JPH01301684A - Production of organometallic compound - Google Patents

Abstract

PURPOSE:To obtain the title compound useful as a raw material for compound semiconductors in electronic industry, raw material for organic syntheses, etc., by directly blending a gallium-magnesium alloy, etc., with an alkyl halide and reacting the mixture with a specific amount of an ether compound. CONSTITUTION:A gallium-magnesium alloy or indium-magnesium alloy is directly mixed with an alkyl halide (e.g. monohalogen compound of lower alkyl such as ethyl, propyl or butyl and halogen such as bromine, chlorine or iodine) in the ratio of preferably 1mol of the former of the alloy (calculated as Ga or In) and 3mol of the latter. The mixture is reacted with <=0.5 equivalent, preferably 0.01-0.5 equivalent based on 1 equivalent magnesium of ether compound (preferably diethyl ether) at 0-150 deg.C for 10 minutes-2 hours to give the aimed compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing organometallic compounds such as alkyl gallium or indium.

The above-mentioned highly pure organometallic compounds are used as raw materials for compound semiconductors in the electronics industry, starting materials and catalysts in organic synthesis, and the like.

[Prior Art] Organometallic compounds such as alkyl gallium or indium are produced by: ■ Reaction of metal gallium or indium with alkyl mercury; ■ Reaction of gallium halide or indium with alkyl zinc; ■ Reaction of gallium halide or indium t1 with alkyl mercury. It is synthesized by the following methods: reaction with aluminum; (1) reaction of gallium or indium halide with a Grignard reagent; (2) reaction of gallium or indium-magnesium alloy with alkyl halide.

Among these, the Grignard reaction method (■, ■) is
A Grignard reagent or a strip of gallium or indium-magnesium alloy was soaked in ether, and an ether solution of an alkyl halide was added dropwise to it with stirring, followed by heating and reaction (for example, in New Experimental Chemistry Course, 1mata p324.1976 round neck publication).

However, when a large amount of ether solvent is used during the reaction, the ether compound (solvent) coordinates with the synthesized organometallic compound to form an etherate, which is difficult to dissociate by simple distillation. Met.

In particular, these organometallic compounds have recently been
(Metalorganjc Chemjcal V
It has been increasingly used as a raw material or dopant for compound semiconductors, including aper deposition. However, when an organometallic compound containing an etherate coordinated with the above-mentioned ether compound is used for such purposes, oxygen is entrained in the crystal growth process, which causes a decrease in the electrical properties of the manufactured semiconductor. Ta.

For this reason, organometallic compounds used for this type of application are
Methods that do not require the use of ether solvents and do not rely on the Grignard reaction (■, ■, ■) have been adopted.

[Problems to be solved by the invention] However, the above method has a slow reaction rate, poor yield, and contains alkylmercury, zinc, and aluminum as impurities, and requires complicated operations to remove them. There is a problem.

As a result of intensive research to solve this problem, the inventors of the present invention found that in the reaction of reacting a gallium-magnesium alloy or an indium-magnesium alloy with an alkyl halide to synthesize alkyl gallium or alkylindium, first, It is believed that magnesium in gallium or indium-magnesium alloys reacts with alkyl halides in the presence of an ether solvent to form the Grignard reagent, but this ether solvent acts catalytically and no excess ether solvent is necessary. I found it.

The present invention was made based on this knowledge, and an object of the present invention is to use a small amount of an ether compound as a solvent,
The object of the present invention is to provide a method for producing highly purified alkyl gallium or alkyl indium with extremely low etherate content efficiently and in high yield.

[Means for Solving the Problems] The present invention provides a method for producing alkylgallium or alkylindium by reacting a gallium-magnesium alloy or an indium-magnesium alloy with an alkyl halide, in which the gallium-magnesium alloy or indium - A magnesium alloy and an alkyl halide are directly mixed, and an ether compound is added in an amount of 0.5 equivalent or less per equivalent of magnesium to the mixture and reacted.

The gallium or indium-magnesium alloy has an atomic ratio of gallium or indium/magnesium of 2 to 1.
It is preferable to use an alloy with a ratio of 0 in order to efficiently proceed with the reaction between these metals and the alkyl halide.

This alloy is obtained by melt-mixing highly pure gallium or indium and magnesium. As the gallium or indium in this case, it is preferable to use a commercially available metal having a purity of six nines, which is obtained by vacuum evaporation purification and vacuum distillation purification of these commercially available metals. As the magnesium, commercially available three-nine or higher magnesium, or those obtained by further reducing the impurity concentration by distillation or the like, can be used.

Furthermore, the halogenated alkyl groups used in the present invention include lower alkyl groups such as ethyl, propyl, isopropyl, butyl, and isobutyl, and bromine.

Examples include monohalogen compounds with halogens such as chlorine and iodine.

The amounts of these alloys and alkyl halides are preferably in a stoichiometric ratio, that is, the alloy is comol as gallium or indium for 3 equivalents of alkyl halides. , 1:3 to 10:1 without any particular problem.

In the present invention, first, the above alloy is charged into a reaction vessel,
Next, the above alkyl halide is added, and the ether compound is added while stirring and heating. This addition is preferably done by dropping.

Further, the amount of the ether compound added is at least 0.5 equivalent of magnesium in the above alloy. More preferably, the amount is appropriately selected within the range of 0.01 to 0.5 equivalents.

The reaction temperature is preferably 0 to 150°C, and particularly when diethyl ether is used, it is preferably carried out under reflux.

As the ether compound, diethyl ether is preferred, but diisopropyl ether, dibutyl ether,
Ethers such as anisole and phenethole can also be used.

The reaction is carried out under normal pressure, if necessary under increased pressure or under reduced pressure, for 1 hour.
It lasts from 0 minutes to 2 hours.

After the reaction is completed, the alkyl gallium or indium is distilled out and recovered. Since this compound has a relatively low decomposition temperature, vacuum distillation is preferably used. The distillation conditions are appropriately selected in consideration of the type of alkyl group, that is, the boiling point and decomposition temperature of the compound. In this distillation, highly pure alkyl gallium or indium can be obtained.

[Example] Example: Gallium with a magnesium/gallium atomic ratio of 5.8
50 g of magnesium alloy chips were placed in a Pyrex flask, 300 ml of ethyl bromide was added thereto, and 5 ml of diethyl ether was added dropwise over 1 hour while stirring. After the dropwise addition was completed, the mixture was heated and stirred at a temperature of 90° C. for 2 hours. As a result, a gray sludge-like reaction product was obtained. Next, attach a distillation device to the flask,
Distilled under reduced pressure at 50 mmHg, and distilled the fraction at 60 to 70°C into 2
I got 4g. This fraction was diluted with toluene, ethanol and water were added, evaporated to dryness, an aqueous hydrochloric acid solution was added, and the gallium content was measured by inductively coupled plasma emission method. As a result, the gallium content was 41-. It was estimated that 6.3% of diethyl ether was contained.

Put 50.0 g of the same alloy used in Example 1 and 300 ml of diethyl ether into a Pyrex flask, and while stirring, drop 300 ml of ethyl bromide over 1 hour. , and other operations were the same as those in Example]. As a result, the gallium content was 25.9%,
It was estimated that 41.7% of diethyl ether was contained.

Put 20.0 g of an indium-magnesium alloy with a magnesium/indium atomic ratio of 2.9 into a Pyrex flask, add ioml of ethyl bromide, and add 7 ml of diethyl ether over 30 minutes while stirring. This was added dropwise and the reaction was continued for 2 hours. Next, 20 Torr
The mixture was distilled under reduced pressure, and 22 g of a fraction at a temperature of 95 to 110°C was collected. As a result of analyzing this fraction by the same method as in Example 1, it was estimated that the indium content was 50.2% and the diethyl ether content was 11.7%.

Comparative Example 2 20.0 g of the same alloy as used in Example 2 and 150 ml of diethyl ether were placed in a Pyrex reactor, and while stirring, ethyl bromide was added dropwise to this over 1 hour. The reaction was allowed to take place for a period of time. Next, vacuum distillation was carried out in the same manner as in Example 2 to give 95 to 110
26.0g of the fraction at ℃ was collected. This fraction was used as Example]
As a result of analysis using the same method as above, the content of indium was 43.0%, and the content of diethyl ether was 24.3%.
It is estimated that it contains %.

[Effects of the Invention] The present invention involves directly mixing gallium or indium-magnesium alloy and an alkyl halide, and adding <W to 1 part by weight of magnesium in the mixture.

Since the reaction is carried out by adding 0.5 parts by weight or less of the C left-thyl compound, it is possible to produce highly pure alkyl gallium or alkylindium efficiently, with high yield, and with extremely low etherate content. It has the effect of

Claims (1)

[Claims] In a method for producing alkylgallium or alkylindium by reacting a gallium-magnesium alloy or an indium-magnesium alloy with an alkyl halide, the gallium-magnesium alloy or indium-
A method for producing an organometallic compound, which comprises directly mixing a magnesium alloy and an alkyl halide, and adding 0.5 equivalent or less of an ether compound per equivalent of magnesium to the mixture for reaction.