JP3383198B2 - Method for producing organic phosphorus compound - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an organophosphorus compound. More specifically, the present invention relates to a method for obtaining a corresponding pentavalent organophosphorus compound by oxidizing the trivalent organophosphorus compound with an aqueous hydrogen peroxide solution without hydrolyzing it.

[0002]

2. Description of the Related Art Haloalkyl phosphates / polyphosphates, trialkyl phosphates, triaryl phosphates, trialkyl phosphates, triaryl phosphates, trialkyl phosphates and the like are representative. The pentavalent organophosphorus compound is mainly used as a plasticizer for synthetic resins, a flame retardant and a stabilizer, a lubricant, a metal extractant and the like. These pentavalent organophosphorus compounds are mainly obtained by oxidizing the corresponding trivalent organophosphorus compounds (Qu
See at.Rev., 16,208-239,1962).

For example, in the reaction product of (n + 1) moles of phosphorus trichloride and (2n + 3) moles of alkylene oxide,
When further reacting n mol of the aliphatic aldehyde or ketone, the following reaction occurs.

[0004]

[Chemical 3]

(Wherein R and Z are the same or different and each is a hydrogen atom or a lower alkyl group, n is an integer of 0 to 10) The compound of the formula (I) obtained is a (trivalent) phosphite /
A (pentavalent) polyphosphonate, which has the formula (IV): by oxidation with various oxidizing agents:

[0006]

[Chemical 4]

(Wherein R, Z and n have the same meanings as in formula (I))
(Pentavalent) phosphate / (pentavalent) polyphosphonate represented by

The compound represented by the formula (I) comprises a trivalent phosphite structure portion A and a pentavalent polyphosphonate structure portion B. The structural portion B is a P—C (phosphorus-carbon) bond, is difficult to hydrolyze, and has excellent heat resistance. On the other hand, the structural portion A contains trivalent phosphorus, is easily hydrolyzed, and has poor heat resistance. Therefore, the compound itself represented by the formula (I) is difficult to be used as a flame retardant or an improving agent for synthetic resins and polyurethane foams, and trivalent phosphorus is replaced with pentavalent phosphorus in order to improve the hydrolyzability and heat resistance. It is necessary to oxidize it to.

Further, the formula (III): (R ¹ O) _3-a P-R ² _a (III) (wherein R ¹ and R ² are the same or different and have 1 to 1 carbon atoms).
8 alkyl group or haloalkyl group, or 6 carbon atoms
The trivalent organic phosphorus compound represented by the aryl group of 10 and a is an integer of 0 to 2 is composed of a structural portion C and a structural portion D as shown in the following formula, for example, when a = 1.

[0010]

[Chemical 5]

(Wherein R ¹ and R ² have the same meanings as in formula (III)) The portion of> P—R ² occupied by this structural portion D is> P—C.
It is a (phosphorus-carbon) bond and is difficult to hydrolyze. On the other hand, the (R ¹ O) ₂ P— portion occupied by the structural portion C is easily hydrolyzed. Therefore, the compound represented by the formula (III) also needs to be stabilized by oxidation.

However, there is a problem in that the trivalent organic phosphorus compound is hydrolyzed by simply using an aqueous solution of hydrogen peroxide as an oxidizing agent. Further, as to the method for oxidizing a trivalent organic phosphorus compound, U.S. Pat. No. 3,027,3
No. 95 (oxidizing agent: propylene trimer hydroperoxide), U.S. Pat. No. 3,042,698 (oxidizing agent: sulfur), U.S. Pat. No. 3,042,700 (oxidizing agent: oxygen / ozone) and JP-A-51-6250 (oxidizing agent). : Chlorine) etc. However, there is no disclosure about an oxidizing method using an aqueous hydrogen peroxide solution as an oxidizing agent.

[0013]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.

Thus, according to the present invention, a trivalent organophosphorus compound is added in the presence of an inorganic or organic base at 0 to 50 ° C.
Oxidation with an aqueous hydrogen peroxide solution at a temperature of 3 to obtain the corresponding pentavalent organophosphorus compound.
The compound has the formula (I):

[Chemical 8] (In the formula, R and Z are the same or different and each is a hydrogen atom or a lower
Alkyl group, n is an integer of 0 to 10), formula (II):

[Chemical 9] (In the formula, R and Z have the same meanings as in formula (I), m is 0 or 1) and
And formula (III): (R ¹ O) _3-a P—R ² _a (III) (wherein R ¹ and R ² are the same or different and have 1 to 18 carbon atoms).
Alkyl group or haloalkyl group of 6 to 6 carbon atoms
10 aryl groups, a is selected from 0 to 2)
Method for producing an organic phosphorus compound which is a compound.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The trivalent organic phosphorus compound used in the present invention has at least one phosphorus atom in the compound of 3 or more.
It is a compound having a trivalent phosphorus atom to which two organic groups are bonded. Specifically, the trivalent organic phosphorus compound used in the present invention has the formula (I):

[0016]

[Chemical 6]

(Wherein R and Z are the same or different and each is a hydrogen atom or a lower alkyl group, n is an integer of 0 to 10), Formula (II):

[0018]

[Chemical 7]

(Wherein R and Z have the same meanings as in formula (I), m is 0 or 1) and formula (III): (R ¹ O) _3-a P—R ² _a (III) (wherein R ¹ and R ² are the same or different and have 1 to 1 carbon atoms.
8 alkyl group or haloalkyl group, or 6 carbon atoms
Compounds selected from aryl groups of 10 to 10 and a is an integer of 0 to 2) are preferable.

The "lower alkyl group" of the substituents R and Z in the above formulas (I) and (II) is a linear or branched alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and the like can be mentioned. The substituent R is preferably a hydrogen atom or a methyl group, and the substituent Z is a hydrogen atom, a methyl group or The ethyl group is preferred.

The "alkyl group having 1 to 18 carbon atoms" of the substituents R ¹ and R ² in the above formula (III) is a linear or branched chain alkyl group or a cyclic alkyl group. Specifically, lower alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, n-pentyl, iso-pentyl and hexyl. , Heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl;
Methylhexyl, methylheptyl, methyloctyl, methylnonyl, methyldecyl, methylundecyl, methyldodecyl, methyltridecyl, methyltetradecyl, methylpentadecyl, methylhexadecyl, methylheptadecyl; dimethylhexyl, dimethylheptyl, dimethyloctyl, dimethyl Nonyl, dimethyldecyl, dimethylundecyl, dimethyldodecyl, dimethyltridecyl, dimethyltetradecyl, dimethylpentadecyl, dimethylhexadecyl; 2-ethylhexyl, ethylheptyl, ethyloctyl, ethylnonyl, ethyldecyl,
Examples include chain alkyl groups such as higher alkyl groups having 7 to 18 carbon atoms such as ethylundecyl, ethyldodecyl, ethyltridecyl, ethyltetradecyl, ethylpentadecyl and ethylhexadecyl, and cyclic alkyl groups such as cyclobutyl and cyclohexyl. Among them, n-butyl, 2-ethylhexyl and cyclohexyl are preferable.

Further, the "haloalkyl group having 1 to 18 carbon atoms" is a linear or branched haloalkyl group,
The thing which substituted the arbitrary hydrogen atom of the said alkyl group with the halogen atom is mentioned. Examples of the halogen atom include fluorine, chlorine, bromine and iodine, with chlorine being preferred. Specific examples include chloroethyl and chloropropyl.

Examples of the "aryl group having 6 to 10 carbon atoms" include phenyl, tolyl, xylyl, cumenyl, mesityl, naphthyl, dimethylphenyl, trimethylphenyl and the like, among which phenyl and tolyl are preferable.

Specific examples of the trivalent organic phosphorus compound represented by the formula (III) include triethyl phosphite, tributyl phosphite, trioctyl phosphite, tridecyl phosphite and tricyclohexyl phosphite when a = 0. Fight, tristearyl phosphite, triphenyl phosphite, tricresyl phosphite, tri (2,
6-dimethylphenyl) phosphite, tri (2,4,4)
6-trimethylphenyl) phosphite, tri (nonylphenyl) phosphite, tris (chloroethyl) phosphite, tris (chloropropyl) phosphite, tris (dichloropropyl) phosphite and the like can be mentioned. When a = 1, an organic phosphonite, a = 2
In the case of, it is an organic phosphinite.

As the trivalent organic phosphorus compound used in the present invention, a reaction product obtained by further reacting a reaction product of phosphorus trichloride and alkylene oxide with an aliphatic aldehyde or ketone can be used. This reaction product may be a mixture of reaction by-products without particular purification.

The inorganic base used in the present invention includes:
Alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates represented by sodium carbonate; alkali metal hydrogen carbonates represented by sodium hydrogen carbonate; ammonia and the like. And can be used in the form of an aqueous solution. Among them, sodium hydroxide aqueous solution is preferable, and the concentration thereof is not particularly limited, but is 10 to 40% (preferably 20 to 30%).

The organic base used in the present invention includes aliphatic amines such as dimethylamine, diethylamine, trimethylamine, triethylamine and tributylamine; aromatic amines represented by dimethylaniline,
Aromatic heterocyclic bases such as pyridine and picoline,
Of these, triethylamine and pyridine are preferable. In addition,
The inorganic and organic bases may be used in a mixed form.

The amount of the inorganic or organic base used in the present invention is preferably an amount that can make the reaction mixture alkaline during the oxidation reaction with the aqueous hydrogen peroxide solution. Specifically, the amount of the reaction mixture is preferably adjusted to pH 8 to 12. Surprisingly, under such conditions, the hydrolysis of the trivalent organic phosphorus compound can be suppressed, the decomposition of hydrogen peroxide can be promoted, and the oxidation reaction can be completed. The base may be added in advance before the start of the oxidation reaction or may be added at the same time as the aqueous hydrogen peroxide solution.

As the aqueous hydrogen peroxide solution used in the oxidation reaction of the present invention, commercially available products can be used. The concentration is not particularly limited, but is 3 to 50% (preferably 20 to
35%). If the concentration is lower than 3%, the volumetric efficiency of the reaction is poor, which is not preferable.

The oxidation reaction of the present invention can be carried out in the presence of a solvent. Examples of the solvent include water or an organic solvent inert to the reaction. Examples of the organic solvent include hexane, aliphatic hydrocarbons such as cyclohexane, benzene, aromatic hydrocarbons such as toluene, chloroform, organic halogen compounds such as dichloroethane, and the like. Among them, benzene,
Dichloroethane is preferred. The organic solvent may be the one used at the time of producing the trivalent organic phosphorus compound. In other words, the reaction liquid used in the production of the trivalent organic phosphorus compound may be used as it is.

The reaction temperature is preferably about 50 ° C. or lower, for example 0 to 50 ° C., more preferably 10 to 30 ° C.
Since the reaction of the present invention is accompanied by intense heat generation, the reaction system is cooled to the above temperature if necessary. The reaction time varies depending mainly on the concentration of the hydrogen peroxide aqueous solution, but is usually 3 to 7 hours.

After the completion of the oxidation reaction, the reaction solution can be subjected to a usual post-treatment of the organic phosphorus compound to separate the target pentavalent organic phosphorus compound. Specifically, it is performed by washing with water (or washing with hot water) -neutralization-washing with water (or washing with hot water) -collection of by-products such as alkyl halides-dehydration under reduced pressure. As a result, the desired pentavalent organophosphorus compound was obtained in a yield of 8
It is obtained from 0 to 95%.

The oxidation method of the present invention comprises phosphite,
The same applies to the oxidation of phosphonite, phosphinite oligomers, polymers and the like. Furthermore, the oxidation method of the present invention can also be applied to the oxidation of trivalent organic phosphorus compounds used as intermediates for agricultural chemicals, pharmaceuticals and the like.

[0034]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but these examples do not limit the scope of the present invention. The intermediate reaction liquid obtained in this example and the pentavalent organophosphorus compound as the final product were evaluated by the following methods.

[Active chlorine concentration] The active chlorine concentration (%) of the reaction liquid of the first-stage reaction for producing the trivalent organic phosphorus compound
Was measured in accordance with "Analytical Chemistry Experimental Method" (Kagaku Dojin Co., Ltd.) "Method for quantifying chloride ion with silver nitrate standard solution" to confirm completion of the first-step reaction.

[Acid value] Second step for producing trivalent organic phosphorus compound
The acid value (KOH mg / g) of the reaction solution at the completion of the step reaction and the final product was measured according to "JIS K0070-1966" (indicator: BTB).

[Phosphite concentration in the phosphite portion (hereinafter, P concentration
Abbreviated as I)], regarding the produced trivalent organic phosphorus compound,
PI (%) was determined by a method of titrating iodine consumed by phosphite with sodium thiosulfate.

[Yield] The yield of the pentavalent organophosphorus compound as the final product is based on the theoretical yield when it is assumed that phosphorus trichloride as a starting material and alkylene oxide react quantitatively. Was calculated.

[Appearance / Specific gravity / Viscosity] The appearance of the pentavalent organophosphorus compound of the final product was visually observed to determine the specific gravity (20
℃) and viscosity (cp, 25 ℃), respectively, "JIS
It was measured according to "K0061" and "JISK2283".

[Composition] The composition of the pentavalent organophosphorus compound of the final product was measured using GPC (gel permeation chromatography: HLC-8020 manufactured by Tosoh Corporation).

[Phosphorus content] The phosphorus content (P%) of the pentavalent organic phosphorus compound of the final product was decomposed by heating by adding nitric acid and perchloric acid to the product, and diluted with distilled water to a constant value. After adding a certain amount of nitric acid, ammonium vanadate solution and ammonium molybdate solution for color development, the absorbance was measured using a spectrophotometer and determined from the absorbance of the product and the phosphorus standard solution.

[Chlorine Content] The chlorine content (Cl%) of the pentavalent organophosphorus compound in the final product was measured after the chloroalkyl chlorine in the product was pyrolyzed with n-butanol / metal sodium. It was determined by potentiometric titration of chlorine with an aqueous silver nitrate solution.

Example 1 First, a trivalent organic phosphorus compound was synthesized by the following first and second stage reactions. First-stage reaction stir bar, thermometer, alkylene oxide blowing tube, 500 ml flask with condenser, phosphorus trichloride 13
7.5 g (1.0 mol), dichloroethane 50.0 g and triethylamine 0.28 g (0.20% / PC
l ₃₎ were charged, and was cooled to 10 ℃ in the bus containing the ice water. Next, 106.0 g (2.4 mol) of ethylene oxide was blown in a gas form from a cylinder through a flow meter.
The reaction temperature was 10 to 30 ° C., and the reaction time was 4 hours.
The active chlorine concentration of the reaction mixture was 8.2% (theoretical value was 8.6).
%)Met.

Second stage reaction Acetone 3 was added to the reaction mixture of the first stage reaction from a dropping funnel.
9.3g (0.68mol) was added at 30-50 ° C over 30 minutes. Then, gradually raise the reaction temperature to 80 to 90 ° C.
And reacted for 4 hours. The acid value of the reaction mixture was 2, and the PI was 4.38% (calculated value: 4.57%).

The trivalent organic phosphorus compound thus obtained was oxidized by the following third step reaction to obtain a pentavalent organic phosphorus compound. Third-step reaction (oxidation reaction) To the reaction mixture of the second-step reaction, at 30 to 20 ° C, 7 g of 30% aqueous sodium hydroxide solution was added in 20 minutes from a dropping funnel. The pH of the reaction mixture was 10.5. Then
43.8 g (0.45 mol) of 35% hydrogen peroxide aqueous solution was added at 10 to 30 ° C. for 4 hours. On the other hand, while the aqueous hydrogen peroxide solution was added, the pH of the reaction mixture was 8.5 to 1
A 30% sodium hydroxide aqueous solution was appropriately added so as to be 0.5. The total amount of 30% aqueous sodium hydroxide solution used was 14.1 g. After the addition of the hydrogen peroxide solution,
The reaction was continued at 30-40 ° C for 2 hours.

Post-treatment step To the reaction mixture of the third stage reaction, 4.3 g of 30% aqueous sodium hydroxide solution was added, and the mixture was stirred at 50 ° C. for 1 hour. Then, the mixture was allowed to stand in a separating funnel and separated into an aqueous layer and an organic layer. The obtained organic layer was washed with 100 ml of warm water (40 to 50 ° C.) for 2 times.
It was washed twice and distilled at 120 ° C. under a reduced pressure of 30 to 80 mmHg. The residual oily substance was 201 g (yield 89.0).
%), The acid value was 0.40, and the PI was 0%. The composition and quality of the product are shown in Table 1.

Comparative Example 1 The reaction was performed in the same manner as in Example 1 except that the aqueous sodium hydroxide solution was not used in the third stage reaction. Hydrolysis occurred vigorously in the third stage reaction, and the acid value of the reaction mixture after the addition of the hydrogen peroxide aqueous solution was 14. Further, the subsequent post-treatment step was not performed because the hydrolysis of the product was severe.

Example 2 A reaction was carried out according to Example 1 using the following raw materials. Raw material 1st stage reaction Phosphorus trichloride 137.5 g (1.0 mol) Triethylamine 0.3 g (0.2% / PCl ₃ ) Ethylene oxide 98.1 g (2.23 mol) 2nd stage reaction Acetaldehyde 39.0 g (0.89 mol) 3rd stage reaction 35% Peroxide Hydrogen aqueous solution 24.6 g (0.25 mol) 25% aqueous sodium hydroxide solution 14.1 g Active chlorine concentration after the 1st stage reaction is 11.3% (theoretical value 1
1.6%), the acid value after the second stage reaction is 1.8, and the PI is 2.
It was 60%. The yield of the obtained product is 167 g.
(Yield 84.8%), the acid value was 0.35, and the PI was 0%. The composition and quality of the product are shown in Table 1.

Example 3 A reaction was carried out according to Example 1 using the following raw materials. Raw material First-stage reaction Phosphorus trichloride 137.5 g (1.0 mol) Triethylamine 0.3 g Propylene oxide 145.0 g (2.5 mol) Second-stage reaction Acetaldehyde 25.3 g (0.58 mol) Third-stage reaction 35% hydrogen peroxide aqueous solution 53.4 g (0.55 Molar) 25% aqueous sodium hydroxide solution 18.5 g Active chlorine concentration after the 1st stage reaction is 5.9% (theoretical value 6.2)
7%), acid value after the second stage reaction is 2.2, PI is 5.0%
Met. Further, the obtained product had a yield of 214 g (yield 83.5%), an acid value of 0.50, and a PI of 0%.
The composition and quality of the product are shown in Table 1.

Example 4 Raw Material First Stage Reaction (1) Phosphorus trichloride 137.5 g (1.0 mol) benzene 90.0 g triethylamine 0.3 g ethylene oxide 141.3 g (3.2 mol) (2) phosphorus trichloride 68.4 g (0.5 mol) ethylene oxide 23.0 g (0.977 mol) Second-stage reaction Acetone 62.0 g (1.069 mol) Third-stage reaction 35% hydrogen peroxide aqueous solution 69.9 g (0.719 mol) Triethylamine 10.3 g (5% / PCl ₃ ) Using the above raw materials, the following procedure Other than that, the reaction was performed according to Example 1.

In the first-step reaction (1), the reaction was carried out according to the reaction conditions of Example 1, then 90 to 100 ° C. and 100 mmHg.
Benzene was recovered under the following reduced pressure to obtain a reaction mixture containing 1 mol of tris (chloroethyl) phosphite. First
In the step reaction (2), phosphorus trichloride was added to the reaction mixture of the first step reaction (1), and then ethylene oxide was reacted to synthesize 0.5 mol of bis (chloroethyl) phosphorochloridate. The active chlorine concentration of the reaction mixture is 8.3%
(Theoretical value was 8.58%).

In the second-step reaction, acetone was added to the reaction mixture of 1-step tris (chloroethyl) phosphite of step (1) and (2) and 0.5 mole of bis (chloroethyl) phosphorochloridate. And reacted at 80 to 100 ° C. for 5 hours. The acid value after the reaction was 2.4, and the PI was 4.5%.

In the third stage reaction, the reaction mixture of the second stage reaction was cooled to 10 ° C. and then triethylamine was added. A 35% hydrogen peroxide aqueous solution was added at 10 to 30 ° C. for 2 hours. The pH of the reaction mixture immediately after the addition of the 35% aqueous hydrogen peroxide solution was 10.8, and the pH after the addition was 8.5.
Met. The reaction was continued at 30 to 35 ° C for 2 hours. The reaction mixture is washed twice with 200 ml of water, 10-50 mmH
Under reduced pressure of g, dichloroethane, water and the like were distilled off. The amount of the obtained product was 294 g (yield 90.0%), the acid value was 0.73, and the PI was 0%. The composition and quality of the product are shown in Table 1.

[0054]

[Table 1]

In Table 1, n, R and Z of the composition corresponded to the formula (I) and were determined from the GPC chart. FIG. 1 shows a GPC chart of the product obtained in Example 4. Figure 1
From the chart, it can be seen that the structural formula n = 5 or more of the product is not divided and shows a shoulder peak.

Example 5 Commercially available triphenylphosphite (TPI, manufactured by Johoku Chemical Co., Ltd., JP360) was oxidized by the method of the present invention. In a flask of the same apparatus except that the alkylene oxide blowing tube of Example 1 was replaced with a dropping funnel, 310 g of TPI was added.
(1 mol), 100 g of benzene as a solvent, 16 g of triethylamine (5% / TPI) were charged, and after cooling to 10 ° C., 107 g of a 35% hydrogen peroxide aqueous solution (1.10).
Mol) at 10-15 ° C over 1 hour. 35%
The pH of the reaction mixture when the aqueous hydrogen peroxide solution is added is 8 to 1
It was 0. Then, after reacting at 10 to 15 ° C for 2 hours, the reaction mixture was washed with an equal amount of warm water (40 to 50 ° C). The washed reaction mixture was neutralized with alkali, further washed with an equal amount of warm water (40 to 50 ° C.), and distilled under a reduced pressure of 3 mmHg. The main fraction distilled at 210 to 220 ° C./3 mmHg was 264 g (yield 81.0%). In addition, this product was a white powder, had a melting point of 48.4 ° C., an acid value of 0.1, and a P of 10.6%.

Comparative Example 2 A reaction was carried out in the same manner as in Example 5 except that the following raw materials were used and triethylamine was not used. PH during reaction
Was 1 to 4. The acid value of the reaction mixture was 10.8. In addition, since the hydrolysis occurred and the acid value was high, the post-treatment step was not performed. Raw material TPI (reagent product) 310 g (1 mol) Solvent benzene 100 g 35% hydrogen peroxide aqueous solution 57 g (10% excess of theoretical amount)

Example 6 Synthesis of tributyl phosphate 122 g of butanol (1.6 g) was added to a 1 liter four-necked flask equipped with a stir bar, thermometer, dropping funnel and condenser.
5 mol), chlorine scavenger pyridine 130 g (1.65 mol), and solvent benzene 200 g are charged, and the temperature is 5 ° C. or lower,
69 g (0.5 mol) of phosphorus trichloride is added in a minute, and another 5
The reaction was carried out at a temperature of not higher than 0 ° C for 2 hours. Then, the reaction product was cooled, the precipitated pyridine hydrochloride was filtered off, and the hydrochloride was converted to benzene 5
It was washed with 0 g to obtain 365 g of a filtrate. Analysis by gas chromatography confirmed that tributylphosphite was produced in the filtrate. The obtained filtrate was charged into the same flask as above, and 5 g of pyridine was added.
Next, 54 g (0.55 mol) of a 35% hydrogen peroxide aqueous solution was added from a dropping funnel at 5 ° C. or lower at 40 minutes. There was an exothermic reaction during the addition of the hydrogen peroxide solution. After the reaction was further performed for 1 hour, the reaction mixture was transferred to a separating funnel and subjected to post-treatments such as washing with water, neutralization with a 5% aqueous sodium hydroxide solution and recovery of benzene, and further vacuum distillation. The amount of the obtained main component was 111 g (yield 83.0%). The product is a transparent liquid with a specific gravity of 0.978.
(20/20 ° C) and the boiling point was 145 to 150 ° C / 3 mmHg. The main component was tributyl phosphate as analyzed by gas chromatography.

[0059]

INDUSTRIAL APPLICABILITY The present invention oxidizes a trivalent organic phosphorus compound with an aqueous hydrogen peroxide solution at a temperature of 0 to 50 ° C. in the presence of an inorganic or organic base to give a corresponding pentavalent organic phosphorus compound. Therefore, the hydrolysis of the trivalent organic phosphorus compound can be suppressed and the oxidation reaction can be smoothly promoted. Further, hydrogen peroxide as an oxidizing agent is industrially inexpensive and easily available, and the reaction process and wastewater treatment are easy, and therefore the method of the present invention is industrially advantageous. Furthermore, according to the method of the present invention, a pentavalent organic phosphorus compound can be obtained in a high yield of 80 to 95%.

[Brief description of drawings]

FIG. 1 is a GPC chart of a pentavalent organophosphorus compound obtained in Example 4 of the present invention.

Continuation of the front page (56) Reference JP-A-56-36512 (JP, A) JP-A-51-108021 (JP, A) JP-B 39-10115 (JP, B1) US Pat. No. 5466852 (US, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C07F 9/09 C08K 5/5317 CA (STN)

Claims (3)

(57) [Claims] 1. A trivalent organic phosphorus compound is oxidized with an aqueous hydrogen peroxide solution at a temperature of 0 to 50 ° C. in the presence of an inorganic or organic base to obtain a corresponding pentavalent organic phosphorus compound.
Consists, trivalent organic phosphorus compound, of formula (I): ## STR1 ## (In the formula, R and Z are the same or different and each is a hydrogen atom or a lower
Alkyl group, n 0 integer), formula (II): 2] (In the formula, R and Z have the same meanings as in formula (I), m is 0 or 1) and
And formula (III): (R ¹ O) _3-a P—R ² _a (III) (wherein R ¹ and R ² are the same or different and have 1 to 18 carbon atoms).
Alkyl group or haloalkyl group of 6 to 6 carbon atoms
10 aryl groups, a is selected from 0 to 2)
A method for producing an organophosphorus compound, which is a compound. 2. The base is an inorganic base of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate and ammonia, and dimethylamine, diethylamine, trimethylamine, triethylamine, tributylamine, dimethylaniline, pyridine and The production method according to claim 1 , wherein the compound is one or more selected from organic bases of picoline. 3. A compound of formula (I) or formula (II)
The production method according to claim 1 or 2 , which is a reaction product obtained by further reacting an aliphatic aldehyde or a ketone with a reaction product of phosphorus trichloride and an alkylene oxide.