Trimethylaminoborane preparation method

IPC classes for russian patent Trimethylaminoborane preparation method (RU 2259373):

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FIELD: organic synthesis.

SUBSTANCE: invention relates to organoboron compounds technology, in particular to aminoboranes and, more specifically, to trimethylaminoborane, which can be used as reducing and hydroboronizing agents as well as in color photography, in magnetic film manufacture, and as fuel additive to decrease amount of deposits in combustion chamber. Method comprises reaction of trimethylamine with gaseous diborane in organic solvent at reduced temperature. Solvent is selected from aliphatic, cycloaliphatic, and aromatic hydrocarbons with melting temperature not higher than -20°C. Reaction is conducted at temperature from -30°C to 0°C, preferably from -15 to -5°C, at trimethylamine-to-solvent volume ratio 1:(1/5-3.5).Proposed method simplifies preparation procedure owing to eliminated laborious solvent removing vacuum distillation stage and stage wherein of aqueous alkali metal hydroxide is introduced to stabilize aminoborane. Yield of desired product, characterized by high purity, achieves 95-98.6%, which is essentially higher than, for example yield (86%) of morpholinoborane regarded as prototype compound in a known process.

EFFECT: enhanced economical efficiency of process.

3 cl, 4 ex

The invention relates to the technology of organoboron compounds, in particular aminoborane, namely trimethylaminuria (TMAB), which can be used as a reducing and hydroperiodide agents, as well as in color photography, in the manufacture of magnetic films, as additives to fuels to reduce the number of products deposits in the combustion chamber, in fine organic synthesis.

A method of obtaining trimethylaminuria based on the interaction of borhydride alkali metals with trimethylamine hydrochloride in an organic solvent (U.S. patent No. 6060623, 2000). So trimethylaminuria was obtained by interaction of a suspension of 60 g (0,628 mol) of trimethylamine hydrochloride in 94 g of 1,2-dimethoxyethane with a suspension of 25 g (0,661 mol) sodium borohydride in 26 g of 1,2-dimethoxyethane at a temperature of 20°With or below. After completion of the reaction (24 hours) 1,2-dimethoxyethan distilled off. To the residue add 140 g of 5%aqueous sodium hydroxide solution to separate the organic and aqueous phase. The organic phase is filtered to remove impurities, the filtrate is cooled and allocate 27 g of trimethylaminuria. After distillation 1,2-dimethoxyethane allocate an additional 14 g of the product. The total yield of 90%. The content of the basic substance, measured statmetrics - 98%. Melting point 94°C.

The disadvantages of this SPO is both of the following applies.

1. The long duration of the process.

2. Utilizing an aqueous solution of sodium hydroxide and sodium chloride, which leads to the complexity of the process.

3. The relatively low yield of the finished product.

The closest analogue to the claimed invention in its technical essence and the achieved result is a method of obtaining a stable aminoborane, in particular of trimethylaminuria (U.S. patent No. 3317525, 1967), which consists in the interaction of tetrahydrofurane (THF-borane)obtained by the reaction of boron hydride sodium efratom of boron TRIFLUORIDE with amines in the environment of tetrahydrofuran. So to suspension 600 g of powdered sodium borohydride in 8-10 liters of dry tetrahydrofuran, cooled to 0°using an ice-water bath, slowly add 2840 g epirate boron TRIFLUORIDE within 1-2 hours, the temperature of the solution while maintained within the range of from 0 to 5°C. After adding all epirate boron TRIFLUORIDE, the reaction mixture was incubated for 1 hour, after which it slowly while mixing add the required amount of amine. Then with rapid stirring, slowly add 10%aqueous sodium hydroxide solution. The mixture defend to the formation of two layers: the top layer contains tetrahydrofuran and about 10-20% of water together with amibara the Ohm, the lower aqueous layer containing caustic and perborate sodium, separated. The upper layer is concentrated by heating and vacuum up until the whole tetrahydrofuran not Argonauts, and remains the solution of trimethylaminuria in the water. This solution is cooled to 0°, aminoborane filtered off, washed with water, cooled with ice, and dried under vacuum at 60-70°With removal of traces of moisture.

According to the known method are water-soluble aminoborane, including trimethylaminuria, but a specific product yield and purity in the patent are not given (output Martinborough 86%). By analogy, we can assume that the output of trimethylaminuria does not exceed the output of Martinborough, as the use of volatile trimethylamine (boiling point about 3° (C) should lead to large losses in the synthesis process than using the research (boiling point 128-130°). In addition, trimethylaminuria is highly volatile (vapor pressure of 105 PA at 23° (C)that leads to dopolnitelnim loss product at the stage of distillation of tetrahydrofuran.

A disadvantage of this known method are:

1. A multi-stage.

2. The use of a large number of reagents (sodium borohydride, apirat boron TRIFLUORIDE, tetrahydrofuran, water, sodium hydroxide, trimethylamine, which means the flax complicates the process.

3. The relatively low yield of the finished product.

4. The impossibility of re-use of solvent without regeneration due to the presence of moisture.

5. Utilizing aqueous solutions of hydroxides and perborate sodium.

These disadvantages of the known method of trimethylaminuria make it uneconomical when implemented in an industrial environment.

The objective of the invention is to develop a simple method of obtaining trimethylaminuria high yield of the finished product.

The problem is solved by a method of obtaining trimethylaminuria, including the interaction of trimethylamine with DIBORANE in an environment of hydrocarbon solvent at low temperature, followed by separation of the finished product. According to the invention, the hydrocarbon solvent are aliphatic, cycloaliphatic or aromatic hydrocarbons with a melting point of not higher than minus 20°and the process is conducted at a temperature from minus 30°0°C, preferably from minus 15 to minus 5°C. as a hydrocarbon solvent at a temperature not higher than minus 20°can be used toluene, o-xylene, m-xylene, cumene, pentane, hexane, heptane, methylcyclohexane and other hydrocarbon solvents, in which good rest is con siderably widening trimethylamine.

Experimental studies have shown that the implementation of the process at temperatures below minus 30°leads to the formation of side products due to the inclusion of one or more groups NR₃to get trimethylaminuria that degrades its quality and increases the flow rate of DIBORANE. Increasing the process temperature is above 0°reduces the yield of the final product and the deterioration of its quality, as the high temperature promotes the formation of degradation products of DIBORANE and their interaction with trimethylamine, as well as ablation of trimethylamine from the reaction mass.

When the selected temperature from minus 30°0°the process is carried out at a volumetric ratio of trimethylamine: hydrocarbon solvent of 1:(1.5-to 3.5). If insufficient quantities of solvent (less than 1:1,5) leads to the formation of dense, poorly mixed suspension, which leads to leakage of DIBORANE and, consequently, reducing trimethylaminuria. In addition, due to insufficient amount of solvent is difficult for the heat transfer, which leads to local overheating, contributing to the formation of the products of decomposition of DIBORANE and their interaction with trimethylamine. The result is a reduction in the quality of the finished product. The increase in the ratio of trimethylamine:coal is hydrogen, the solvent is more than 1:3,5 impractical as indicators of the quality of the target product and its output does not change, but it leads to increased energy consumption for cooling of the reaction mass and ultimately increase the cost of the final product.

It is the choice of the optimal temperature range of the process, using as solvent a hydrocarbon solvent with a melting point of not higher than minus 20°and conducting the process at the optimum volumetric ratio of trimethylamine:hydrocarbon solvent is allowed to simplify the technology of obtaining trimethylaminuria, making it a waste that does not require the utilization of by-products, and to increase the yield of the target product with its high quality.

The method is as follows.

The process is conducted in a reactor equipped with a stirrer, a reflux condenser, a siphon for the dosage of DIBORANE and a thermometer. Before downloading the source components of the reactor is rinsed with an inert gas such as nitrogen. Then charged to the reactor a hydrocarbon solvent, is cooled to subzero temperatures and add under a layer of solvent trimethylamine, chilled to minus 5 minus 3°C. the Volumetric ratio of trimethylamine:hydrocarbon solvent is 1:(1.5-to 3.5), respectively. In the reaction mixture serves stoichiometric amounts, the creation of gaseous DIBORANE, maintaining the temperature in the range from minus 30°0°C. Upon completion of the dispensing of DIBORANE reaction mass is stirred for 30 minutes to complete the process and conduct stabilization by Stripping gaseous nitrogen dissolved in the hydrocarbon solvent of DIBORANE. The precipitation of trimethylaminuria is filtered at a temperature of the reaction mass 2-5°and dried under reduced pressure at room temperature for 60-90 minutes. The filtered hydrocarbon solvent does not require recycling, and recyclized for use in the following syntheses of obtaining trimethylaminuria.

Get trimethylaminuria with the content of the basic substance to 98.1-98.6 per cent. Output 95-98,6%.

Below are examples of the proposed method.

Example 1.

Getting trimethylaminuria carried out in a reactor equipped with a stirrer, reflux condenser, thermometer and a siphon for supplying gaseous DIBORANE. Before loading the reactor is blown dry with nitrogen. Trimethylamine and toluene take in a volume ratio of 1:1,5. Charged to the reactor 91,5 cm³toluene, cool it down to minus 20°and added under a layer of toluene 61 cm³trimethylamine, chilled to minus 5°C. the Solution is cooled to minus 15°and it serves a stoichiometric amount of gaseous dibor is on, with such a speed that the temperature of the reaction mass was maintained below minus 15°C. Upon completion of the dosage of DIBORANE reaction mass is stirred for 30 minutes at the same temperature and are stabilized by Stripping gaseous nitrogen dissolved in toluene of DIBORANE. The precipitation of trimethylaminuria is filtered at a temperature of the reaction mass 2-5°and dried. The output of trimethylaminuria 97,3%, the content of the basic substance to 98.1%, melting point 94°C.

Example 2.

Getting trimethylaminuria carried out analogously to example 1. The volumetric ratio of trimethylamine:toluene 1:2,5. The temperature of the reaction mixture are supported by about minus 10°C. Receive trimethylaminuria with the content of the basic substance to 98.6%; the yield of the final product to 98.6%; melting point 94°C.

Example 3.

Getting trimethylaminuria carried out analogously to example 1. The volumetric ratio of trimethylamine:toluene 1:3,5. The temperature of the reaction mixture in the synthesis support about minus 5°C.

Get trimethylaminuria with a basic substance content of 98.5%; the yield of the final product 95,0%, melting point 94°C.

Example 4.

Getting trimethylaminuria carried out analogously to example 1. As the solvent used hexane. The volumetric ratio of trimethylamine:exon of 1:3.5. The temperature of the reaction mixture in the synthesis support about minus 10°C.

Get trimethylaminuria with a basic substance content of 98.2%; the yield of the final product to 98.6%, melting point 94°C.

Thus, it is experimentally proved that the technical-economic indicators of the proposed technical solution is higher in comparison with the known. Replacement of essential hydrocarbon solvent in combination with an optimum temperature mode of operation and an optimal ratio of trimethylamine:hydrocarbon solvent allows you to:

to simplify the process by eliminating time-consuming stage vacuum distillation in the separation of organic solvent from the target product and the stage of introduction of the aqueous solution of alkali metal hydroxide to highlight trimethylaminuria. This eliminates the need for disposal of produced by-products;

to increase the yield of the final product up to 95-98,6% (on prototype output of trimethylaminuria is not given, and the output of Martinborough 86%) while maintaining high product quality;

- implement in industrial environments simple, waste-free and cost-effective technology.

Sources of information

1. U.S. patent No. 6060623, 2000

2. U.S. patent No. 3317525, 1967

1. The method of receiving trimethylaminuria, R is the overall interaction of trimethylamine with boranova reagent in the medium of organic solvent at low temperature, followed by separation of the final product, characterized in that as boranova reagent using DIBORANE as the organic solvent used hydrocarbon solvent with a melting point of not higher than minus 20°and the process is conducted at a temperature from minus 30 to 0°C.

2. The method according to claim 1, characterized in that the hydrocarbon solvent used toluene.

3. The method according to claim 1, wherein the process is conducted at a volumetric ratio of trimethylamine: hydrocarbon solvent, equal 1:(1,5-3,5).