CN1159322C - Preparation method of compound triphenyl phosphine - Google Patents
Preparation method of compound triphenyl phosphine Download PDFInfo
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- CN1159322C CN1159322C CNB011032774A CN01103277A CN1159322C CN 1159322 C CN1159322 C CN 1159322C CN B011032774 A CNB011032774 A CN B011032774A CN 01103277 A CN01103277 A CN 01103277A CN 1159322 C CN1159322 C CN 1159322C
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- chlorobenzene
- alkylbenzene
- triphenylphosphine
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Abstract
The present invention discloses a method for using metal sodium, chlorobenzene and phosphorus trichloride to react for preparing compound triphenylphosphine. In the method, under the protection of gas with inactive chemical properties, metal sodium is dispersed in organic solvents; under the condition of stirring, a small amount of chlorobenzene is added, and initiating agents in proper quantity are dropped; then, the mixed solution of chlorobenzene, phosphorus trichloride and organic solvents prepared according to reacting weight are slowly dropped; triphenylphosphine products are obtained by reactants through water washing, distillation, decolorization, etc. The method has the advantages of stable reaction, easy control, little material consumption, less side reaction, high yield and high purity of products.
Description
The present invention relates to a kind of preparation method of compound triphenyl phosphine, mainly relate to a kind of method with sodium Metal 99.5, chlorobenzene and phosphorus trichloride prepared in reaction compound triphenyl phosphine.
The method that is equipped with triphenylphosphine with the sodium legal system, mainly contain two kinds at present, a kind of is step synthesis, it is under 20-30 ℃, earlier chlorobenzene and sodium Metal 99.5 reaction is made sodium phenide, adds the reaction of phosphorus trichloride and sodium phenide then and produces triphenylphosphine, this method reactions steps complexity, reaction mechanism is long, and side reaction is many, and the product yield is low.Another kind method is a German Patent Ger.offen1618116 disclosed method, it is to splash into chlorobenzene and phosphorus trichloride and sodium Metal 99.5 reaction simultaneously to produce triphenylphosphine under 50-60 ℃, though this method is simple, but the chlorobenzene of initiation reaction and the amount of phosphorus trichloride are difficult to grasp, and add-on is few, cause overlong time, how add-on makes reaction too violent again, the system temperature sudden change is difficult to control, also can cause the accident sometimes.More than two kinds of prior aries because sodium disperses badly, easily cause level of response little, material consumption is big, defect of high cost.
The object of the present invention is to provide a kind of technical process simple, reasonable, material consumption is low, and reaction is easy to control, and yield is big, the preparation method of the triphenylphosphine that product purity is high.
For achieving the above object, the preparation method of triphenylphosphine of the present invention is: under the protection of chemical property inactive gas, sodium Metal 99.5 is joined in the organic solvent, be warming up to 98-110 ℃, under high-speed stirring, make sodium Metal 99.5 be dispersed into particulate; When being cooled to 40-60 ℃, under condition of stirring, adding and drip an amount of initiator behind a spot of chlorobenzene; This initiator is phenols, haloalkane or Fatty Alcohol(C12-C14 and C12-C18), to be triggered finish temperature steadily after, in 40-60 ℃ scope, slowly drip the mixing solutions of press chlorobenzene, phosphorus trichloride and organic solvent that reacting weight prepares, after dropwising, continue to be stirred to and react completely; Reactant gets the triphenylphosphine crude product after washing, distillation, crude product gets the triphenylphosphine product behind decolorizing and refining.
The said chemical property inactive gas of the present invention is meant: helium, neon, argon, krypton, xenon rare gas element, nitrogen.Preferred nitrogen wherein.
Organic solvent of the present invention is meant not and sodium Metal 99.5, chlorobenzene, phosphorus trichloride generation chemical reaction and solubilized triphenylphosphine, the organic solvent of boiling point more than the sodium Metal 99.5 fusing point.Mainly be meant alkylbenzene, alkane and composition thereof etc., or dimethyl formamide, wherein preferred C
1-C
6Alkylbenzene, especially preferred C
1-C
4Alkylbenzene, toluene most preferably.
Initiator of the present invention is meant phenols, haloalkane or Fatty Alcohol(C12-C14 and C12-C18), and wherein phenols is meant phenol, naphthols or alkylphenol, and haloalkane is meant the haloalkane of fluorine, chlorine, bromine, iodine, wherein preferred C
1-C
6Haloalkane, Fatty Alcohol(C12-C14 and C12-C18) mainly is meant C
1-C
8Fatty Alcohol(C12-C14 and C12-C18), wherein preferred C
1-C
5Fatty Alcohol(C12-C14 and C12-C18).
Owing to adopted at first in the technique scheme and in organic solvent, sodium Metal 99.5 be dispersed into particulate, and then with the method for reactant reaction, so preparation method's reacting balance of triphenylphosphine of the present invention, be easy to control, material consumption is little, side reaction is few, and product yield can reach 97% through last, and refining back product can reach more than 99.5% through Hewlett-Packard's 5890 type gas chromatograph purity assay.
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment one
60ml toluene is added in the 500ml flask with four necks,round bottom, under nitrogen protection, add the 25g sodium Metal 99.5, be warming up to 103 ℃, under high-speed stirring, sodium Metal 99.5 is dispersed into particulate; Be cooled to 100 ℃, stop to stir, be chilled to 45 ℃, under condition of stirring, after adding the 7.5g chlorobenzene, drip 0.6g ethanol and make initiator, to be triggered finish temperature steadily after, keep in 45 ± 2 ℃ of scopes, slow Dropwise 5 7.5g chlorobenzene in 1.5 hours, the mixing solutions of 24.8g phosphorus trichloride and 150ml toluene is after dropwising, continue to react 1.5 hours to reacting completely, stop to stir; System adds the 1000ml water dissolution after being cooled to room temperature, leaves standstill, and isolates water layer and organic layer, water layer after filtration, distillation, crystallization, industrial sodium-chlor 48.4g; Organic layer reclaims toluene and chlorobenzene through distillation, underpressure distillation, and gets triphenylphosphine crude product 46.9g; The crude product triphenylphosphine is put into the 500ml there-necked flask, add 200ml dehydrated alcohol and 5g gac, under condition of stirring, refluxed 1 hour, after filtration, cooling, stirring, crystallization get elaboration 45.9g, productive rate 97.1%.Analyze content 99.7% through Hewlett-Packard's 5890 type gas chromatographs.
Embodiment two
80ml N.N-dimethyl formamide is added in the 500ml flask with four necks,round bottom, under nitrogen protection, add the 20g sodium Metal 99.5, be warming up to 110 ℃, under high-speed stirring, sodium Metal 99.5 is dispersed into particulate; Be cooled to 95 ℃, stop to stir, be chilled to 55 ℃, under condition of stirring, after adding the 13g chlorobenzene, drip the 1.5g Pentyl alcohol and make initiator, to be triggered finish temperature steadily after, keep in 50 ± 2 ℃ of scopes, slowly dripped the 37g chlorobenzene in 2 hours, the mixing solutions of 19g phosphorus trichloride and 120ml N.N-dimethyl formamide is after dropwising, continue to react 1 hour to reacting completely, stop to stir; System adds the 900ml water dissolution after being cooled to room temperature, leaves standstill, and isolates water layer and organic layer, water layer after filtration, distillation, crystallization, industrial sodium-chlor 32.8g; Organic layer reclaims N.N-dimethyl formamide and chlorobenzene through distillation, underpressure distillation, and gets triphenylphosphine crude product 35.8g; The crude product triphenylphosphine is put into the 500ml there-necked flask, add 200ml dehydrated alcohol and 4.5g gac, under condition of stirring, refluxed 0.5 hour, after filtration, cooling, stirring, crystallization get elaboration 35.2g, productive rate 97.2%.Analyze content 99.6% through Hewlett-Packard's 5890 type gas chromatographs.
Embodiment three
80ml kerosene is added in the 500ml flask with four necks,round bottom, under nitrogen protection, add the 16g sodium Metal 99.5, be warming up to 98 ℃, under high-speed stirring, sodium Metal 99.5 is dispersed into particulate; Be cooled to 90 ℃, stop to stir, be cooled to 60 ℃, under condition of stirring, after adding the 12g chlorobenzene, drip the 1.8g octanol and make initiator, to be triggered finish temperature steadily after, keep in 60 ± 2 ℃ of scopes, slowly dripped the 28g chlorobenzene in 5 hours, the mixing solutions of 16g phosphorus trichloride and 120ml kerosene is after dropwising, continue to react 1.5 hours to reacting completely, stop to stir; System adds the 900ml water dissolution after being cooled to room temperature, leaves standstill, and isolates water layer and organic layer, water layer after filtration, distillation, crystallization, industrial sodium-chlor 30.8g; Organic layer reclaims kerosene and chlorobenzene through distillation, underpressure distillation, and gets triphenylphosphine crude product 28.1g; The crude product triphenylphosphine is put into the 500ml there-necked flask, add 200ml dehydrated alcohol and 1.6g gac, under condition of stirring, refluxed 2 hours, after filtration, cooling, stirring, crystallization get elaboration 27.8g, productive rate 97.6%.Analyze content 99.5% through Hewlett-Packard's 5890 type gas chromatographs.
Embodiment four
80ml dimethylbenzene is added in the 500ml flask with four necks,round bottom, under argon shield, add the 25g sodium Metal 99.5, be warming up to 105 ℃, under high-speed stirring, sodium Metal 99.5 is dispersed into particulate; Be cooled to 90 ℃, stop to stir, be cooled to 40 ℃, under condition of stirring, after adding the 3.2g chlorobenzene, drip 1.6g phenol and make initiator, to be triggered finish temperature steadily after, keep in 40 ± 2 ℃ of scopes, slow Dropwise 5 9.8g chlorobenzene in 1 hour, the mixing solutions of 24.9g phosphorus trichloride and 120ml dimethylbenzene is after dropwising, continue to react 1 hour to reacting completely, stop to stir; System adds the 1000ml water dissolution after being cooled to room temperature, leaves standstill, and isolates water layer and organic layer, water layer after filtration, distillation, crystallization, industrial sodium-chlor 47.8g; Organic layer reclaims dimethylbenzene and chlorobenzene through distillation, underpressure distillation, and gets triphenylphosphine crude product 47.0g; The crude product triphenylphosphine is put into the 500ml there-necked flask, add 160ml dehydrated alcohol and 6g gac, under condition of stirring, refluxed 1 hour, after filtration, cooling, stirring, crystallization get elaboration 46.0g, productive rate 97%.Analyze content 99.6% through Hewlett-Packard's 5890 type gas chromatographs.
Embodiment five
80ml ethylbenzene is added in the 500ml flask with four necks,round bottom, under argon shield, add the 20g sodium Metal 99.5, be warming up to 108 ℃, under high-speed stirring, sodium Metal 99.5 is dispersed into particulate; Be cooled to 95 ℃, stop to stir, be cooled to 45 ℃ of C, under condition of stirring, after adding the 5g chlorobenzene, drip 1g monochloroethane and make initiator, to be triggered finish temperature steadily after, keep in 45 ± 2 ℃ of scopes, slowly dripped the 45g chlorobenzene in 2 hours, the mixing solutions of 19g phosphorus trichloride and 140ml ethylbenzene is after dropwising, continue to react 2 hours to reacting completely, stop to stir; System adds the 800ml water dissolution after being cooled to room temperature, leaves standstill, and isolates water layer and organic layer, water layer after filtration, distillation, crystallization, industrial sodium-chlor 31.4g; Organic layer reclaims ethylbenzene and chlorobenzene through distillation, underpressure distillation, and gets triphenylphosphine crude product 35.5g; The crude product triphenylphosphine is put into the 500ml there-necked flask, add 160ml dehydrated alcohol and 5g gac, under condition of stirring, refluxed 0.5 hour, after filtration, cooling, stirring, crystallization get elaboration 35.1g, productive rate 97%.Analyze content 99.5% through Hewlett-Packard's 5890 type gas chromatographs.
Embodiment six
The own benzene of 80ml is added in the 500ml flask with four necks,round bottom, under the helium protection, add the 23g sodium Metal 99.5, be warming up to 100 ℃, under high-speed stirring, sodium Metal 99.5 is dispersed into particulate; Be cooled to 95 ℃, stop to stir, be cooled to 50 ℃, under condition of stirring, after adding the 8.7g chlorobenzene, drip the 1.8g n-butyl bromide and make initiator, to be triggered finish temperature steadily after, keep in 50 ± 2 ℃ of scopes, slowly dripped the 49.3g chlorobenzene in 3 hours, the mixing solutions of 22.8g phosphorus trichloride and the own benzene of 140ml is after dropwising, continue to react 1.5 hours to reacting completely, stop to stir; System adds the 900ml water dissolution after being cooled to room temperature, leaves standstill, and isolates water layer and organic layer, water layer after filtration, distillation, crystallization, industrial sodium-chlor 40.5g; Organic layer reclaims own benzene and chlorobenzene through distillation, underpressure distillation, and gets triphenylphosphine crude product 43.0g; The crude product triphenylphosphine is put into the 500ml there-necked flask, add 160ml dehydrated alcohol and 4.5g gac, under condition of stirring, refluxed 1 hour, after filtration, cooling, stirring, crystallization get elaboration 42.2g, productive rate 97.1%.Analyze content 99.7% through Hewlett-Packard's 5890 type gas chromatographs.
Claims (10)
1, a kind of preparation method of compound triphenyl phosphine, it comprises the following steps: successively
(a) under the protection of chemical property inactive gas, sodium Metal 99.5 is joined in the organic solvent, be warming up to 98-110 ℃, under high-speed stirring, make sodium Metal 99.5 be dispersed into particulate;
When (b) being cooled to 40-60 ℃, under condition of stirring, adding and drip an amount of initiator behind a spot of chlorobenzene, this initiator is phenols, haloalkane or Fatty Alcohol(C12-C14 and C12-C18);
(c) to be triggered finish temperature steadily after, in 40-60 ℃ of scope, slowly drip the mixing solutions of press chlorobenzene, phosphorus trichloride and organic solvent that reacting weight prepares, after dropwising, continue to be stirred to and react completely;
(d) reactant gets the triphenylphosphine crude product after washing, distillation, and crude product gets the product triphenylphosphine behind decolorizing and refining.
2, preparation method according to claim 1, wherein the chemical property inactive gas is a nitrogen.
3, preparation method according to claim 1, wherein organic solvent is alkylbenzene or alkane and composition thereof.
4, preparation method according to claim 3, wherein alkylbenzene is C
1-C
6Alkylbenzene.
5, preparation method according to claim 3, wherein alkylbenzene is C
1-C
4Alkylbenzene.
6, preparation method according to claim 3, wherein alkylbenzene is a toluene.
7, preparation method according to claim 1, wherein initiator is a phenols.
8, preparation method according to claim 1, wherein initiator is C
1-C
6Haloalkane.
9, preparation method according to claim 1, wherein initiator is C
1-C
8Fatty Alcohol(C12-C14 and C12-C18).
10, preparation method according to claim 9, wherein Fatty Alcohol(C12-C14 and C12-C18) is C
1-C
5Fatty Alcohol(C12-C14 and C12-C18).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011032774A CN1159322C (en) | 2001-01-20 | 2001-01-20 | Preparation method of compound triphenyl phosphine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011032774A CN1159322C (en) | 2001-01-20 | 2001-01-20 | Preparation method of compound triphenyl phosphine |
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| CN1367175A CN1367175A (en) | 2002-09-04 |
| CN1159322C true CN1159322C (en) | 2004-07-28 |
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| CNB011032774A Expired - Fee Related CN1159322C (en) | 2001-01-20 | 2001-01-20 | Preparation method of compound triphenyl phosphine |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210031B (en) * | 2006-12-29 | 2010-10-13 | 中国石油大学(北京) | Method for producing triphenylphosphine |
| CN101270132B (en) * | 2007-11-08 | 2010-11-03 | 陈国君 | Method for preparing triphenylphosphine with diphenylbenzene phosphine oxide |
| CN109970789B (en) * | 2019-04-25 | 2021-05-07 | 大连理工大学 | Preparation method of triarylphosphine compound |
| CN113912645B (en) * | 2021-11-09 | 2022-10-14 | 湖南经世新材料有限责任公司 | Preparation method of triphenylphosphine |
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