KR830000552B1 - Process for preparing phosphoric acid esters and thiophosphoric acid esters - Google Patents

Abstract

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Description

Process for preparing phosphoric acid esters and thiophosphoric acid esters

The present invention relates to a novel method for producing phosphate esters and thiophosphate esters by reacting an organic compound containing a hydroxyl group with phosphorus oxychloride or phosphorus thiochloride.

Phosphate esters and thiophosphate esters, which are reaction products of alcohols or phenols with phosphorus oxychloride or phosphorus thiochloride, have been used for a long time as pesticides, plasticizers and raw materials for their preparation. For example, trixylene phosphate (hereinafter referred to as TCP), a reaction product of cresol and phosphorus oxychloride, was initially developed as a plasticizer for cellulose nitrate, but has since been widely used as a plasticizer for polyvinyl chloride. As described above, various methods have been proposed for a long time.

The reaction kinetics of the TCP preparation method is described in Japanese "Chemical and Industrial" Volume 4, NO 12, pages 17 to 12. The production method is described in the above documents, and is classified into four types: (a) a noncatalytic method, (b) a basic catalyst method, (c) an acid catalyst method, and (d) a metal salt method.

(a) In the noncatalytic method, since more chlorine atoms of phosphorus oxychloride are substituted by the phenyl group, the esterification reaction of phosphorus oxychloride is delayed and the frequency factor is reduced.

(b) The basic catalyst method usually uses tertiary amines, but the production rate of mono and diesters is improved, but these catalysts are ineffective in improving the production of triesters.

(c) The acid catalyst method uses anhydrous aluminum chloride, iron chloride, magnesium chloride, and the like. When aluminum chloride is used, the production rate of di and triesters is not reduced. Although possible, the use of aluminum chloride results in a Friedel-Krafts reaction resulting in undesirable compounds in which one or more phenyl groups are bonded directly to phosphorus atoms.

(d) The metal salt method is the most typical method used in the field of organic synthesis. Using this method, the reaction can be terminated at low temperature in a short time, and the product can be obtained in quantitative yield, but it is not industrially suitable due to economic adverse effects such as the need to convert cresol to metal salt. It is described.

It is an object of the present invention to provide a method for producing phosphate esters or thiophosphate esters from organic compounds containing hydroxyl groups and phosphorus oxychloride or phosphorus thiochloride in easy and good yields.

It is another object of the present invention to use organic compounds containing one or more other functional groups and hydroxyl groups reactive with phosphorus oxychloride or phosphorus thiochloride, so that only the hydroxyl groups of the organic compound selectively react with phosphorus oxychloride or phosphorus thiochloride Phosphate esters characterized by shikim

The above objects are one or more alkali metal compounds (a), water (b) and organic solvents selected from the group consisting of hydroxides and carbonates of alkali metals with organic compounds containing hydroxyl groups and phosphorus oxychloride or phosphorus thiochloride; It can be completed by making it react by coexistence with (c) and manufacturing the ester compound chosen from the group which consists of phosphate ester and thiophosphoric acid ester.

It is preferable to select the compound containing a hydroxyl group from the group which consists of the compound represented by the following general formula (I), and the compound represented by the following general formula (II).

Wherein R ¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxyalkyl group, an aryl group, an aralkyl group, an aryloxy group or an arylsulfonyl group, and the organic group represented by R ¹ is also one or more halogen atoms, lower alkyl groups Or a lower alkoxy substituent, R ² is a hydrogen atom, a nitro group, a nitro group, an amino group, a mono or dialkylamino group, or a mono or diacylamino group, R ³ is a hydrogen atom or a halogen atom, Ar Is an aromatic group, X, Y and Z are numbers from 0 to 5, the sum of x + y + z is equal to or less than 5, and is an alkyl group, alkenyl

The present inventors react phosphate esters and thiophosphate esters by reacting an organic compound containing a hydroxyl group with phosphorus oxychloride or phosphorus thiochloride at a relatively low temperature in the presence of alkali metal hydroxides or carbonates, water and an organic solvent. It has been found that it can be produced in yield.

In the past, since phosphorus oxychloride and phosphorus thiochloride are considered to be hydrolyzed when they come into contact with water, phosphate esters are reacted by reacting organic compounds containing hydroxyl groups with phosphorus oxychloride or phosphorus thiochloride in the presence of alkali and water. It is a fact that it is a fact that manufactures or a thiophosphoric acid ester in good yield.

The present inventors thought that the reaction between the hydroxyl group and the phosphorus oxychloride or the phosphorus thiochloride proceeds faster than the hydrolysis of phosphorus oxychloride or phosphorus thiochloride in the presence of alkali and water.

The reaction between the organic compound containing a hydroxyl group and phosphorus oxychloride or phosphorus thiochloride can be carried out by various methods. According to one preferred embodiment, the mixture formed by adding phosphorus oxychloride or phosphorus thiochloride to an organic compound containing a hydroxyl group in the presence of an organic solvent is maintained at a temperature of less than 80 ° C., and an aqueous solution of hydroxide or carbonate of an alkali metal Or the suspension is added dropwise. According to another preferred embodiment, a mixture formed by adding a hydroxide or carbonate of an alkali metal and water to an organic compound containing a hydroxyl group is added.

As described above, the organic compound containing a hydroxyl group is preferably selected from the group of compounds represented by the general formulas (I) and (II).

As an example of a compound represented by general formula (I), it is phenol; Mono, di, tri, tetra and pentaalkylphenols; Mono, di and trialkoxyphenols; Alkylalkoxy phenols; Mono and dialkylphenols; Alkenylalkoxy phenols; Mono, di, tri, tetra and pentahalophenols; Alkyl halophenols, alkoxy halophenols and nitrohalophenols; Mono, di and trinitrophenols; Alkyl nitrophenols and alkoxynitrophenols; Aminophenols; N-monoalkylaminophenols and N, N-dialkylaminophenols; N-monoacylamino phenols and N, N- diacyl amino phenols; Aminoalkyl phenols; Aminonitrophenols and aminohalophenols; Phenyl phenols; Phenyl alkyl phenols; Cyclohexyl phenols; Cyclohexyl alkyl phenols; Phenoxyphenols; Phenylsulfonylphenols; Isomers of cyclohexyloxyphenols and the aforementioned compounds, and compounds obtained by substituting benzene nuclei in the aforementioned compounds with naphthalene nuclei.

Examples of the compounds represented by the general formula (II) include alkanols, alkenols, cyclohexanols, alkylcyclohexanols, alkoxyalkanols, phenylalkanols, alkylphenylalkanols, halophenylalkanols, haloalkanols and the foregoing. There is an isomer of one compound. These compounds can be used individually or in mixture of up to 3 types of components.

The organic compound containing a hydroxyl group and phosphorus oxychloride or phosphorus thiochloride are used in a molar ratio within the range of 2.5: 1 to 20: 1. Phosphorus oxychloride or phosphorus thiochloride is usually dependent on a hydrolysis reaction at the time of the reaction, so a hydroxyl group is usually used to improve the yield.

The alkali metal compound (hereinafter referred to as alkali) is selected from hydroxides and carbonates of sodium and potassium, and is used as an aqueous solution or suspension containing alkali at a concentration of 20 to 60% by weight (hereinafter referred to as alkaline water). desirable.

Alkali is preferably used in the same amount or slightly excess of stoichiometric amount, that is, 3 moles per mole of phosphorus oxychloride or thiochloride.

As described above, the alkali concentration in the alkali water is preferably in the range of 20 to 60% by weight. When this concentration is less than 20% by weight, the remaining chlorine atoms and intermediate products (mono and diesters) of phosphorus oxychloride or phosphorus thiochloride are easy to hydrolyze. If the concentration is 60% by weight or more, the hydrolysis reaction of phosphorus oxychloride or phosphorus thiochloride in alkaline water proceeds faster than the esterification reaction, resulting in a decrease in reaction rate. The preferred concentration range is therefore 30 to 50% by weight.

As described above, water is preferably added in the reaction system in the form of alkaline water. Alternatively, only water may be added to the reaction system, followed by alkali. In this case, the amount of water must be added so that the alkali concentration in the alkali water formed in the reaction system is 20 to 60% by weight.

The organic solvent may be any organic solvent which is inert to phosphorus oxychloride or phosphorus thiochloride and capable of dissolving an organic compound containing a hydroxyl group used as a raw material.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, and diethyl ketone; Ethers such as isopropyl ether, n-butyl ether, 1,4-dioxane, diethylene glycol, and dimethyl ether; Chlorinated aliphatic hydrocarbons such as chloroform, methylene chloride and ethylene dichloride; Unsubstituted or substituted aromatic hydrocarbons such as benzene, toluene, xylene, diethylbenzene, monochlorobenzene and dichlorobenzene. In some cases, the compound may be used in excess so that the organic compound containing a hydroxyl group can act as a solvent.

The reaction temperature is preferably less than 80 ° C, more preferably in the range of 0 ° to 50 ° C. If the reaction temperature is higher than this range, the decomposition reaction of phosphorus oxychloride or phosphorus thiochloride occurs, resulting in an adverse effect of increasing the formation of by-products, and if the reaction temperature is too lower than this range the reaction rate is reduced The reaction time is prolonged, leading to increased production of undesirable hydrolysates. The reaction temperature is most preferably in the range of 20 ° to 40 ° C.

The reaction time depends on the reaction temperature, but in general, the reaction time is preferably 1 to 6 hours within the above-mentioned ideal reaction temperature range.

In the case of producing the triester according to the present invention, since the reaction mixture may contain a small amount of mono and diesters, organic compounds containing unreacted hydroxyl groups, hydrolyzates thereof and the like, first the reaction mixture is vacuum distilled. Unreacted with organic solvents

If the product is liquid, the reaction mixture is washed with alkaline water and then with water and then distilled.

According to the method of the present invention, a phosphate ester or a thiophosphate ester can be produced in good yield from an organic compound containing a hydroxyl group and phosphorus oxychloride or phosphorus thiochloride. Even if an organic compound containing a hydroxyl group contains one or more functional groups reactive with phosphorus oxychloride or phosphorus thiochloride (eg p-aminophenol), only the hydroxyl group selectively reacts with phosphorus oxychloride or phosphorus thiochloride Therefore, the desired product [eg, tris (4-aminophenyl) phosphate or tris (4-aminophenyl) thiophosphate] can be produced directly.

In such a case, since the reaction of an amino group with phosphorus oxychloride or phosphorus thiochloride cannot be avoided by the conventional method, it was thought that it is very impossible to selectively react only a hydroxyl group. Therefore, various methods have been proposed for the manufacturing method of the above-mentioned products. For example, as a method of synthesizing triphenyl ester (triphenylphosphate or triphenylthiophosphate), there is a method of nitrating and then reducing the resulting nitro compound to the corresponding amine, and another method is sodium p-nitro. There is a method of reacting phenate with phosphorus oxychloride or phosphorus thiochloride and then reducing the resulting nitro compound to the corresponding amine. However, their method of nitro compound width

In addition, the method of the present invention is superior to the metal salt method because the step of converting an organic compound containing a hydroxyl group to a metal salt can be eliminated and the reaction can be easily performed at a relatively low temperature in a shorter time.

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited only to these examples.

Example 1

To a 3-liter four-necked flask equipped with a stirrer, thermometer, condenser, and dropping funnel, 2,000 ml of acetone and 139.1 g (1.0 mole) of p-nitrophenol were added to the resulting solution, followed by 55.2 g (0.36 mole) of phosphorus oxychloride. Immediately thereafter, 96.0 g (1.08 mol) of 45% (W / W) aqueous sodium hydroxide solution was added dropwise to the solution with vigorous stirring (600 rpm) over a dropping funnel over 10 minutes. At this time, after cooling with water to maintain the reaction temperature below 30 ℃, the reaction was continued for 5 hours.

The reaction mixture was concentrated at 30 ° to 40 ° C. under reduced pressure, and then 30% (W / W) aqueous sodium hydroxide solution was added dropwise until the pH of the reaction mixture reached 11. The resulting precipitate was filtered off and washed with water and then vacuum dried at 60 ° C. to 80 ° C. for 12 hours.

The strongly alkaline mother liquor contained p-nitrophenol, mono and diesters, and their hydrolysates to obtain 98.4 g of tris (p-nitrophenyl) phosphate of white crystals having a melting point of 154.0 ° to 156.0 ° C. The yield was 64% with respect to the amount of p-nitrophenol used as a raw material. After recrystallization from methanol and purification, elemental analysis yielded the following results.

Elemental Analysis: (C ₁₈ H ₁₂ O ₁₀ N ₃ P)

Calculated: C 46.85 (%) H 2.60 (%) N 9.11 (%) P 6.72 (%)

Found: 48.68 2.66 8.87 6.75

Example 2

The procedure of Example 1 was repeated except that 62.7 g (0.37 mol) of phosphorus thiochloride was used instead of phosphorus oxychloride to give a tris (p-nitrophenyl) thiophosphate 143.1 of white crystals having a melting point of 171 ° to 175 ° C. g (0.30 mol) was obtained. The yield was 30% with respect to the amount of p-nitrophenol used as a raw material. Purification by recrystallization with methanol and elemental analysis yielded the following results.

Elemental Analysis: (C ₁₈ H ₁₂ O ₁₀ N ₃ PS)

Calculated Value: C 45.28 (%) H 2.52 (%) N 8.81 (%) P 6.50 (%) S 6.71 (%)

Found: 45.01 2.60 8.59 6.42 6.63

Example 3

The procedure of Example 1 was repeated except that 94.1 g (1.0 mol) of phenol was used instead of p-nitrophenol to give 63.0 g of white crystal triphenylphosphate having a melting point of 47.5 ° to 49 ° C. The yield was 58% with respect to the amount of phenol used as a raw material. Purification by recrystallization with methanol and elemental analysis yielded the following results.

Elemental Analysis: (C ₁₈ H ₁₅ O ₄ P)

Calculated Value: C 66.26 (%) H 4.60 (%) P 9.50 (%)

Found: 66.20 4.66 9.48

Example 4

The procedure of Example 1 was repeated except that 151.2 g (1.0 mol) of N-acetyl-p-aminophenol instead of p-nitrophenol and 62.7 g (0.37 mol) of phosphorus thiochloride were used instead of phosphorus oxychloride. 157.3 g of tris (N-acetyl-p-aminophenyl) thiophosphate as white crystals having a melting point of 194 ° to 196 ° C was obtained. The yield was 92% with respect to N-acetyl-p-aminophenol used as a raw material. After recrystallization from methanol and purification, elemental analysis yielded the following results.

Elemental Analysis: (C ₂₄ H ₂₄ O ₆ N ₃ PS)

Calculated value: C 56.14 (%) H 4.70 (%) P 6.03 (%) S 6.24 (%) P 8.18 (%)

Found: 53.23 4.65 6.00 6.21 8.21

Example 5

Melting point was repeated by repeating the procedure of Example 1 except that 32.8 g (0.30 mol) of p-aminophenol was used instead of p-nitrophenol and the amount of phosphorus oxychloride was reduced to 16.6 g (0.108 mol). 22.3 g of tris (p-aminophenyl) phosphate as white crystals were obtained from 153 ° to 155 ° C. The yield was 60% with respect to the amount of p-aminophenol used as a raw material. Purification by recrystallization with methanol and elemental analysis yielded the following results.

Elemental Analysis: (C ₁₈ H ₁₈ O ₄ NP)

Calculated value: C 58.22 (%) H 4.89 (%) N 11.32 (%) P 8.36 (%)

Found: 58.13 5.0 11.28 8.20

Example 6

Except for using 32.8 g (0.3 mole) of p-aminophenol instead of p-nitrophenol and 18.3 g (0.108 mole) of phosphorus thiochloride instead of phosphorus oxychloride, the operation of Example 1 was repeated to achieve a melting point of 154 °. Tris (p-aminophenyl) thiophosphate of white crystals, which was 156 占 폚, was obtained. The yield was 64% with respect to the amount of p-aminophenol used as a raw material.

Purification by recrystallization with methanol and elemental analysis yielded the following results.

Elemental Analysis: (C ₁₈ H ₁₈ O ₃ N ₃ PS)

Calculated Value: C 56.0 (%) H 4.6 (%) N 10.8 (%) P 8.0 (%) S 8.2 (%)

Found: 55.6 4.8 10.7 8.2 8.1

Example 7

Take 900 ml of toluene in a 2 liter four-necked flask equipped with a stirrer, thermometer, condenser and dropping funnel, and dissolve 108.1 g (1.0 mole) of p-cresol and 55.2 g (0.36 mole) of phosphorus oxychloride in the resulting solution. After the addition of), 96.0 g (1.08 mol) of 45% (W / W) aqueous sodium hydroxide solution was added dropwise to the solution with vigorous stirring (600 rpm) over a dropping funnel over 10 minutes. At this time, the reaction temperature was maintained at 30 ° C. by cooling with water, and the reaction was continued at this temperature for 5 hours.

내지 260

인 무색 투명한 액체인 트리스(p-메틸페닐) 포스페이트(

1.16~1.17) 108g(0.29몰)을 얻었다. 수율은 원료로 사용한 p-크레졸양에 대하여 87%이었다. 원소분석 결과치는 하기와 같다.While maintaining the reaction temperature below 30 ° C, the reaction mixture was washed with 30% (W / W) sodium hydroxide solution and then washed with water. The resulting toluene layer was separated with toluene and vacuum distilled to give a melting point of 245 at an absolute pressure of 5 mmHg.

To 260

Tris (p-methylphenyl) phosphate as a colorless transparent liquid

1.16-1.17) 108 g (0.29 mol) were obtained. The yield was 87% with respect to the amount of p-cresol used as a raw material. Elemental analysis results are as follows.

Elemental Analysis: (C ₂₁ H ₂₁ O ₄ O)

Calculated Value: C 68.48 (H) H 5.71 (%) P 8.42 (%)

Found: 68.30 5.79 8.40

Example 8

The procedure of Example 7 was repeated except that 130 g (1.0 mole) of 2-ethylhexyl alcohol was used instead of p-cresol, and the melting point was 210 ° to 220 ° C. under 5 mmHg absolute pressure.

Elemental Analysis: (C ₂₄ H ₅₁ O ₄ P)

Calculated Value: C 66.36 (%) H 11.75 (%) P 7.14 (%) O 14.75 (%)

Found: 66.33 11.76 7.11-

Example 9

In the reactor used in Example 1, 136.2 g (0.9 mol) of N-acetyl-p-aminophenol and 2.160 g of acetone were added, followed by stirring at room temperature for 30 minutes to prepare a solution. 77.1 g (0.93 mol) of 48.2% (W / W) aqueous sodium hydroxide solution were added dropwise to the solution with vigorous stirring over 15 minutes. At this time, cooling was performed outside to maintain the reaction temperature at 10 ° C to 15 ° C and stirring was continued for 30 minutes. Next, 50.7 g (0.3 mol) of phosphorus thiochloride was added to the solution over 1 hour, and the reaction was continued for 5 hours.

After distillation at 60 ° C. to remove acetone from the reaction mixture, the resulting concentrate was poured into 3000 g of ice water (0 ° to 10 ° C.), stirred for 30 minutes, and the mixture was left overnight. The resulting precipitate was filtered to crush the wet media in a mortar and then transferred into a 3 L beaker. 2000 g of ice water and 45 (W / W) sodium hydroxide aqueous solution were added thereto, followed by stirring at 10 ° to 20 ° C. for 2 hours.

The resulting precipitate was filtered, washed with water and dried in vacuo at 80 ° C. for 10 hours. Tris (4-acetylaminophenonyl) tee with white crystals having a melting point of 193 ° to 196 ° C.

Claims (1)

General formula

(R is an amino, monoalkylamino, dialkylamino, monoacylamino or diacylamino group, m is an integer of 1 to 5) and a phenol compound and phosphorus oxychloride or phosphorus thiochloride

(R and m are as defined above and Y is oxygen or sulfur atom) 1 selected from the group consisting of hydroxides and carbonates of alkali metals in the process for the preparation of ester compounds selected from the group consisting of triaryl phosphates and triphosphates A process for producing an ester compound, characterized in that the reaction is carried out at a temperature of 80 ° C. or less in the presence of at least an alkali metal compound, water and an inert organic solvent.