under stirring at 1G. After the reaction was completed, the mixed catalyst was filtered and the reaction solvent was distilled off to obtain 82.5 g (yield: 97.4%) of the desired product, 8-octamethylenediamine. The purity of this product was 96.0% as measured by gas chromatography.

Example 2 The same process as in Example 1 was carried out, except that 80 g of suberonitrile, 1.5 g of a manganese-modified cobalt-based developing catalyst, and 1.09 g of a nickel developing catalyst were used. As a result, the purity was 92.0%.
8'1.79 of 1,8-octamethylenediamine was obtained (yield 96.5%).

Example 3 The same procedure as in Example 1 was carried out except that 80 g of suberonitrile, 27 g of methanol, and 0.19 g of potassium hydroxide were used. As a result, 81.4 cJ of 1.8-octamethylenediamine with a purity of 91.0% was obtained (yield: 96.2%).

Example 4 3.3--(ethylenedioxy>-dipropionitrile'LNC-C2'A+-0-C21'lDou-0-C2H
The process was carried out in the same manner as in Example 1, except that 4-CM] was applied. As a result, a diamine compound [HyoN-CaHrO-C2H4-0-C2H4-NH
4I 80 , 39 was obtained (yield 96.2%).

Comparative Example 1 As a hydrogenation catalyst, “Raney Cobalt 0FT-6042” was used as a hydrogenation catalyst.
, 4g was applied, but the same process as in Example 1 was carried out. As a result, 81.3 g of 1,8-octamethylenediamine with a purity of 83.7% was obtained (yield: 95.8%).

Comparative Example 2 As a hydrogenation catalyst, “Raney Nickel NDHT90J”
The treatment was carried out in the same manner as in Example 1, except that 2.4 g was applied. As a result, 80.5 g of 1.8-octamethylenediamine with a purity of 67.7% was obtained (yield: 95.1%).

[Effects of the Invention] According to the production method according to the present invention, an aliphatic tertiary amine corresponding to an aliphatic nitrile as a raw material can be obtained with high purity and high yield without using ammonia.

Patent applicant Shin Nippon Rika Co., Ltd. Voluntary amendment to the procedure) February 11, 1990 2, Name of invention Process for producing aliphatic primary amine 3, Person making the amendment Related to the case Patent applicant's amendment Contents (1) 1 Japanese Patent Application Publication No. 1989-5 stated in the second line from the bottom of the second specification
5-122744" is corrected to "JP-A-55-122744 (Special Publication No. 1-52381@) J.

(2) "J in a mixed solvent of ether/water" written in the first line from the bottom of page 2 to the first line of page 3 of the specification is corrected to "in a mixed solvent of ammonia/ether/water."

(3) "Contains cobalt and manganese as constituent components" written on page 8, lines 10-11 of the specification is corrected to "contains cobalt and manganese as constituent components."

(4) "Raney cobalt" written in the fifth line from the bottom of page 8 of the specification is corrected to "Raney nickel."

(5) I obtained the item stated in the fourth line from the bottom of page 12 of the specification.”
Delete.

(6) The word "obtained" written in the second line of page 13 of the specification is deleted.

(7) "Aliphatic tertiary amine" stated in page 13, line 7 of the specification is corrected to "aliphatic primary amine."

Claims (1)

[Claims] 1. When producing an aliphatic primary amine by catalytic hydrogenation of an aliphatic nitrile, a mixed catalyst of a cobalt-manganese catalyst and a nickel catalyst is used as a catalyst in an aliphatic alcohol having 1 to 3 carbon atoms. A method for producing an aliphatic primary amine, the method comprising hydrogenation in the presence of an aliphatic primary amine.