The way to obtain tert-butylaniline

C07C211/07 - containing one, two or three alkyl groups, each having the same number of carbon atoms in excess of three

 

(57) Abstract:

The invention relates to a method for producing tert-butylaniline that can be used as a selective reducing agent in aqueous and organic media. Describes how to obtain tert-butylaniline, including interaction of tert-butylamine with boranova the complex tetrahydrofuranyl or dimethylsulfide in the environment of the solvent, followed by separation of the final product, and the process is conducted at a molar ratio of bananowy complex: tert-butylamine, is equal to 1:0,95-1,2 respectively. The solvent may be tetrahydrofuran or dimethyl sulfide. 5 C. p. F.-ly.

The invention relates to a technology for alkylamidoamines, in particular the production of tert-butylamine, which can be used as a selective reducing agent in aqueous and organic media.

A method of obtaining aminoborane, in particular tert-butylaniline, including the interaction of alkali metal borohydride, acid and water in the presence of tert-butylamine (U.S. Pat. USA 3127448, 31.03.64).

The known method is as follows. At 20oWith a mix of 9.5 ply 1.5 mol of water. Stirring is continued until cessation of hydrogen evolution, the mixture is filtered. The filtrate is evaporated to dryness in a vacuum. The solid residue is extracted with diethyl ether, receiving 19 g of tert-butylamine with a melting point 92-94oC. the product Yield is 43.8%.

However, the known method of obtaining tert-butylamine has the following disadvantages:

low yield of finished product;

the low quality of the obtained tert-butylaniline, which was evaluated by its melting point 92-94oWith; it is known that more pure tert-butylamine has a melting point of from 93 to 97oWith that complies with the basic substance content not less than 97% (see Fluka, Chemical reagents for analytical work, 2001/2002);

use in reactions such starting components, as sodium borohydride and boron anhydride leads to the formation of large amounts of salt waste, which requires additional costs for their disposal.

The closest analogue to the claimed invention in its technical essence and the achieved result is a method of obtaining aminoborane, including the interaction of sodium borohydride salt of the amine in the organic p is nborn (example 2). The reaction is carried out at room temperature or below between the amine salt, in particular the hydrochloride tert-butylamine and sodium borohydride in dimethoxyethane taken in approximately equal molar proportions. The duration of reaction of 0.5-1.5 hours. Upon completion of the reaction, the obtained solution is filtered, remove dimethoxyethane and receive tert-butylamine with a melting point 92-94oC. However, the example does not specify the output of the finished product. Although in another example, describing the receipt of dimethylaminoborane, output is 87%. It should be noted that in such syntheses yield depends on the nature of amines and their salts, as well as the solubility of reagents. In this method of obtaining aminoborane, in particular tert-butylaniline, as a solvent used dimethoxyethan, in which sodium borohydride is dissolved bad, so the yield of the target product cannot practically exceed 90%. The content of the basic substance in the final product is also not included, however, for the specified melting temperature (92-94o(C) the content of the basic substance is less than 97%.

Furthermore, the presence of salt waste and the use of relatively expensive solvent - dimethoxyethane - conditions.

To eliminate the above disadvantages of the task was to develop a new method of obtaining tert-butylaniline with a high content of basic substance, with high output and cost-effective when implemented in an industrial environment.

The problem is solved developed method to obtain tert-butyl-aminoborane, including interaction of tert-butylamine with boron-containing compound in the environment of the solvent, followed by separation of the final product, the boron compounds are used bananowy complex - tetrahydrofuranyl or dimethylsulfide - and the process is conducted at a molar ratio of bananowy complex: tert-butylamine, is equal to 1: (0,95-1,2).

When using tetrahydrofurane (THF-borane) as a solvent during the process is mainly used tetrahydrofuran. When using dimethylsulfide as a solvent during the process is mainly used dimethyldisulfide. However, this does not preclude the use of other solvents, such as aromatic, aliphatic hydrocarbons, simple aliphatic and cyclic ethers, esters carbonex:tert-butylamine, equal to 1:(from 0.95 to 1.2). The deviation from the selected molar ratio bananowy complex: tert-butylamine less than 1:0,95 reduces the yield of the target product due to incomplete entry into the reaction boranova complex, in particular tetrahydrofurane or dimethylsulfide. In addition, when using recycle THF or dimethyl sulfide in the subsequent syntheses is the decline in the quality of the finished product due to the interaction of tert-butylamine with the products of decomposition of the unreacted THF-borane or dimethylsulfide respectively. The increase in the ratio over 1:1,2 is impractical because the indicators in the quality and yield of the finished product are not changed, this increases the time of the process and the energy consumption for cooling the reaction mixture, which increases the cost of the final product.

Studies have shown that during the process at the desired molar ratio of the reactants, it is preferable to use a concentration of tetrahydrofurane from 0.01 to 2.9 M, in the case of dimethylsulfide is from 0.01 to 10.2 M Concentration of THF-borane, equal to 2.9 M, and the concentration of dimethylsulfide equal to 10.2 M are the maximum for the data of the second complex less than 0.01 M impractical because it gives no advantages in quality and yield of the final product, but increases the energy consumption for cooling of the reaction mixture and heating during distillation of tetrahydrofuran or dimethyl sulfide, and increases during the process.

The temperature of the process ranges from minus 30 to plus 40oC, preferably from minus 20 to plus 30oC. carrying out the process at temperatures below minus 30oSince it is not economically feasible, because it does not increase the yield of tert-butylamine or improve its quality, but increases the cost of the final product due to the increase in energy consumption for cooling of the reaction mixture. Increasing the synthesis temperature above 40oWith leads to the decomposition of THF-borane or dimethylsulfide and interaction of tert-butylamine with the products of decomposition, which reduces the quality and yield of the finished product.

In case of carrying out the process at temperatures below 10oAfter completion of dosing of the reagents, the reaction mass is preferably stand for stabilization at a temperature selected from a range from 10 to 60oC. thus obtain tert-butylamine with high stability - the main content is the new method allows to obtain tert-butylamine with a high content of the basic substance of 99.1-99.5% and the yield of the target product 93-96,6% of theory, however tert-butylamine has high stability.

Below are examples of the proposed method.

Example 1.

Obtain tert-butylaniline carried out in a reactor equipped with a stirrer, a thermometer and a funnel for feeding tert-butylamine. Before loading the reactor is blown dry with nitrogen. Charged to the reactor 0.4 mol (200 ml) 2 M THF-borane containing 34.4 g THF-borane and 143,6 g of THF, and cooled it to minus 10oC. is poured Into the funnel 0.44 mol (46,3 ml) of tert-butylamine and submit it to the reactor at such a speed that the temperature of the reaction mixture was maintained below minus 10oC. After the filing of tert-butylamine reaction mass is heated to 20oC and maintained at this temperature with stirring until complete stabilization. Then the tetrahydrofuran is distilled off under reduced pressure. The output of tert-butylamine to 96.6% of theory, the basic substance content of 99.5%, the melting point of 97.5oC.

Example 2.

Obtain tert-butylaniline carried out in a reactor equipped with a stirrer, thermometer and funnel that feeds dimethylsulfide. Before loading the reactor is blown dry with nitrogen. In the reactor load of 1.05 mo is l (196 ml) 5.1 M of dimethylsulfide in dimethyl sulfide and submit it to the reactor with such speed, to the temperature of the reaction mixture was maintained below minus 10oC. After the filing of tert-butylamine reaction mass is heated to 20oC and maintained at this temperature with stirring until complete stabilization. The output of tert-butylamine after separation of the reaction mass to 96.6% of theory, the basic substance content of 99.5%, the melting temperature is 97.6oC.

Example 3.

Obtain tert-butylaniline carried out analogously to example 1. The temperature of the reaction mixture in the synthesis support about 20oC. the Molar ratio of THF-borane: TBA is 1:1,1. The THF concentration of 1 M borane

Receive tert-butylamine with a basic substance content of 99.4%; the yield of the final product 96%, melting point of 97.5oC.

Thus, it was proved experimentally that the proposed new method allows

to obtain stable tert-butylamine with high technical and economic indicators compared to the prototype (the content of the basic substance in the target product to 99.1-99.5% pure, melting point of 97.5-98oWith the release of the final product 93-96,6%);

to simplify the process by eliminating time-consuming stage of the technology.

Sources of information

1. U.S. patent 3127448, 31.03.64.

2. Flucka. Chemical reagents for analytical work 2001/2002.

3. The Japan Patent 81158792, 07.12.81.

1. The way to obtain tert-butylaniline, including interaction of tert-butylamine with boron-containing compound in the environment of the solvent, followed by separation of the final product, characterized in that boron compounds are used bananowy complex - tetrahydrofuran-borane or dimethyl sulfide-borane and the process is conducted at a molar ratio of bananowy complex: tert-butylamine, is equal to 1:0,95-1,2 respectively.

2. The method according to p. 1, characterized in that as boranova complex using tetrahydrofuran-borane with a concentration of 0.01 to 2.9 M

3. The method according to p. 1, characterized in that as boranova complex use of dimethyl sulfide-borane with a concentration of 0.01-10,2 M

4. The method according to PP.1 and 2, characterized in that the solvent used tetrahydrofuran.

5. The method according to PP.1, 3, characterized in that the solvent used dimethyldisulfide.

6. The method according to PP.1-5, characterized in that the process is carried out at a temperature from minus 20 to plus 30C.

 

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