JP2851274B2 - Method for producing N, N-diisopropylethylamine - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing N, N-diisopropylethylamine (hereinafter referred to as DIPEA), and more particularly to DIPEA by catalytic reduction reaction using ethylamine and acetone as starting materials in the presence of a noble metal catalyst. And DIPEA by performing a catalytic reduction reaction while supplying acetaldehyde into the reaction system in the presence of a noble metal catalyst using diisopropylamine (hereinafter referred to as DIPA) and acetaldehyde as starting materials.
A method for producing the same. DIPEA is a compound useful as a raw material for medical and agricultural chemicals.

[0002]

2. Description of the Related Art
As a method for producing DIPEA, a method is known in which DIPA is ethylated with diethyl sulfate (Chem. Be).
r. , 91, 380-392 (1958)). According to this method, DIPA as a raw material and DIP as a target substance are added to a reactor.
EA was charged in equimolar amounts, and diethyl sulfuric acid was added, and 140 ° C.
For 3.5 hours to obtain DIPEA with a yield of 90%. However, although this method has a high yield, it is hard to say that it is an industrially advantageous method such as adding a target substance to promote the reaction. As another production method, DIPA is ethylated with ethyl iodide (JOC, 1).
6, 1911 (1951)), but the yield is about 50%.
It is difficult to say that it is a low and preferable method. An object of the present invention is to provide a method for obtaining DIPEA in a good yield using raw materials that can be obtained at low cost.

[0003]

Means for Solving the Problems and Embodiments of the Invention The first invention of the present invention is characterized in that DI is subjected to a catalytic reduction reaction of ethylamine and acetone in the presence of a noble metal catalyst.
This is a method for producing PEA.

A second invention of the present invention is characterized in that DIPA and acetaldehyde are subjected to a catalytic reduction reaction in the presence of a noble metal catalyst to produce DIPEA, wherein the reaction is carried out while supplying acetaldehyde into the reaction system.
This is a method for producing PEA.

Conventionally, the method of the first invention has not been known surprisingly. The reason is that when an isopropyl group is introduced into ethylamine by catalytic reduction with acetone, the introduction of one isopropyl group is relatively easy, but the introduction of another isopropyl group is based on the intermediate N-isopropyl. It is presumed that this was thought to be difficult due to a decrease in the activity of the nitrogen atom caused by steric hindrance by the alkyl group of ethylamine (hereinafter referred to as MIPEA).

Accordingly, the present inventor has attempted a catalytic reduction reaction of ethylamine and acetone using a Raney Ni catalyst which is extremely widely used as a hydrogenation catalyst. The main product is isopropyl alcohol, which is a reduced form of acetone. There was almost no DIPEA formation. As a result of further studies, the present inventors have surprisingly found that the use of a noble metal catalyst significantly improves the yield of DIPEA, and completed the first invention of the present invention.

In the production of a tertiary amine by a catalytic reduction reaction of a secondary amine and an aldehyde as in the second invention of the present invention, generally, all of the secondary amine and the aldehyde are charged in an autoclave and hydrogen is charged. A method of performing a catalytic reduction reaction in the presence of a conversion catalyst is employed. However, in the production of DIPEA by the catalytic reduction reaction of diisopropylamine and acetaldehyde, in such a general method, acetaldehyde causes a reaction other than the object of the present invention with any of the noble metal catalyst and Raney Ni catalyst, and the yield of DIPEA is extremely low. Or the formation of DIPEA is hardly noticeable. As described above, DIPEA cannot be obtained with a high yield by the conventional method.

Accordingly, the present inventors have conducted intensive studies and, as a result, surprisingly, DIPEA was carried out by performing a catalytic reduction reaction of DIPA and acetaldehyde while supplying raw material acetaldehyde in the presence of a noble metal catalyst.
It has been found that the yield of the present invention is significantly improved, and the second invention of the present invention has been completed. By the way, while supplying the raw material acetaldehyde into the reaction system in the presence of Raney Ni catalyst, DI
Even if the catalytic reduction reaction of PA and acetaldehyde is performed,
The main product is ethanol, which is a reduced form of acetaldehyde, and the formation of DIPEA is hardly observed.

In the second invention, it is important to use a noble metal catalyst as the hydrogenation catalyst and to carry out the catalytic reduction reaction while supplying acetaldehyde into the reaction system. Examples of the noble metal catalyst used in the method of the present invention include commonly used noble metal catalysts for hydrogenation, and specific examples thereof include palladium-carbon, ruthenium-carbon, and rhodium-.
Carbon, platinum-carbon and the like. The amount of the noble metal catalyst used is preferably in the range of 1 to 20% by weight based on ethylamine or diisopropylamine from the viewpoint of reaction efficiency and catalyst efficiency.

[0010] The method of the first invention of the present invention will be further described. The amount of acetone used is usually 2 to ethylamine.
The reaction proceeds suitably when used in an excess of 1 to 30 moles, preferably 4 to 16 moles. If the amount of acetone used is less than twice the mole of ethylamine, D
The production rate of MIPEA is higher than that of IPEA. Ethylamine can be subjected to the reaction as an aqueous solution. As the ethylamine aqueous solution, a 70% product that is industrially easily available is used.

The reaction of the first invention of the present invention is to produce DIPEA via MIPEA which can be produced at a relatively low temperature. According to one preferred embodiment of the first invention of the present invention, ethylamine, acetone and a noble metal catalyst are charged into an autoclave and 100 to 100 while introducing hydrogen.
The temperature may be gradually increased to 180 ° C., preferably 130 to 160 ° C., and the introduction of hydrogen may be continued at a normal pressure or higher and preferably 5 to 60 atm while maintaining the temperature. 3-1 after the start of hydrogen introduction
At 0 hours, the absorption of hydrogen ends, and ethylamine is almost consumed. In another preferred embodiment, room temperature to 9
Ethylamine and acetone are subjected to a catalytic reduction reaction in the presence of a noble metal catalyst at about 0 ° C. to produce and isolate MIPEA. Then, the isolated MIPEA and acetone are isolated in the presence of a noble metal catalyst.
A two-step method of producing DIPEA by performing a catalytic reduction reaction at 00 to 180 ° C, preferably 130 to 160 ° C.

In the method of the first invention of the present invention, MIPEA contained in the reaction solution can be induced to DIPEA by isolating from the reaction solution and subjecting it to a catalytic reduction reaction with acetone in the presence of a noble metal catalyst.

Next, the method of the second invention of the present invention will be further described. The acetaldehyde to be supplied into the reaction system is preferably used in a theoretical amount or an excess of 1 to 2.0 times mol of DIPA. In the present invention, a solvent is not particularly required, but since acetaldehyde has a low boiling point, it is easier to operate by diluting with a solvent and supplying it. As the solvent, water or an organic solvent inert to amine and acetaldehyde can be used, but water having good operability in post-treatment is preferable. The amount of the solvent is not particularly limited, but is preferably 0.5 to 3 times the weight of acetaldehyde in consideration of production efficiency.

[0014] The reaction temperature is usually from room temperature to 200 ° C, preferably from 70 to 150 ° C. The reaction pressure is not lower than normal pressure and preferably 5 to 60 atm. A supply time of acetaldehyde of 1 to 6 hours is sufficient, and DIPA is almost consumed.

The DIPEA produced by the method of the present invention can be obtained very easily and in a high purity by a general isolation and purification means, for example, by removing the catalyst from the reaction solution by filtration and distilling the filtrate.

[0016]

EXAMPLES The method of the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 70% in a magnetic stirring type autoclave having a capacity of 1 liter
64 g (1.0 mol) of an ethylamine aqueous solution, acetone 4
64 g (8.0 mol) and palladium-carbon 6.4
g, hydrogen was introduced therein, and heated to 160 g.
The temperature was raised to 50 ° C. and a pressure of 50 atm to perform a catalytic reduction reaction. Next, while maintaining the temperature and the pressure, introduction of hydrogen was continued to perform a catalytic reduction reaction. Hydrogen absorption was completed 7 hours after the start of hydrogen introduction. After cooling, the reaction solution was filtered to remove the catalyst, and the filtrate was distilled to obtain 82.8 g of DIPEA (yield: 6).
4.2%) and 20.3 g of MIPEA (yield 23.3).
%)Obtained.

Example 2 A reaction and a post-treatment were carried out in the same manner as in Example 1 except that the reaction temperature was changed to 180 ° C., and 57.7 g of DIPEA (44.7% yield) and 29.6 g of MIPEA were obtained. Yield 3
4.0%).

Example 3 The reaction and post-treatment were carried out in the same manner as in Example 1 except that the 70% ethylamine aqueous solution was replaced by 45 g (0.7 mol) and the acetone by 487 g (8.4 mol), and DIPEA was added to 60%. 0.8 g (67.3% yield) and MIPEA.
0 g (19.7% yield) was obtained.

Example 4 257 g (4 mol) of a 70% ethylamine aqueous solution, 232 g (4 mol) of acetone and 3.5 g of palladium-carbon were reacted in the same manner as in Example 1 except that the reaction temperature was changed to 70 ° C. And post-processing is performed, and MIPEA is set to 334.
4 g (96.1% yield) was obtained. The hydrogen absorption was completed 4 hours after the start of hydrogen introduction.

Then, 100 g of the obtained MIPEA was obtained.
(1.15 mol), 333 g (5.75 mol) of acetone
And 7.4 g of palladium-carbon was charged into a 1-liter electromagnetic stirring type autoclave, and a catalytic reduction reaction was carried out at 160 ° C. and 40 atm for 5 hours while introducing hydrogen into the autoclave. After cooling, the reaction solution was filtered to remove the catalyst, and the filtrate was distilled to obtain 105.9 g of DIPEA (yield: 71.4).
%), 8.4 g of unreacted MIPEA (recovery rate 8.4%)
Obtained.

Example 5 DIP was added to a magnetic stirring autoclave having a capacity of 1 liter.
A 202 g (2.0 mol) and palladium-carbon 1
2.9 g was charged, hydrogen was introduced into the mixture, and the mixture was heated to 120 g.
° C and 25 atm. Next, 184 g (2.1 mol) of a 50% acetaldehyde aqueous solution was subjected to a catalytic reduction reaction while supplying hydrogen into the autoclave over 3 hours by a high-pressure metering pump and keeping 25 atm. After cooling, the reaction solution was filtered to separate the catalyst, and the oil layer of the filtrate separated into two layers was distilled to obtain 210.0 g of DIPEA (yield 8).
1.4%) and 17.8 g of unreacted DIPA (recovery rate: 8.8%). In addition, 10.4 g of ethanol (yield 1
0.8%).

Example 6 The reaction and post-treatment were carried out in the same manner as in Example 5 except that 7.7 g of palladium-carbon and 228 g (2.6 mol) of a 50% aqueous acetaldehyde solution were used.
A, 236.1 g (91.5% yield), unreacted DIP
A remained almost at 0.6 g (recovery 0.3%). 10.5 g of ethanol (8.8% yield)
It was a by-product.

COMPARATIVE EXAMPLE 1 DIP was added to a 1-liter electromagnetic stirring type autoclave.
A 202 g (2.0 mol), 184 g (2.1 mol) of a 50% aqueous solution of acetaldehyde and 7.7 g of palladium-carbon were charged, and hydrogen was introduced into the mixture.
When the catalytic reduction reaction was performed at 25 ° C. and 25 ° C., the absorption of hydrogen stopped in 1 hour and 30 minutes, and the reaction was completed. After cooling, the reaction solution was filtered to separate the catalyst, and the oil layer of the filtrate separated into two layers was distilled to obtain 23.5 g of DIPEA (yield 9.
1%) and 68.3 g of unreacted DIPA (recovery: 33.3%).
8%). In addition, many high-boiling substances were by-produced.

Comparative Example 2 A reaction and a post-treatment were carried out in the same manner as in Example 6 except that 52 g of Raney Ni was used instead of palladium-carbon. DI
The amount of produced PEA is a trace, and the amount of unreacted DIPA was 1
94.9 g (recovery rate 96.5%) and ethanol
8 g (98.7% yield) was obtained.

[0026]

According to the first and second aspects of the present invention, DIPEA can be obtained at a good yield with less expensive raw materials than the conventional method.

Claims (1)

(57) [Claims] Claims: 1. A catalytic reduction reaction of diisopropylamine and acetaldehyde in the presence of a noble metal catalyst to give N, N-
A method for producing N, N-diisopropylethylamine, wherein the reaction is carried out while supplying acetaldehyde into the reaction system when producing diisopropylethylamine.