CN1660862A - Method for synthesizing triphenyl phosphine dichloride - Google Patents
Method for synthesizing triphenyl phosphine dichloride Download PDFInfo
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- CN1660862A CN1660862A CN 200410073584 CN200410073584A CN1660862A CN 1660862 A CN1660862 A CN 1660862A CN 200410073584 CN200410073584 CN 200410073584 CN 200410073584 A CN200410073584 A CN 200410073584A CN 1660862 A CN1660862 A CN 1660862A
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- CN
- China
- Prior art keywords
- synthetic method
- phosgene
- triphenyl
- triphenylphosphine oxide
- triphenyl dichloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title abstract description 7
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- ASWXNYNXAOQCCD-UHFFFAOYSA-N dichloro(triphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Cl)(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ASWXNYNXAOQCCD-UHFFFAOYSA-N 0.000 title description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 14
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 22
- -1 triphenyl dichloride phosphine Chemical compound 0.000 claims description 21
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 11
- 238000010189 synthetic method Methods 0.000 claims description 11
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012434 nucleophilic reagent Substances 0.000 claims description 4
- 239000003849 aromatic solvent Substances 0.000 claims description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract 2
- 239000012011 nucleophilic catalyst Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000007239 Wittig reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for synthesizing phosphine triphenyldichloride features the reaction between phosphine triphenyloxide and triphosgene or biphosgene in organic solvent under existance of the nucleophilic catalyst chosen from N,N-dimethyl formamide, triethylamine, pyridine, etc.
Description
Technical field
What the present invention relates to is the synthetic method of triphenyl phosphine dichloride.
Background technology
Triphenyl dichloride phosphine is the important intermediate of synthetic triphenylphosphine, is raw material at the byproduct triphenylphosphine oxide with the Wittig reaction especially, and in the method for synthetic triphenylphosphine, triphenyl dichloride phosphine is crucial intermediate.
By being raw material with the triphenylphosphine oxide, the existing a lot of patents of preparation triphenyl dichloride phosphine are reported for work, patent US 3405180 has reported with triphenylphosphine oxide and phosphorus pentachloride or triphenylphosphine oxide and thionyl chloride and has reacted in the orthodichlorobenzene equal solvent, generated triphenyl dichloride phosphine; Patent US 3855310 has reported that generating the triphenyl dichloride with triphenylphosphine oxide and phosphorus trichloride and chlorine reaction sees; Above-mentioned three kinds of methods, expensive raw material price, productive rate is low, and it is many, big for environment pollution that reaction produces refuse.
Patent US 4301301 adopts the method that feeds carbon monoxide and chlorine in containing the solution of triphenylphosphine oxide, generate triphenyl dichloride phosphine, the deoxygenation that need dewater of this method solvent for use, reaction needed pressurization, and carbon monoxide and chlorine toxicity are big, and normal temperature is gas transport cost height.
Patent US 4249023 reacts in different organic solvents with the triphenylphosphine oxide photoreactive gas with US 5527966, generates triphenyl dichloride phosphine, and this method is used the phosgene of severe toxicity, and is dangerous high, and the gas phosgene is unfavorable for transportation.
Summary of the invention
The purpose of this invention is to provide a kind of productive rate height, production cost is low, safe, environmental pollution is little, easily realize the triphenyl dichloride phosphine synthetic method of suitability for industrialized production.
The present invention is a raw material with triphenylphosphine oxide and triphosgene or two phosgene, and in appropriate organic solvent, with N, active nucleophilic reagent such as dinethylformamide, triethylamine is a catalyzer, and reaction generates triphenyl dichloride phosphine.
This invention is characterised in that, replaces phosgene to react with triphosgene or two phosgene, and the amount of triphosgene can be 0.25～2mol/mol triphenylphosphine oxide, is good with 0.33～1mol/mol triphenylphosphine oxide especially; The amount of two phosgene can be 0.4～3mol/mol triphenylphosphine oxide, is good with 0.66～1.5mol/mol triphenylphosphine oxide especially.
Used solvent can be aromatic solvents such as toluene, chlorobenzene, dichlorobenzene, and perhaps chloride organic solvent in phosgene, chloroform, the tetracol phenixin equimolecular is good with chlorobenzene, toluene.
Used catalyzer can be N, and a kind of in the active nucleophilic reagent such as dinethylformamide, triethylamine, pyridine, tetrabutylammonium chloride, N-Methylimidazole or two kinds are good with triethylamine especially wherein.
Temperature of reaction can be carried out under-20 ℃～80 ℃, is good with 30 ℃～60 ℃ especially.
Advantage of the present invention is: 1) adopt normal temperature down for the two phosgene replacement gas phosgene of solid triphosgene or liquid is a raw material, raw material is easy to transportation, preserves.2) few, the solvent of reaction solvent consumption easily recovery set use.3) byproduct of reaction is few, and reaction raw materials can make things convenient for recovery set to use.4) Fan Ying mild condition can well be reacted at normal temperatures and pressures.
Embodiment
Following embodiment will make a more detailed description the present invention.
Embodiment 1
In the four neck flasks of 100ml, add 8g triphenylphosphine oxide and 25ml toluene, stirring makes it dissolving fully, add a spot of triethylamine catalyzer, under 20 ℃, slowly be added dropwise to the 15ml toluene solution that contains triphosgene 3.0g then, drip half an hour, continue then to stir 8 hours, molar yield is 82.2%.
Embodiment 2
In the four neck flasks of 100ml, add 8g triphenylphosphine oxide and 25ml chlorobenzene, stirring makes it dissolving fully, add a spot of triethylamine catalyzer, under 40 ℃, slowly be added dropwise to the 15ml chlorobenzene solution that contains triphosgene 3.0g then, drip half an hour, continue then to stir 6 hours, molar yield is 85.7%.
Embodiment 3
In the four neck flasks of 100ml, add 8g triphenylphosphine oxide and 25ml toluene, stirring makes it dissolving fully, add a spot of triethylamine catalyzer, under 60 ℃, slowly be added dropwise to the 15ml toluene solution that contains triphosgene 3.0g then, drip half an hour, continue then to stir 6 hours, molar yield is 88.8%.
Embodiment 4
In the four neck flasks of 100ml, add 10.2g triphenylphosphine oxide and 40ml toluene, stir and make it dissolving fully, add a spot of DMF catalyzer, under 0 ℃, slowly be added dropwise to then and contain two phosgene 3.8g, drip half an hour, continue then to stir 12 hours, molar yield is 81.6%.
Embodiment 5-11
Being similar to embodiment 1, is raw material with triphosgene, under differing temps, uses different catalyzer respectively, gets following result (table one) after reaction finishes:
Table one
| Embodiment | Temperature | Catalyzer | Reaction times | Productive rate |
| ????5 | ??-20℃ | N, dinethylformamide | ????18 | ????75.4％ |
| ????6 | ??-10℃ | Triethylamine | ????15 | ????78.0％ |
| ????7 | ??10℃ | Tetrabutylammonium chloride | ????12 | ????71.1％ |
| ????8 | ??20℃ | Pyridine | ????12 | ????81.6％ |
| ????9 | ??40℃ | The N-Methylimidazole | ????6 | ????76.5％ |
| ????10 | ??60℃ | Pyridine+N-Methylimidazole | ????6 | ????86.4％ |
| ????11 | ??80℃ | Triethylamine+pyridine | ????5 | ????82.3％ |
Claims (8)
1, a kind of synthetic method of triphenyl dichloride phosphine, it is characterized in that: with triphenylphosphine oxide and triphosgene or two phosgene is raw material, in aromatic solvents, or in the chloride organic solvent solvent, with N, active nucleophilic reagent such as dinethylformamide, triethylamine, pyridine, tetrabutylammonium chloride, N-Methylimidazole is a catalyzer, and reaction generates triphenyl dichloride phosphine.
2, the synthetic method of triphenyl dichloride phosphine according to claim 1 is characterized in that: the amount of used raw material triphosgene is 0.25～2mol/mol triphenylphosphine oxide, is good with 0.33～1mol/mol triphenylphosphine oxide especially;
3, the synthetic method of triphenyl dichloride phosphine according to claim 1 is characterized in that: the amount of used raw material two phosgene is 0.4～3mol/mol triphenylphosphine oxides, is good with 0.66～1.5mol/mol triphenylphosphine oxide especially.
4, the synthetic method of triphenyl dichloride phosphine according to claim 1, it is characterized in that: used aromatic solvents is: toluene, chlorobenzene, dichlorobenzene a kind of.
5, the synthetic method of triphenyl dichloride phosphine according to claim 1, it is characterized in that: used chloro-carbon solvent is: phosgene, chloroform, tetracol phenixin a kind of
6, the synthetic method of triphenyl dichloride phosphine according to claim 1, it is characterized in that: used catalyzer is N, one or both in the active nucleophilic reagent such as dinethylformamide, triethylamine, pyridine, tetrabutylammonium chloride, N-Methylimidazole.
7, the synthetic method of triphenyl dichloride phosphine according to claim 1, it is characterized in that: triphenylphosphine oxide is dissolved in the organic solvent, add catalyzer, be added dropwise to the organic solution of triphosgene or two phosgene or directly add the solid triphosgene or liquid two phosgene, reaction generates the triphenyl dichloride.
8, the synthetic method of triphenyl dichloride phosphine according to claim 1 is characterized in that: be reflected under the temperature-20～80 ℃ and carry out-10～60 ℃ of the bests.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410073584 CN1271075C (en) | 2004-12-23 | 2004-12-23 | Method for synthesizing triphenyl phosphine dichloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410073584 CN1271075C (en) | 2004-12-23 | 2004-12-23 | Method for synthesizing triphenyl phosphine dichloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1660862A true CN1660862A (en) | 2005-08-31 |
| CN1271075C CN1271075C (en) | 2006-08-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410073584 Active CN1271075C (en) | 2004-12-23 | 2004-12-23 | Method for synthesizing triphenyl phosphine dichloride |
Country Status (1)
| Country | Link |
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| CN (1) | CN1271075C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665393B (en) * | 2009-09-08 | 2012-06-27 | 浙江工业大学 | Synthesis method of polysubstituted allyl chloride derivative |
| CN103450183A (en) * | 2013-08-16 | 2013-12-18 | 威海迪素制药有限公司 | Preparation method of succinic acid solifenacin |
| CN103819410A (en) * | 2014-01-26 | 2014-05-28 | 江苏新瀚有限公司 | Preparation method for (6-Chloro-pyridazino-3-yl) formic acid |
| CN107011252A (en) * | 2017-06-09 | 2017-08-04 | 浙江工业大学 | The method for drawing azole intermediate and medicine is prepared using the green technology for substituting the poisonous and harmful substances such as phosgene, thionyl chloride |
| CN110294458A (en) * | 2019-06-04 | 2019-10-01 | 利尔化学股份有限公司 | A kind of method and apparatus that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online |
| CN112174907A (en) * | 2020-10-12 | 2021-01-05 | 新发药业有限公司 | Environment-friendly preparation method of substituted oxazole compound |
-
2004
- 2004-12-23 CN CN 200410073584 patent/CN1271075C/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665393B (en) * | 2009-09-08 | 2012-06-27 | 浙江工业大学 | Synthesis method of polysubstituted allyl chloride derivative |
| CN103450183A (en) * | 2013-08-16 | 2013-12-18 | 威海迪素制药有限公司 | Preparation method of succinic acid solifenacin |
| CN103450183B (en) * | 2013-08-16 | 2017-09-12 | 威海迪素制药有限公司 | A kind of preparation method of butanedioic acid Solifenacin |
| CN103819410A (en) * | 2014-01-26 | 2014-05-28 | 江苏新瀚有限公司 | Preparation method for (6-Chloro-pyridazino-3-yl) formic acid |
| CN103819410B (en) * | 2014-01-26 | 2015-09-30 | 江苏新瀚有限公司 | A kind of preparation method of 6-chlorine pyridazine-3-formic acid |
| CN107011252A (en) * | 2017-06-09 | 2017-08-04 | 浙江工业大学 | The method for drawing azole intermediate and medicine is prepared using the green technology for substituting the poisonous and harmful substances such as phosgene, thionyl chloride |
| CN107011252B (en) * | 2017-06-09 | 2018-06-08 | 浙江工业大学 | The method for drawing azole intermediate and drug is prepared using the green technology for substituting the poisonous and harmful substances such as phosgene, thionyl chloride |
| CN110294458A (en) * | 2019-06-04 | 2019-10-01 | 利尔化学股份有限公司 | A kind of method and apparatus that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online |
| CN112174907A (en) * | 2020-10-12 | 2021-01-05 | 新发药业有限公司 | Environment-friendly preparation method of substituted oxazole compound |
| WO2022077196A1 (en) * | 2020-10-12 | 2022-04-21 | 新发药业有限公司 | Environmentally friendly preparation method for substituted oxazole compound |
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| Publication number | Publication date |
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| CN1271075C (en) | 2006-08-23 |
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Owner name: ZHEJIANG XINHECHENG CO., LTD. SHANGYU XINHECHENG B Free format text: FORMER OWNER: ZHEJIANG XINHECHENG CO., LTD. Effective date: 20120229 |
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Effective date of registration: 20120229 Address after: Hangzhou City, Zhejiang province 310027 Ancient Jade Road 20 Co-patentee after: Zhejiang Xinhecheng Co., Ltd. Patentee after: Zhejiang University Co-patentee after: Shangyu Xinhecheng Bio-Chemical Co., Ltd. Co-patentee after: Zhejiang NHU Pharmaceutical Co., Ltd. Address before: Hangzhou City, Zhejiang province 310027 Ancient Jade Road 20 Co-patentee before: Zhejiang Xinhecheng Co., Ltd. Patentee before: Zhejiang University |