JPH05310764A - Producltion of high-purity monoalkyl-or monoarylarsine compound - Google Patents

Abstract

(57) [Summary] [Structure] In a method of reacting an arsenic trihalogenide with a Grignard reagent, and then reducing the reaction product, the reaction between the Grignard reagent and the arsenic trihalogenide is performed from the boiling point of the reaction product. A method for producing monoalkyl or monoarylarsine, which comprises performing the reduction in the presence of an organic solvent having a low boiling point and in the presence of an organic solvent having a boiling point higher than that of the reduction product. [Effect] High-purity monoalkyl or monoarylarsine that does not contain diethyl ether or the like can be produced in high yield and safely.

Description

Detailed Description of the Invention

[0001]

The present invention is particularly applicable to MOCVD (Metalo
The present invention relates to a method for producing high-purity monoalkyl or monoarylarsine used as a raw material when forming a compound semiconductor thin film by using the rganic Chemical Vapor Deposition method or the like.

[0002]

2. Description of the Related Art III-V group compound semiconductor materials such as indium-phosphorus and gallium-arsenic are useful as materials for producing electronic devices. As a method for forming this compound semiconductor thin film, MBE (Molecular Beam Epita
xy), halide CVD, MOCVD, MOMBE (Metalorganic
Molecular Beam Epitaxy). Among these M
OCVD and MOMBE have been widely used recently because it is not necessary to maintain a high vacuum inside the crystal growth system, the exchange of raw materials is easy, and maintenance is easy. However,
When arsenic is used as the group V element in the III-V group compound semiconductor, arsine is generally used as the raw material. However, since this arsine is highly toxic, safety problems in its handling have been highlighted when it comes to mass use in mass production.

Therefore, recently, the use of alkylarsine in place of this arsine has been proposed. Particularly, since monoalkylarsine has two hydrogen atoms in the molecule, carbon contamination in the semiconductor thin film is small and toxicity is reduced. Has attracted attention as a material (for example, Appl.Phys.Lett., 50 ,
(5), 1987].

Conventionally, as a synthetic method of monoalkyl or monoarylarsine, a method of reducing monoalkyldihalogenoarsine with lithium aluminum hydride

[Chemical 1] Method by reaction of arsine and olefin

[Chemical 2] (In the above formula, R represents an alkyl group or an aryl group, X represents a halogen, and R = represents an alkene).

[0005]

The above method is not preferable in terms of safety because di- or tri-alkylarsine is produced and the yield of monoalkylarsine is low, and highly toxic arsine is used. ..

On the other hand, in the above method, diethyl ether is conventionally used as a reaction solvent for the reduction reaction (Zeitschrift fuer anorganische und allgemeine Ch
emie.Band 336. 1965). However, many monoalkyl or monoaryl arsines generally have a low boiling point,
It was difficult to separate the monoalkyl or monoaryl arsine produced by the reduction reaction from the reaction solvent diethyl ether, which was an obstacle to high purification.

Lithium aluminum hydride has been conventionally used as a reducing agent. Since this lithium aluminum hydride is usually produced by using diethyl ether as a solvent, a small amount of diethyl ether is contained in the lithium aluminum hydride. It is contaminated, and this is contaminated in the reduction reaction product, monoalkyl or monoarylarsine. In addition, lithium aluminum hydride has a large difference in reactivity between product lots, and the variation in the yield in the reduction reaction is large. Further, lithium aluminum hydride is a powder having an ignitability and an explosive property, and is difficult to handle.

The present invention solves these problems, and an object of the present invention is to provide a method for safely producing a high-purity monoalkyl or monoarylarsine containing no diethyl ether in a high yield. To provide.

[Means for Solving the Problems]

That is, according to the present invention, in the method of reacting a trihalogenated arsenic with a Grignard reagent and then reducing the reaction product, the reaction between the Grignard reagent and the trihalogenated arsenic is performed from the boiling point of the reaction product. In the presence of an organic solvent having a low boiling point, and a method for producing a monoalkyl or monoaryl arsine, which comprises performing the reduction in the presence of an organic solvent having a higher boiling point than the reduction product, particularly preferably, It consists of using sodium bis (2-methoxyethoxy) aluminum hydride as a reducing agent.

The present invention can be applied to the production of arsine having any type of alkyl group or aryl group, but isopropyl, tert-butyl, which is a raw material for forming a compound semiconductor thin film by the MOCVD method, It is suitable for producing monoalkyl or monoaryl arsines such as phenyl and cyclohexyl.

The Grignard reagent used in the present invention can be obtained by dropping an alkyl halide or aryl halide in an ether solvent containing magnesium. In this case, it is desirable that the magnesium be in the form of chips in order to increase the reaction efficiency. As the ether solvent, it is preferable to use the same one as used for the reaction between the Grignard reagent and arsenic trihalogenide, and particularly diethyl ether, tetrahydrofuran or the like is preferable because of the solubility of the Grignard reagent.

In the reaction of the arsenic trihalogenide with the Grignard reagent, an organic solvent having a lower boiling point than the boiling point of the reaction product monoalkyl or monoaryldihalogenoarsine is used as the reaction solvent. A solvent is preferable, and when the alkyl group or aryl group is isopropyl, tert-butyl, phenyl or cyclohexyl, diethyl ether or tetrahydrofuran can be exemplified. This is because all the raw materials used in the reaction have a lower boiling point than the product, and by distillation, the unreacted raw materials can be distilled out together with the reaction solvent, and a high-purity reaction product can be obtained.

As the trihalogenated arsenic, any of arsenic trichloride, arsenic tribromide, arsenic triiodide and the like can be used, but in particular, from the viewpoint of boiling point, price and stability, arsenic trichloride is used. Is preferred.

As the organic solvent for reducing the monoalkyl or monoaryldihalogenoarsine, a solvent having a boiling point higher than that of the reduction product monoalkyl or monoarylarsine is used. As the organic solvent, an ether solvent is used. When the alkyl or aryl group is isopropyl, tert-butyl, phenyl or cyclohexyl, it is particularly preferable to use, for example, di-n-butyl ether, diisopentyl ether or the like. This is because the monoalkyl or monoaryl arsine obtained by the reduction has a low boiling point, so only this reduction product is distilled off by distillation, and unreduced dihalogeno arsine is left as a bottom residue together with the reaction solvent to obtain a high-purity mono This is because alkyl or monoaryl arsine is obtained.

As the reducing agent in this reduction, lithium aluminum hydride, sodium borohydride, sodium bis (2-methoxyethoxy) aluminum hydride or the like having an active hydride in the molecule can be used. However, sodium bis (2-methoxyethoxy) aluminum hydride is preferably used from the viewpoints of no contamination with diethyl ether, reaction activity, safety, and easy handling. This sodium hydrogen bis
Since (2-methoxyethoxy) aluminum is usually marketed as a 70% toluene solution, it is desirable to distill off the toluene by heating before the reduction reaction.

From the viewpoint of reaction rate, it is preferable to add the reducing agent in an amount of 1.5 times equivalent or more with respect to the amount of monoalkyl or monoaryldihalogenoarsine.

The monoalkyl or monoaryl arsine as the reduction reaction product obtained as described above can be easily separated and purified by distillation.

[0018]

【Example】

(Example 1) All reactions were performed under an inert atmosphere. Synthesis of Grignard reagent To 137 g (5.63 mol) of magnesium chips, 600 ml of ethyl ether and 30 ml of tert-butyl chloride were added,
600 ml of tert-butyl chloride and 12 ether
00 ml of the mixed solvent was added dropwise for reaction. The total amount of tert-butyl chloride used was 630 ml (5.73 mol). After completion of the reaction, the mixture was left to stand to precipitate the precipitate, and then filtered through a glass filter to obtain a pale yellow liquid.

5 ml of this was sampled and 20 ml of 1M
After hydrolysis with hydrochloric acid aqueous solution, titration with 1M aqueous sodium hydroxide solution gave a concentration of 1.9 mol / l and a yield of 67.
%Met.

Synthesis of tert-butyldichloroarsine 202 g (1.11 mol) of arsenic trichloride was added to diethyl ether 6
00 ml was added thereto, and 580 ml (1.13 mol) of a diethyl ether solution of the Grignard reagent prepared above was added dropwise under cooling. Immediately after dropping, attach a distillation device,
After the diethyl ether was distilled off under reduced pressure, the reaction vessel was heated to 120
The mixture was heated to ℃, decompressed at 5 mmHg, and the fraction was collected while cooling the receiver. The obtained colorless transparent liquid was subjected to precision distillation under reduced pressure of 30 mmHg using a 50 cm distillation column to obtain 175 g (0.86 mol) of a white solid. ^{By 1} H-NMR, the solid is t
Identified as ert-butyldichloroarsine. Yield 77
%Met.

Synthesis of mono-tert- butylarsine Commercially available sodium bis (2-methoxyethoxy) aluminum hydride 70% solution in toluene 374 g (1.30 mol)
Was placed in a flask, and toluene was distilled off under reduced pressure with heating at 100 ° C., 5 mmHg for 2 hours. After returning to room temperature, 700 ml of di-n-butyl ether was added and cooled to -10 ° C. To this, 175 g (0.86 mol) of tert-butyldichloroarsine dissolved in 225 ml of di-n-butyl ether was added dropwise. After completion of the dropping, the mixture was heated and stirred at 70 ° C. for 1 hour. After returning to room temperature, it was cooled to about -10 ° C again, and 600 ml of 3N hydrochloric acid aqueous solution was gradually added. The reaction solution became cloudy, and when further added, two layers were completely separated. The upper organic phase was separated, washed with water and then distilled to obtain 87 g of a colorless transparent liquid.

When this was subjected to precision distillation using a 50 cm distillation column, the fraction was 65 g. ^{By 1} H, ¹³ C-NMR, mono te
It was identified as rt-butylarsine. The yield was 56%. As a result of quantification by gas chromatography, the amount of diethyl ether and di-n-butyl ether was 5 ppm or less.

Comparative Example 1 55 ml of diethyl ether was added to 3.2 g (0.084 mol) of lithium aluminum hydride to give a suspension. On the other hand, tert-butyldichloroarsine 2
0 g (0.10 mol) was dissolved in 30 ml of diethyl ether,
It was added dropwise to a suspension of lithium aluminum hydride cooled to -10 ° C. After the dropping, the mixture was refluxed at 70 ° C. for 1 hour. After returning to room temperature, it is cooled at -10 ° C and 3N hydrochloric acid aqueous solution 2
00 ml was added. The two layers were separated, the upper organic phase was taken out, washed with water and then distilled to obtain 6.6 g of a colorless transparent liquid.
Further precise distillation gave a fraction of 3.4 g. The yield was 25%. Diethyl ether was contaminated by 1% by gas chromatography.

Comparative Example 2 To 4.4 g (0.12 mol) of lithium aluminum hydride was added 68 ml of di-n-butyl ether to give a suspension. On the other hand, tert-butyldichloroarsine 2
3 g (0.11 mol) was dissolved in 30 ml of di-n-butyl ether and added dropwise to a suspension of lithium aluminum hydride cooled to -10 ° C. After the dropping, the mixture was refluxed at 70 ° C. for 1 hour. After returning to room temperature, it was cooled to -10 ° C and 150 ml of 3N hydrochloric acid aqueous solution was added. Two layers were separated, the upper organic phase was washed with water and then distilled to obtain 7.3 g of a colorless transparent liquid. Further precise distillation was carried out to obtain 5.8 g of a fraction. The yield was 40%.
Gas chromatography showed 20
It was mixed with 0 ppm.

[0025]

According to the present invention, high-purity monoalkyl or monoarylarsine containing no diethyl ether or the like can be produced in high yield and safely.

Claims (2)

[Claims] 1. A method of reacting an arsenic trihalogenide with a Grignard reagent to give a monoalkyl or monoaryldihalogenoarsine, which is then reduced to produce a monoalkyl or monoarylarsine. The reaction of arsenic with a Grignard reagent is carried out in the presence of an organic solvent having a boiling point lower than that of the reaction product monoalkyl or monoaryldihalogenoarsine, and the reduction is carried out from the reduction reaction product monoalkyl or monoarylarsine. A method for producing a high-purity monoalkyl or monoarylarsine compound, which is carried out in the presence of a high-boiling organic solvent. 2. The method for producing a high-purity monoalkyl or monoarylarsine compound according to claim 1, wherein sodium bis (2-methoxyethoxy) aluminum hydride is used as a reducing agent in the reduction reaction.