CN100336819C

CN100336819C - Method for synthesizing phosphonium salt by three organo-phosphines and alkyl halide hydrocarbon

Info

Publication number: CN100336819C
Application number: CNB2003101001747A
Authority: CN
Inventors: 赵勇军; 李靖; 王宇; 黄小钟; 赵新; 靳跃春; 刘春华
Original assignee: Beijing Hechuang Tongsheng Science & Technology Co Ltd
Current assignee: Beijing Hechuang Tongsheng Science & Technology Co., Ltd.
Priority date: 2003-10-15
Filing date: 2003-10-15
Publication date: 2007-09-12
Anticipated expiration: 2023-10-15
Also published as: CN1607203A

Abstract

The present invention discloses a method for synthesizing a phosphonium salt by three organic phosphorus and alkane halide. The method comprises the synthesizing steps of grignardreagent, three organic phosphorus and phosphonium salt; meanwhile, a ether solvent and a solvent selected from one of benzene, toluene, dimethylbenzene and ethylenzene or the mixture solution of any two or more than two of the benzene, the toluene, the dimethylbenzene and the ethylenzene are recovered and reutilized so that the use efficiency of the solvent is enhanced. The method adopts the control step of adding alkane halide after distilling the solvent to reach the product yield of 70%.

Description

A kind of three organic phosphines are Chenged the method for phosphonium salt with halogenated alkane He

Technical field

The invention relates to the synthetic method of a phosphonium salt, the method for further saying so and closing into phosphonium salt about a kind of three organic phosphines and halogenated alkane.

Background technology

Phosphonium salt can be used for tensio-active agent, antiseptic-germicide, antistatic agent and catalyzer etc.

In clear 30-9067, disclose triphenyl phosphatization hydrogen and alkane or butyl halide and be with or without under the condition of organic solvent, with halogenide the method that the catalyzer heating obtains.

In clear 63-119491, disclosed method is with after three organic phosphines and the halogenated alkane reaction, with this reaction solution neutralization.

The smelly problem of disclosed method Shi Zhen Dui phosphonium salt Zhong De Phosphonium among the JP11-124388 is carried out oxide treatment to the reaction solution of three organic phosphines and halogenated alkane, for example uses H ₂O ₂With three organic phosphines of complete reaction not in the reaction solution, be oxidized to oxide compound, make Suo De phosphonium salt no longer include special odor.

Summary of the invention

It is low to the purpose of this invention is to provide a kind of cost, the method for the He Cheng phosphonium salt that product yield is high.

Method provided by the invention comprises: (1) halohydrocarbon and MAGNESIUM METAL are synthesized Grignard reagent; (2) in the presence of Grignard reagent, add synthetic three organic phosphines of phosphorus trichloride and (3) with three organic phosphines and the step that a kind of haloalkane hydrocarbon reaction closes into phosphonium salt, it is characterized in that:

Step (1) makes haloalkane and MAGNESIUM METAL obtain Grignard reagent in the ether medium under the anhydrous and oxygen-free condition;

Step (2) with phosphorus trichloride and a kind of solvent after, be lower than 0 ℃ of following hybrid reaction 1～5 hour with Grignard reagent, 70～90 ℃ steam ether, hydrolysis forms water and organic phase again, and wherein said solvent is selected from a kind of in benzene,toluene,xylene and the ethylbenzene or two or more mixture arbitrarily wherein;

Step (3) water phase separated and organic phase be not higher than under 120 ℃ of temperature, and the solvents distillation of 5～95 heavy % in the organic phase that step (2) is obtained is reclaimed, and adds halogenated alkane again, 140～150 ℃ of reactions 2～20 hours, reclaims product through aftertreatment.

In the method provided by the invention, the said halogenated alkane of step (3) is the halogenated alkane with 10～18 carbon atoms, for example halo dodecane, the halo tetradecane or halo n-Hexadecane.

In the method provided by the invention, in the said step (3), the said solvent distillation is reclaimed adopted water trap, not only can take away the less water that wherein contains, and system temperature can be brought up to desired reaction temperature rapidly.

In the said step of method provided by the invention (3), before adding halogenated alkane, can also in organic phase, add alkali lye, the aqueous solution of sodium bicarbonate for example, the pH that makes organic phase is 8～9.

The process that said aftertreatment is reclaimed in the step (3) is meant and adds the water filtration removal of impurity and add the organic solvent extraction water, with the outstanding process that obtains solid phase prod of steaming of the water that obtains.

Method provided by the invention can also be used for reference the scheme of prior art, in step (3), in reaction solution, add hydrogen peroxide not three organic phosphines of complete reaction be oxidized to oxide compound, make Suo De phosphonium salt no longer include special odor.

The method of He Cheng phosphonium salt provided by the invention is utilized the solvent recuperation of ether and adding simultaneously again, has improved the solvent service efficiency, has reduced cost; And adopt the controlled step that before adding halogenated alkane, solvent is partly steamed, and make product yield higher, can reach about 70%.

Embodiment

Among the embodiment, except that specifying, agents useful for same is chemically pure reagent, Beijing Chemical Plant's product.

Embodiment 1

In the anhydrous and oxygen-free environment, 10 milliliters of chlorobutanes and 9 gram MAGNESIUM METAL are reacted in 100 milliliters of ether media and obtain Grignard reagent; 250 milliliters of weighing phosphorus trichloride 13.7 grams and toluene add in the constant pressure funnel, and cryosel is bathed and cooled to-5 ℃, is added dropwise in the Grignard reagent, keep temperature to be no more than 0 ℃.Be warmed up to 80 ℃, ether is steamed and reclaims; With ice-water bath system is cooled to below 0 ℃ again, add 150 milliliter 5% aqueous hydrochloric acid hydrolysis, obtain organic layer and aqueous phase layer, under protection of nitrogen gas, take out the phase of anhydrating.

At 110 ℃, add 20.5 gram chlorinated dodecanes again after distilling out 10% toluene, be warmed up to 140～150 ℃ of reactions and obtained product in 6 hours.

Product aftertreatment: add 100 ml waters, remove by filter impurity, divide aqueous phase extracted three times with 150 milliliters sherwood oil again, the outstanding steaming of the water that obtains obtained product.Product yield is 68.2%.

Embodiment 2

In the anhydrous and oxygen-free environment, 10 milliliters of chlorobutanes and 9 gram MAGNESIUM METAL are reacted in 100 milliliters of ether media and obtain Grignard reagent; 200 milliliters in weighing phosphorus trichloride 13.7 grams and ethylbenzene add in the constant pressure funnel, and cryosel is bathed and cooled to-5 ℃, is added dropwise in the Grignard reagent, keep temperature to be no more than 0 ℃.Be warmed up to 80 ℃, ether is steamed and reclaims; With ice-water bath system is cooled to below 0 ℃ again, add the hydrolysis of 70 milliliter of 10 heavy % ammonium chloride, obtain organic layer and aqueous phase layer, under protection of nitrogen gas, take out the phase of anhydrating.

Under 120 ℃, add 20.5 gram chlorinated dodecanes again after distilling out 90% ethylbenzene, be warmed up to 140～150 ℃ of reactions and obtained product in 6 hours.

Product aftertreatment: add 100 ml waters, remove by filter impurity, divide aqueous phase extracted three times with 150 milliliters sherwood oil again, the outstanding steaming of the water that obtains obtained product.Product yield is 72.5%.

Embodiment 3

In the anhydrous and oxygen-free environment, 10 milliliters of chlorobutanes and 9 gram MAGNESIUM METAL are reacted in 100 milliliters of ether media and obtain Grignard reagent; 250 milliliters of weighing phosphorus trichloride 13.7 grams and dimethylbenzene add in the constant pressure funnel, and cryosel is bathed and cooled to-5 ℃, is added dropwise in the Grignard reagent, keep temperature to be no more than 0 ℃.Be warmed up to 90 ℃, ether is steamed and reclaims; With ice-water bath system is cooled to below 0 ℃ again, add 100 milliliter 5% hydrochloric acid hydrolysis, obtain organic layer and aqueous phase layer, under protection of nitrogen gas, take out the phase of anhydrating.

Phosphonium salt synthetic: under 120 ℃, add 20.5 gram chlorinated dodecanes again after distilling out 20% dimethylbenzene, be warmed up to 140～150 ℃ of reactions 6 hours.

Product aftertreatment: add 100 ml waters, remove by filter impurity, divide aqueous phase extracted three times with 150 milliliters sherwood oil again, the outstanding steaming of the water that obtains obtained product.Product yield is 70.8%.

Embodiment 4

In the anhydrous and oxygen-free environment, 10 milliliters of chlorobutanes and 9 gram MAGNESIUM METAL are reacted in 100 milliliters of ether media and obtain Grignard reagent; 250 milliliters of weighing phosphorus trichloride 13.7 grams and toluene add in the constant pressure funnel, and cryosel is bathed and cooled to-5 ℃, is added dropwise in the Grignard reagent, keep temperature to be no more than 0 ℃.Be warmed up to 90 ℃, ether is steamed and reclaims; With ice-water bath system is cooled to below 0 ℃ again, add the hydrolysis of 200 milliliter of 10 heavy % ammonium chloride, obtain organic layer and aqueous phase layer, under protection of nitrogen gas, take out the phase of anhydrating.

Phosphonium salt synthetic: under 120 ℃, distill out in the organic phase 70% toluene after, add 100 milliliters of saturated aqueous solution of sodium bicarbonate, add 20.5 gram chlorinated dodecanes again, be warmed up to 140～150 ℃ of reactions and obtained product in 10 hours.

Product aftertreatment: add 100 ml waters, remove by filter impurity, divide aqueous phase extracted three times with 150 milliliters sherwood oil again, the outstanding steaming of the water that obtains obtained product.Product yield is 74.1%.

Embodiment 5

In the anhydrous and oxygen-free environment, 10 milliliters of chlorobutanes and 9 gram MAGNESIUM METAL are reacted in 100 milliliters of ether media and obtain Grignard reagent; 250 milliliters of weighing phosphorus trichloride 13.7 grams and toluene add in the constant pressure funnel, and cryosel is bathed and cooled to-5 ℃, is added dropwise in the Grignard reagent, keep temperature to be no more than 0 ℃.Be warmed up to 90 ℃, ether is steamed and reclaims; With ice-water bath system is cooled to below 0 ℃ again, add 150 milliliter of 5% hydrochloric acid hydrolysis, obtain organic phase and water, under protection of nitrogen gas, take out the phase of anhydrating.

Phosphonium salt synthetic: under 120 ℃, distill out 10 milliliters of hydrogen peroxide that add 20.5 gram chlorinated dodecanes and 25% behind 60% the toluene again, be warmed up to 140～150 ℃ of reactions and obtained product in 17 hours.

Product aftertreatment: add 100 ml waters, remove by filter impurity, divide aqueous phase extracted three times with 150 milliliters sherwood oil again, the outstanding steaming of the water that obtains obtained product.Product yield is 66%.

Claims

1, a kind of three organic phosphines are Chenged the method for phosphonium salt with halogenated alkane He, it is characterized in that this method comprises the steps:

Step (1): under the condition of anhydrous and oxygen-free, make haloalkane and MAGNESIUM METAL in the ether medium, obtain Grignard reagent;

Step (2): after phosphorus trichloride and a kind of solvent, again with step (1) synthetic Grignard reagent-15 ℃ of-5 ℃ of following hybrid reactions 1～5 hour, 40～90 ℃ steam ether, hydrolysis forms water and organic phase again, and wherein said solvent is selected from a kind of in benzene,toluene,xylene and the ethylbenzene or two or more mixture arbitrarily wherein;

Step (3): water phase separated and organic phase, be not higher than under 120 ℃ the temperature, the solvents distillation of 5～95 heavy % in the organic phase that step (2) is obtained is reclaimed, and adds halogenated alkane again, obtained reaction solution in 2～20 hours 140～150 ℃ of reactions, reclaim product through aftertreatment.

2,, it is characterized in that said halogenated alkane is the halogenated alkane of 10～18 carbon atoms in the step (3) according to the method for claim 1.

3,, it is characterized in that said halogenated alkane is halo dodecane, the halo tetradecane or halo n-Hexadecane according to the method for claim 2.

4, according to the method for claim 1, it is characterized in that adding in the step (3) before the halogenated alkane, adding alkali lye in organic phase, to make the pH of organic phase be 8～9.

5,, it is characterized in that said alkali lye is the aqueous solution of sodium bicarbonate according to the method for claim 4.

6,, it is characterized in that in the reaction solution of step (3) adding hydrogen peroxide not three organic phosphines of complete reaction is oxidized to oxide compound according to the method for claim 1.