CN102731570A - Synthesis process of triphenyl alkoxyl phosphine salt - Google Patents
Synthesis process of triphenyl alkoxyl phosphine salt Download PDFInfo
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- CN102731570A CN102731570A CN2012102370540A CN201210237054A CN102731570A CN 102731570 A CN102731570 A CN 102731570A CN 2012102370540 A CN2012102370540 A CN 2012102370540A CN 201210237054 A CN201210237054 A CN 201210237054A CN 102731570 A CN102731570 A CN 102731570A
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Abstract
The invention relates to a synthesis process of triphenyl alkoxyl phosphine salt, which comprises the following steps that: triphenyl phosphine oxide is dissolved in an organic solvent at the room temperature; an epoxy compound is added in the solution and mixed uniformly; Lewis acid is dripped into the solution slowly; the temperature of the reaction system is kept at 10-20 DEG C; the solution is then mixed for 10-50min; and after the reaction, excess precipitant is added in the obtained solution to perform precipitation separation to obtain the triphenyl alkoxyl phosphine salt. Compared with the prior art, the synthesis process has the following technical effects that the triphenyl alkoxyl phosphine salt prepared by the method is white; the preparation process is simple; the reaction conditions are mild; the temperature is not higher than 20 DEG C; the reaction time is shorter, and the reaction is carried out for no more than 50min; the yield of the reaction products is up to 98%; the products have good stability, for example, the reaction activity is not changed after the products are stored for 6 months. The triphenyl alkoxyl phosphine salt can be taken as an intermediate for organic synthesis to obtain various organic products.
Description
Technical field
The present invention relates to a kind of synthesis technique of triphenyl alkoxyl group phosphonium salt.
Background technology
In many reactions of organophosphorus chemistry, the alkoxyl group phosphonium salt is one type of important reaction intermediate.The general preparation method of alkoxyl group phosphonium salt activates trialkyl phosphine with electrophilic reagent, and produces the phosphine ion midbody of hyperergy.In the Appel reaction, activate triphenylphosphine with halogenic molecule or carbon tetrahalide, form halogenation triphenylphosphine ion, then reaction forms corresponding alkyl halide through acyloxy phosphine ion midbody with alcohol.Mukaiyama and its colleague use triphenylphosphine and two (2-pyridine) disulfonic acid reagent from carboxylic acid, to obtain alkoxyl group phosphine ion midbody.In the Mitsunobu reaction, triphenylphosphine is activated by the azoethane dicarboxylic ester, in the middle of alcohol formation alkoxyl group phosphine ion.Robinson forms the diethoxy triphenylphosphine with the reaction of ethyl peroxide and triphenylphosphine, and this midbody quickens glycol in the neutral medium again and more leniently changes into cyclic ethers.Fr yen and juvvik [9] handle triphenylphosphine and N-bromosuccinic acid in the presence of low temperature and alcohol, can make primary alconol and primary amine or secondary amine be converted into secondary amine or tertiary amine.Taniguchi finds that under the iron phthalein mountain valley with clumps of trees and bamboo complex catalysis triphenylphosphine can be activated by air and form acyloxy triphenylphosphine ion midbody, and it can make the esterification of alcohol and carboxylic acid quicken.In these reactions, because midbody triphenylphosphine ionic reactive behavior is big, general triphenylphosphine ion has not been isolated, and directly descends step prepared in reaction product.
Another method of preparation alkoxyl group phosphine ionic is with trialkyl phosphine and cationoid reaction, produces alkoxyalkyl phosphine ion midbody.Finley has studied the synthetic and reaction with several kinds of four stable alkoxyl group phosphine ionic of triethyl phosphate and triethyl oxygen Tetrafluoroboric acid or trimethyl phosphate and trimethylammonium oxygen Tetrafluoroboric acid prepared in reaction.DeBruin is with 1-phenyl-2,2,3,4,4-pentamethyl-phosphine oxide and triethyl oxygen six antimony chloride prepared in reaction stable
Cis-And trans-1-oxyethyl group-1-phenyl-2,2,3,4,4-pentamethyl-phosphine six antimony chlorides.In these methods, because of cationic kind and stability reasons, it does not have actual value on synthetic, generally be used for the research to the stability and the performance of alkoxyl group phosphonium salt.
Summary of the invention
Technical problem to be solved by this invention is the synthesis technique that proposes a kind of triphenyl alkoxyl group phosphonium salt to above-mentioned prior art, and it obtains stable triphenyl alkoxyl group phosphonium salt, and it is constant to store six months reactive behavioies.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the synthesis technique of triphenyl alkoxyl group phosphonium salt, it is characterized in that at room temperature triphenylphosphine oxide being dissolved in the organic solvent, and add epoxy compounds; After stirring, slowly drip Lewis acid, 10～20 ℃ of the temperature of maintenance system; Restir 10～50 minutes; Reaction adds excessive precipitator after accomplishing in gained solution, precipitate and separate promptly gets triphenyl alkoxyl group phosphonium salt.
Press such scheme, described triphenyl alkoxyl group phosphonium salt has the general structure that formula I is represented:
Wherein, R is H, alkyl, substituted alkyl, phenyl or substituted phenyl in the formula, and MXn is BF
3, SnCl
4, AlCl
3Or ZnCl
2
Press such scheme, described epoxy compounds is oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, epoxy styrene, epoxy iso-butylene, oxirane ring hexene, monocycle oxygen butylene or bis-epoxy butylene.
Press such scheme, described organic solvent is 1,2-ethylene dichloride, trichloromethane, methylene dichloride or pimelinketone.
Press such scheme, described precipitation agent is benzene, toluene, ether, sherwood oil, ETHYLE ACETATE, hexanaphthene or normal hexane.
Press such scheme, described Lewis acid is boron trifluoride, anhydrous stannic chloride, aluminum trichloride (anhydrous) or Zinc Chloride Anhydrous.
Press such scheme, the time of described reaction is 15～35 minutes.
Press such scheme, the churning time of described precipitate and separate is 5～30 minutes.
The reaction formula of institute of the present invention synthetic triphenyl alkoxyl group phosphine is following:
In this reaction, the Lewis acid of dropping is at first closed with the oxo of epoxy compounds, and triphenylphosphine oxide impels epoxy bond fracture and open loop obtains title product.
Compared with present technology, the technique effect that reached of the present invention:
Triphenyl alkoxyl group phosphonium salt through method of the present invention preparation be white, and the preparation process is simple, and is that feedstock production triphenyl alkoxyl group phosphine ion midbody is compared with the triphenylphosphine; The present invention is the triphenyl alkoxyl group phosphine ion of feedstock production with the triphenylphosphine oxide, and reaction conditions is gentle, and its temperature is no more than 20 ℃; Reaction times is shorter; Reaction is no more than 50 minutes, and the reaction product productive rate is high, up to 98%.Product stability is good, and it stores 6 months, and reactive behavior is constant.With with cationoid reactions such as triphenylphosphine oxide and methyl, ethyls; Producing alkoxyalkyl phosphine ion midbody compares; The present invention is of a great variety because of epoxy compounds of the triphenyl alkoxyl group phosphine ion of feedstock production with epoxy compounds and Lewis acid; As the midbody of organic synthesis, can obtain miscellaneous organic product, for example the terminal hydroxy group Hydrin.
Embodiment
For a better understanding of the present invention, further illustrate content of the present invention, but content of the present invention not only is confined to following embodiment below in conjunction with embodiment.
Embodiment 1
In the there-necked flask of stirrer is housed, add the 20ml chloroform successively, the 0.02mol triphenylphosphine oxide makes its dissolving, adds the 0.02mol epoxy chloropropane then; Keep solution temperature at 15～20 ℃, under agitation drip the 0.02mol boron trifluoride, drip the back restir after 30 minutes; Add sherwood oil, fully stir 20 minutes after, filter; Isolate product 2-chloromethyl, 2-oxyethyl group boron trifluoride triphenylphosphine oxide, productive rate 98%.
Application implementation example 2
, the there-necked flask of stirrer adds 1 successively in being housed; The 2-ethylene dichloride, embodiment 1 gained initiator product 2-chloromethyl, 2-oxyethyl group boron trifluoride triphenylphosphine oxide; Stir down at 0 ℃; Add catalyzer boron trifluoride (it is 1:1 with the initiator ratio), and slowly add epoxy chloropropane, keep 0 ℃ of reaction 24 hours with constant pressure funnel.The alcoholic solution that adds 10ml terminator KOH (10%) then finishes reaction.Use the deionized water wash crude product, the product after will washing then reduces pressure down to take out at 60 ℃ with Rotary Evaporators and desolvates and the small molecules volatile matter, obtains water white transparency terminal hydroxy group Hydrin thick liquid, productive rate 85%.
Embodiment 3
, the there-necked flask of stirrer adds 20ml1 in being housed successively, the 2-ethylene dichloride, and the 0.02mol triphenylphosphine oxide makes its dissolving; Add the 0.02mol propylene oxide then, keep solution temperature, under agitation drip the 0.02mol boron trifluoride, drip the back restir after 20 minutes at 15～20 ℃; Add ether, fully stir 10 minutes after, filter; Isolate product 1-methyl, 2-oxyethyl group boron trifluoride triphenylphosphine oxide, productive rate 99%.
Embodiment 4
In the there-necked flask of stirrer is housed, add the 20ml methylene dichloride successively, the 0.02mol triphenylphosphine oxide makes its dissolving, adds the 0.02mol epoxy styrene then; Keep solution temperature under 15～20 ℃, under agitation drip the 0.02mol boron trifluoride, drip the back restir after 30 minutes; Add sherwood oil, fully stir 20 minutes after, filter; Isolate product 1-phenyl, 2-oxyethyl group boron trifluoride triphenylphosphine oxide, productive rate 97%.
Embodiment 5
, the there-necked flask of stirrer adds 20ml1 in being housed successively, the 2-ethylene dichloride, and the 0.02mol triphenylphosphine oxide makes its dissolving; Add 0.02mol oxirane ring hexene then, keep solution temperature under 15～20 ℃, under agitation drip the 0.02mol anhydrous stannic chloride; Drip back restir after 30 minutes, add benzene, fully stir 20 minutes after; Filter, isolate product tetrahydrobenzene oxygen base tin tetrachloride triphenylphosphine oxide, productive rate 95%.
Embodiment 6
, the there-necked flask of stirrer adds 20ml1 in being housed successively, the 2-ethylene dichloride, and the 0.02mol triphenylphosphine oxide makes its dissolving; Add the 0.02mol epoxy styrene then, keep solution temperature under 15～20 ℃, under agitation drip the 0.02mol anhydrous stannic chloride, drip the back restir after 30 minutes; Add hexanaphthene, fully stir 20 minutes after, filter; Isolate product 1-phenyl, 2-oxyethyl group tin tetrachloride triphenylphosphine oxide, productive rate 96%.
Embodiment 7
In the there-necked flask of stirrer is housed, add the 20ml methylene dichloride successively, the 0.02mol triphenylphosphine oxide makes its dissolving; Add 0.02mol monocycle oxygen butylene then, keep solution temperature, under agitation drip the 0.02mol boron trifluoride at 15～20 times; Drip back restir after 30 minutes, add toluene, fully stir 20 minutes after; Filter, isolate product 1-vinyl-2-oxyethyl group boron trifluoride triphenylphosphine oxide, productive rate 97%.
Embodiment 8
In the there-necked flask of stirrer is housed, add the 30ml pimelinketone successively, the 0.02mol triphenylphosphine oxide makes its dissolving, adds the 0.02mol epoxy chloropropane then; Keep solution temperature under 15～20 ℃, under agitation drip the second cyanogen solution of 0.02mol aluminum trichloride (anhydrous), drip the back restir after 30 minutes; Add ether, fully stir 20 minutes after, filter; Isolate product 2-chloromethyl, 2-oxyethyl group aluminum chloride triphenylphosphine oxide, productive rate 95%.
Embodiment 9
, the there-necked flask of stirrer adds 20ml1 in being housed successively, the 2-ethylene dichloride, and the 0.02mol triphenylphosphine oxide makes its dissolving; Add the 0.02mol propylene oxide then, keep solution temperature under 15～20 ℃, under agitation drip the second cyanogen solution of 0.02mol aluminum trichloride (anhydrous), drip the back restir after 30 minutes; Add sherwood oil, fully stir 20 minutes after, filter; Isolate product 1-methyl, 2-oxyethyl group aluminum chloride triphenylphosphine oxide, productive rate 96%.
Embodiment 10
In the there-necked flask of stirrer is housed, add the 20ml methylene dichloride successively, the 0.02mol triphenylphosphine oxide makes its dissolving, adds the 0.02mol epoxy chloropropane then; Keep solution temperature under 15～20 ℃, under agitation drip the second cyanogen solution of 0.02mol Zinc Chloride Anhydrous, drip the back restir after 30 minutes; Add toluene, fully stir 20 minutes after, filter; Isolate product 2-chloromethyl, 2-oxyethyl group zinc chloride triphenylphosphine oxide, productive rate 96%.
Embodiment 11
In the there-necked flask of stirrer is housed, add the 20ml chloroform successively, the 0.02mol triphenylphosphine oxide makes its dissolving, adds the 0.02mol propylene oxide then; Keep solution temperature under 15～20 ℃, under agitation drip the second cyanogen solution of 0.02mol Zinc Chloride Anhydrous, drip the back restir after 30 minutes; Add benzene, fully stir 20 minutes after, filter; Isolate product 1-methyl, 2-oxyethyl group boron trifluoride triphenylphosphine oxide, productive rate 95%.
Claims (8)
1. the synthesis technique of triphenyl alkoxyl group phosphonium salt is characterized in that at room temperature triphenylphosphine oxide being dissolved in the organic solvent, adds epoxy compounds; After stirring, slowly drip Lewis acid, 10～20 ℃ of the temperature of maintenance system; Restir 10～50 minutes; Reaction adds excessive precipitator after accomplishing in gained solution, precipitate and separate promptly gets triphenyl alkoxyl group phosphonium salt.
2. by the synthesis technique of the described triphenyl alkoxyl group of claim 1 phosphonium salt, it is characterized in that described triphenyl alkoxyl group phosphonium salt, have the general structure that formula I is represented:
Wherein, R is H, alkyl, substituted alkyl, phenyl or substituted phenyl in the formula, and MXn is BF
3, SnCl
4, AlCl
3Or ZnCl
2
3. by the synthesis technique of claim 1 or 2 described triphenyl alkoxyl group phosphonium salts, it is characterized in that described epoxy compounds is oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, epoxy styrene, epoxy iso-butylene, oxirane ring hexene, monocycle oxygen butylene or bis-epoxy butylene.
4. by the synthesis technique of claim 1 or 2 described triphenyl alkoxyl group phosphonium salts, it is characterized in that described organic solvent is 1,2-ethylene dichloride, trichloromethane, methylene dichloride or pimelinketone.
5. by the synthesis technique of claim 1 or 2 described triphenyl alkoxyl group phosphonium salts, it is characterized in that described precipitation agent is benzene, toluene, ether, sherwood oil, ETHYLE ACETATE, hexanaphthene or normal hexane.
6. by the synthesis technique of claim 1 or 2 described triphenyl alkoxyl group phosphonium salts, it is characterized in that described Lewis acid is boron trifluoride, anhydrous stannic chloride, aluminum trichloride (anhydrous) or Zinc Chloride Anhydrous.
7. by the synthesis technique of claim 1 or 2 described triphenyl alkoxyl group phosphonium salts, it is characterized in that described churning time is 15～35 minutes.
8. by the synthesis technique of claim 1 or 2 described triphenyl alkoxyl group phosphonium salts, the churning time that it is characterized in that described precipitate and separate is 5～30 minutes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541889A (en) * | 2016-01-23 | 2016-05-04 | 武汉工程大学 | Preparation method for boron difluoride diphenyl sulphur tetrafluoroborate compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701063A (en) * | 2009-11-18 | 2010-05-05 | 武汉工程大学 | Preparation method of polyepichlorohydrin |
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| CN101701063A (en) * | 2009-11-18 | 2010-05-05 | 武汉工程大学 | Preparation method of polyepichlorohydrin |
Non-Patent Citations (3)
| Title |
|---|
| JOSEPH H. FINLEY ET AL.: "Synthesis and Reactions of Some Tetraalkoxyphosphonium Salts", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIET》, vol. 91, no. 21, 8 October 1969 (1969-10-08), pages 5826 - 5831 * |
| KENNETH E. DEBRUIN ET AL.: "Topological Representation of the Stereochemistry of Displacement Reactions at Phosphorus in Phosphonium Salts and Cognate Systems", 《JOURNAL OF ORGANIC CHEMISTRY》, vol. 91, no. 25, 3 December 1969 (1969-12-03), pages 7031 - 7040 * |
| 李再峰等: "端羟基聚环氧氯丙烷醚的合成及表征", 《聚氨酷工业》, vol. 13, no. 3, 31 March 1998 (1998-03-31), pages 16 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541889A (en) * | 2016-01-23 | 2016-05-04 | 武汉工程大学 | Preparation method for boron difluoride diphenyl sulphur tetrafluoroborate compound |
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