JP2002255983A - Method for producing primary phosphine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for selectively producing a primary phosphine in high yield. SOLUTION: This method for producing the primary phosphine by reacting a phosphine with an alkyl halide in an alkaline aqueous solution and an organic solvent in the presence of a catalyst comprises using an alkyl bromide represented by the formula: R<1> Br (R<1> is a 3-8C linear or branched alkyl group, a cycloalkyl group, a benzyl group or an allyl group) as the alkyl halide, and a tetraalkylphosphonium bromide as the catalyst, regulating the molar ratio of the phosphine to the alkyl bromide so as to be <=1.5, successively introducing the catalyst by dividing the catalyst into several times or regulating the adding rate into the reaction system, and carrying out the reaction at <=60 deg.C to provide the primary phosphine represented by the formula: R<1> PH2 .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a high-purity primary phosphine useful as a flame retardant for fibers and plastics, an antistatic agent, a phosphorus material used in a metalorganic chemical vapor deposition method such as an epitaxial growth method, and the like. It is about.

[0002]

2. Description of the Related Art Primary phosphine compounds are used as flame retardants for fibers and plastics, as resin modifiers, antistatic agents, and the like. In recent years, they have been used for metalorganic chemical vapor deposition (MOCVD) such as epitaxial growth. It is also used as a phosphorus raw material.

[0003] Since primary phosphine has two highly reactive hydrogen groups, it can be added to a compound having an unsaturated bond and, if necessary, oxidized to form various useful compounds. it can. For example, a bifunctional compound useful as a flame retardant or the like can be easily obtained by adding allyl alcohol or acrylic acid, and a phosphine having a different alkyl chain length can be obtained by adding an unsaturated alkyl group. And further, a phosphine oxide and a phosphonium salt can be obtained. In addition, by oxidizing the primary phosphine, phosphinic acid and phosphonic acid can be sequentially converted into various useful functional compounds.

Conventionally, as a method for producing primary phosphine, an attempt has been made to synthesize with a radical polymerization catalyst. However, a reaction using a radical catalyst produces a mixture of primary to tertiary phosphine, from which a mixture of primary to tertiary phosphine is formed. It is very difficult to isolate only the primary phosphine and the yield of the obtained primary phosphine is low [“J. Org. Chem.”, 26, 5138-51.
45 (1961)].

Another known reaction between phosphine and an alkene is an acid catalyst [“J. Org. Chem.”, 2
4 356-359 (1959); U.S. Pat.
4,112]. Also in this method, as in the case of using a radical catalyst, it is impossible to avoid by-products of secondary phosphine and tertiary phosphine.

Also, a method of hydrolyzing an organophosphonium halide (Japanese Patent Application Laid-Open No. 50-116426), a method wherein phosphine is converted to a halogenated hydrocarbon or the like under specific conditions in the presence of an aqueous alkali metal hydroxide solution and dimethyl sulfoxide. Reaction method (Japanese Patent Laid-Open No. 01-10209)
No. 1) has also been proposed.

Further, Japanese Patent Application Laid-Open No. 01-11397 discloses a process for producing a primary phosphine in which a phosphine and an alkyl halide are reacted with a catalyst of a tetraalkylammonium salt or a tetraalkylphosphonium salt in the presence of an alkali hydroxide. A method has been proposed.

[0008]

However, even if the method described in JP-A-01-11397 is actually applied to primary phosphines, it is difficult to obtain primary phosphine compounds in high yield. Can not. That is, in this method for producing a primary phosphine, the alkali hydroxide and the tetraalkylphosphonium salt of the catalyst are all added at the same time as the raw materials are charged. Here, it is generally known that a phosphonium salt reacts with a high concentration of a base to cause a decomposition reaction. Since the decomposition reaction of the phosphonium salt itself of the catalyst proceeds competitively with the synthesis reaction of the primary phosphine, the concentration of the catalyst acting on the synthesis reaction of the intended primary phosphine is reduced, and the primary phosphine is decomposed. There is a problem that the yield is low.

The phosphine used in the above-mentioned method for producing a primary phosphine is a purified phosphine having a high purity. On the other hand, as a method for industrially producing phosphine gas, phosphine gas is generated by a reaction between yellow phosphorus and an alkali. The gas generated here is a mixture of a hydrogen gas and a phosphine gas, and the hydrogen gas is a by-product of about 1 to 3 times (volume ratio) the phosphine gas. As a method of separating phosphine gas, a method of compressing and cooling, liquefying phosphine and separating it from hydrogen, and the like are employed, but a multi-step process is required. For this reason, if phosphine gas can be used as a reaction raw material while hydrogen gas remains mixed,
This is extremely advantageous industrially.

In view of the above problems, the present inventors have conducted intensive studies on a method for producing a primary phosphine. As a result, the presence of a tetraalkylphosphonium salt catalyst in an aqueous alkaline solution and an organic solvent was examined using phosphine and an alkyl halide. In the method for producing a primary phosphine by reacting below, while using a specific alkyl halide, using a specific phosphonium salt as a catalyst, the molar ratio of the raw material phosphine to the alkyl halide is in a specific range. And that the desired primary phosphine can be easily obtained in good yield by introducing the catalyst into the reaction system such that an effective amount of the catalyst is present until the reaction is completed. Thus, the present invention has been completed.

Further, in the above-mentioned method for producing a primary phosphine, when a reaction is carried out with an alkyl halide using purified and high-purity phosphine gas as a raw material, a high-yield reaction proceeds. The unreacted gas is a high-purity phosphine gas, and sufficient care must be taken in handling the exhaust gas. On the other hand, when the reaction is performed in a state in which at least one of hydrogen and nitrogen coexists in the phosphine gas as the raw material, the reaction proceeds as in the case of using the phosphine gas having undergone the above-described purification step, and the highly toxic phosphine gas is produced. It is possible to use a compressed phosphine gas obtained by compressing a phosphine gas containing hydrogen gas by-produced during the production of sodium hypophosphite as an impurity as a raw material gas, which is safe because the concentration can be reduced, Further, it was found that there was no by-product of the secondary phosphine and the tertiary phosphine compound during the reaction, and the desired primary phosphine was easily obtained in high yield.

That is, the first invention of the present invention uses a specific alkyl halide and a specific catalyst under specific conditions,
An object of the present invention is to selectively obtain a primary phosphine in a high yield by dividing the catalyst into two or more portions or continuously introducing the catalyst without adding the catalyst at once.

Further, the second invention of the present invention relates to an industrial method in which a desired primary phosphine can be obtained in a high yield by coexisting at least one of hydrogen and nitrogen in a phosphine gas as a raw material. It is an object to provide an advantageous method for producing primary phosphines.

[0014]

The first invention to be provided by the present invention is to produce a primary phosphine by reacting a phosphine with an alkyl halide in an aqueous alkali solution and an organic solvent in the presence of a catalyst. In the method, the alkyl halide is represented by the following general formula (1)

[0015]

Embedded image (In the formula, R ¹ represents a linear or branched alkyl group having 3 to 8 carbon atoms, a cycloalkyl group, a benzyl group or an allyl group.)

An alkyl bromide represented by the formula (1) is reacted with a tetraalkylphosphonium bromide as a catalyst, wherein the molar ratio of phosphine to the alkyl bromide is 1.5 times or more, and the amount of catalyst required for the reaction is used twice. It is introduced into the reaction system continuously by dividing into the above or adjusting the addition rate.
The following general formula (2) characterized in that the reaction is carried out at 0 ° C. or higher.

[0017]

Embedded image (Wherein, R ¹ has the same meaning as described above). The reaction is preferably performed under a pressure of 0.5 MPa or more.

The second invention which the present invention seeks to provide is:
In a method of producing a primary phosphine by reacting a phosphine and an alkyl halide in an alkaline aqueous solution and an organic solvent in the presence of a catalyst, in a state where at least one of hydrogen and nitrogen coexists with the phosphine in the reaction system, The following general formula (3) is used as the alkyl halide.

[0019]

Embedded image (In the formula, R ² represents a linear or branched alkyl group having 1 to 16 carbon atoms, a cycloalkyl group, a benzyl group or an allyl group.)

Using a tetraalkylphosphonium bromide as a catalyst, the alkyl bromide represented by the formula (1) is used twice in a molar ratio of phosphine to the alkyl bromide of 1.5 times or more and a necessary amount of the catalyst for the reaction. It is introduced into the reaction system continuously by dividing into the above or adjusting the addition rate.
The following general formula (4) characterized in that the reaction is carried out at 0 ° C. or higher.

[0021]

Embedded image (Wherein, R ² has the same meaning as described above).

The above-mentioned reaction system in which at least one of hydrogen and nitrogen coexists with phosphine may be a compressed phosphine gas obtained by compressing a phosphine gas containing hydrogen gas by-produced in the production of sodium hypophosphite. It is preferable to carry out the reaction. It is preferable to introduce the compressed phosphine gas into the reaction system in two or more portions. The reaction is preferably performed under a pressure of 0.98 to 3.0 MPa.

In the first and second inventions, it is preferable to carry out the reaction under the following conditions. The tetraalkylphosphonium bromide of the catalyst is preferably at least one selected from tributylhexadecylphosphonium bromide, tetrabutylphosphonium bromide and tributyldodecylphosphonium bromide. The aqueous alkaline solution is preferably an aqueous potassium hydroxide solution. The amount of the alkali added is preferably at least 2.5 times mol per mol of alkyl bromide.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The method for producing a primary phosphine of the present invention comprises, in an aqueous alkaline solution and an organic solvent, phosphine and an alkyl halide,
In the method for producing a primary phosphine to be reacted in the presence of a catalyst, a significant feature is that the reaction raw material, catalyst and reaction conditions are specified.

That is, an alkyl bromide represented by the above general formula (1) is used as an alkyl halide as a reaction raw material, and a tetraalkylphosphonium bromide is used as a catalyst. The point is that the catalyst is introduced into the reaction system until the reaction is completed until the reaction is completed, and the reaction is carried out under heating. Another feature is that an alkyl bromide represented by the general formula (3) is used as an alkyl halide as a reaction raw material, and the reaction is carried out in a reaction system in which at least one of hydrogen and nitrogen coexists with phosphine.

(Phosphine raw material) The raw material phosphine is
It may be based on any manufacturing method, for example,
(1) A phosphine gas obtained by reacting red phosphorus with steam, and (2) A crude phosphine by-produced in the production of sodium hypophosphite is dehydrated, dearsinized, and purified to obtain a dephosphorized lower hydrogenated phosphorus compound. Phosphine gas,
(3) Compressed phosphine gas (hereinafter, referred to as compressed phosphine gas) obtained by compressing the compressed phosphine gas and (4) liquefied phosphine obtained by liquefying compressed phosphine gas and separating it from hydrogen are used. Liquefied phosphine and compressed phosphine gas can be suitably used. This compressed phosphine gas usually contains 50 vol% or more of hydrogen gas as an impurity. In the present invention, this hydrogen gas can be used as a phosphine raw material without separation and removal.

The amount of phosphine to be added is usually 1.5 to 3 times, preferably 1.8 to 2.times.
It is 1 mole. The reason is that the reaction yield of primary phosphine tends to decrease when the molar ratio is less than 1.5 times, while the reaction proceeds even when the molar ratio exceeds 3 times, but the primary The phosphine yield is low and not practical. The phosphine may be added to the reaction system at one time at the start of the reaction, or may be added separately from the start of the reaction. The amount of phosphine added here indicates the total amount of addition including those added during the reaction as well as at the start of the reaction.

(Alkyl Bromide) In the first invention, an alkyl bromide represented by the following general formula (1) is used as the other reaction raw material.

[0029]

Embedded image

In the general formula (1), R ¹ represents a linear or branched alkyl, cycloalkyl, benzyl or allyl group having 3 to 8 carbon atoms. Specific examples of the alkyl group include n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-hexyl group, iso-hexyl group, n-heptyl group, iso-
-Heptyl group, n-octyl group, iso-octyl group and the like. Among them, an alkyl group having 3 to 6 carbon atoms is preferable.

In the second invention, an alkyl bromide represented by the following general formula (3) is used.

[0032]

Embedded image

In the general formula (3), R ² has 1 to 16 carbon atoms.
A linear or branched alkyl group, a cycloalkyl group,
It represents a benzyl group or an allyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso group.
-Propyl group, n-butyl group, iso-butyl group, se
c-butyl group, n-hexyl group, iso-hexyl group,
n-heptyl group, iso-heptyl group, n-octyl group, iso-octyl group, n-decyl group, iso-decyl group, n-dodecyl group, iso-dodecyl group, n-tetradecyl group, iso-tetradecyl group, Examples thereof include an n-hexadecyl group and an iso-hexadecyl group, among which an alkyl group having 1 to 8 carbon atoms is preferable.

(Catalyst) The tetraalkylphosphonium bromide of the catalyst is represented by the following general formula (3)

[0035]

Embedded image

Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and represent a linear or branched alkyl group having 1 to 18 carbon atoms. Used. In the formula of the general formula (3), the alkyl group of R ^{3 to} R ⁶ includes a methyl group, an ethyl group, a propyl group, a butyl group,
An octyl group, an alkyl group having 1 to 18 carbon atoms such as a hexadecyl group.Specific compounds include, for example, tributylmethylphosphonium bromide, tetrabutylphosphonium bromide, trioctylmethylphosphonium bromide, trioctylethylphosphonium bromide, tributyl Examples thereof include phosphonium salts such as dodecylphosphonium bromide, tributylhexadecylphosphonium bromide, and trioctylethylphosphonium bromide. These can be used alone or in combination of two or more.

Of these phosphonium salts, tributyl dodecyl phosphonium bromide, tetrabutyl phosphonium bromide and tributyl hexadecyl phosphonium bromide are particularly preferred.

The addition amount of the tetraalkylphosphonium bromide is usually 0.1 to 3 with respect to the alkyl halide.
Mol%, preferably 1-2 mol%. In the present invention, the introduction of this catalyst into the reaction system of tetraalkylphosphonium bromide is carried out continuously by dividing the necessary amount of the catalyst into two or more portions or adjusting the addition rate as described later. It is important that the catalyst is introduced into the reaction system so that the required amount of the catalyst is present in the reaction system until the reaction is completed.

Examples of the aqueous alkali solution include aqueous alkali hydroxide solutions such as sodium hydroxide and potassium hydroxide. Of these, potassium hydroxide is preferred. These are usually used as aqueous solutions of 40 to 70% by weight, preferably 50 to 60% by weight, and the amount of the aqueous alkali solution is usually 2.5 times or more mol, preferably 2.5 to 500 mol, per mol of alkyl bromide. The molar amount is 4 times, more preferably 3 times.

Examples of the organic solvent include aromatics such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, anisole, nitrobenzene and nitrotoluene: pentane, hexane, heptane,
Aliphatic hydrocarbons such as octane, nonane, ligroin, and cyclohexane: ether solvents such as diethyl ether, isopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, benzyl ether, dioxane, and tetrahydrofuran: methanol, ethanol, 2-propanol, and 2- Alcohols such as butanol and 2-methyl-2-propanol:
Organic polar solvents such as N, N-dimethylacetamide, hexamethylphosphoramide, sulfolane and the like can be mentioned, and these can be used alone or in combination of two or more. Of these organic solvents, toluene is particularly preferred.

<Reaction Conditions> In the production method of the present invention, the above-described alkyl bromide, an aqueous alkali solution and an organic solvent are charged in a reaction vessel, and then phosphine gas is charged.
After heating to 60 ° C. or higher, a catalyst, tetraalkylphosphonium bromide, is added into the reaction system, and the reaction is performed under pressure.

[0042] The reaction is carried out in alkaline aqueous solution and an organic solvent, the phosphine is H ⁺ is removed by the presence of an alkali, PH ₂ ^- and becomes, this process is facilitated by the presence of tetraalkyl phosphonium bromide catalyst, P
H ₂ ^- is (R ^{1) +} -Br ^-, or (R ^{2) +} -Br ^- reacts with (alkyl bromide), primary phosphines of R ¹ PH ₂ or R ² PH ₂ the target product Is obtained.

In the production method of the present invention, the above-mentioned catalyst is not added at once, but is added at least twice or continuously so that an amount of the catalyst necessary for the reaction is present until the reaction is completed. Is an important requirement. The reason is that the catalyst, tetraalkylphosphonium bromide, decomposes by reacting with the alkali source in the reaction system, and this decomposition reaction proceeds competitively with the target primary phosphine synthesis reaction. This is because the yield of primary phosphine, which is the target product, decreases because the catalyst concentration decreases. Therefore, the addition of the catalyst to the reaction system of tetraalkylphosphonium bromide is preferably carried out gradually over time or in several stages in several stages. The amount of the catalyst may be appropriately selected depending on the conditions of the apparatus and the like, but the multi-stage addition is industrially advantageous because the amount of the catalyst can be easily controlled.

More specifically, when the catalyst tetraalkylphosphonium bromide is added twice or more, the first addition amount is 0.05 to 2.0 mol%, preferably, 0.05 to 2.0 mol% based on the alkyl halide. The second and subsequent additions may be made 0.5 to 1.0 mol%, and approximately 2 to 3 hours after the completion of the first addition. In the present invention, the term "adding in two or more portions" means that it is usually preferable to add in two portions. The second addition amount is preferably 0.05 to 1.0 mol%, and more preferably 0.5 to 1.0 mol%, based on the alkyl halide.

On the other hand, when the rate of addition of the tetraalkylphosphonium bromide is adjusted and gradually added to the reaction system, it may be gradually introduced in about 5 to 6 hours.

The reaction temperature is usually 60 ° C. or higher, preferably 70 to 100 ° C. The reaction temperature is appropriately selected depending on the reactivity between the alkyl bromide and the phosphine. In general, the lower the alkyl bromide, the higher the reactivity, and the reaction proceeds even at a lower reaction temperature. However, if the reaction temperature is lower than 60 ° C., the reaction tends to be difficult to proceed, and the yield of primary phosphine, which is the target product, is undesirably reduced. On the other hand, if the reaction temperature is higher than 100 ° C., the amount of phosphine gas dissolved in the organic solvent in the reaction field decreases and the efficiency becomes poor, and the pressure in the reaction system becomes unnecessarily high, which is industrially disadvantageous. Therefore, it is not preferable.

The reaction pressure varies depending on the type of phosphine gas used as a reaction raw material. When liquefied phosphine is used, the reaction pressure is usually 0.5 MPa or more, preferably 0.5 to 0.5 MPa.
When the reaction is carried out in a state where at least one of hydrogen and nitrogen coexists with phosphine in the reaction system, the pressure is 0.98 to 3.0 MPa. 0.98-3.0M
The reaction takes place at Pa. The reaction time is usually 5 hours or more,
Preferably, it is 10 to 15 hours.

In the present invention, when the reaction is carried out in a reaction system in which at least one of hydrogen and nitrogen coexists with phosphine, the phosphine content is at least 40 vol%, preferably 40 to 90 vol%, and at least one of hydrogen and nitrogen is contained. 60 Vol% or less, preferably 10 to 60 Vo
It is preferable to use a mixture of 1%.

The mixed gas may be added to the reaction system all at once at the start of the reaction, or may be added several times at the start and during the reaction. The addition amount of phosphine is usually 1.5 to 3 with respect to the alkyl bromide as described above, including the total addition amount including the one added during the reaction, as well as at the start of the reaction. The molar ratio is preferably in the range of 1.8 times, preferably 1.8 times to 2.1 times.

In the present invention, when the reaction is carried out using a compressed phosphine gas containing hydrogen gas by about 1 to 3 times (volume ratio) with respect to the phosphine gas, the hydrogen gas is almost completely contained in the organic solvent. When the whole amount is pressed into the reaction system because it does not dissolve, the pressure in the reaction system is usually 50 kg / cm ²
Because of the high pressure described above, it is preferable to inject the compressed phosphine gas several times while proceeding the reaction to replenish the phosphine gas consumed in the reaction.

When the reaction is carried out in the presence of at least one of hydrogen and nitrogen in the above-mentioned phosphine gas as a raw material, the reaction proceeds in the same manner as in the case of using the phosphine gas which has undergone the above-mentioned purification step. The desired primary phosphine can be obtained in high yield without secondary tertiary phosphine or tertiary phosphine compound. Further, even when the reaction is carried out using a compressed phosphine gas (PH ₃ : H ₂ = 40: 60 (vol%)), the same yield as that obtained when liquefied phosphine is used is obtained, and the product is similarly produced. The desired primary phosphine having a high purity is obtained.

When a mixed gas of a phosphine gas and an inert gas such as H ₂ or N ₂ is used for the reaction, the phosphine gas is dissolved in an organic solvent and consumed for the reaction with the alkyl halide. Does not participate in the reaction with the alkyl halide. The reaction between the phosphine gas and the alkyl halide in the mixed gas is carried out in an organic solvent, the yield is the same as when liquefied phosphine is used, and the product also has a high purity of the intended primary phosphine. It is. Furthermore, the concentration of the unreacted phosphine gas in the residual gas after the reaction is relatively decreased because the phosphine gas is consumed in the reaction. For this reason, compared with the case where liquefied phosphine gas is used for the reaction, the residual gas has a lower concentration of highly toxic phosphine gas, and has an advantage of improving safety in terms of toxicity.

After the completion of the above-mentioned reaction, unreacted phosphine gas remaining in the reaction vessel, or unreacted phosphine gas and hydrogen gas or nitrogen gas when the reaction is carried out in the presence of hydrogen gas or nitrogen gas. Is preferably separated.
In this case, the inside of the reaction vessel is replaced with an inert gas such as nitrogen gas, and if necessary, the mixture is heated and refluxed so that the solvent and the primary phosphine remain in the reaction vessel while the phosphine gas and the hydrogen gas or the nitrogen gas remain. Is discharged out of the system, and the reaction solution is collected and separated to obtain a product. Thus, the desired primary phosphine can be obtained selectively and in high yield.

[0054]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Test Example 1 <Catalyst Decomposition Test>
3 g (1.05 mol), 100 ml of toluene, and 47.9 g (0.35 mol) of 1-bromobutane in 300 ml
Into a four-necked flask and 400 rpm using a stirrer.
m. Here, 2.41 g (4.72 mmol) of tri-n-butylhexadecylphosphonium bromide was used.
10 minutes after charging 1), the toluene phase in the reaction solution was sampled and subjected to ³¹ P NMR analysis. Thereafter, the temperature was raised to 40 ° C. or 80 ° C. with stirring, and after 1 hour, the toluene phase was collected again and subjected to ³¹ P NMR analysis. The results are shown in Table 1.

As can be seen from Table 1, at 1 hour after contact with alkali at both 40 ° C. and 80 ° C., tri-n-butylhexadecylphosphonium bromide, which is a phosphonium salt, is decomposed to tri-n-butylphosphine oxide. You can see that.

The aqueous phase 1 hour after contact with the alkali
^{When 31} P NMR analysis was performed, it was found that both tri-n-butylhexadecylphosphonium bromide and tri-n-butylphosphine oxide had smaller peaks than those in the toluene phase, and were hardly dissolved in the aqueous phase. . From the above results, it is suggested that almost all of tri-n-butylhexadecylphosphonium bromide has been decomposed in one hour after contact with alkali.

[0058]

[Table 1]

(Note) PX-416B: tri-n-butylhexadecylphosphonium bromide PO-4: tri-n-butylphosphine oxide

Example 1 At room temperature, 105.4 g (1.05 m
ol), toluene 70 ml, 1-bromobutane 48.0
g (0.35 mol) in a 1 L autoclave,
After the atmosphere was sufficiently purged with nitrogen, the mixture was stirred at 400 rpm using a stirrer. Here, 23.8 g of liquefied phosphine gas was used.
(0.7 mol) was charged. Thereafter, the temperature was raised to 80 ° C. The internal pressure when the temperature reached 80 ° C. was 1.5 MPa.

Next, 50% by weight of a solution of 2.4 g (4.72 mmol) of tri-n-butylhexadecylphosphonium bromide dissolved in 30 ml of toluene was added to 10%.
Pressed in over a minute. Internal pressure after press-fitting is 1.35MPa
Met. After aging at 80 ° C for 2 hours, the remaining 50% by weight
Of toluene solution of tetra-n-butylphosphonium bromide was again injected over 10 minutes. After the press-in, the internal pressure was 0.91 MPa. The temperature was kept at this temperature overnight. The internal pressure after the completion of the reaction was 0.85 MPa.

After cooling to room temperature, 50 g of water was injected and stirred for a while to dissolve KBr as a by-product, and then unreacted phosphine gas was released until the pressure became normal. Then, pressurize nitrogen gas to about 1.5 MPa and add it to the autoclave,
The operation of releasing to normal pressure was repeated several times to sufficiently purge with nitrogen. Thereafter, the inside of the autoclave was pressurized again with nitrogen gas to about 0.3 MPa to separate the liquid, and the aqueous phase was discarded. Further, 100 ml of water was added thereto, followed by washing with water. After standing, the aqueous phase was separated and discarded to obtain a target toluene solution of mono-n-butylphosphine. The product was analyzed by gas chromatography (GC analysis).

Example 2 At room temperature, 105.4 g (1.05 m
ol), toluene 70 ml, 1-bromobutane 48.0
g (0.35 mol) of the 1 L autoclave was sufficiently purged with nitrogen, and stirred at 400 rpm with a stirrer. Here, 23.8 g of liquefied phosphine gas (0.7 m
ol). Next, the temperature was raised to 80 ° C. The internal pressure when the temperature reached 80 ° C. was 1.5 MPa.

Next, 1.3 g of tetra-n-butylphosphonium bromide dissolved in 30 ml of toluene was used.
(3.8 mmol) solution was injected over 20 minutes. The internal pressure after the completion of the press-fitting was 1.0 MPa. After aging for about 2 hours at 80 ° C., tetra-
1.2 g of n-butylphosphonium bromide (3.5 m
mol) was again injected over 20 minutes. After the press-in, the internal pressure was 0.6 MPa. The temperature was kept at this temperature overnight. The internal pressure after the completion of the reaction was 0.57 MPa.

After cooling to room temperature, 50 g of water was injected and stirred for a while to dissolve KBr as a by-product, and then unreacted phosphine gas was discharged until the pressure became normal. Then, pressurize nitrogen gas to about 1.5 MPa and add it to the autoclave,
The operation of releasing to normal pressure was repeated several times to sufficiently purge with nitrogen. Thereafter, the inside of the autoclave was pressurized again with nitrogen gas to about 0.3 MPa to separate the liquid, and the aqueous phase was discarded. Further, 100 ml of water was added thereto, followed by washing with water. After standing, the aqueous phase was separated and discarded to obtain a target toluene solution of mono-n-butylphosphine. The product was analyzed by gas chromatography.

Example 3 At room temperature, 105.4 g (1.05 m
ol), toluene 100 ml, 1-bromobutane
A 1 L autoclave charged with 0 g (0.35 mol) was sufficiently purged with nitrogen, and stirred at 400 rpm with a stirrer. Here, 23.8 g of liquefied phosphine gas (0.
7 mol). Next, the temperature was raised to 60 ° C. The internal pressure when the temperature reached 60 ° C. was 1.25 MPa.

Then, tri-n-butyldodecylphosphonium bromide 1.6 dissolved in 30 ml of toluene was used.
g (3.5 mmol) solution was injected over 15 minutes. The internal pressure after the completion of the press-fitting was 1.15 MPa. After aging at 60 ° C. for about 2 hours, 1.6 g of tri-n-butyldodecylphosphonium bromide dissolved in 30 ml of toluene.
(3.5 mmol) were again injected over 15 minutes. After the completion of the press-fitting, the internal pressure was 0.9 MPa. The temperature was kept at this temperature overnight. Internal pressure after reaction is 0.7MPa
Was shown.

After cooling to room temperature, 50 g of water was injected and stirred for a while to dissolve KBr as a by-product, and then unreacted phosphine gas was released until the pressure became normal. Subsequently, the operation of pressurizing nitrogen gas to about 1.5 MPa and adding it to the autoclave, and discharging the gas to normal pressure was repeated several times to sufficiently purge with nitrogen. Thereafter, the inside of the autoclave was pressurized again with nitrogen gas to about 0.3 MPa to separate the liquid, and the aqueous phase was discarded.
Further, 100 ml of water was added thereto, followed by washing with water. After standing, the aqueous phase was separated and discarded to obtain a target toluene solution of mono-n-butylphosphine. The product was analyzed by gas chromatography.

Comparative Example 1 At room temperature, 9.96 g of a 56% KOH aqueous solution (99.4 mm
ol), 19 ml of toluene, 5.29 of 1-bromobutane
g (38.6 mmol), 0.22 g (0.43 mmol) of tri-n-butylhexadecylphosphonium bromide
The autoclave charged with 1) was sufficiently purged with nitrogen, and stirred at 300 rpm with a stirrer. Here, 2.27 g (66.7 mmol) of phosphine gas was charged. Thereafter, the temperature was raised to 60 ° C. The internal pressure when the temperature reached 60 ° C. was 0.65 MPa. The temperature was kept at this temperature overnight. The internal pressure after completion of the reaction was 0.6 MPa.

After cooling to room temperature, 10 g of water was injected and stirred for a while to dissolve KBr as a by-product, and then unreacted phosphine gas was released until normal pressure was reached. Then, pressurize nitrogen gas to about 1.5 MPa and add it to the autoclave,
The operation of releasing to normal pressure was repeated several times to sufficiently purge with nitrogen. Thereafter, the inside of the autoclave was pressurized again with nitrogen gas to about 0.3 MPa to separate the liquid, and the aqueous phase was discarded. Further, 100 ml of water was added thereto, followed by washing with water. After standing, the aqueous phase was separated and discarded to obtain a target toluene solution of mono-n-butylphosphine. The product was analyzed by gas chromatography. Table 3 shows the results.

Comparative Example 2 A reaction was carried out in the same manner as in Comparative Example 1, except that the reaction temperature was changed to 40 ° C. The product was analyzed by gas chromatography.

Comparative Example 3 A reaction was carried out in the same manner as in Example 1 except that 1-chlorobutane was used instead of 1-bromobutane. The product was analyzed by gas chromatography.

Comparative Example 4 A reaction was carried out in the same manner as in Example 1 except that the amount of 56% KOH was changed to 2 times the molar amount of 1-bromobutane in Example 1 instead of 3 times. .

Comparative Example 5 A reaction was carried out in the same manner as in Example 1 except that 1-bromohexadecane was used instead of 1-bromobutane.

Table 2 shows the experimental conditions of Examples 1 to 3 and Comparative Examples 1 to 6, and Table 3 shows the results.

[0076]

[Table 2]

(Note) RX: alkyl halide PH ₃ : phosphine BuBr: 1-bromobutane BuCl: 1-chlorobutane C ₁₆ H ₃₃ Br: 1-bromohexadecane 416B: tri-n-butylhexadecylphosphonium bromide 4B; tetra n- Butylphosphonium bromide 412B: tri-n-butyldodecylphosphonium bromide

[0078]

[Table 3]

(Note) RX: alkyl halide BuPH ₂ : mono-normal butylphosphine BuBr: 1-bromobutane BuCl: 1-chlorobutane C ₁₆ H ₃₃ Br: 1-bromohexadecane

Example 4 105.4 g of a 56% aqueous potassium hydroxide solution at room temperature
(1.05 mol), 70 ml of toluene and 48.0 g (0.35 mol) of 1-bromobutane were sufficiently purged with nitrogen in a 1 L autoclave, and the mixture was stirred at 400 r with a stirrer.
Stirred at pm. Phosphine compressed gas (phosphine gas 43.4 vol.) By-produced from the sodium hypophosphite production process
%, 56.6 vol% of hydrogen gas) was charged into 11.0 g (0.300 mol of phosphine, 0.392 mol of hydrogen). Thereafter, the temperature was raised to 80 ° C. The internal pressure at that time is 2.2
MPa.

Next, a solution of 2.4 g (4.72 mmol) of tri-n-butylhexadecylphosphonium bromide dissolved in 30 ml of toluene was first injected with 34% by weight over 15 minutes. The internal pressure after the completion of the press-fitting was 2.2 MPa. This temperature was maintained for 2 hours, and when the internal pressure dropped to 2.1 MPa, the unreacted compressed gas was released to normal pressure, and 10.0 g of the phosphine compressed gas by-produced again from the sodium hypophosphite production step was produced. (0.273 mol of phosphine, 0.356 mol of hydrogen). The internal pressure at this time was 2.4 MPa. Furthermore,
A toluene solution of 33% by weight of tri-n-butylhexadecylphosphonium bromide was charged by press-in over 7 minutes. At this time, the internal pressure in the reaction system is 2.4 MPa.
Met. Again, this temperature is maintained for 1 hour and 40 minutes, and when the internal pressure falls to 2.1 MPa, the unreacted compressed gas is released to normal pressure, and the phosphine compressed gas by-produced again from the sodium hypophosphite production process 6.0 g (phosphine 0.163 mol, hydrogen 0.214 mol) were charged. The internal pressure at this time was 1.8 MPa. Further, the remaining 33% by weight of a toluene solution of tri-n-butylhexadecylphosphonium bromide was pressurized and charged over 8 minutes. At this time, the internal pressure in the reaction system was 1.8 M
Pa. Keep it at 80 ° C overnight,
The reaction was terminated. The internal pressure at this time was 1.7 MPa.

Then, after cooling to room temperature, 100 g of water
After pressurizing and stirring for a while, unreacted phosphine gas was released until normal pressure was reached. Next, nitrogen gas is added for 1.5 times.
The operation of pressurizing to about MPa and adding to the autoclave and releasing to normal pressure was repeated several times, and the atmosphere was sufficiently replaced with nitrogen.

Thereafter, the inside of the autoclave was pressurized again with nitrogen gas to about 0.3 MPa, and liquid separation was performed, and the aqueous phase was discarded. Further, 100 ml of water was added thereto, followed by washing with water. After standing, the aqueous phase was separated and discarded to obtain a target toluene solution of mono-n-butylphosphine. The product was analyzed by gas chromatography.

Example 5 A reaction was carried out in the same manner as in Example 4 except that the addition temperature of the catalyst, tri-n-butylhexadecylphosphonium bromide, was changed to 100 ° C. The product was analyzed by gas chromatography.

Example 6 The liquefied phosphine gas of Example 2 was 23.8 g (0.70 m
ol) instead of 23.8 g of liquefied phosphine gas (0.
70 mol), and then 0.6 g (0.30 hydrogen) of hydrogen.
mol)), except that the reaction was carried out in the same manner as in Example 2.

Example 7 23.8 g (0.70 m) of the liquefied phosphine gas of Example 2
ol) instead of 23.8 g of liquefied phosphine gas (0.
70 mol), and then 8.4 g (0.30 g) of nitrogen.
mol)), except that the reaction was carried out in the same manner as in Example 2.

Example 8 23.8 g of liquefied phosphine gas of Example 2 (0.70 m
ol) instead of 23.8 g of liquefied phosphine gas (0.
70 mol) and then 0.4 g (0.20 hydrogen) of hydrogen.
mol) and 2.8 g (0.10 mol) of nitrogen, and the reaction was conducted in the same manner as in Example 2.

Example 9 23.8 g (0.70 m) of the liquefied phosphine gas of Example 2
ol) instead of 23.8 g of liquefied phosphine gas (0.
70 mol), and then 0.6 g (0.30 hydrogen) of hydrogen.
mol), and 18.0 g of 1-bromobutane (0.
77.41 g of 1-bromodecane instead of 35 mol)
(0.35 mol) and 10
The reaction was performed in the same manner as in Example 2 except that the reaction was performed at 0 ° C.

Table 4 shows the reaction conditions of Examples 4 to 9 described above.
Table 5 shows the results.

[0090]

[Table 4]

(Note) RX: alkyl halide BuBr: 1-bromobutane C ₁₀ H ₂₁ Br: 1-bromodecane

[0092]

[Table 5]

(Note) RX: alkyl halide RPH ₂ : primary phosphine

Example 10 A reaction was carried out in the same manner as in Example 1 except that an aqueous NaOH solution was used instead of the aqueous KOH solution. Although the yield was slightly lower than that of Example 1, mono-normal butylphosphine was obtained.

[0095]

As described above, according to the production method of the present invention, the desired primary phosphine can be produced with a higher yield than when the entire amount of the catalyst is introduced at once.
Further, even if hydrogen and nitrogen are used in the reaction system in the presence of phosphine, almost no by-products are generated, and only the desired primary phosphine can be obtained in good yield.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tsutomu Watanabe 9-11-1, Kameido, Koto-ku, Tokyo Nippon Kagaku Kogyo Co., Ltd. (72) Eiichi Ryutani 9-11 Kameido, Koto-ku, Tokyo No. 1 F-term in the Research & Development Division of Nippon Kagaku Kogyo Co., Ltd. (Reference) 4H039 CA10 CA19 CA90 CD10 CD20 4H050 AA02 BA53 BB10 BB11 BB12 BB15 BB31 BB45 BB61 BC10 BC11 BC31 BC34 BD21 BE10 WA12 WA26

Claims (12)

[Claims] 1. A method for producing a primary phosphine by reacting a phosphine with an alkyl halide in an alkaline aqueous solution and an organic solvent in the presence of a catalyst, wherein the alkyl halide is a compound represented by the following general formula (1): ] (Wherein, R ¹ represents a linear or branched alkyl group, a cycloalkyl group, a benzyl group or an allyl group having 3 to 8 carbon atoms) represented by the following formula: Using a bromide, the molar ratio of the phosphine to the alkyl bromide is 1.5 times or more, and the amount of the catalyst required for the reaction is divided into two or more times or the addition rate is adjusted to continuously form the reaction system. 60 ℃
The reaction is carried out as described above, characterized by the following general formula (2): (Wherein R ¹ has the same meaning as described above). 2. The method according to claim 1, wherein the reaction is performed under a pressure of 0.5 MPa or more. 3. The method for producing a primary phosphine according to claim 1, wherein the tetraalkylphosphonium bromide of the catalyst is at least one selected from tributylhexadecylphosphonium bromide, tetrabutylphosphonium bromide and tributyldodecylphosphonium bromide. 4. The method for producing a primary phosphine according to claim 1, wherein the aqueous alkaline solution is an aqueous potassium hydroxide solution. 5. The method according to claim 1, wherein said alkali is added in an amount of 1 mole of alkyl bromide.
The method for producing a primary phosphine according to claim 1, wherein the molar amount is at least 2.5 times the molar amount. 6. A method for producing a primary phosphine by reacting a phosphine and an alkyl halide in an alkaline aqueous solution and an organic solvent in the presence of a catalyst, wherein at least one of hydrogen and nitrogen coexists with the phosphine in the reaction system. In this state, an alkyl halide is represented by the following general formula (3): (Wherein R ² represents a linear or branched alkyl group having 1 to 16 carbon atoms, a cycloalkyl group, a benzyl group or an allyl group) represented by the following formula: Using a bromide, the molar ratio of the phosphine to the alkyl bromide is 1.5 times or more, and the amount of the catalyst required for the reaction is divided into two or more times or the addition rate is adjusted to continuously form the reaction system. Introduced to 60
The reaction is carried out at a temperature of not less than ℃, the following general formula (4): (Wherein, R ² has the same meaning as described above). 7. The compressed phosphine gas obtained by compressing a phosphine gas containing hydrogen gas by-produced in the production of sodium hypophosphite, wherein at least one of hydrogen and nitrogen coexists with phosphine in the reaction system. 7. The method for producing a primary phosphine according to claim 6, wherein the reaction is carried out by using. 8. The method for producing a primary phosphine according to claim 6, wherein the compressed phosphine gas is introduced into the reaction system in two or more portions. 9. The method for producing a primary phosphine according to claim 6, wherein the reaction is carried out under a pressure of 0.98 to 3.0 MPa. 10. The method for producing a primary phosphine according to claim 6, wherein the tetraalkylphosphonium bromide of the catalyst is at least one selected from tributylhexadecylphosphonium bromide, tetrabutylphosphonium bromide and tributyldodecylphosphonium bromide. 11. The method according to claim 6, wherein the aqueous alkaline solution is an aqueous potassium hydroxide solution. 12. The method for producing a primary phosphine according to claim 6, wherein the amount of the alkali added is at least 2.5 times mol per mol of the alkyl bromide.