CN1486986A - Preparation method of monoacylphosphine oxide - Google Patents
Preparation method of monoacylphosphine oxide Download PDFInfo
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- CN1486986A CN1486986A CNA021383928A CN02138392A CN1486986A CN 1486986 A CN1486986 A CN 1486986A CN A021383928 A CNA021383928 A CN A021383928A CN 02138392 A CN02138392 A CN 02138392A CN 1486986 A CN1486986 A CN 1486986A
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Abstract
The invention discloses a preparation method of monoacyl phosphine oxide, which comprises the following steps: bimetallic bonding of organic phosphines to R1COCl reaction, RX reaction and oxidation to obtain monoacylphosphine oxide. Wherein: r is phenyl, substituted phenyl, aromatic heterocyclic radical and alkyl; r1Is phenyl, substituted phenyl, aromatic heterocyclic radical and alkyl; r2，R3Independently of one another, hydrogen, substituted alkyl, alkoxy, halogen; x is a readily leaving group including halogen, silyl, sulfonyl, sulfonate; because the invention does not use expensive Ph2PCl and PhPCl2And an expensive acid-binding agent is not used, so that the preparation cost is low; the reaction period is short, the yield of the reaction reaches about 70%, the post-treatment is simple, the purification is easy, the generation of liquid by-products is avoided, the purity of the obtained monoacylphosphine oxide is more than 99.0%, and the by-products are few.
Description
Technical field:
The present invention relates to the novel preparation method of monoacyl phosphine oxide.
Background technology:
Germany BASF AG discloses in US 4710523 with phenyl phosphonium chloride Ph
2PCl is an initial feed, gets Ph with pure condensation
2P (OR), the Benzoyl chloride that replaces with alkyl carries out A Busong-Marshall (Arbusow-Michaelies) reaction and prepares the monoacyl oxidation and see again.
Ph in above-mentioned technology
2It is bigger that PCl prepares difficulty, prepared the transformation efficiency low (being generally less than 40%) of diphenyl phosphine chloride by phenylphosphonic dichloride; Product purification difficulty is big, often has residual dichloride to exist; Preparation Ph
2PCl often need use PCl
3And POCl
3, big to the influence of environment.
In the condensation step of above-mentioned reaction, need to use a large amount of comparatively expensive acid binding agents, as N, accelerine and N, N-Diethyl Aniline.A large amount of acid binding agents use the back to reclaim difficulty, make the preparation cost of end product rise greatly.Condensation reaction gained intermediate Ph
2P (OR), need distill under the condition of high vacuum degree condition and obtain, and are also higher to the requirement of equipment so yield is often lower, and suitable difficulty is arranged when scale operation.
It is long that A Busong-Marshall often reacts reaction time, generally more than 24 hours.In this reaction system, cause the aftertreatment complexity easily.A kind of chief reason is because Ph
2Contain PhPCl among the PCl
2, cause liquid by-product to generate, and wrap up mutually with principal product, be difficult to purify.
Summary of the invention:
The invention provides with Ph
2The precursor compound PhPCl of PCl
2Method for feedstock production monoacyl phosphine oxide.This method avoids using the Ph that costs an arm and a leg
2PCl.The preparation technology who is adopted comprises following four steps, is followed successively by:
Step 1: utilize dichloride organic phosphine PhPCl
2With active metal [Me] prepared in reaction active intermediate PhP[Me]
2
Step 2: with the active intermediate PhP[Me that step 1 obtained]
2With R
1The COX effect is prepared into active intermediate PhP (COR
1) [Me] (mono-Acyl Organic Metal Phosphines is hereinafter to be referred as AOMP); Step 3: with the active intermediate PhP (COR that step 2 obtained
1) [Me] and RX prepared in reaction get the organic tertiary phosphine PhP of monoacyl (R) C (O) R
1
Step 4: the organic tertiary phosphine PhP of monoacyl (R) C (O) R that is obtained with oxygenant oxidation step 3
1Thereby, be prepared into (R) C (O) R of monoacyl phosphine oxide PhP (O)
1
Wherein: R is phenyl, substituted-phenyl, aromatic heterocyclic, alkyl;
R
1Be phenyl, substituted-phenyl, aromatic heterocyclic, alkyl;
R
2, R
3Alkyl, alkoxyl group, halogen for replacing independently of one another;
X is easy leavings group, comprises halogen, silylation, alkylsulfonyl, sulfonate group;
In the step 1 in above-mentioned process program, with PhPCl
2Prepare PhP[Me with the activity metal function]
2(being OMP), wherein the active metal can be any among basic metal, alkaline-earth metal and Al, Zn, Mg, the Sn, also can be the mixed system or the alloying substance of two or more metals wherein; Active metal and dichlorated organic phosphine PhPCl
2The ratio of amount of substance is 1: 10～10: 1, ideal ratio situation is that this ratio is 2.5: 1～6: 1 (theoretical than be 4: 1) when the monovalence of active metal, this ratio is 0.8: 1～3: 1 (theoretical than be 2: 1) when the divalence of active metal, optimum proportion situation when selecting other metal, its scope arrives between theoretical equivalence ratio * 180% at theoretical equivalence ratio * 40%; Range of reaction temperature is at-78 ℃～110 ℃, and optimal reaction temperature is-30 ℃～80 ℃; Reaction times is 0.5～24 hour, and the concrete reaction times decides on the replacement structure on the phenyl and the character of metallics; Under some certain conditions, mainly be meant under the long partially situation of reaction times, consider to add appropriate catalyst, as the biaryl cyclic cpds of the condensed-nuclei aromatics of naphthalene, anthracene or biphenyl, bisglyoxaline; This reactions steps needs good agitation condition, in order to improve dispersiveness, considers to use the whipping appts of high-shear formula; This reaction can be carried out having under solvent or the solvent-free situation, and suitable solvent comprises a kind of in benzene,toluene,xylene, sym-trimethylbenzene, tetrahydrofuran (THF), ether, the isopropyl ether, or two or more compound system wherein.
In the step 2 of above-mentioned process program, with PhP[Me]
2(being OMP) and R
1COCl prepared in reaction PhP (COR
1) [Me] (being AOMP), R
1COCl and PhP[Me]
2The ratio of amount of substance is 1: 20～20: 1, and ideal ratio is 0.8: 1～3: 1.Suitable R
1The COCl addition need guarantee farthest to obtain PhP (COR
1) [Me], avoid occurring PhP (COR simultaneously
1)
2Or guarantee the least possible amount, can successfully proceed to guarantee reaction.If R
1COCl and PhP[Me]
2When all having high reaction activity and high, consider to adopt approximate equivalent proportionlity; Its temperature of reaction is-78 ℃～120 ℃, and optimal reaction temperature is-30 ℃～80 ℃; Reaction times is 1～10 hour; This is reflected at and directly adds R in the above-mentioned reaction system
1COCl gets final product, R
1When being solid-state, COCl considers to select to add again after the suitable dissolution with solvents in batches, suitable solvent can be selected consistent with the solvent of last step reaction, also can select to be different from the solvent of step reaction, suitable solvent comprises a kind of in benzene,toluene,xylene, sym-trimethylbenzene, tetrahydrofuran (THF), ether, the isopropyl ether, or two or more compound system wherein.
In the step 3 of above-mentioned process program, with PhP (COR
1) [Me] (being AOMP) and RX prepared in reaction PhP (R) C (O) R
1, RX and PhP (COR
1) ratio of [Me] amount of substance is 1: 10～30: 1, ideal ratio is 0.8: 1～6: 1.Concrete ratio situation is decided on R group and X group characteristic.Suitably excessive RX helps the raising of reaction conversion ratio, but removes the workload of excess raw material can the augmenting response aftertreatment time.Suitable R X addition need guarantee farthest to obtain PhP (R) C (O) R
1, reduce simultaneously the workload that the aftertreatment that brings owing to RX is excessive removes as far as possible; Its temperature of reaction is-50 ℃～160 ℃, and optimal reaction temperature is-30 ℃～120 ℃; Reaction times is 2～20 hours; This is reflected at, and the direct RX of adding gets final product in the above-mentioned reaction system, when being solid-state, RX considers to select to add again after the suitable dissolution with solvents in batches, suitable solvent can be selected consistent with the solvent of last step reaction, also can select to be different from the solvent of step reaction, suitable solvent comprises a kind of in benzene,toluene,xylene, sym-trimethylbenzene, tetrahydrofuran (THF), ether, the isopropyl ether, or two or more compound system wherein.
In the step 4 in above-mentioned process program, with PhP (R) C (O) R
1The organic tertiary phosphine of monoacyl carries out oxidation and gets (R) C (O) R of monoacyl phosphine oxide PhP (O)
1Suitable oxygenant can be hydrogen peroxide, potassium permanganate, potassium bichromate, phenyl peroxy acid, pure oxygen and airborne a kind of.Reaction conditions is looked oxygenant and the oxidation system selected for use and can be decided.If selecting pure oxygen or air to carry out oxidation needs under stress to implement to guarantee that oxidizing reaction has higher transformation efficiency.Oxygenant is 1: 1～20: 1 with the ratio of organic tertiary phosphine amount of substance, and ideal ratio is 1: 1～5: 1; Temperature of reaction is 0～140 ℃, and ideal temperature of reaction is 20～100 ℃; Reaction times is 0.5～24 hour.Can consider to adopt the method or the dripping method that add to add oxygenant in batches; Under the specific situation, can consider to select necessary sequestrant or promotor can farthest be converted into the monoacyl phosphine oxide with the oxidizing reaction of the organic tertiary phosphine of bonding acyl group.
In above-mentioned process program, it is very important selecting rational ingredient proportion, PhP[Me in this reaction scheme]
2With R
1The COCl reaction, the organic tertiary phosphine of preparation monoacyl.The transformation efficiency of reaction and the charging capacity of selectivity have bigger relation.In case control badly, two acylphosphine oxide structures or trialkyl organic phosphine structure can appear, and all be disadvantageous to reaction.When crude product purity was bad, the difficulty of purification then increased accordingly, because Rf value each other is more approaching.
Compare with original technology, the present invention avoids using expensive Ph
2PCl, and use its precursor compound PhPCl instead
2, preparation cost reduces greatly; Avoided the use of expensive acid binding agent; Shorten reaction time greatly, from PhPCl
2The production cycle of preparation monoacyl phosphine oxide is about 12 hours; The yield of this reaction reaches about 70%; Aftertreatment is simple, purifies easily, has avoided the generation of liquid by-product, and the purity of gained monoacyl phosphine oxide is greater than 99.0%, and this is the index that adopts the Arbusow-Michaelies reaction to be difficult to reach.
Simultaneously because technical scheme of the present invention is with PhPCl
2Be initial feed, its preparation is simple, and it is convenient to purify, and purity is higher, guarantees that reaction has higher transformation efficiency and selectivity preferably, and byproduct is few.
The active intermediate of metal organic phosphines such as OMP, AOMP is provided in the present invention, and the synthesizing mean that its meaning is introduced as specific structure unit in technology of preparing has great importance.
In addition, operational path of the present invention can realize under the situation of " one kettle way ", need not intermediate section from, very convenient in operation.
Embodiment:
Concrete exemplifying embodiment is as follows:
Example one: in 100 liter reactors, add THF50Kg, the sodium Metal 99.5 grain (0.15kmol) of 3.45Kg chopping stirs, and drips phenyl phosphorus dichloride 6.71Kg (0.0375kmol), keeps 20 ℃ of temperature.After dropwising, stirred 3 hours, in reaction system, drip 2,4,6-tri-methyl chloride 6.85Kg (0.0375kmol).30 ℃ of controlled temperature.Stirred 3 hours, and continued in reaction system, to drip PhCl5.0Kg (0.0444kmol), restir 10 hours.Decompression removes solvent THF, excessive PhCl.Add toluene 50Kg, drip 30% hydrogen peroxide 4.5Kg (0.04kmol).Stirred 3 hours, TLC follows the tracks of, and oxidation finishes after washing, alkali cleaning, and decompression removes solvent toluene.Residue vacuum-drying gets the crude product acylphosphine oxide.Get decorating film 9.1Kg (0.026mol) with petrol ether/ethyl acetate pulp after-filtration.m.p.：90.2～92.4℃。Purity is greater than 99.0%, and yield is 70%.
Example two: in 100 liter reactors, add THF50Kg, the sodium Metal 99.5 grain (0.15kmol) of 3.45Kg chopping stirs, and drips phenyl phosphorus dichloride 6.71Kg (0.0375kmol), keeps 50 ℃ of temperature.After dropwising, stirred 3 hours, in reaction system, drip 2,4,6-tri-methyl chloride 18.3Kg (0.1kmol).40 ℃ of controlled temperature.Stirred 3 hours, and continued in reaction system, to drip PhBr11.8Kg (0.075kmol), restir 10 hours.Decompression removes solvent THF, excessive PhBr.Add toluene 50Kg, drip 30% hydrogen peroxide 4.5Kg (0.04kmol).Stirred 3 hours, TLC follows the tracks of, and oxidation finishes after washing, alkali cleaning, and decompression removes solvent toluene.Residue vacuum-drying gets the crude product acylphosphine oxide.Get decorating film 8.7Kg (0.025mol) with petrol ether/ethyl acetate pulp after-filtration.m.p.：90.2～92.4℃。Purity is greater than 99.0%, and yield is 67%.
Example three: in 100 liter reactors, add toluene 50Kg, the sodium Metal 99.5 grain (0.15kmol) of 3.45Kg chopping stirs, and drips phenyl phosphorus dichloride 6.71Kg (0.0375kmol), keeps 80 ℃ of temperature.After dropwising, stirred 3 hours, in reaction system, drip 2,4,6-tri-methyl chloride 9.1Kg (0.05kmol).80 ℃ of controlled temperature.Stirred 3 hours, and continued in reaction system, to drip PhBr11.8Kg (0.075kmol), restir 10 hours.Decompression removes partial solvent toluene, excessive PhBr.Add toluene 50Kg, drip 30% hydrogen peroxide 4.5Kg (0.04kmol).Stirred 3 hours, TLC follows the tracks of, and oxidation finishes after washing, alkali cleaning, and decompression removes solvent toluene.Residue vacuum-drying gets the crude product acylphosphine oxide.Get decorating film 8.7Kg (0.025mol) with petrol ether/ethyl acetate pulp after-filtration.m.p.：90.2～92.4℃。Purity is greater than 99.0%, and yield is 67%.
Claims (9)
1, a kind of preparation method of monoacyl phosphine oxide, its preparation technology carries out as follows:
Step 1: utilize dichloride organic phosphine PhPCl
2With active metal [Me] prepared in reaction active intermediate PhP[Me]
2
Step 2: with the active intermediate PhP[Me that step 1 obtained]
2With R
1The COX effect is prepared into active intermediate PhP (COR
1) [Me] (hereinafter to be referred as AOMP);
Step 3: with the active intermediate PhP (COR that step 2 obtained
1) [Me] and RX prepared in reaction get the organic tertiary phosphine PhP of monoacyl (R) C (O) R
1
Step 4: the organic tertiary phosphine PhP of monoacyl (R) C (O) R that is obtained with oxygenant oxidation step 3
1Thereby, be prepared into (R) C (O) R of monoacyl phosphine oxide PhP (O)
1
Wherein: R is phenyl, substituted-phenyl, aromatic heterocyclic, alkyl;
R
1Be phenyl, substituted-phenyl, aromatic heterocyclic, alkyl;
R
2, R
3Alkyl, alkoxyl group, halogen for replacing independently of one another;
X is easy leavings group, comprises halogen, silylation, alkylsulfonyl, sulfonate group;
In step 1, described active metal [Me] is any among basic metal, alkaline-earth metal and Al, Zn, Mg, the Sn, also can be the mixed system or the alloying substance of two or more metals wherein, described active metal and dichloride organic phosphine PhPCl
2The ratio of amount of substance is 1: 10～10: 1, and temperature of reaction is-78 ℃～110 ℃, and the reaction times is 0.5 hour～24 hours;
In step 2, R
1COCl and PhP[Me]
2The ratio of amount of substance is 1: 20～20: 1, and its temperature of reaction is-78 ℃～120 ℃, and the reaction times is 1 hour～10 hours;
In step 3, RX and PhP (COR
1) ratio of [Me] amount of substance is 1: 10～30: 1, its temperature of reaction is-50 ℃～160 ℃, the reaction times is 2 hours～20 hours;
In step 4, described oxygenant is any of hydrogen peroxide, potassium permanganate, potassium bichromate, phenyl peroxy acid, pure oxygen and air, oxygenant is 1: 1～20: 1 with the ratio of organic tertiary phosphine amount of substance, and temperature of reaction is 20 ℃～140 ℃, and the reaction times is 0.5 hour～24 hours.
2, according to the preparation method of the described monoacyl phosphine oxide of claim 1, it is characterized in that: in step 1, described active metal and dichloride organic phosphine PhPCl
2The ratio of amount of substance is: when the active metal is monovalence, this ratio is 2.5: 1～6: 1, and when the active metal was divalence, this ratio was 0.8: 1～3: 1, when the active metal was other metal, this ratio was that theoretical equivalence ratio * 40% is to theoretical equivalence ratio * 180%; Temperature of reaction is-30 ℃～80 ℃.
3, according to the preparation method of the described monoacyl phosphine oxide of claim 1, it is characterized in that: in step 2, R
1COCl and PhP[Me]
2Amount of substance is 0.8: 1～3: 1; Temperature of reaction is-30 ℃～80 ℃; Reaction times was at 1 hour～10 hours.
4, according to the preparation method of the described monoacyl phosphine oxide of claim 1, it is characterized in that: in step 3, RX and PhP (COR
1) ratio of [Me] amount of substance is 0.8: 1～6: 1; Temperature of reaction is-30 ℃～120 ℃; Reaction times was at 2 hours～20 hours.
5, according to the preparation method of the described monoacyl phosphine oxide of claim 1, it is characterized in that: in step 4, oxygenant is 1: 1～5: 1 with the ratio of organic tertiary phosphine amount of substance; Temperature of reaction is 20 ℃～100 ℃; Reaction times is 0.5 hour～24 hours.
6, according to the preparation method of the arbitrary described monoacyl phosphine oxide of claim 1 to 5; it is characterized in that: carry out under the situation that is reflected at solvent of each step; suitable solvent is any in benzene,toluene,xylene, sym-trimethylbenzene, tetrahydrofuran (THF), ether, the isopropyl ether, or two or more compound system wherein.
7, according to the preparation method of the arbitrary described monoacyl phosphine oxide of claim 1 to 5, it is characterized in that: in step 1, any catalyzer in the biaryl cyclic cpds of the condensed-nuclei aromatics of adding naphthalene, anthracene or biphenyl, bisglyoxaline improves speed of response; Use the dispersiveness of the whipping appts raising system of high-shear formula.
8, according to the preparation method of the described monoacyl phosphine oxide of claim 6, it is characterized in that: in step 1, any catalyzer in the biaryl cyclic cpds of the condensed-nuclei aromatics of adding naphthalene, anthracene or biphenyl, bisglyoxaline improves speed of response; Use the dispersiveness of the whipping appts raising system of high-shear formula.
9, according to the preparation method of the arbitrary described monoacyl phosphine oxide of claim 1 to 5, it is characterized in that: above-mentioned process program realizes under the situation of " one kettle way ", need not intermediate section from.
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|---|---|---|---|
| CNA021383928A CN1486986A (en) | 2002-10-03 | 2002-10-03 | Preparation method of monoacylphosphine oxide |
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|---|---|---|---|
| CNA021383928A CN1486986A (en) | 2002-10-03 | 2002-10-03 | Preparation method of monoacylphosphine oxide |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7439401B2 (en) * | 2003-07-18 | 2008-10-21 | Ciba Specialty Chemicals Corporation | Process for preparing acylphosphanes and derivatives thereof |
| CN101830931A (en) * | 2010-04-01 | 2010-09-15 | 天津久日化学工业有限公司 | Preparation method of 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and derivative thereof |
| CN104592298A (en) * | 2014-12-31 | 2015-05-06 | 湖北固润科技股份有限公司 | Acylphosphine efficient photoinitiator and preparation method thereof |
| CN105884809A (en) * | 2015-01-14 | 2016-08-24 | 郑成 | Preparing method for acyl phosphate (oxide) or sulfonyl phosphate (oxide) compound |
| CN105884824A (en) * | 2014-10-16 | 2016-08-24 | 郑成 | Preparation method of acyl phosphine (oxygen) or sulfonyl phosphine (oxygen) compounds |
| JP2018165249A (en) * | 2017-03-28 | 2018-10-25 | 国立大学法人千葉大学 | Production method of acyl phosphine |
| CN112175005A (en) * | 2020-10-29 | 2021-01-05 | 天津久日新材料股份有限公司 | Application of activator in reduction reaction of phenyl phosphine dichloride |
| WO2022088569A1 (en) * | 2020-10-29 | 2022-05-05 | 天津久日新材料股份有限公司 | Preparation method for bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide |
-
2002
- 2002-10-03 CN CNA021383928A patent/CN1486986A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7439401B2 (en) * | 2003-07-18 | 2008-10-21 | Ciba Specialty Chemicals Corporation | Process for preparing acylphosphanes and derivatives thereof |
| CN101830931A (en) * | 2010-04-01 | 2010-09-15 | 天津久日化学工业有限公司 | Preparation method of 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and derivative thereof |
| CN105884824A (en) * | 2014-10-16 | 2016-08-24 | 郑成 | Preparation method of acyl phosphine (oxygen) or sulfonyl phosphine (oxygen) compounds |
| CN104592298A (en) * | 2014-12-31 | 2015-05-06 | 湖北固润科技股份有限公司 | Acylphosphine efficient photoinitiator and preparation method thereof |
| CN105884809A (en) * | 2015-01-14 | 2016-08-24 | 郑成 | Preparing method for acyl phosphate (oxide) or sulfonyl phosphate (oxide) compound |
| JP2018165249A (en) * | 2017-03-28 | 2018-10-25 | 国立大学法人千葉大学 | Production method of acyl phosphine |
| CN112175005A (en) * | 2020-10-29 | 2021-01-05 | 天津久日新材料股份有限公司 | Application of activator in reduction reaction of phenyl phosphine dichloride |
| WO2022088569A1 (en) * | 2020-10-29 | 2022-05-05 | 天津久日新材料股份有限公司 | Preparation method for bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide |
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