CN103467517B - A kind of microwave synthesis method of diphosphite three (3,3 ', 5,5 '-tetramethyl--2,2 '-xenol) ester - Google Patents
A kind of microwave synthesis method of diphosphite three (3,3 ', 5,5 '-tetramethyl--2,2 '-xenol) ester Download PDFInfo
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- CN103467517B CN103467517B CN201310469886.XA CN201310469886A CN103467517B CN 103467517 B CN103467517 B CN 103467517B CN 201310469886 A CN201310469886 A CN 201310469886A CN 103467517 B CN103467517 B CN 103467517B
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Abstract
The invention discloses a kind of diphosphite three (3,3 ˊ, 5,5 ˊ-tetramethyl--2,2 ˊ-xenol) microwave synthesis method of ester, the method take mol ratio as the trialkyl phosphite and 3 of 1:1-10:1,3 ˊ, 5,5 ˊ-tetramethyl--2,2 ˊ-xenol is raw material, aryl replaces phosphorus chloride or alkyl replacement phosphorus chloride is catalyzer, diphosphite three (3,3 ˊ, 5 are synthesized under solvent-free microwave radiation condition, 5 ˊ-tetramethyl--2,2 ˊ-xenol) ester, microwave irradiation power is 100-1000w, and the microwave reaction time is 5-30 minute.Present invention process has the features such as bis-phosphite productive rate is high, by product is few, the reaction times is short, solvent-free process, environmental friendliness are pollution-free, aftertreatment is simple.
Description
Technical field:
The microwave synthesis method of what the present invention related to is a kind of diphosphite three (3,3', 5,5'-tetramethyl--2,2'-xenol) ester.
Background technology:
Diphosphite three (3,3', 5,5'-tetramethyl--2,2'-xenol) in ester ligand molecular structure containing two coordinating phosphorus atoms, can form the metal complex of two chelating ligands with transition-metal catalyst coordination, this part has important effect in transition-metal catalysis.
Synthetic method disclosed in prior art is mainly divided into two steps: (1) phosphorus trichloride and 3,3', the two phenoxy group phosphine chloromethylated intermediate of 5,5'-tetramethyl--2,2'-xenol reaction generation 3,3', 5,5'-tetramethyl--2,2'-; (2) this intermediate reacts with 3,3', 5,5'-tetramethyl--2,2'-xenol and generates diphosphite three (3,3', 5,5'-tetramethyl--2,2'-xenol) ester under the effect of acid binding agent.
All adopt phosphorus trichloride as phosphorization reagent and 3,3' in existing public technology, 5,5'-tetramethyl--2,2'-xenol reacts.But phosphorus trichloride gas is poisonous, have strong impulse and severe corrosive, can make conjunctiva inflammation after sucking phosphorus trichloride gas, laryngalgia and eye tissue destroy, and have hormesis to lung and mucous membrane.Above characteristic is very difficult when making to adopt phosphorus trichloride to operate, and can cause huge harm to operator and environment.And because the acid binding agent that have employed organic bases and so on (as triethylamine, pyridine etc.) in technique the hydrochloric acid that produces in absorption reaction process, a large amount of organic basis of hydrochloride byproducts can be formed.And the diphosphite three (3 adopting this technique to obtain, 3', 5,5'-tetramethyl--2,2'-xenol) in the thick product of ester containing a large amount of chloride ion impurities, needing to adopt comparatively complicated purification process could remove guarantee chloride ion impurities can not make poisoning of catalyst.
Summary of the invention:
The object of this invention is to provide a kind of microwave synthesis method of diphosphite three (3,3', 5,5'-tetramethyl--2,2'-xenol) ester, adopt phosphorus trichloride to be the series of problems that raw material brings in order to solve in prior art.
The invention provides a kind of microwave synthesis method of diphosphite three (3,3', 5,5'-tetramethyl--2,2'-xenol) ester, it is characterized in that it comprises the following steps:
A mol ratio is the trialkyl phosphite, 3 of 1:1-10:1 by (), 3', 5,5'-tetramethyl--2,2'-xenol and the organic chloride phosphorus catalyst accounting for raw material gross weight 0.5-10.0% are placed in microwave reaction device, be under the microwave radiation of 100-1000w at power, reaction 5-30 minute, described organic chloride phosphorus catalyst is selected from the one in aryl replacement phosphorus chloride and alkyl replacement phosphorus chloride;
B () will react thick product organic solvent recrystallization after having reacted, obtain diphosphite three (3,3', 5,5'-tetramethyl--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 mol ratio is the trialkyl phosphite of 1:1-3:1 by (), 3, 3', 5, 5'-tetramethyl--2, 2'-xenol and the aryl accounting for raw material gross weight 2.0-5.0% replace phosphorus chloride or alkyl and replace phosphorus chloride catalyzer and be placed in microwave reaction device, arranging microwave irradiation power is 200-500w, reaction times is 10-20 minute, wherein said trialkyl phosphite is selected from trimethyl phosphite, triethyl-phosphite, one in tripropyl phosphite and tributyl phosphate, aryl replaces phosphorus chloride and is selected from phenyl dichloro phosphorus, one 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', 5,5'-tetramethyl--2,2'-xenol) ester product, recrystallization organic solvent used be selected from benzene, toluene, ethyl acetate, acetonitrile, normal hexane, sherwood oil, ethanol and ether one or more.
According to microwave synthesis method of the present invention, it is characterized in that, it comprises the following steps:
A mol ratio is the trialkyl phosphite, 3 of 1:1-3:1 by (), 3', 5,5'-tetramethyl--2,2'-xenol and the aryl accounting for raw material gross weight 2.0-5.0% replace phosphorus chloride catalyzer and are placed in microwave reaction device, arranging microwave irradiation power is 200-500w, reaction times is 10-20 minute, wherein said trialkyl phosphite is selected from the one in trimethyl phosphite, triethyl-phosphite, and aryl replacement phosphorus chloride is selected from the one in phenyl dichloro phosphorus, diphenyl phosphorus chloride;
B () will react thick product organic solvent recrystallization after having reacted, obtain diphosphite three (3,3', 5,5'-tetramethyl--2,2'-xenol) ester product, recrystallization organic solvent used be selected from toluene, normal hexane, sherwood oil and ethyl acetate one or more.
The present invention replaces phosphorus trichloride as raw material and 3 using trialkyl phosphite, 3', 5,5'-tetramethyl--2,2'-xenol synthesizes diphosphite three (3,3' under microwave action, 5,5'-tetramethyl--2,2'-xenol) ester, there is the advantages such as bis-phosphite product yield is high, by product is few, the reaction times is short, solvent-free process, environmental friendliness are 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
By the triethyl-phosphite of 16.6 grams, 24.2 grams 3, 3', 5, 5'-tetramethyl--2, 2'-xenol and 2.0 grams of diphenyl phosphorus chloride catalyzer are placed in microwave reaction device, be react 15 minutes under the microwave radiation of 200w at power after mixing and stirring, thick product toluene and normal hexane mixed solvent recrystallization will be reacted 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', 5, 5'-tetramethyl--2, 2'-xenol) ester, (yield is with 3 for yield 93%, 3', 5, 5'-tetramethyl--2, 2'-xenol is benchmark).
Embodiment 2
By the triethyl-phosphite of 49.8 grams, 24.2 grams 3, 3', 5, 5'-tetramethyl--2, 2'-xenol and 0.8 gram of phenyl dichloro phosphorus catalyst are placed in microwave reaction device, be react 15 minutes under the microwave radiation of 200w at power after mixing and stirring, thick product recrystallized from acetonitrile will be reacted 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', 5, 5'-tetramethyl--2, 2'-xenol) ester, (yield is with 3 for yield 92%, 3', 5, 5'-tetramethyl--2, 2'-xenol is benchmark).
Embodiment 3
By the trimethyl phosphite of 24.8 grams, 24.2 grams 3, 3', 5, 5'-tetramethyl--2, 2'-xenol and 4.9 grams of diphenyl phosphorus chloride catalyzer are placed in microwave reaction device, be react 10 minutes under the microwave radiation of 500w at power after mixing and stirring, thick product ethyl acetate and sherwood oil mixed solvent recrystallization will be reacted 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', 5, 5'-tetramethyl--2, 2'-xenol) ester, (yield is with 3 for yield 95%, 3', 5, 5'-tetramethyl--2, 2'-xenol is benchmark).
Embodiment 4
By the trimethyl phosphite of 12.4 grams, 24.2 grams 3, 3', 5, 5'-tetramethyl--2, 2'-xenol and 1.1 grams of diphenyl phosphorus chloride catalyzer are placed in microwave reaction device, be react 15 minutes under the microwave radiation of 300w at power after mixing and stirring, thick product toluene and normal hexane mixed solvent recrystallization will be reacted 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', 5, 5'-tetramethyl--2, 2'-xenol) ester, (yield is with 3 for yield 96%, 3', 5, 5'-tetramethyl--2, 2'-xenol is benchmark).
Embodiment 5
By the trimethyl phosphite of 124.1 grams, 24.2 grams 3, 3', 5, 5'-tetramethyl--2, 2'-xenol and 0.7 gram of di-t-butyl phosphorus chloride catalyzer are placed in microwave reaction device, be react 15 minutes under the microwave radiation of 100w at power after mixing and stirring, thick product ethyl acetate and sherwood oil recrystallization will be reacted 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', 5, 5'-tetramethyl--2, 2'-xenol) ester, (yield is with 3 for yield 90%, 3', 5, 5'-tetramethyl--2, 2'-xenol is benchmark).
Claims (3)
1. the microwave synthesis method of diphosphite three (3,3', 5,5'-tetramethyl--2, a 2'-xenol) ester, it is characterized in that, it comprises the following steps:
A) by mol ratio be the trialkyl phosphite, 3 of 1:1-10:1,3', 5,5'-tetramethyl--2,2'-xenol and the organic chloride phosphine catalyst accounting for raw material gross weight 0.5-10.0% are placed in microwave reaction device, be under the microwave radiation of 100-1000w at power, reaction 5-30 minute, described organic chloride phosphine catalyst is selected from the one in aryl replacement phosphonium chloride and alkyl replacement phosphonium chloride, wherein aryl replacement phosphonium chloride is selected from the one in phenylphosphonic dichloride, diphenyl phosphine chloride, and it is di-t-butylchlorophosphine that alkyl replaces phosphonium chloride;
B) thick product organic solvent recrystallization will be reacted after having reacted, obtain diphosphite three (3,3', 5,5'-tetramethyl--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 mol ratio is the trialkyl phosphite of 1:1-3:1 by (), 3, 3', 5, 5'-tetramethyl--2, 2 '-xenol and the aryl accounting for raw material gross weight 2.0-5.0% replace phosphonium chloride or alkyl and replace phosphonium chloride catalyzer and be placed in microwave reaction device, arranging microwave irradiation power is 200-500w, reaction times is 10-20 minute, wherein said trialkyl phosphite is selected from trimethyl phosphite, triethyl-phosphite, one in tripropyl phosphite and tributyl phosphate, aryl replaces phosphonium chloride and is selected from phenylphosphonic dichloride, one in diphenyl phosphine chloride, it is di-t-butylchlorophosphine that alkyl replaces phosphonium chloride,
B () will react thick product organic solvent recrystallization after having reacted, obtain diphosphite three (3,3', 5,5'-tetramethyl--2,2'-xenol) ester product, recrystallization organic solvent used be selected from benzene, toluene, ethyl acetate, acetonitrile, normal hexane, sherwood oil, ethanol and ether one or more.
3. method according to claim 1, is characterized in that, it comprises the following steps:
A) by mol ratio be the trialkyl phosphite, 3 of 1:1-3:1,3', 5,5'-tetramethyl--2,2'-xenol and the aryl accounting for raw material gross weight 2.0-5.0% replace phosphonium chloride catalyzer and are placed in microwave reaction device, and arranging microwave irradiation power is 200-500w, and the reaction times is 10-20 minute, wherein said trialkyl phosphite is selected from the one in trimethyl phosphite, triethyl-phosphite, and aryl replacement phosphonium chloride is selected from the one in phenylphosphonic dichloride, diphenyl phosphine chloride;
B) thick product organic solvent recrystallization will be reacted after having reacted, obtain diphosphite three (3,3', 5,5'-tetramethyl--2,2'-xenol) ester product, recrystallization organic solvent used be selected from toluene, normal hexane, sherwood oil and ethyl acetate one or more.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4403563A1 (en) * | 2023-01-18 | 2024-07-24 | Evonik Oxeno GmbH & Co. KG | Diphosphite with a me-wing component and a tbu-wing component |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999006358A1 (en) * | 1997-07-29 | 1999-02-11 | E.I. Du Pont De Nemours And Company | Hydrocyanation processes and multidentate phosphite ligand and nickel catalyst compositions therefor |
| 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 | Synthesis method of diphosphite ligand |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999006358A1 (en) * | 1997-07-29 | 1999-02-11 | E.I. Du Pont De Nemours And Company | Hydrocyanation processes and multidentate phosphite ligand and nickel catalyst compositions therefor |
| 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 | Synthesis method of diphosphite ligand |
Non-Patent Citations (1)
| Title |
|---|
| 一步法合成二亚磷酸三(2，2"-联苯酚)酯;朱善斌，等;《石油化工》;20111231;第40卷(第5期);545-549 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4403563A1 (en) * | 2023-01-18 | 2024-07-24 | Evonik Oxeno GmbH & Co. KG | Diphosphite with a me-wing component and a tbu-wing component |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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