JP3160304B2 - Method for producing β-branched alkyl primary amines - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a .beta.-branched alkyl primary amine in which the .beta.-position of an amino group is useful as a surfactant or the like.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a long-chain aliphatic primary amine, an alkali or ammonia such as an alkali metal hydroxide is used as a reaction aid in the presence of a catalyst such as Raney nickel or Raney cobalt. A method for producing a chain aliphatic nitrile by hydrogenation is known (Japanese Patent Publication No. Sho 3
8-21353).

However, in this method, an alkyl group having a β-position branched from a nitrile group, particularly Guerbet, is used.
When a corresponding primary amine having a γ-position branched to an amino group is produced from a nitrile having an alkyl group of the type, the catalytic activity of these catalysts is extremely low, and the corresponding primary amine is produced in high yield. Was difficult to manufacture. It should be noted that such a decrease in the catalytic activity is also seen when compared with each catalytic reaction in oxo alcohol and Guerbet alcohol. This is because the oxo alcohol is
In general, the catalytic activity is lower than that of oxo alcohols because Guerbet alcohols have a long-chain branched alkyl group at the β-position of the hydroxyl group, whereas the Guerbet alcohol has a short chain such as a methyl group at the position or center. It has been.

Accordingly, as an alternative to the above primary amine, a primary amine having a β-position branched to an amino group can be easily and in high yield produced from a corresponding nitrile having an α-position branched to a nitrile group. It is desired to do.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a method for easily and in high yield from alkane nitriles having α-branched nitrile groups to primary alkylamines having β-branched amino groups. It is an object of the present invention to provide a process for producing β-branched primary alkylamines that can be produced.

[0006]

Means for Solving the Problems The present inventors have developed a hydrogenation catalyst having high activity and high selectivity for the above reaction, and have accomplished the present invention.

That is, the present invention relates to a nitrile having a C ₈ -C ₃₆ alkyl group having a branched chain structure at the α-carbon atom of the nitrile group, or a mixture containing the same, comprising copper-zinc-
In the presence of a Group 8 white metal catalyst and an alkali metal hydroxide and / or ammonia,
A method for producing a β-branched alkyl primary amine in which the β-position of the amino group is branched, wherein the reaction is performed at a reaction temperature of 50 ° C. and a hydrogen gas pressure of atmospheric pressure to 50 atm (gauge pressure),
provide.

[0008] nitriles is a raw material used in the present invention, alpha-carbon atoms (i.e., carbon atom to which the nitrile group attached) having an alkyl group of C ₈ -C ₃₆ having a branched chain structure at. As such nitriles, the general formula

Embedded image [In the formula, 1 is an integer of 5 to 14. ] The compound represented by this is mentioned.

As another nitrile, a compound represented by the general formula

Embedded image [Wherein, m is an integer of 1 to 5, n is an integer of 5 to 10, and m + n = 10 to 11. ] The compound represented by this is mentioned.

Still other nitriles include compounds of the formula

Embedded image The compound represented by these is mentioned.

In the production method of the present invention, one or more of the above nitriles may be used as a raw material. Also, as a raw material,
Mixtures containing the above nitriles may be used.

The above nitriles can be obtained by a conventional method, for example, by reacting the corresponding α-branched fatty acids with ammonia. Α- corresponding to nitriles [I]
Examples of branched fatty acids include Guerbet-type fatty acids. Examples of the α-branched fatty acids corresponding to the nitriles [II] include fatty acids obtained by oxidizing an oxo alcohol obtained from an α-olefin by the oxo method. Specific examples of such α-branched fatty acids include isomyristic acid, isopalmitic acid, Diadol 18GA (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.), and alcohols having β-branched long-chain alkyl groups [for example, Calcol 1
60GD, 200GD, 280GD (Kao Corporation)
Manufactured), Fine Oxocol 140, 1600, 18
0, 180N, 1800, 2000, 2600 (or more,
Nissan Chemical Co., Ltd.)] and the like.

[0013] The zinc contained in the hydrogenation catalyst of the present invention improves selectivity and activity. The Group 8 white metal element contained in the hydrogenation catalyst of the present invention is used to increase the activity of the catalyst, whereby the reduction reaction can be completed with a small amount of the catalyst in a short time. Specifically, the eighth
The group III metal element includes ruthenium, palladium, platinum, rhodium and the like, and one or more of these may be used.

In addition, the hydrogenation catalyst of the present invention may contain an alkali metal, an alkaline earth metal or the like. In the composition of the hydrogenation catalyst of the present invention, the compounding ratio of copper and zinc (copper / zinc) is 99/1 to 10/90, especially 99/90 by weight of metal.
/ 1 to 50/50 are preferred. Mixing ratio is 99/1 to 10
If the ratio deviates from / 90, the yield decreases. The compounding ratio of copper and the Group 8 white metal element (copper / Group 8 white metal element) is 1 / 0.0001 to 1 / 0.1, particularly 1 / 0.001 in terms of metal weight ratio.
１ ／ 1 / 0.01 is preferred. The compounding ratio is 1 / 0.0001-
When the ratio deviates from 1 / 0.1, the yield also decreases.

The metal constituting the catalyst may be contained in the hydrogenation catalyst used in the present invention in any form, for example, a simple metal, a metal oxide, a metal hydroxide, or various other metal salts or metal ions. Good. In other words, the metal constituting the catalyst may be present in the reaction system as a part of the catalyst composition, and may be brought into contact with the starting nitrile under a predetermined condition.

The hydrogenation catalyst may be in any form commonly used, for example, the above-mentioned simple metals, metal oxides, metal hydroxides, other various metal salts or mixtures thereof may be used as such as the catalyst. Further, the catalyst constituent metal may be supported on a suitable carrier. Furthermore,
The hydrogenation catalyst may be a salt of an aliphatic carboxylic acid of a metal constituting the catalyst or a complex stabilized by a suitable ligand.
If necessary, the above various catalyst forms may be mixed and used. In the method of the present invention, as a more preferable form of the catalyst, from the viewpoint of stabilization of the catalyst metal by immobilizing the active surface and durability of the catalyst against non-toxic substances, these metal components are supported on a suitable carrier. Things are good.

When the metal component constituting the catalyst of the present invention is supported on a carrier, suitable carriers include those generally used as carriers, for example, alumina, silica, silica alumina, diatomaceous earth, activated carbon, natural and artificial zeolites, and the like. Can be used. The amount of the catalyst metal supported on the carrier can be arbitrarily determined, but is usually 5 to 70% by weight.
Is preferable. Various methods can be selected as a method for supporting these metal components on a carrier. In this case, the form of the catalyst raw metal is an oxide, a hydroxide, various metal salts (for example, chloride, sulfate, nitrate, acetate and aliphatic carboxylate), or a metal complex (for example, acetylacetone complex or Dimethyl oxime complex) can be used. In order to produce a catalyst by a method of supporting on a carrier using these metal raw material species, for example, a method in which a carrier is put into a solution containing an appropriate metal salt and sufficiently impregnated (impregnation), To the aqueous solution containing the catalytic metal salt, a method of adding an alkaline aqueous solution such as ammonia, sodium hydroxide and sodium carbonate to precipitate the metal salt on the carrier, or simultaneously adding the aqueous alkali solution and the aqueous metal salt solution to the aqueous slurry of the carrier, Any conventionally known method such as a method of precipitating a metal salt on a support or a method of ion-exchanging a catalytic metal component with sodium and potassium contained in zeolite (ion exchange method) may be used.

Although the amount of the hydrogenation catalyst of the present invention is not particularly limited, it is usually 0.1 to 0.1% based on the starting material nitriles.
5% by weight is preferred. In the production method of the present invention, in addition to the above-mentioned hydrogenation catalyst, reduction is carried out in the presence of an alkali metal hydroxide and / or ammonia for improving selectivity. Examples of the alkali metal hydroxide include, for example, sodium hydroxide, potassium hydroxide and the like,
One or more of these may be used. When the alkali metal hydroxide is used, the amount is preferably 0.05 to 1.0% by weight based on the nitriles as the raw material. If it is less than 0.05% by weight, sufficient selectivity cannot be obtained, and 1.0% by weight.
If the amount is more than 10% by weight, the catalytic activity decreases, which is not preferable.
When ammonia is used, the partial pressure of ammonia is preferably 1/100 to 50/100 with respect to the partial pressure of hydrogen.

In the hydrogenation reaction, the reaction temperature ranges from 150 to
The temperature is 250 ° C, preferably 150 to 200 ° C. If the reaction temperature is lower than 150 ° C., hydrogenation is not sufficiently performed, and
If the temperature exceeds 50 ° C., undesirable side reactions occur. The hydrogen pressure is from atmospheric pressure to 50 atm (gauge pressure), preferably 5 to 2 atm.
0 atm. If the hydrogen pressure is lower than the atmospheric pressure, the hydrogenation is not sufficiently performed, and if the hydrogen pressure is higher than 50 atm, a side reaction such as decomposition proceeds. The reaction time is appropriately selected, for example, 0.1 to 2
It may be 0 hours.

Next, the production method of the present invention will be briefly described.
A nitrile as a raw material, a catalyst, and an alkali metal hydroxide are charged into a pressure-resistant reaction vessel equipped with a tube for introducing hydrogen and a tube for sampling. After replacing the system with nitrogen,
Introduce hydrogen to a predetermined pressure. The hydrogen pressure is from atmospheric pressure to 50 atm (gauge pressure). Next, the temperature of the reactor is raised.
Since a decrease in hydrogen pressure due to reduction of the catalyst is observed with the temperature increase, the temperature is raised to the reaction temperature while correcting the hydrogen pressure. The reaction is carried out at a temperature of 150 to 250 ° C. After the completion of the reaction, the reaction product is separated from the catalyst by distilling or filtering the reaction product as it is.

[0021]

According to the production method of the present invention, primary alkylamines having β-branched amino groups from alkane nitriles having α-branched nitrile groups can be prepared in a short time with a small amount of catalyst. It can be easily produced with high yield and high quality.
The catalyst of the present invention has a feature that the catalyst activity hardly decreases even after several to several tens of times of recovery and reuse.

[0022]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Preparation of hydrogenation catalyst (Reference Example 1): Preparation of copper-zinc-ruthenium catalyst supported on synthetic zeolite 500 g of ion-exchanged water, 20 g of synthetic zeolite, 50 g of copper nitrate, 10 g of zinc nitrate and 50 mg of ruthenium chloride were placed in a 1 liter flask. The mixture was heated while stirring. At 90 ° C., 255 g of a 10% aqueous sodium carbonate solution was added dropwise. After aging for 1 hour, the precipitate was filtered, washed with water, dried at 100 ° C for 10 hours, and then dried at 500 ° C for 2 hours.
After calcining for an hour, a copper-zinc-ruthenium catalyst was obtained.

(Reference Example 2): Preparation of copper-zinc-palladium catalyst supported on synthetic zeolite A copper-zinc-palladium catalyst was obtained in the same manner as in Reference Example 1, except that 500 mg of palladium chloride was used instead of ruthenium chloride. Was.

(Reference Example 3): Preparation of copper-zinc-rhodium catalyst supported on synthetic zeolite A copper-zinc-rhodium catalyst was obtained in the same manner as in Reference Example 1, except that 300 mg of rhodium chloride was used instead of ruthenium chloride. Was.

Synthesis of Starting Nitrile (Synthesis Example 1) 500 g of 2-hexyl-1-undecanoic acid [Diadol 18GA (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.)] and zinc oxide [Katayama Chemical Co., Ltd.] were placed in a dehydrating tube. The flask was charged into a 1-liter round-bottomed flask and heated to 100 ° C. while introducing nitrogen. Thereafter, introduction of gaseous ammonia was started at a rate of 20 l / h, and the temperature was raised to 300 ° C. to perform a reaction. The reaction was performed until the acid value became 1 or less. The reaction time is 1
It took two hours. Thereafter, purification by distillation was performed to obtain a nitrile (C ₉ H ₁₉ ) (C ₇ H ₁₅ ) CH-CN having a purity of 99%.

(Synthesis Examples 2 to 4) Synthesis Example 1 was repeated except that 500 g of isomyristin, 500 g of fine oxocol NA and 500 g of 2-lauryl-1-palmitic acid were used instead of 2-hexyl-1-undecanoic acid. Similarly, each nitrile

Embedded image I got

Production of β-branched alkyl primary amines (Examples 1 to 4 and Comparative Examples 1 to 4) A pressure-resistant reaction vessel having an internal volume of 1 liter equipped with a tube for introducing hydrogen and a tube for sampling is provided. , 300 g of each raw material nitrile shown in Table 1,
Charge each hydrogenation catalyst and 0.6 g of sodium hydroxide,
After replacing the inside of the system with nitrogen, hydrogen was introduced to 20 atm (gauge pressure), and the temperature was raised. Since a decrease in hydrogen pressure due to reduction of the catalyst was observed as the temperature was raised, the temperature was raised to a reaction temperature of 210 ° C. while correcting the hydrogen pressure, and the reduction reaction was performed for each time shown in Table 1. Thereafter, the product was separated from the catalyst by filtration. Table 1 shows the product composition.
Shown in

[0028]

[Table 1]

[0029]

Embedded image 5): U.S. Pat. No. 2,225,05 to Lazier et al.
No. 9 copper-cobalt catalyst.

As is clear from the results shown in Table 1, the production method of the present invention (Examples 1 to 4) is different from the conventional method (Comparative Examples 1 to 4) in that the alkane in which the α-position is branched relative to the nitrile group is obtained. It can be seen that primary alkylamines in which the β-position to the amino group is branched from nitriles can be easily produced with high yield in a short period of time and with high quality using a small amount of catalyst.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07C 211/00 C07C 209/00 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] A nitrile having a C ₈ -C ₃₆ alkyl group having a branched structure at the α-carbon atom of the nitrile group or a mixture containing the same is mixed with a copper-zinc-group VIII white metal catalyst. Characterized in that it is reduced at a reaction temperature of 150 to 250 ° C. under a hydrogen gas pressure of atmospheric pressure to 50 atm (gauge pressure) in the presence of an alkali metal hydroxide and / or ammonia, or amino. Β is branched at the β-position of the group
A process for producing branched alkyl primary amines. 2. The process for producing a β-branched alkyl primary amine according to claim 1, wherein said Group VIII white metal catalyst is selected from the group consisting of ruthenium, palladium, platinum and rhodium. 3. The method for producing a β-branched alkyl primary amine according to claim 1, wherein the alkali metal hydroxide is sodium hydroxide or potassium hydroxide or any one of them. 4. The nitrile has a general formula: [In the formula, 1 is an integer of 5 to 14. The β-branched alkyl first compound according to any one of claims 1 to 3, which is a compound represented by the formula:
Method for producing secondary amine. 5. The nitrile has a general formula: [Wherein, m is an integer of 1 to 5, n is an integer of 5 to 10, and m + n = 10 to 11. The β-branched alkyl first compound according to any one of claims 1 to 3, which is a compound represented by the formula:
Method for producing secondary amine. 6. The nitriles of the formula The method for producing a β-branched alkyl primary amine according to any one of claims 1 to 3, which is a compound represented by the formula: