JPS60163890A - Production of diphenylalkoxyphosphine - Google Patents

Abstract

PURPOSE:To obtain the titled substance useful as an intermediate of a diphenylphosphine derivative for reaction reagent, etc., economically in an industrial scale, by carrying out the reaction of a halogenated phenyl magnesium with a dichloroalkoxyphosphine in a specific reaction solvent adding the reactant dropwise to the reaction system. CONSTITUTION:The objective compound of formula III can be produced by adding dichloroalkoxyphosphine of formula II (R is lower alkyl) dropwise to the halogenated phenyl magnesium of formula I (X is Br or Cl) preferably keeping the system temperature at -5-+10 deg.C using a reaction solvent comprising a mixture of THF and an aromatic hydrocarbon (e.g. toluene) at a volume ratio of preferably 2:1-1:3, keeping the compound of formula I constantly in excess to the compound of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing diphenylalkoxyphosphine. More specifically, a mixed solvent of tetrahydrofuran and an aromatic hydrocarbon is used as a reaction solvent, and a phenylmagnesium halide represented by the general formula (If) (wherein, X represents a bromine atom or a chlorine atom) is reacted with the general formula ( 2) Drop diphenylalkoxyphosphine represented by (% formula %) (wherein R represents a lower alkyl group) (wherein R is the same as above) in a safe and easy manner. The present invention provides a method for obtaining high yields through simple operations.

The method of the present invention is illustrated as follows.

(wherein, X and R are the same as above) The diphenylalkoxyphosphine of the general formula (1) according to the present invention is extremely important as an intermediate for diphenylphosphine derivatives useful as reaction reagents and transition metal catalyst ligands. It is.

Therefore, a simple method for producing diphenylalkoxyposphines has been desired.

Conventionally, diphenylalkoxyphosphine was produced by reacting phosphorus trichloride and excess benzene using aluminum chloride as a catalyst under reflux heating conditions for several hours, and then reacting with a strong Lewis base such as phosphorus oxychloride or pyridine. A method has been adopted in which diphenylchlorophosphine is isolated by phase exchange and derivatized into diphenylalkoxyphosphine. However, with this method, not only is it not possible to obtain the target diphenylalkoxyphosphine in a high yield, but also the 5-reaction procedure is complicated, so it cannot be called a practical production method.

In addition, as a method for producing alkoxyphosphine derivatives,
Dichloroethoxyphosphine and butylmagnesium bromide were reacted to produce dibutylethoxyphosphine (yield 63
(1'-Ohem, Be) is known.
r, J Vol. 93, p. 1227 (1960)).

In this reaction, since the reactivity of butylmagnesium bromide is extremely strong, it is essential to drop butylmagnesium bromide into dichloroethoxyphosphine at a low temperature.

In the above production method, if phenylmagnesium halogenide is used instead of butylmagnesium bromide, a large amount of by-products will be produced, and the desired product, diphenylalkoxyphosphine, cannot be obtained in high yield. .

Further, the use of diethyl ether on an industrial scale is not preferable from the viewpoint of safety such as its flammability and explosiveness.

The present inventors have conducted extensive research to improve the drawbacks of such known manufacturing methods. As a result, when reacting phenylmagnesium compound of general formula (II) with dichloroalkoxyphosphine of general formula (III), the purpose The present invention was completed by discovering a method for obtaining diphenylalkoxyphosphine of the general formula (■) in a safe and simple manner in high yield.

In the method for producing diphenylalkoxyphosphine of the present invention, a reaction solvent other than a mixed solvent of tetrahydrofuran and an aromatic hydrocarbon (for example, tetrahydrofuran or diethyl ether alone or a mixture of diethyl ether and an aromatic hydrocarbon) is used as the reaction solvent. solvent)
When used as a reaction solvent, large amounts of diphenylchlorophosphine and triphenylphosphine are produced as by-products. In this case, diphenylchlorophosphine can be converted into the desired diphenylalkoxyphosphine of general formula (1) by alkoxylating it with an alcohol and an organic base, so the yield of the desired product can be improved by post-treatment. can be improved. However, this method has many practical problems in terms of industrialization, such as requiring a large excess of alcohol and organic base for post-treatment and also making the 5-reaction process complicated. Furthermore, the triphenylphosphine by-produced in this reaction cannot be converted to the target product, general diphenylalkoxyphosphine of formula (1), so ultimately the yield cannot be expected to improve beyond a certain limit. However, it is difficult to separate it from the target product, which poses an obstacle to industrialization and the treatment of by-products.

It cannot be put into practical use. In addition, in a mixed solvent of tetrahydrofuran and an aliphatic hydrocarbon, the solubility of phenylmagnesium halide is poor, and stirring and mixing within the system is difficult, resulting in problems in reaction operability.

In contrast, according to the method for producing diphenylalkoxyphosphine of the present invention discovered by the present inventors, there are almost no by-products, so the desired product can be obtained in high yield without the need for troublesome post-treatment. I can do it. Furthermore, the reaction operation is safe and simple, making it an excellent manufacturing method on an industrial scale. Therefore, it is extremely useful as a method for producing diphenylalkoxyphosphine of general formula (1) in large quantities and at low cost. The manufacturing method of the present invention will be explained in detail below.

First, in the production method of the present invention, the halogenated phenylmagnesium of general formula (II) used as a raw material is
It can be easily obtained by reacting halogenated benzene and metallic magnesium using tetrahydrofuran alone or a mixed solvent of tetrahydrofuran and an aromatic hydrocarbon as the reaction solvent.

In the production method of the present invention, the halogenated phenylmagnesium of general formula (n) obtained as described above is
of dichloroalkoxyposphine is added dropwise. In this case, dichloroalkoxyphosphine may be added dropwise alone, or may be added dropwise after being dissolved in tetrahydrofuran or aromatic hydrocarbon alone or in a mixed solvent thereof. The amount of the mixed solvent of tetrahydrofuran and aromatic hydrocarbon used as a reaction solvent is determined from the viewpoint of both reactivity and economy, based on 1 mole of phenylmagnesium halide of general formula (II). It is preferable to use it in a proportion of ~2L. Further, the mixing ratio (volume ratio) of tetrahydrofuran and aromatic hydrocarbon can be arbitrarily selected from 2:1 to 1=3, but considering the solubility of phenylmagnesium halide in the general formula (Ill), 1 to 1:
A ratio of 2 is desirable.

Specific examples of aromatic hydrocarbons used in the method for producing diphenylalkoxyphosphine of the present invention include benzene,
Examples include toluene and xylene.

The temperature in the system when the dichloroalkoxyphosphine having the general formula is added dropwise is preferably -5 to 10°C. As the temperature increases in this reaction, the production of the by-product triphenylphosphine increases, so it is preferable to control the reaction temperature to within the above range. In addition, when reacting on an industrial scale, it takes a long time to drop dichloroalkoxyphosphine of the general formula (In), or the temperature cannot be maintained within the above range in the system. The phenylmagnesium halide of general formula (II) is not charged all at once into the system, but the system is kept in such a way that the phenylmagnesium halide of general formula (II) is always in excess of the dichloroalkoxyphosphine of general formula (2). The above temperature conditions can be met by charging the halogenated phenylmagnesium of the general formula (II) and the dichloroalkoxyphosphine of the general formula (immediately) simultaneously while maintaining the same temperature. The formation of phenylphosphine can be suppressed, and the desired diphenylalkoxyphosphine can be obtained in high yield.

10- - After the dichloroalkoxyphosphine of general formula (I .

After the reaction is completed, in order to prevent hydrolysis of the generated diphenylalkoxyphosphine of general formula (1),
Add an alkaline aqueous solution such as sodium carbonate to the reaction solution to dissolve the magnesium salt produced L7 and transfer it to the aqueous layer.
Separate the organic layer. After washing the separated organic layer with water, the solvent is distilled off, and the desired diphenylalkoxyphosphine of general formula (1) can be obtained by distillation under reduced pressure.

The present invention will be described in detail below with specific examples.

Example 1 1! A volumetric fungus flask was purged with nitrogen, and 655- of a solution of phenylmagnesium bromide (0.72 mol) in muchtrahydrofuran-toluene (volume ratio 1:2) was added. Next, a solution of dichloromethoxyphosphine 3999 ((1.3 mol) dissolved in toluene 1201 was added dropwise to the system over 2 hours while stirring the system at 0 to -5°C while cooling with ice water. After the dropwise addition was completed, the ice water bath was removed. was removed and stirring continued for 1 hour.

After 90 ml of 5T sodium carbonate solution was added to the reaction mixture for hydrolysis, the supernatant of the organic layer was separated, washed with water, and the solvent was distilled off. Internal standard quantitative analysis of the reaction product by gas chromatography revealed that the reaction yield of diphenylmethoxyphosphine was 85%. In addition, triphenylphosphine 2 and diphenylchlorophosphine [L5%] were produced as by-products.

Example 2 A 1°C capacity fungi flask was purged with nitrogen, and 655 ttl of a solution of mutitrahydrofuran-toluene (volume ratio 1:2) containing phenylmagnesium chloride (0.72 mol) was added. Next, dichloroethoxyphosphine 44.19 (0,3
A solution prepared by dissolving mol) in 120 d of toluene was added dropwise over 1.5 hours. After the addition was completed, the ice bath was removed and stirring was continued for 1 hour.

After the reaction, the same treatment operations as in Example 1 were carried out and quantitative analysis was performed, and the reaction yield of diphenylethoxyphosphine was 88%. Other by-products include 1% triphenylphosphine and 0.2% diphenylchlorophosphine.
% was generated.

Example 3 A 1° C. capacity fungi flask was purged with nitrogen, and 655 d of a tetrahydrofuran-toluene (volume ratio 1:2) solution containing 13-phenylmagnesium chloride (0.72 mol) was added. Next, while stirring the system at a temperature of 0 to -5°C while cooling with ice water, dichloron-butoxyphosphine 52
．． A solution of 59 (0.3 mol) dissolved in 120 nIl of toluene was added dropwise over 1.5 hours. After the addition was completed, the ice bath was removed and stirring was continued for 1 hour.

After the reaction, the same processing operations as in Example 1 were carried out and quantitative analysis was performed, and the reaction yield of diphenyl-n-butoxyphosphine was 86%.

Triphenylphosphine 1 was also produced as a by-product.

Example 4 A 12-volume fungi flask was purged with nitrogen, and 660 ml of a muchtitrahydrofuran-benzene (volume ratio 1:2) 14-solution containing phenylmagnesium bromide (0.72 mol) was added. Then cooled with ice water at O~-5
While stirring the system at a temperature of .degree. C., a solution of dichloroethoxyphosphine 44.1j (0.3 mol) dissolved in benzene 120d was added dropwise over 2 hours. After the addition was completed, the ice bath was removed and stirring was continued for 1 hour.

After the reaction, the same treatment operations as in Example 1 were carried out, and quantitative analysis revealed that the reaction yield of diphenylethoxyphosphine was 85%. In addition, triphenylphosphine 2% and diphenylchlorophosphine 0% were produced as by-products. .2chi was generated.

Example 5 A 11-capacity neck flask was purged with nitrogen, and 660 scraps of a solution of tetrahydrofuran-xylene (volume ratio 1:1) containing phenylmagnesium chloride (0.72 mol) was added thereto. Next, while stirring the system at a temperature of O to -5°C while cooling with ice water, dichloroethoxyphosphine 44. ．． 19(0,
3→Nil)Woxylene 120+Ll solution dissolved in 2
It was dripped over one sip. After the addition was completed, the ice bath was removed and stirring was continued for 1 hour.

After the reaction, the same treatment operations as in Example 1 were performed and quantitative analysis revealed that diphenylethoxyphosphine was obtained with a reaction yield of 84 cm. In addition, 2% of triphenylphosphine and 0.3% of diphenylchlorophosphine were obtained as by-products.

Example 6 A 12-capacity neck-neck flask was purged with nitrogen, and 650 volumes of a solution of phenylmagnesium chloride (0.72 mol) in ttr tetrahydrofuran-toluene (volume ratio 1:1) was added. Next, dichloroethoxyphosphine 44.151 (α3
1.5 mol) dissolved in 120+ tl of toluene
It dripped over time. After the addition was completed, the ice bath was removed and stirring was continued for 1 hour.

After the reaction, the same treatment operations as in Example 1 were performed and quantitative analysis revealed that the reaction yield of diphenylethoxyphosphine was 86%. Triphenylphosphine 1 was also produced as a by-product.

Comparative Example 1 In this example, tetrahydrofuran was used as the reaction solvent and phenylmagnesium bromide was used as the Grignard reagent in the dropping method described by Berichte supra.

A 500-capacity neck-neck flask was purged with nitrogen and 14.751 (0.1 mol) of dichloroethoxyphosphine and 80+w/w of tetrahydrofuran were added. Next, 220 ml of a tetrahydrofuran solution containing phenylmagnesium bromide ([124 moles]) was added dropwise to the mixture over 25 hours while stirring the system at a temperature of D to -5 DEG C. while cooling with ice water. After dropping, the ice water bath was removed and the mixture was stirred for 1 hour.

After the reaction, the same treatment operations as in Example 1 were carried out and quantitative analysis was performed, and the reaction yield of diphenylethoxyphosphine was 3.
It was 0chi. In addition, triphenylphosphine 13 and diphenylchlorophosphine 1B were produced as by-products.

Comparative Example 2 In this example, phenylmagnesium bromide was used as a Grignard reagent using the dropping method described by Berichte supra.

500 mml1. A volumetric neck-neck flask was replaced with nitrogen, and 1.79 ([1.1 mol) of dichloroethoxyphosphine was added.
and diethyl ether 8o- were added. Next, 225 ml of a diethyl ether solution containing phenylmagnesium bromide ([1.24 mol)] was added dropwise over t5 hours while stirring the system at a temperature of 0 to -5 DEG C. while cooling with ice water. After dropping, the ice water bath was removed and the mixture was stirred for 1 hour.

After the reaction, the same treatment operations as in Example 1 were carried out and quantitative analysis revealed that the reaction yield of diphenylethoxyphosphine was 46%. In addition, 8% of triphenylphosphine and 8% of diphenylchlorophosphine were produced as by-products.

Patent Applicant: Hokuko Chemical Industry Co., Ltd. 19- Procedural Amendment May 7, 1985 Manabu Shiga, Commissioner of the Patent Office 1, Indication of the Case 1982 Patent Application No. 1.950 ] No. 2, Name of the Invention: Diphenylaco Production method of xyphosphine 3, relationship with the case of the person making the amendment Patent applicant address: 4-2, Nihonbashi Honseki-cho, Chuo-ku, Tokyo Name: Hokuko Chemical Industry Co., Ltd. 4, Agent 5, Date of amendment order (voluntary) 6 , Detailed description of the invention in the specification subject to amendment Z Contents of the amendment 1) Page 5, lines 6-6, ``In addition, industrial scale...''
・Undesirable. ” to be deleted.

2) Page 7, lines 3 to 6, “Not only is there no hope, but...
...Cannot be put into practical use. " is corrected to "Not expected."

3) Page 10, lines 16-14, “If you drop it...
...Thus by-products" by dropping "by-products"
and correct it.

4) Page 11, line 9 [dissolve the salt and transfer it to the aqueous layer, -1
is corrected as ``salt is precipitated.''

5) On page 17, line 13, r5 [10mm7J is “50
〇－” and correct it.

6) Change r500mmlJ on page M18, line 1A to “500-
” he corrected.

7) Insert the following statement after the 10th line of the 19th pass.

2- Comparative Example 6 In this example, tetrahydrofuran-toluene (volume ratio 1:2) was used as the reaction solvent by the dropping method described by Berichte above.
Then, phenylmagnesium chloride was used as the Grignard reagent.

A neck flask with a capacity of 500 fnl was purged with nitrogen, and 14.710.1 mol of dichloroethoxyphosphine) and 40 ml of toluene were added. Then cooled with ice water for 0 to -5
226 ml of a tetrahydrofuran-toluene (volume ratio 1:2) solution containing phenylmagnesium chloride (0.24 mol) was added dropwise over 2.5 hours while stirring the system at a temperature of .degree. After dropping, the ice water bath was removed and the mixture was stirred for 1 hour.

After the reaction, the same treatment operations as in Example 1 were carried out and quantitative analysis was performed, and the reaction yield of diphenylethoxyphosphine was 69%.

3- In addition, triphenylphosphine 1 and diphenylchlorophosphine 6 were produced as by-products. ” Above 4-

Claims (1)

[Claims] Using a mixed solvent of tetrahydrofuran and an aromatic hydrocarbon as a reaction solvent, halogenated phenylmagnesium represented by the general formula (wherein, X represents a bromine atom or a chlorine atom) is reacted with the general formula %. % (wherein R represents a lower alkyl group) of diphenylalkoxyphosphine represented by the general formula (wherein R is the same as above), characterized by dropping dichloroalkoxyphosphine represented by Manufacturing method.