CN101885739B - Preparation method of 2,4,6-trimethylbenzene formacylphenyl phosphinicacid ethyl ester and derivative thereof - Google Patents

Abstract

The invention relates to a preparation method of 2,4,6-trimethylbenzene formacylphenyl phosphinicacid ethyl ester and a derivative thereof. The method comprises the following steps of: carrying out substitution and condensation reactions on benzene phosphorous oxydichloride and alcohol or sulfur alcohol and then carrying out an addition reaction with 2,4,6-trimethylbenzaldehyde; and then oxidizing by using an oxidant in the presence of the catalysis of a catalyst. The prepared 2,4,6-trimethylbenzene formacylphenyl phosphinicacid ethyl ester can be used as a photoinitiator of liquid and has the advantages of low price and easy obtaining of required raw materials, simple process equipment, easy operation, environmental protection, low cost, high yield and high purity, and the purity of products can reach higher than 95 percent. The 2,4,6-trimethylbenzene formacylphenyl phosphinicacid ethyl ester can be commercially prepared and produced in a large scale and meets the ever-increasing market requirements at present.

Description

The preparation method of 2,4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester

Technical field

The present invention relates to the preparation method of 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester (following abbreviation TPO-L) and derivative thereof.

Background technology

2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester and derivative thereof are widely used in having low extractability in various paint, printing ink and the coating, low migration and low volatility as light trigger or photosensitizers.US Patent No. 5679863 has been reported with phenyl ethoxy phosphonium chloride and 2,4, the 6-trimethylbenzaldehyde carries out addition reaction, and then carries out oxidation with organic oxidizing agents such as tertbutanol peroxide, Peracetic Acid, dicumyl peroxides and obtain TPO-L, and the yield of oxidation step only is 55%.The shortcoming of the method is that starting raw material phenyl ethoxy phosphonium chloride is difficult to preparation, yield is low, the organic oxidizing agent cost is high, and the by product after the part organic oxidizing agent is reduced residues in the water, can't separate, cause certain difficulty for the recovery of product, and caused the pollution of environment and product, be unfavorable for suitability for industrialized production.

Summary of the invention

The purpose of this invention is to provide a kind of 2,4, the preparation method of 6-trimethylbenzoyl phenyl phosphinic acid ethyl ester and derivative thereof.The present invention is simple with technique, processing ease, and cost is low, and yield is high, environmental friendliness, equipment requirements is low, can prepare large-scale commercially and produce, and satisfies the current ever-increasing market requirement.

Provided by the invention 2; 4; the preparation method of 6-trimethylbenzoyl phenyl phosphinic acid ethyl ester and derivative thereof is that phenylphosphonic dichloride and alcohol or mercaptan carry out substituted condensed reaction; again with 2; 4,6-trimethylbenzaldehyde carries out addition reaction, then under catalyst; carry out oxidation with oxygenant, reaction scheme:

R is selected from C_1-6Alkyl; C_1-12Alkoxyl group, C_3-6Cycloalkyl.X represents O, S.R in preferred this compound is ethyl; Preferred X is O.Be: C₁₈H₂₁O₃P, 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester.

Catalyzer be tungstic anhydride, tungstate, molybdic acid anhydride, molybdate, phosphomolybdate, Suanphosphotungstate and other heteropolyacid or heteropolyacid salt one or more, oxygenant is hydrogen peroxide (H₂O₂) or hydrogen peroxide.

Provided by the invention 2,4, the step that the preparation method of 6-trimethylbenzoyl phenyl phosphinic acid ethyl ester comprises:

1) organic solvent, dehydrated alcohol are mixed, cool, stir the lower phenylphosphonic dichloride that slowly adds, rise to room temperature, reacted 1-2 hour;

Dehydrated alcohol and phenylphosphonic dichloride weight ratio: 1: 1-1: 2; Cooling temperature is 5-10 ℃;

2) low pressure steams the monochloroethane of excessive ethanol and generation, cools, and slowly drips 2,4,6-trimethylbenzaldehyde, rises to room temperature, reacts 1-2 hour;

The weight ratio of phenylphosphonic dichloride and 2,4,6-trimethylbenzaldehyde: 1: 1-1: 3; Cooling temperature is 5-10 ℃;

3) cool, slowly drip the 20%NaOH aqueous solution and regulate pH to 1-4, add successively catalyzer, phase-transfer catalyst slowly drips oxidant hydrogen peroxide, and reaction is 10-20 hour under this temperature;

The weight ratio of phenylphosphonic dichloride and hydrogen peroxide: 1: 1-1: 2; The weight ratio 10 of hydrogen peroxide and catalyzer: 1-20: 1;

The weight ratio of hydrogen peroxide and phase-transfer catalyst is 50: 1-80: 1; Cooling temperature is 5-10 ℃;

4) gained solution saturated common salt water washing, standing demix;

5) organic phase is with 10% Na₂SO₃Washing, gained solution 5%NaOH aqueous solution conditioned reaction liquid pH to 7-8, standing demix is got organic phase;

6) underpressure distillation obtains light yellow thick liquid, and namely 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester.

Described organic solvent is one or more in benzene class, ester class, chloroparaffin, the nitrile; A kind of in preferred toluene, methylene dichloride, chlorobenzene, the ethylene dichloride or their mixing.

Step 3) catalyzer can be tungstic anhydride, tungstate, molybdic acid anhydride, molybdate, phosphomolybdate, Suanphosphotungstate and other heteropolyacid or heteropolyacid salt or their mixing.

Step 3) phase-transfer catalyst can be level Four An Huo phosphonium salt or their mixing such as Tetrabutyl amonium bromide, tetrabutylammonium chloride, benzyltriethylammoinium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, bromination Shi six alkyl San Ding Ji Phosphonium.

Step 3) oxygenant can be hydrogen peroxide, hydrogen peroxide or their mixing; Hydrogen peroxide is the aqueous solution of hydrogen peroxide.

2,4 of the present invention's preparation, 6-trimethylbenzoyl phenyl phosphinic acid ethyl ester can be used as the light trigger of liquid, is used for paint, varnish, enamel, lacquer, the curing of pigment or ink.Present device requires low, and raw material is easy to get, and technique is simple, processing ease, and cost is low, and yield is high, and purity is high, and product purity can reach more than 95%.In addition employed raw material phenylphosphonic dichloride and oxidant hydrogen peroxide in the operating process, cheap, be easy to get, operation steps is simple, and the product that also originates in of hydrogen peroxide is water, and is environmentally friendly, be convenient to process, can effectively reduce pollution, can prepare large-scale commercially and produce, satisfy the current ever-increasing market requirement.

Embodiment

The present invention will be described further by following embodiment.

The reagent that the present invention uses is the commercially available prod.

Embodiment 1:2, the preparation of 4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester

880kg toluene, 150kg dehydrated alcohol are mixed, be cooled to 5 ℃, stir the lower 180kg phenylphosphonic dichloride that slowly adds, rise to room temperature, reacted 2 hours.Low pressure steams the monochloroethane of excessive ethanol and generation, is cooled to 5 ℃, drips 200kg2, and 4,6-trimethylbenzaldehyde rises to room temperature, reacts 2 hours.Be cooled to 5 ℃, slowly drip the 20%NaOH aqueous solution and regulate pH to 2, add successively 12kgWO₃, the 3kg Tetrabutyl amonium bromide slowly drips the 190kg hydrogen peroxide, and reaction is 16 hours under this temperature.

The saturated common salt water washing of gained solution, standing demix, organic phase is with 10% Na₂SO₃5%NaOH aqueous solution conditioned reaction liquid pH to 7 is used in washing again, and standing demix is got organic phase.Underpressure distillation gets the light yellow thick liquid of 286kg, and namely 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester, content 96.8%, yield 90%.

b.p./10Pa：180℃。

¹HNMR(CDCl₃)δ：1.287(t，3H)，2.10(s，6H)，2.21(s，3H)，4.11(q，2H)，6.76(s，2H)，7.40-7.44(m，2H)，7.51-7.55(m，1H)，7.77-7.82(m，2H)。

Embodiment 2:2, the preparation of 4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester

880kg toluene, 150kg dehydrated alcohol are mixed, be cooled to 5 ℃, stir the lower 180kg phenylphosphonic dichloride that slowly adds, rise to room temperature, reacted 2 hours.Low pressure steams the monochloroethane of excessive ethanol and generation, is cooled to 5 ℃, drips 200kg2, and 4,6-trimethylbenzaldehyde rises to room temperature, reacts 2 hours.Be cooled to 5 ℃, slowly drip the 20%NaOH aqueous solution and regulate pH to 2, add successively 12kg (NH₄)₂MoO₄, the 3kg Tetrabutyl amonium bromide slowly drips the 200kg hydrogen peroxide, and reaction is 20 hours under this temperature.

The saturated common salt water washing of gained solution, standing demix, organic phase is with 10% Na₂SO₃5%NaOH aqueous solution conditioned reaction liquid pH to 8 is used in washing again, and standing demix is got organic phase.Underpressure distillation gets the light yellow thick liquid of 283kg, and namely 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester, content 97%, yield 89%.

Embodiment 3:2, the preparation of 4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester

880kg toluene, 150kg dehydrated alcohol are mixed, be cooled to 5 ℃, stir the lower 180kg phenylphosphonic dichloride that slowly adds, rise to room temperature, reacted 2 hours.Low pressure steams the monochloroethane of excessive ethanol and generation, is cooled to 5 ℃, drips 200kg2, and 4,6-trimethylbenzaldehyde rises to room temperature, reacts 2 hours.Be cooled to 5 ℃, slowly drip the 20%NaOH aqueous solution and regulate pH to 2, add successively 15kg (NH₄)₃[P (Mo₁₂O₁₀)] 6H₂O (heteropolyacid, ammonium phosphomolybdate), the 3kg Tetrabutyl amonium bromide slowly drips the 200g hydrogen peroxide, and reaction is 13 hours under this temperature.

The saturated common salt water washing of gained solution, standing demix, organic phase is with 10% Na₂SO₃5%NaOH aqueous solution conditioned reaction liquid pH to 7 is used in washing again, and standing demix is got organic phase.Underpressure distillation gets the light yellow thick liquid of 289kg, and namely 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester, content 97%, yield 91%.

Embodiment 4:2, the preparation of 4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester

With 880kg toluene, 150kg dehydrated alcohol and mix, be cooled to 5 ℃, stir the lower 180kg phenylphosphonic dichloride that slowly adds, rise to room temperature, reacted 2 hours.Low pressure steams the monochloroethane of excessive ethanol and generation, is cooled to 5 ℃, drips 200kg2, and 4,6-trimethylbenzaldehyde rises to room temperature, reacts 2 hours.Be cooled to 5 ℃, slowly drip the 20%NaOH aqueous solution and regulate pH to 2, add successively 12kgWO₃, the 3kg Trimethyllaurylammonium bromide slowly drips the 210kg hydrogen peroxide, and reaction is 15 hours under this temperature.

The saturated common salt water washing of gained solution, standing demix, organic phase is with 10% Na₂SO₃5%NaOH aqueous solution conditioned reaction liquid pH to 8 is used in washing again, and standing demix is got organic phase.Underpressure distillation gets the light yellow thick liquid of 286kg, and namely 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester, content 96.9%, yield 90%.

Embodiment 5:2, the preparation of 4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester

With 880kg toluene, 150kg dehydrated alcohol and mix, be cooled to 5 ℃, stir the lower 180kg phenylphosphonic dichloride that slowly adds, rise to room temperature, reacted 2 hours.Low pressure steams the monochloroethane of excessive ethanol and generation, is cooled to 5 ℃, drips 200kg2, and 4,6-trimethylbenzaldehyde rises to room temperature, reacts 2 hours.Be cooled to 5 ℃, slowly drip the 5%NaOH aqueous solution and regulate pH to 2, add successively 16kgNa₃[P (W₁₂O₁₀)], the 4kg benzyltriethylammoinium chloride slowly drips the 200kg hydrogen peroxide, and reaction is 11 hours under this temperature.

The saturated common salt water washing of gained solution, standing demix, organic phase is with 10% Na₂SO₃5%NaOH aqueous solution conditioned reaction liquid pH to 8 is used in washing again, and standing demix is got organic phase.Underpressure distillation gets the light yellow thick liquid of 286kg, and namely 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester, content 97.2%, yield 90%.

Embodiment 6:2, the preparation of 4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester

With 880kg toluene, 150kg dehydrated alcohol and mix, be cooled to 5 ℃, stir the lower 180kg phenylphosphonic dichloride that slowly adds, rise to room temperature, reacted 2 hours.Low pressure steams the monochloroethane of excessive ethanol and generation, is cooled to 5 ℃, drips 200kg2, and 4,6-trimethylbenzaldehyde rises to room temperature, reacts 2 hours.Be cooled to 5 ℃, slowly drip the 5%NaOH aqueous solution and regulate pH to 2, add successively 16kgH₇[(PMo₂O₇)₆] XH₂O, 2kg tri-n-octyl methyl ammonium chloride and 1kg 4-butyl ammonium hydrogen sulfate slowly drip the 200kg hydrogen peroxide, and reaction is 13 hours under this temperature.

The saturated common salt water washing of gained solution, standing demix, organic phase is with 10% Na₂SO₃5%NaOH aqueous solution conditioned reaction liquid pH to 7 is used in washing again, and standing demix is got organic phase.Underpressure distillation gets the light yellow thick liquid of 280kg, and namely 2,4,6-trimethylbenzoyl phenyl phosphinic acid ethyl ester, content 97%, yield 90%.

Claims (11)

1. one kind 2,4, the preparation method of 6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester is characterized in that comprising the steps:

1) organic solvent, dehydrated alcohol are mixed, cool, stir the lower phenylphosphonic dichloride that slowly adds, rise to room temperature, reacted 1-2 hour;

2) low pressure steams the monochloroethane of excessive ethanol and generation, cools, and slowly drips 2,4,6-trimethylbenzaldehyde, rises to room temperature, reacts 1-2 hour;

3) cool to 5-10 ℃, slowly drip the 20%NaOH aqueous solution and regulate pH to 1-4, add successively catalyzer, phase-transfer catalyst slowly drips oxidant hydrogen peroxide, and reaction is 10-20 hour under this temperature;

4) after gained solution is used the saturated common salt water washing, standing demix;

5) organic phase is with 10% Na₂SO₃Washing, gained solution 5%NaOH aqueous solution conditioned reaction liquid pH to 7-8, standing demix is got organic phase;

6) underpressure distillation obtains light yellow thick liquid, and namely 2,4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester;

Step 3 wherein) catalyzer is selected from one or more in tungstic anhydride, tungstate, molybdic acid anhydride, molybdate, phosphomolybdate, the Suanphosphotungstate.

2. preparation method according to claim 1 is characterized in that described organic solvent is one or more in benzene class, ester class, chloroparaffin, the nitrile.

3. preparation method according to claim 1 is characterized in that described organic solvent is a kind of in toluene, methylene dichloride, chlorobenzene, the ethylene dichloride or their mixing.

4. preparation method according to claim 1 is characterized in that step 1) dehydrated alcohol and phenylphosphonic dichloride weight ratio: 1: 1-1: 2.

5. preparation method according to claim 1 is characterized in that step 1) cooling temperature be 5-10 ℃.

6. preparation method according to claim 1 is characterized in that step 2) 2,4, the weight ratio of 6-trimethylbenzaldehyde and phenylphosphonic dichloride: 1: 1-3: 1.

7. preparation method according to claim 1 is characterized in that step 2) cooling temperature be 5-10 ℃.

8. preparation method according to claim 1 is characterized in that step 3) phase-transfer catalyst be selected from Tetrabutyl amonium bromide, tetrabutylammonium chloride, benzyltriethylammoinium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, bromination Shi six alkyl San Ding Ji Phosphonium or their mixing.

9. preparation method according to claim 1 is characterized in that step 3) hydrogen peroxide and the weight ratio of phenylphosphonic dichloride: 1: 1-2: 1.

10. preparation method according to claim 1 is characterized in that step 3) hydrogen peroxide and the weight ratio 10 of catalyzer: 1-20: 1.

11. preparation method according to claim 1 is characterized in that step 3) hydrogen peroxide and the weight ratio of phase-transfer catalyst be 50: 1-80: 1.