CN103467523A - Bis-phosphorous acid triphenyl (3,3'-tetra-dimethyl-5,5'-di-tert-butyl-2,2'-xenol) ester microwave synthesis method - Google Patents
Bis-phosphorous acid triphenyl (3,3'-tetra-dimethyl-5,5'-di-tert-butyl-2,2'-xenol) ester microwave synthesis method Download PDFInfo
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- CN103467523A CN103467523A CN2013104696633A CN201310469663A CN103467523A CN 103467523 A CN103467523 A CN 103467523A CN 2013104696633 A CN2013104696633 A CN 2013104696633A CN 201310469663 A CN201310469663 A CN 201310469663A CN 103467523 A CN103467523 A CN 103467523A
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Abstract
The invention discloses a bis-phosphorous acid triphenyl (3,3'-tetra-dimethyl-5,5'-di-tert-butyl-2,2'-xenol) ester microwave synthesis method. According to the method, phosphorous acid trialkyl ester and 3,3'-tetra-dimethyl-5,5'-di-tert-butyl-2,2'-xenol are used as raw materials, wherein the molar ratio of the phosphorous acid trialkyl ester and the 3,3'-tetra-dimethyl-5,5'-di-tert-butyl-2,2'-xenol is 1:1-10:1; aryl substitute phosphoric chloride or alkyl substitute phosphoric chloride serves as a catalyst; bis-phosphorous acid triphenyl (3,3'-tetra-dimethyl-5,5'-di-tert-butyl-2,2'-xenol) ester is formed by synthesis under microwave radiation without solvent; microwave radiation power is 100-1000w, and microwave reaction time is 5-30min. The method has the advantages of being high in bis-phosphite acid ester yield, small in number of by-products, short in reaction time, capable of achieving solvent-free operation, environmentally friendly, free of pollution, simple in aftertreatment and the like.
Description
Technical field:
What the present invention related to is the microwave synthesis method of a kind of diphosphite three (3,3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-xenol) ester.
Background technology:
Diphosphite three (3,3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-xenol) contain two coordination phosphorus atom in ester ligand molecular structure, can form the metal complex of two chelating coordinations with the transition-metal catalyst coordination, this part has important effect in transition-metal catalysis.
The disclosed synthetic method of prior art mainly is divided into two steps: (1) phosphorus trichloride and 3, and 3 '-dimethyl-5,5 '-di-t-butyl-2, the reaction of 2 '-xenol generates 3,3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-bis-phenoxy group phosphine chloromethylated intermediates; (2) this intermediate is again with 3,3 '-dimethyl-5, and 5 '-di-t-butyl-2,2 '-xenol reacts and generates diphosphite three (3,3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-xenol) ester under the effect of acid binding agent.
In existing public technology, all adopt phosphorus trichloride as phosphorization reagent 3,3 '-dimethyl-5,5 '-di-t-butyl-2, the reaction of 2 '-xenol.Yet phosphorus trichloride gas is poisonous, there is strong impulse and severe corrosive, can make the conjunctiva inflammation after suction phosphorus trichloride gas, laryngalgia and eye tissue destroy, and lung and mucous membrane are had to hormesis.Above characteristic makes while adopting phosphorus trichloride to be operated very difficult, can cause huge harm to operator and environment.And, because the acid binding agent that has adopted organic bases and so on (as triethylamine, pyridine etc.) in technique carrys out the chlorion produced in the absorption reaction process, can form a large amount of organic basis of hydrochloride byproducts.And the diphosphite three (3 that adopts this technique to obtain, 3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-xenol) contain a large amount of chloride ion impurities in the thick product of ester, need to adopt comparatively complicated method just can remove the guarantee chloride ion impurities and can not make poisoning of catalyst.
Summary of the invention:
The purpose of this invention is to provide the microwave synthesis method of a kind of diphosphite three (3,3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-xenol) ester, is the series of problems that raw material brings in order to solve the available technology adopting phosphorus trichloride.
The invention provides the microwave synthesis method of a kind of diphosphite three (3,3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-xenol) ester, it is characterized in that it comprises the following steps:
(a) trialkyl phosphite that is 1:1-10:1 by mol ratio, 3,3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-xenol and the organic chloride phosphorus catalyst that accounts for raw material gross weight 0.5-10.0% are placed in the microwave reaction device, under the microwave radiation that is 100-1000w at power, reaction 5-30 minute, described organic chloride phosphorus catalyst is selected from aryl and replaces phosphorus chloride and alkyl and replace a kind of in phosphorus chloride;
(b) will react thick product organic solvent recrystallization after having reacted, obtain diphosphite three (3,3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-xenol) ester product A;
Wherein, chemical equation is as follows:
According to microwave synthesis method of the present invention, it is characterized in that it comprises the following steps:
(a) trialkyl phosphite that is 1:1-3:1 by mol ratio, 3, 3 '-dimethyl-5, 5 '-di-t-butyl-2, 2 '-xenol and the aryl that accounts for raw material gross weight 2.0-5.0% replace phosphorus chloride or alkyl and replace the phosphorus chloride catalyzer and be placed in the microwave reaction device, it is 200-500w that microwave irradiation power is set, reaction times is 10-20 minute, wherein said trialkyl phosphite is selected from trimethyl phosphite, triethyl-phosphite, a kind of in tripropyl phosphite and tributyl phosphate, aryl replaces phosphorus chloride and is selected from the phenyl phosphorus dichloride, a kind of in diphenyl phosphorus chloride, it is di-t-butyl phosphorus chloride that alkyl replaces phosphorus chloride,
(b) will react thick product organic solvent recrystallization after having reacted, obtain diphosphite three (3,3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-xenol) ester product, recrystallization organic solvent used is selected from one or more in benzene, toluene, ethyl acetate, acetonitrile, normal hexane, sherwood oil, ethanol and ether.
According to microwave synthesis method of the present invention, it is characterized in that it comprises the following steps:
(a) trialkyl phosphite that is 1:1-3:1 by mol ratio, 3,3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-xenol and the aryl that accounts for raw material gross weight 2.0-5.0% replace the phosphorus chloride catalyzer and are placed in the microwave reaction device, it is 200-500w that microwave irradiation power is set, reaction times is 10-20 minute, wherein said trialkyl phosphite is selected from a kind of in trimethyl phosphite, triethyl-phosphite, and aryl replaces phosphorus chloride and is selected from a kind of in phenyl phosphorus dichloride, diphenyl phosphorus chloride;
(b) will react thick product organic solvent recrystallization after having reacted, obtain diphosphite three (3,3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-xenol) ester product, recrystallization organic solvent used is selected from one or more in toluene, normal hexane, sherwood oil and ethyl acetate.
The present invention is usingd trialkyl phosphite replacement phosphorus trichloride as raw material and 3,3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-xenol is synthetic diphosphite three (3 under microwave action, 3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-xenol) ester, there is the advantages such as the bis-phosphite product yield is high, by product is few, the reaction times is short, solvent-free process, environmental friendliness is pollution-free, aftertreatment is simple.
Embodiment:
The present invention will be further described for the following examples, but not thereby limiting the invention.
Embodiment 1
Triethyl-phosphite by 16.6 grams, 32.6 gram 3, 3 '-dimethyl-5, 5 '-di-t-butyl-2, 2 '-xenol and 1.7 gram diphenyl phosphorus chloride catalyzer are placed in the microwave reaction device, under the microwave radiation that is 200w at power after mixing and stirring, reaction is 20 minutes, to react toluene and normal hexane mixed solvent recrystallization for thick product after having reacted, obtain white crystal, through proton nmr spectra, phosphorus spectrum and efficient liquid phase chromatographic analysis checking, product is diphosphite three (3, 3 '-dimethyl-5, 5 '-di-t-butyl-2, 2 '-xenol) ester, yield 90%(yield is with 3, 3 '-dimethyl-5, 5 '-di-t-butyl-2, 2 '-xenol is benchmark).
Embodiment 2
Triethyl-phosphite by 49.8 grams, 32.6 gram 3, 3 '-dimethyl-5, 5 '-di-t-butyl-2, 2 '-xenol and 0.7 gram phenyl phosphorus dichloride catalyzer are placed in the microwave reaction device, under the microwave radiation that is 200w at power after mixing and stirring, reaction is 20 minutes, to react thick product acetonitrile recrystallization after having reacted, obtain white crystal, through proton nmr spectra, phosphorus spectrum and efficient liquid phase chromatographic analysis checking, product is diphosphite three (3, 3 '-dimethyl-5, 5 '-di-t-butyl-2, 2 '-xenol) ester, yield 92%(yield is with 3, 3 '-dimethyl-5, 5 '-di-t-butyl-2, 2 '-xenol is benchmark).
Embodiment 3
Trimethyl phosphite by 24.8 grams, 32.6 gram 3, 3 '-dimethyl-5, 5 '-di-t-butyl-2, 2 '-xenol and 4.3 gram diphenyl phosphorus chloride catalyzer are placed in the microwave reaction device, under the microwave radiation that is 500w at power after mixing and stirring, reaction is 15 minutes, to react ethyl acetate and sherwood oil mixed solvent recrystallization for thick product after having reacted, obtain white crystal, through proton nmr spectra, phosphorus spectrum and efficient liquid phase chromatographic analysis checking, product is diphosphite three (3, 3 '-dimethyl-5, 5 '-di-t-butyl-2, 2 '-xenol) ester, yield 94%(yield is with 3, 3 '-dimethyl-5, 5 '-di-t-butyl-2, 2 '-xenol is benchmark).
Embodiment 4
Trimethyl phosphite by 12.4 grams, 32.6 gram 3, 3 '-dimethyl-5, 5 '-di-t-butyl-2, 2 '-xenol and 0.9 gram diphenyl phosphorus chloride catalyzer are placed in the microwave reaction device, under the microwave radiation that is 300w at power after mixing and stirring, reaction is 20 minutes, to react toluene and alcohol mixed solvent recrystallization for thick product after having reacted, obtain white crystal, through proton nmr spectra, phosphorus spectrum and efficient liquid phase chromatographic analysis checking, product is diphosphite three (3, 3 '-dimethyl-5, 5 '-di-t-butyl-2, 2 '-xenol) ester, yield 92%(yield is with 3, 3 '-dimethyl-5, 5 '-di-t-butyl-2, 2 '-xenol is benchmark).
Embodiment 5
Trimethyl phosphite by 124.1 grams, 32.6 gram 3, 3 '-dimethyl-5, 5 '-di-t-butyl-2, 2 '-xenol and 0.7 gram di-t-butyl phosphorus chloride catalyzer are placed in the microwave reaction device, under the microwave radiation that is 100w at power after mixing and stirring, reaction is 25 minutes, to react thick product ether recrystallization after having reacted, obtain white crystal, through proton nmr spectra, phosphorus spectrum and efficient liquid phase chromatographic analysis checking, product is diphosphite three (3, 3 '-dimethyl-5, 5 '-di-t-butyl-2, 2 '-xenol) ester, yield 88%(yield is with 3, 3 '-dimethyl-5, 5 '-di-t-butyl-2, 2 '-xenol is benchmark).
Claims (3)
1. the microwave synthesis method of a diphosphite three (3,3'-dimethyl-5,5'-di-t-butyl-2,2'-xenol) ester, is characterized in that, it comprises the following steps:
A) trialkyl phosphite that is 1:1-10:1 by mol ratio, 3,3'-dimethyl-5,5'-di-t-butyl-2,2'-xenol and the organic chloride phosphorus catalyst that accounts for raw material gross weight 0.5-10.0% are placed in the microwave reaction device, under the microwave radiation that is 100-1000w at power, reaction 5-30 minute, described organic chloride phosphorus catalyst is selected from aryl and replaces phosphorus chloride and alkyl and replace a kind of in phosphorus chloride;
B) will react thick product organic solvent recrystallization after having reacted, obtain diphosphite three (3,3'-dimethyl-5,5'-di-t-butyl-2,2'-xenol) ester product A;
Wherein, chemical equation is as follows:
2. method according to claim 1, is characterized in that, it comprises the following steps:
(a) trialkyl phosphite that is 1:1-3:1 by mol ratio, 3, 3'-dimethyl-5, 5'-di-t-butyl-2, 2'-xenol and the aryl that accounts for raw material gross weight 2.0-5.0% replace phosphorus chloride or alkyl and replace the phosphorus chloride catalyzer and be placed in the microwave reaction device, it is 200-500w that microwave irradiation power is set, reaction times is 10-20 minute, wherein said trialkyl phosphite is selected from trimethyl phosphite, triethyl-phosphite, a kind of in tripropyl phosphite and tributyl phosphate, aryl replaces phosphorus chloride and is selected from the phenyl phosphorus dichloride, a kind of in diphenyl phosphorus chloride, it is di-t-butyl phosphorus chloride that alkyl replaces phosphorus chloride,
(b) will react thick product organic solvent recrystallization after having reacted, obtain diphosphite three (3,3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-xenol) ester product, recrystallization organic solvent used is selected from one or more in benzene, toluene, ethyl acetate, acetonitrile, normal hexane, sherwood oil, ethanol and ether.
3. method according to claim 1, is characterized in that, it comprises the following steps:
A) trialkyl phosphite that is 1:1-3:1 by mol ratio, 3,3'-dimethyl-5,5'-di-t-butyl-2,2'-xenol and the aryl that accounts for raw material gross weight 2.0-5.0% replace the phosphorus chloride catalyzer and are placed in the microwave reaction device, it is 200-500w that microwave irradiation power is set, reaction times is 10-20 minute, wherein said trialkyl phosphite is selected from a kind of in trimethyl phosphite, triethyl-phosphite, and aryl replaces phosphorus chloride and is selected from a kind of in phenyl phosphorus dichloride, diphenyl phosphorus chloride;
B) will react thick product organic solvent recrystallization after having reacted, obtain diphosphite three (3,3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-xenol) ester product, recrystallization organic solvent used is selected from one or more in toluene, normal hexane, sherwood oil and ethyl acetate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102177171A (en) * | 2008-10-08 | 2011-09-07 | 陶氏技术投资有限公司 | Slurry process for synthesis of bisphosphites |
| CN102266796A (en) * | 2006-12-22 | 2011-12-07 | 中国科学院上海有机化学研究所 | Propylene hydroformylation catalyzing system and method |
| CN102432638A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Synthesizing method for bis-phosphite ligand |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266796A (en) * | 2006-12-22 | 2011-12-07 | 中国科学院上海有机化学研究所 | Propylene hydroformylation catalyzing system and method |
| CN102177171A (en) * | 2008-10-08 | 2011-09-07 | 陶氏技术投资有限公司 | Slurry process for synthesis of bisphosphites |
| CN102432638A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Synthesizing method for bis-phosphite ligand |
Non-Patent Citations (3)
| Title |
|---|
| E. CINI ET AL: "Microwave-Assisted Domino Hydroformylation without Syngas", 《SYNLETT》, no. 2, 23 December 2010 (2010-12-23), pages 199 - 202 * |
| R. ANGHARAD BABER ET AL: "Chiral palladium bis(phosphite)PCP-pincer complexesvialigand C–H activation", 《CHEM.COMMUN.》, 29 August 2006 (2006-08-29), pages 3880 - 3882 * |
| 朱善斌等: "一步法合成二亚磷酸三( 2，2’－联苯酚) 酯", 《石油化工》, vol. 40, no. 5, 15 May 2011 (2011-05-15), pages 545 - 549 * |
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