JPH0687874A - Production of high-purity organic phosphine compound - Google Patents

Abstract

PURPOSE:To produce a high-purity organic phosphine compound free from intermixing of diethyl ether, etc. CONSTITUTION:In a method for producing an organic phosphine compound by reducing an organic halogenophosphorus compound or a phosphorus oxoacid ester with a reducing agent, lithium aluminum hydride obtained by reacting lithium hydride with an aluminum halide in a high-boiling organic solvent is used as the reducing agent, especially preferably the high-boiling organic solvent used in the synthesis reaction of the lithium aluminum hydride is not separated and used as it is to produce the organic phosphine compound.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a high-purity organic phosphine compound, particularly MOCVD (Metalorgani).
c Chemical Vapor Depositi
on) method or the like, and a method for producing high-purity alkyl or aryl phosphine as a raw material when forming a compound semiconductor film.

[0002]

2. Description of the Related Art III-including indium-phosphorus
The group V compound semiconductor thin film is useful as a material for producing an electronic device. The method for forming the compound semiconductor thin film includes (1) MBE (Molecular Beam)
Epitaxy method, (2) Halide CVD method, (3)
MOCVD method, (4) MOMBE (Metalorga)
nic Molecular Beam Epitax
y) Law, etc. Among these, the MOCVD method or the MOMBE method is a crystal growth method that is attracting attention because it is easily used because it is not necessary to maintain a high vacuum in the crystal growth system and the material can be easily exchanged.

However, according to these methods, III-
When a phosphorus compound semiconductor is manufactured, since phosphine, which is a highly toxic phosphorus hydride, is used as a raw material of a phosphorus compound, there is concern about large-scale use of the raw material due to mass production.

Therefore, in recent years, a method has been proposed in which an alkyl or aryl phosphine is used in place of phosphine as the phosphorus raw material. Among them, monoalkyl or aryl phosphine is a low-toxic alternative to phosphine, in which carbon is hardly mixed in the semiconductor film. It is regarded as a material (for example, J.
Crystal Growth, 77 (1986) 1
1)

As a method for producing these organic phosphine compounds, a method in which an organic halogenoline compound or an oxo acid ester of phosphorus is reduced by a reducing agent is generally known. As the reducing agent in this case, lithium aluminum hydride is used. , It is used exclusively because of its high yield (New Experimental Chemistry Course Volume 12, p421, published by Maruzen in 1976).

[0006]

However, lithium aluminum hydride is produced by using diethyl ether as a solvent, and therefore, diethyl ether remains in lithium aluminum hydride. Therefore, when an organic phosphine compound is produced using this as a reducing agent, a trace amount of diethyl ether is mixed in the reduction product, and the removal thereof is extremely difficult, which has been an obstacle to high purification of the organic phosphine compound. .

The present invention has solved the above problems, and an object of the present invention is to produce a high-purity organic phosphine compound using lithium aluminum hydride as a reducing agent in a good yield and free of diethyl ether and the like. To provide.

[0008]

The present invention is a method for producing an organic phosphine compound by reducing an organic halogenoline compound or an oxo acid ester of phosphorus with a reducing agent, wherein lithium hydrogen is used as a reducing agent in an organic solvent having a high boiling point. And lithium aluminum hydride obtained by reacting with aluminum halide, and particularly preferably used as the reducing agent as it is without separating the high boiling point organic solvent or the produced salt from the reaction mixture of lithium aluminum hydride after the reaction. It is a method for producing an organic phosphine compound.

The present invention can be applied to the production of various organic phosphine compounds, but especially MOCVD.
Suitable for producing monoalkyl or monoarylphosphine such as isopropyl, tert-butyl, phenyl, which is a raw material when forming a compound semiconductor thin film by a method or the like,
A phosphine compound containing few impurities can be obtained.

The organic halogenoline compound referred to in the present invention is an organic dihalogenoline compound such as phosphonyl dihalide (RPX ₂ ) or phosphonyl dihalide [RP (O) X ₂ ], or phosphinyl halide ( R ₂ PX) or phosphinyl halide [R ₂ P
Examples of the organic monohalogenoline compounds such as (O) X], in particular, R is isopropyl, tert-butyl,
Organic halogenoline compounds consisting of monoalkyl or monoaryl groups such as phenyl are preferred.

As the oxo acid ester of phosphorus, phosphonous acid ester [RP (OR ') ₂ ], phosphonic acid ester [RP (O) (OR') ₂ ], phosphinic acid ester (R ₂ P (OR ') )), Phosphinic acid ester [R
₂ P (O) (OR ′)] and the like, and particularly preferred is an oxo acid ester of phosphorus in which R is a monoalkyl or monoaryl group such as isopropyl, tert-butyl and phenyl.

An organic phosphine compound can be obtained by reducing the above organic halogenoline compound or phosphorus oxoacid ester with a reducing agent. In the present invention, the reducing agent is lithium hydrogen and aluminum halide in a high boiling point organic solvent. Lithium aluminum hydride synthesized from is used.

In the synthesis of this lithium aluminum hydride, about 4 times as much mole of lithium hydride as aluminum halide is used, but it is preferable to use a small excess of lithium hydride. In this case, a high-boiling point organic solvent is used as the reaction solvent, and it is preferable that this solvent has a large boiling point difference from the organic phosphine compound as the reduction product. Particularly, when producing a low boiling point alkyl or aryl phosphine, 1-methylnaphthalene, n-dibutyl ether,
It is preferable to use diisopentyl ether, phenetole, anisole and the like.

When the solubility of lithium aluminum hydride in the high boiling point organic solvent is small, lithium halide and lithium aluminum hydride precipitate together. However, in the subsequent reduction reaction, this lithium halide does not particularly hinder. This lithium aluminum hydride may be used by separating it from the high boiling point organic solvent, but it is convenient and preferable to use it without separating the high boiling point organic solvent. In this case, an organic halogenoline compound or an oxo acid ester of phosphorus, which is a substance to be reduced, may be added to the solution after the synthesis for reduction.

In the reduction reaction, the amount of reducing agent is 1.
From the viewpoint of reaction rate, it is desirable to add 5 times equivalent or more. Further, this reduction reaction is carried out in the presence of an organic solvent, but it is preferable to use the same high boiling point organic solvent as used in the synthesis of the lithium aluminum hydride, since the subsequent solvent recovery operation and the like will be simple. After completion of the reduction reaction, the organic phosphine compound is extracted into the organic layer by adding hydrochloric acid, so that the organic phosphine compound can be phase-separated and recovered and purified by distillation or the like. From the viewpoint of reaction yield, it is preferable to add a large amount of 6N hydrochloric acid after the completion of this reaction, but from the viewpoint of reducing the content of alkyl halide, it is preferable to add as little hydrochloric acid as possible. preferable. There is no problem if hydrolyzed with water.

[0016]

【Example】

(Example) 25 g of commercially available special grade lithium hydride (3.1
In a dry ice bath, 71 g (0.5 mol) of commercial grade special-grade aluminum chloride was added to a suspension of 5 mol of n-dible ether.
3 mol) of n-dibutyl ether solution was added dropwise to 40
The reaction was carried out by heating at ℃ for 1 hour. Here, 41 g of t-butylphosphonyl dichloride (0.
23 mol) of n-dibutyl ether solution was added dropwise to react. After completion of the reaction by heating at 70 ° C. for 1 hour, hydrolysis was performed with water, and t-butylphosphine was isolated from the obtained ether layer by distillation. The yield was 13 g and the yield was 63%. The amount of diethyl ether and dibutyl ether in this is below the detection limit of gas chromatography, and is estimated to be 10 ppm or less.

Comparative Example Commercially available special grade lithium aluminum hydride 22 g (0.58 mol) in a suspension of n-dibutyl ether in a dry ice bath, 50 g of t-dichloride.
A solution of butylphosphonyl (0.29 mol) in n-dibutyl ether was added dropwise and reacted. After completion of the reaction by heating at 70 ° C. for 1 hour, the ether layer obtained by hydrolysis with water was distilled. 6 g of 18 g of t-butylphosphine
Obtained in a yield of 9%. In this, 0.05% of diethyl ether contained in lithium aluminum hydride was mixed.

[0018]

INDUSTRIAL APPLICABILITY According to the present invention, a high-purity organic phosphine compound free from contamination with diethyl ether and the like can be produced in good yield.

Claims (3)

[Claims] 1. A method for producing an organic phosphine compound by reducing an organic halogenoline compound or an oxo acid ester of phosphorus with a reducing agent, comprising reacting lithium hydride and aluminum halide in a high boiling point organic solvent as the reducing agent. A method for producing an organic phosphine compound, which comprises using the lithium aluminum hydride obtained as described above. 2. A method for producing an organic phosphine compound by reducing an organic halogenoline compound or an oxo acid ester of phosphorus with a reducing agent, which is obtained by reacting lithium hydrogen and aluminum halide in a high boiling point organic solvent as the reducing agent. A method for producing an organic phosphine compound, characterized in that the solvent and the produced salt are used without separation from the obtained lithium aluminum hydride. 3. The method for producing an organic phosphine compound according to claim 1, wherein the high boiling point organic solvent is dibutyl ether.