The method of obtaining unsaturated organomagnesium

 

(57) Abstract:

The invention relates to the production of alkenylsilanes used in the synthesis of Organoelement compounds. Intensification method of producing vinyl and phenylmagnesium interaction alkenylamine powder or shavings of magnesium in the environment of tetrahydrofuran is achieved by treating the reaction mixture with ultrasound with the frequency of vibration of 20-40 kHz. 2 C. p. F.-ly, 1 table.

The invention relates to the production of unsaturated organomagnesium, in particular phenyl and miniministerial used as in the synthesis of Organoelement compounds, and as reagents in obtaining various classes of organic compounds.

It is known that organomanganese are formed by the interaction of magnesium in the form of chips or sawdust with organohalogenated in organic solvents [1] . Magnesium powder (according to literature data) for manyorganizations synthesis is not suitable. Usually the process takes place in solvents essential nature - diethyl ether, disutility ether, tetrahydrofuran. The speed of the reaction, the composition and output generated magyarkanizsa soedinenii, and properties used magnesium. Upon receipt of organomagnesium or iodides in the environment of diethyl ether, the process goes fairly quickly - within a few hours. Organochloride, except chloroalkanes behave in this reaction is less active. Unsaturated organochloride chloride vinyl chloride and benzene, as well as their substituted, react with magnesium only in the environment of tetrahydrofuran (THF) [2]. A characteristic feature of the process is that you must first spend the initiation of reaction. To a mixture of magnesium, solvent, and a small part of organohalogens (5 - 10% of total load) add 0.1 - 0.2 g of the initiator that promotes early education magyarkanizsa connection. When initiating a sharp increase in the temperature of the reaction mass, the so - called "challenge". As the initiators used were synthesized - methyl-ethyl or 1,2-dibromethane.

It should be noted that the process of obtaining organomagnesium, and vinyl - and formanilide in particular, despite the large number devoted to him, patents and publications, is to date poorly understood both in theory and in practical quiet assume as a radical path of the process [3], and ion [4] . Practical results of the reaction at the present time largely depend on the skill and luck of the experimenter.

All of the above to an even greater extent refers to the process of obtaining vinyl and formanilide. Reaction formation organomagnesium for chlorobenzene and vinyl chloride is very slow. On its intensity significantly affects the nature of the used solvents, the most active process is carried out in tetrahydrofuran. So in the case of vinyl chloride for the formation of several gram-moles magyarkanizsa connection requires more than 10 h, which is a significant drawback. The use of other solvents including diethyl ether, even more increases the duration of the process. This duration of the process creates significant difficulties for the industrial implementation of the method, as it requires a large amount of the reaction apparatus and creates difficulties in providing the necessary for the process conditions of heat and mass transfer. Attempts to accelerate the reaction by activation of the magnesium, the introduction of various additives, the intensification of the mixing effect is not given. Holding reacci to reduce the requirements to the quality of the used solvent to increase the allowable moisture content) or to carry out the reaction in hydrocarbon environments without additives esters, but does not reduce the time of the process.

The closest in technical essence to the invention is the traditional way of obtaining magyarkanizsa compounds by the reaction of chloride or chlorobenzene with magnesium turnings in the environment of tetrahydrofuran (THF) [5] . This method was adopted for the prototype. The main disadvantage is the long duration of the reaction.

The objective of the invention is to develop ways of intensification of the process of obtaining unsubstituted organomagnesium, in particular vinyl and formanilide, which would significantly reduce the time of the process to reduce the volume of the reaction apparatus and thus greatly increase the removal of the target product per unit volume of the reactor, as well as to reduce production costs.

Several experimental studies have been unexpectedly found that the solution of this problem is achieved when exposed to the reaction medium by ultrasound in certain conditions. The use of ultrasound for the intensification of the process of obtaining magyarkanizsa products are not described in literature. It was found that the interaction of saturated alkene is but reduces the time of reaction formation alkenylsilanes. Magyarkanizsa compounds according to the results of condensing them with trimethylchlorosilane remains at level 85 - 90% of theoretical. As alkenylamine use vinyl chloride or chlorobenzene. Magnesium metal charge in the form of powder milling or shaving.

A characteristic feature of the proposed method is that the influence of ultrasound has a positive effect only in the frequency range 20 - 40 kHz, and only when, the influence of ultrasound preceded stage "call" reaction.

To explain the observed effect of reducing the process time by increasing the intensity of mixing of the reagents or simply additional grinding of magnesium is not possible, as in contrast to the proposed method of intensification of the process of increasing the intensity of mixing of reagents other methods and preliminary grinding of magnesium using ultrasound with its subsequent use in the synthesis of effect do not give.

When the ultrasound frequency less than 20 kHz and 40 kHz noticeable speed increase of transformations in the process not found.

Example 1. Getting formanilide without application of ultrasonic irradiation.

In reaction Inoi funnel for submission of chlorobenzene and a stirrer, download 48.6 g (2 g-mol) magnesium turnings, 100 ml of tetrahydrofuran (THF) and 10 g of chlorobenzene. Initiate the reaction by adding 1 ml of 1,2-dibromethane, the temperature of the reaction mass rises to 50 - 60oC. After initiation of the start stirring and simultaneously flow from the dropping funnel a mixture of 215 g of chlorobenzene and 400 ml of THF. The feed mixture is conducted with such a speed that the temperature in the reaction flask was kept at 60 to 70oC. the Process is carried out until complete dissolution of the magnesium and lowering the temperature in the flask to 25 - 30oC. Output formanilide was estimated by reaction with trimethylchlorosilane and chromatographicaliy reaction products. The synthesis of formanilide in this experiment was 6 o'clock

Example 2. Getting formanilide using ultrasonic irradiation.

In the reaction apparatus consisting of a 2-liter chetyrehkolkoy flask, equipped with reflux condenser, thermometer, dropping funnel for submission of chlorobenzene and ultrasonic emitter, download 48.6 g (2 g-mol) magnesium turnings, 100 ml of tetrahydrofuran (THF) and 10 g of chlorobenzene. Initiate the reaction by adding 1 ml of 1,2-dibromethane, the temperature of the reaction mass rises to the oscillations of 22 kHz with simultaneous submission of the dropping funnel a mixture of 215 g of chlorobenzene and 400 ml of THF. The feed mixture is conducted with such a speed that the temperature in the reaction flask was kept at 60 to 70oC. the Process is carried out until complete dissolution of the magnesium and lowering the temperature in the flask to 25 - 30oC. Output formanilide was estimated by reaction with trimethylchlorosilane and chromatographicaliy reaction products. The synthesis of formanilide in this experiment was 3 o'clock

Example 3. Getting vinylmania without application of ultrasonic irradiation.

In the reaction apparatus consisting of a 2-liter chetyrehkolkoy flask, equipped with a reverse two-section refrigerator (the first section is cooled by water, the second with a mixture of acetone and dry ice), thermometer, barbaterom-funnel for supplying chloride and a stirrer, was loaded to 48.6 g (2 g-mol) magnesium turnings, 100 ml of tetrahydrofuran (THF). On barbaterom serves vinyl chloride up to saturation of the reaction mass begins scapania condensed chloride from the second section of the back of the fridge. Initiate the reaction by adding 1 ml of 1,2-dibromethane, the temperature of the reaction mass rises to 50 - 60oC. After initiation of the start stirring and simultaneously the supply of vinyl chloride on barbaterom. The two times after 2 and 4 h after initiation and the start of the input of chloride added to the reaction flask in 200 ml of THF. The process is carried out until complete dissolution of the magnesium and lowering the temperature in the flask to 25 - 30oC. Output vinylmania is estimated by reaction with trimethylchlorosilane and chromatographicaliy reaction products. The synthesis of vinylmania this experience was 14 PM

Example 4. Getting vinylmania using ultrasonic irradiation.

In the reaction apparatus consisting of a 2-liter chetyrehkolkoy flask, equipped with a reverse two-section refrigerator (the first section is cooled by water, the second with a mixture of acetone and dry ice), thermometer, barbaterom for submitting chloride and an ultrasonic emitter, download 48.6 g (2 g-mol) magnesium turnings, 100 ml of tetrahydrofuran (THF). On barbaterom serves vinyl chloride up to saturation of the reaction mass begins scapania condensed chloride from the second section of the back of the fridge. Initiate the reaction by adding 1 ml of 1,2-dibromethane, the temperature of the reaction mass rises to 50 - 60oC. After initiation begins to affect the reaction flask ultrasound with a frequency of 22 kHz with a simultaneous supply of vinyl chloride on barbaterom. The feed mixture is conducted with such scoresthe and the start input of chloride added to the reaction flask in 200 ml of THF. The process is carried out until complete dissolution of the magnesium and lowering the temperature in the flask to 25 - 30oC. Output vinylmania was estimated by reaction with trimethylchlorosilane and chromatographicaliy reaction products. The synthesis of vinylmania in this experiment was 6 o'clock

The results of the other experiments presented in the table.

Comparing the results of the proposed method with the prototype shows that in the first case there is a decrease in time of the process 2-3 times, while maintaining the yield of the target organomagnesium at the same level.

1. The method of obtaining unsaturated organomagnesium, including the interaction of alkenylamine with metallic magnesium in the presence of initiator and solvent, characterized in that the interaction of these reagents carried out under the influence of ultrasound with a frequency of 20 to 40 kHz.

2. The method according to p. 1, characterized in that the exposure to ultrasound is carried out after the stage of initiating a "call" process.

3. The method according to p. 1, characterized in that as alkenylamine use vinyl chloride, chloride, benzene, or derivatives thereof.

 

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