KR930001338B1 - Process for the preparation of substituted mono olefin compound by amino alkyl - Google Patents

Abstract

The aminoalkyl-substituted mono-olefin compound of formula (I) is produced by reacting an aromatic compound of formula (II) with an alkali metal and an ethylene diamine in the presence of a lower alcohol i.e. methanol, ehtanol, propanol or butanol at 40-140 deg.C. In the formulas, R is H or C1-4 lower alkyl; Y is amino or nitrile; n is 1-3. The alkali metal is pref. lithium, sodium or potassium. The method presents better productivity.

Description

Method for preparing monoolefin compound substituted with aminoalkyl

The present invention relates to a method for producing a monoolefin compound substituted with an aminoalkyl, and more particularly, by producing an aromatic compound having a functional group as a monoolefin using an alkali metal, it is more industrial than the conventional hydrogenation reaction and reduction reaction A method for producing monoalkyl substituted monoolefins which is useful for production and which can be produced more economically.

In general, a method for producing a monoolefin compound substituted with an aminoalkyl from an aromatic compound having a functional group is a low temperature by dissolving an aromatic compound having a functional group that can be reduced to an amine or an aromatic compound having an amine functional group in an alkali metal and a lower amine. To prepare monoolefins substituted with aminoalkyl in [J. Am. Chem. Soc., 1955,77,6042: J. Am, Chem. Soc., 1958,80,6573] and a method for preparing monoolefins substituted with aminoalkyls by metal hydrogenation or reduction of monoolefin compounds having functional groups capable of reduction with amines [US Pat. No. 2,634,273, 1953]. ; Helv. Chim. Acta. 33, 187, 1439, 1950, and the like.

However, in the former method, expensive lithium metal is used as the alkali metal, and metal amine or ethyl amine which is highly volatile as the lower amine is not only economically useful for industrial use, but also due to manufacturing by-products. There is a problem that the yield is reduced to about 49%.

In addition, the latter method is very inexpensive to use industrially because the price of Raney-Nickel used in the hydrogenation reaction using a metal catalyst is very high, and the industrial utilization is very low. That's the way it is. In addition, in the reduction reaction using a reducing agent, the production yield is generally high, about 60%. However, the cost of lithium aluminum hydride used as a reducing agent is expensive, which is also an uneconomical method.

Therefore, the present invention, unlike the conventional methods as described above, by using an alkali metal and a diamine compound, an aromatic compound substituted with an aminoalkyl group or an aromatic compound substituted with a functional group that can be reduced to an amine, by using an economic method to replace the aminoalkyl It is an object of the present invention to provide a method for preparing a monoolefin compound.

Hereinafter, the present invention will be described in detail.

In the present invention, in preparing a monoolefin compound substituted with an aminoalkyl from an aromatic compound substituted with a functional group, an alkali metal and ethylenediamine are reacted with a compound represented by the following general formula (II) and represented by the following general formula (I). It is characterized by the preparation of monoolefin compounds substituted with aminoalkyl.

In the above formulas, R is a hydrogen atom or a lower alkali of C _{1 to} C ₄ , specifically, represents a methyl group, an ethyl group, a propyl group or a butyl group, Y represents an amino group or a nitrile group, and n represents an integer of 1 to 3 .

The present invention is characterized in that the compound represented by the general formula (I) is prepared from the compound represented by the general formula (II) by an economic method, and the compound represented by the general formula (I) of the present invention The preparation method can be easily prepared using the mixed solution of the alkali metal compound and ethylenediamine from the general formula (II), and the manufacturing process will be described in detail as follows.

First, an alkali metal, ethylenediamine and lower alcohol are mixed in the reaction reactor, and a suspension solution is prepared between 40 ° C and 140 ° C.

Then, after raising the temperature of the reaction solution, the compound represented by the general formula (II) is added dropwise, the reaction is carried out at that temperature.

When the reaction is complete, a solid mixture is obtained. When this is economical, a compound represented by the general formula (I) to be obtained can be obtained.

Instead of ethylenediamine, a conventional diamine compound similar to the above may be used in the general manufacturing process according to the present invention. As the alkali metal, lithium, sodium, or potassium may be used, and such a diamine compound and an alkali metal may be suspended. The solution can increase the electronic activity of the alkali metal to facilitate the (electronic reduction) reaction of the alkali metal with the compounds represented by the general formulas (I) and (II).

In addition, due to the high boiling point of the diamine compound, it is possible to prepare a variety of suspension solutions within a wide temperature range of 40 ℃ to 140 ℃ when preparing a suspension solution with the alkali metal, it is possible to control the electronic activity of the alkali metal.

In addition, as the lower alcohol used in the suspension solution, methanol, ethanol, propanol or butanol may be usefully used.

On the other hand, the reaction temperature during the reaction can be carried out smoothly between 40 ℃ to 140 ℃, it is preferred between 70 ℃ to 90 ℃.

After this reaction, by-products can be produced, which can be easily removed using a conventional fractional distillation method.

As described above, the manufacturing method according to the present invention can produce industrially useful targets with high yields while using cheaper raw materials than conventionally known methods. In addition, the final product produced can be very useful as a fine chemical product.

Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1

11 g of lithium metal, 64 g of ethylenediamine, and 150 ml of anhydrous methanol were added to a flask equipped with a reflux column and a stirrer, and the temperature was raised to 80 ° C. while stirring using a stirrer. After stirring for 1 hour at 80 ° C., 40 g of phenethylamine was added dropwise for 30 minutes, followed by stirring for 4 hours. After cooling to room temperature, 100 ml of anhydrous methanol was added dropwise, followed by 100 ml of water. The resulting colorless solution was concentrated to 70 ml, extracted twice with 100 ml of chloroform and 50 ml. The layers of chloroform were collected and washed twice with 50 ml of water and 20 ml.

Thereafter, the chloroform layer was evaporated and concentrated to obtain a crude compound. The fractional distillation again gave 24.5 g (yield: 59.3%) of 2- (1-cyclohexenyl) ethylamine as a final product.

¹ H-NMR (CDCl ₃ / TMS), δ, J (Hz): 1.16 (s, 2H), 1.16 (m, 4H), 1.99 (m, 6H), 2.74 (t, 2H, J = 7.0) , 5.45 (br, s, 1 H).

Example 2

Into a flask equipped with a reflux column and a stirrer, 88 g of sodium metal, 84 g of ethylenediamine, and 150 ml of anhydrous methanol were added thereto, followed by stirring using a stirrer to raise the temperature to 80 ° C.

After stirring for 1 hour at 80 ° C., 40 g of phenethylamine was added dropwise for 40 minutes, followed by a stirring reaction for 4 hours. After cooling to room temperature, 200 ml of anhydrous methanol was added dropwise, followed by 100 ml of water.

The resulting colorless solution was concentrated to 70 ml, extracted twice with 100 ml of chloroform and 50 ml, and then the chloroform layers were collected and washed twice with 50 ml of water and 20 ml.

The chloroform layer is then concentrated by evaporation to give crude compound, which is fractionally distilled to give 28.5 g (yield: 68.9%) of 2- (1-cyclohexenyl) ethylamine as the final product.

Example 3

Into a flask equipped with a reflux column and a stirrer, 75 g of sodium metal, 84 g of ethylenediamine, and 150 ml of anhydrous methanol were added, and then the temperature was raised to 80 ° C. while stirring using a stirrer.

After stirring at 80 ° C. for 1 hour, 45 g of benzyl cyanide was added dropwise for 40 minutes, followed by a stirring reaction for 4 hours. After cooling to room temperature, 150 ml of anhydrous methanol was added dropwise, followed by 100 ml of water.

The resulting colorless solution was concentrated to 80 ml, extracted twice with 100 ml of chloroform and 50 ml. The layers of chloroform were collected and washed twice with 50 ml of water and 20 ml.

Thereafter, the chloroform layer was concentrated by evaporation to give a crude compound, which was then fractionally distilled to give 30.8 g (yield: 64.0%) of 2- (1-cyclohexenyl) ethylamine as the final product.

Claims (4)

In preparing a monoolefin compound substituted with aminoalkyl from an aromatic compound substituted with a functional group, an aminoalkyl represented by the following general formula (I) by reacting an alkali metal and ethylenediamine with a compound represented by the following general formula (II) Method for preparing a monoolefin compound substituted with.

In the above formulas, R is a hydrogen atom or lower alkyl of C _{1 to} C ₄ , specifically, represents a methyl group, an ethyl group, a propyl group or a butyl group, Y represents an amino group or a nitrile group, and n represents an integer of 1 to 3 . The method of claim 1, wherein the alkali metal is any one selected from lithium, sodium, and potassium. The method for preparing an aminoalkyl substituted monoolefin compound according to claim 1, wherein the reaction is performed at 40 ° C to 140 ° C. The method of claim 1 or 3, wherein the reaction is carried out in the presence of a lower alcohol selected from methanol, ethanol, propanol and butanol.