CN112979702B - Preparation method of organic phosphine compound - Google Patents
Preparation method of organic phosphine compound Download PDFInfo
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- CN112979702B CN112979702B CN201911291642.0A CN201911291642A CN112979702B CN 112979702 B CN112979702 B CN 112979702B CN 201911291642 A CN201911291642 A CN 201911291642A CN 112979702 B CN112979702 B CN 112979702B
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- trichloride
- phosphine
- aluminum trichloride
- mixture
- phosphate
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 71
- -1 phosphine compound Chemical class 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 97
- 239000000203 mixture Substances 0.000 claims abstract description 89
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000003756 stirring Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 28
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 16
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000001119 stannous chloride Substances 0.000 claims abstract description 6
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 30
- 239000010452 phosphate Substances 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 30
- YYQRGCZGSFRBAM-UHFFFAOYSA-N Triclofos Chemical group OP(O)(=O)OCC(Cl)(Cl)Cl YYQRGCZGSFRBAM-UHFFFAOYSA-N 0.000 claims description 19
- 229960001147 triclofos Drugs 0.000 claims description 19
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 18
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 12
- OURAHXRKYMQCSN-UHFFFAOYSA-N Cl.Cl.Cl.Cl.PC1=CC=CC=C1 Chemical compound Cl.Cl.Cl.Cl.PC1=CC=CC=C1 OURAHXRKYMQCSN-UHFFFAOYSA-N 0.000 claims description 11
- LOOCNDFTHKSTFY-UHFFFAOYSA-N 1,1,2-trichloropropyl dihydrogen phosphate Chemical compound CC(Cl)C(Cl)(Cl)OP(O)(O)=O LOOCNDFTHKSTFY-UHFFFAOYSA-N 0.000 claims description 9
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 9
- NNZCTPVMZKLSNT-UHFFFAOYSA-N Cl.Cl.Cl.C=1C=CC=CC=1PC1=CC=CC=C1 Chemical group Cl.Cl.Cl.C=1C=CC=CC=1PC1=CC=CC=C1 NNZCTPVMZKLSNT-UHFFFAOYSA-N 0.000 claims description 8
- 238000005292 vacuum distillation Methods 0.000 claims description 8
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 7
- DGWFDTKFTGTOAF-UHFFFAOYSA-N P.Cl.Cl.Cl Chemical compound P.Cl.Cl.Cl DGWFDTKFTGTOAF-UHFFFAOYSA-N 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims description 5
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical compound P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 26
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 239000003063 flame retardant Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- ONRKUGHFZWYUJP-UHFFFAOYSA-N methylphosphane dihydrochloride Chemical compound Cl.Cl.PC ONRKUGHFZWYUJP-UHFFFAOYSA-N 0.000 description 6
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 229940117389 dichlorobenzene Drugs 0.000 description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- VZZJVOCVAZHETD-UHFFFAOYSA-N diethylphosphane Chemical compound CCPCC VZZJVOCVAZHETD-UHFFFAOYSA-N 0.000 description 1
- UHUMDOUHVGSPDJ-UHFFFAOYSA-N diethylphosphane;hydrochloride Chemical compound [Cl-].CC[PH2+]CC UHUMDOUHVGSPDJ-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- AZAQDXJWNHXLOG-UHFFFAOYSA-N phenylphosphanium;chloride Chemical compound [Cl-].[PH3+]C1=CC=CC=C1 AZAQDXJWNHXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/52—Halophosphines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses a preparation method of an organic phosphine compound, which comprises the following steps: (1) reacting an [ organic phosphine-aluminum trichloride ] complex obtained by reacting alkane or arene under the catalysis of aluminum trichloride with phosphorus trichloride with chlorine to obtain a polychlorinated organic phosphine intermediate and aluminum trichloride mixture; (2) adding a solvent into the mixture of the polychlorinated organic phosphine intermediate and aluminum trichloride obtained in the step (1), stirring and layering, wherein the polychlorinated organic phosphine intermediate and the aluminum trichloride are positioned on different layers; (3) and (3) reacting the polychlorinated organic phosphine intermediate obtained in the step (2) with yellow phosphorus or stannous chloride and tin powder to obtain the target product organic phosphine after the reaction. The method has the advantages of high reaction yield up to 92%, less waste residues, recycling and reusing of the catalyst aluminum trichloride and other intermediate treating agents, and cost saving.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a separation method of a complex in the process of preparing an organic phosphine compound.
Background
With the increasing requirements of high polymer materials such as organic fibers, engineering plastics, rubber, resin and the like on fireproof flame-retardant safety performance, halogen flame retardants with ideal effects are forbidden to be used in most markets because combustion products contain toxic chlorides; the nitrogen-containing flame retardant with a certain flame retardant effect also has the risk of releasing HCN toxic gas after combustion; the safest flame retardants are therefore phosphorus-containing flame retardants and inorganic flame retardants, such as zinc oxide, zinc borate and hydroxides of magnesium, aluminum, etc. Inorganic flame retardants generally increase the specific gravity of the material, decrease the mechanical strength of the material, and also increase the viscosity of the liquid material, which adversely affects subsequent processes.
The phosphorus-containing flame retardant includes red phosphorus, phosphoric acid esters, organic phosphine compounds, and the like. Phosphate esters are generally obtained by reacting phosphorus oxychloride with hydroxyl-containing compounds, such phosphate esters being generally inert as flame retardants, but being inert when mixed in flame retardant modifiers; the flame retardant effect is deeply affected by the dispersion degree of the phosphate flame retardant in the matrix material, and generally, the dispersion degree is not very efficient, so that the efficacy of the flame retardant is not fully exhibited. The organic phosphine is defined as PH3 or a substance formed by substituting H in the organic phosphine by alkyl or phenyl, the synthesis of the organic phosphine is prepared by reacting alkane or arene with phosphorus trichloride under the catalysis of anhydrous aluminum trichloride, and the product is a very useful alkyl phosphine chloride or phenyl phosphine chloride intermediate and can be used for synthesizing various active flame retardants or phosphonyl substances. Since P in the organic phosphine has a pair of lone pair electrons, and Al in the anhydrous aluminum trichloride is electron-deficient, the organic phosphine intermediate product and the catalyst aluminum trichloride are always combined together in the form of a complex, and an effective method is required to separate the organic phosphine product.
US patent 2137792 relates to the reaction of alkanes having 5 or more carbons with phosphorus trichloride and a solvent under the catalysis of aluminum trichloride to form the corresponding [ alkyl dichlorophosphinane-aluminum trichloride ] complex from which the corresponding alkyl dichlorophosphinane is released, the aluminum trichloride being removed by water washing.
Chinese patent CN201810443908.8 relates to a method for dissociating methyl phosphine dichloride and aluminum trichloride complex, comprising using solvent petroleum ether and dissociating agent dimethyl phthalate, diethyl phthalate, dipropyl phthalate, linear or branched C1-C4 carboxylic acid methyl ester, linear or branched C1-C4 carboxylic acid ethyl ester or linear or branched C1-C4 carboxylic acid propyl ester; the product and petroleum ether are separated by rectification, and the dissociating agent and aluminum trichloride are separated by adding water for reaction.
Chinese patent CN201610095303.5 discloses the preparation of ligand [ CH ] by reacting methyl chloride with phosphorus trichloride in the presence of aluminum trichloride catalyst using petroleum ether as solvent 3 PCl 4 ·AlCl 3 ]After petroleum ether is distilled off, aluminum powder, sodium chloride and catalyst diethyl phthalate and magnesium are added, and finally the product methyl phosphine dichloride is obtained.
The patent CN201210473945.6 and the patent CN107501322A both relate to phenyl phosphine dichloride obtained by reacting benzene and phosphorus trichloride in an ionic liquid. The method has the problems that the ionic liquid is repeatedly used for a limited time, and a large amount of three wastes are required to be treated. The patent US3864394A, US4409152A, CN201610068097.9 and CN109575072a both relate to the preparation of phenyl phosphine dichloride and diphenyl phosphine chloride by reacting yellow phosphorus with chlorobenzene and phosphorus trichloride in a kettle type reaction kettle or a tubular reactor. The yellow phosphorus method has high corrosion resistance to chlorobenzene, and thus has extremely high requirement on the corrosion resistance of the material of the reaction kettle or the pipeline, because the temperature is higher than 300 ℃.
The aluminum trichloride catalyst used in the method is usually removed by washing after being treated and separated from a target product, so that a large amount of three wastes are generated, the catalyst cannot be recycled, and resources are wasted.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of an organic phosphine compound, which is convenient and efficient to release target products (alkyl phosphine dichloride, dialkyl phosphine chloride, phenyl phosphine dichloride or diphenyl phosphine chloride) from an alkyl phosphine dichloride, dialkyl phosphine chloride, phenyl phosphine dichloride or diphenyl phosphine chloride and aluminum trichloride complex system and to recycle aluminum trichloride, thereby solving the problems of large waste residue production, high production cost and the like in the main stream process of the preparation of the existing organic phosphine.
The technical scheme for realizing the aim of the invention is a preparation method of an organic phosphine compound, which comprises the following steps:
(1) and reacting the [ organic phosphine-aluminum trichloride ] complex obtained by reacting alkane or arene under the catalysis of aluminum trichloride with phosphorus trichloride with chlorine to obtain a polychlorinated organic phosphine intermediate and aluminum trichloride mixture.
The organic phosphine in the [ organic phosphine-aluminum trichloride ] complex is alkyl phosphine dichloride, dialkyl phosphine chloride, phenyl phosphine dichloride or diphenyl phosphine chloride.
(2) Adding a solvent into the mixture of the polychlorinated organic phosphine intermediate and aluminum trichloride obtained in the step (1), stirring and layering, wherein the polychlorinated organic phosphine intermediate and the aluminum trichloride are located on different layers.
(3) And (3) reacting the polychlorinated organic phosphine intermediate obtained in the step (2) with yellow phosphorus or stannous chloride and tin powder to obtain the target product organic phosphine after the reaction.
In the step (1), adding the [ organic phosphine-aluminum trichloride ] complex into a reaction vessel, adding chlorinated paraffin into the reaction vessel, uniformly stirring the mixture, heating the mixture to 45+/-2 ℃, starting to introduce chlorine, and ending the reaction when the chlorine is not absorbed any more; and standing for layering after the reaction is finished, separating the upper chlorinated paraffin, wherein the lower layer is a mixture of the polychlorinated organic phosphine intermediate and aluminum trichloride.
Further, in the step (1), the temperature in the reaction vessel is kept between 50 ℃ and 55 ℃ in the chlorine gas introducing process for the [ alkyl phosphine dichloride-aluminum trichloride ] complex or the [ dialkyl phosphine chloride-aluminum trichloride ] complex; for the [ phenyl phosphine dichloride-aluminum trichloride ] complex, maintaining the temperature in a reaction vessel at 78-85 ℃ in the chlorine gas introducing process; for the [ diphenylphosphine chloride-aluminum trichloride ] complex, the temperature in the reaction vessel was kept gradually rising to 200℃during the chlorine gas introduction.
In the step (2), the step of (C),
adding chloralkane or phosphate and phosphorus trichloride into a mixture of polychlorinated organic phosphine intermediate and aluminum trichloride, which is obtained by reacting an [ alkyl phosphine dichloride-aluminum trichloride ] complex with chlorine, stirring uniformly, and standing for layering; the upper layer is a mixture of alkyl phosphine tetrachloride and phosphorus trichloride, and the lower layer is a mixture of chloralkane or phosphate and aluminum trichloride; the phosphate is trichloroethyl phosphate or trichloropropyl phosphate.
Adding chloralkane or phosphate and phosphorus trichloride into a mixture of polychlorinated organic phosphine intermediate and aluminum trichloride, which is obtained by reacting a [ dialkylphosphine chloride-aluminum trichloride ] complex with chlorine, stirring uniformly, and standing for layering; the upper layer is a mixture of dialkyl phosphine trichloride and phosphorus trichloride, and the lower layer is a mixture of chloralkane or phosphate and aluminum trichloride; the phosphate is trichloroethyl phosphate or trichloropropyl phosphate.
Adding chlorinated aromatic hydrocarbon or phosphate and phosphorus trichloride into a mixture of polychlorinated organic phosphine intermediate and aluminum trichloride, which is obtained by reacting a [ phenyl phosphine dichloride-aluminum trichloride ] complex with chlorine, uniformly stirring, standing and layering, wherein the upper layer is a mixture of chlorinated aromatic hydrocarbon or phosphate and aluminum trichloride, and the lower layer is a mixture of phenyl phosphine tetrachloride and phosphorus trichloride; the phosphate is trichloroethyl phosphate or trichloropropyl phosphate.
Adding chlorinated aromatic hydrocarbon or phosphate into a mixture of polychlorinated organic phosphine intermediate and aluminum trichloride, which is obtained by reacting a [ diphenyl phosphine chloride-aluminum trichloride ] complex with chlorine, stirring uniformly, standing and layering, wherein the upper layer is a mixture of chlorinated aromatic hydrocarbon or phosphate and aluminum trichloride, and the lower layer is diphenyl phosphine trichloride; the phosphate is trichloroethyl phosphate or trichloropropyl phosphate.
In the step (3), the mixture of the upper alkyl phosphine tetrachloride or the dialkyl phosphine trichloride and the phosphorus trichloride obtained after layering in the step (2) is transferred into a flask, yellow phosphorus is added for reaction, and then normal pressure distillation is carried out, and fractions between corresponding distillation ranges of the alkyl phosphine dichloride or the dialkyl phosphine trichloride are collected.
When chloralkane and phosphorus trichloride are added in the step (2), the chloralkane is distilled off from the mixture of the lower chloralkane and the aluminum trichloride obtained after layering in the step (2), and the aluminum trichloride is recovered.
When adding phosphate and phosphorus trichloride, adding chlorinated alkane or chlorinated aromatic hydrocarbon into the mixture of the phosphate and the aluminum trichloride obtained after layering in the step (2), stirring uniformly, and standing to obtain liquid-solid two phases; filtering to obtain aluminum trichloride; the filtrate is a mixture of phosphate and chlorinated alkane or chlorinated aromatic hydrocarbon, and the phosphate is recovered after the chlorinated alkane or chlorinated aromatic hydrocarbon is distilled off.
In the step (3), the mixture of the lower layer phenyl phosphine tetrachloride and phosphorus trichloride obtained in the layering of the step (2) is transferred into a flask, yellow phosphorus or stannous chloride and tin powder are added for reaction, the phosphorus trichloride is distilled off under normal pressure, and then the phenyl phosphine dichloride is collected by vacuum distillation.
And (3) transferring the lower diphenyl phosphine trichloride obtained after layering in the step (2) into a flask, adding chlorinated paraffin, stirring uniformly, slowly adding anhydrous stannous chloride and tin powder for reaction, and then carrying out vacuum distillation to collect the diphenyl phosphine chloride.
The invention has the positive effects that:
(1) According to the preparation method of the organic phosphine, a continuous chlorination method is adopted for an [ organic phosphine-aluminum trichloride ] complex obtained by catalyzing alkane or arene and inorganic phosphorus reaction by aluminum trichloride, P in the organic phosphine is chlorinated to obtain a novel polychlorinated organic phosphine intermediate, the polychlorinated organic phosphine intermediate and the aluminum trichloride do not form a complex, the polychlorinated organic phosphine intermediate and the aluminum trichloride can be effectively separated, and redundant chlorine is removed again from the polychlorinated organic phosphine intermediate obtained after separation, so that the target organic phosphine product is obtained.
The method avoids the problem that the complex is decomplexed by using sodium chloride or potassium chloride at present, and the formed complex of sodium chloride or potassium chloride and aluminum trichloride can wrap part of organic phosphine products to cause difficult treatment: the high-salt solid waste is not suitable for incineration treatment, sodium chloride or potassium chloride is generally recovered by a method of adding water for dissolution, aluminum trichloride is completely dissolved in the treatment process, and the pungent HCl and other odorous substances are released, so that the environmental impact is great; and the aluminum trichloride is treated to prepare the water treatment agent only.
(2) The method has the advantages of high reaction yield up to 92%, less waste residues, recycling and reusing of the catalyst aluminum trichloride and other intermediate treating agents, and cost saving.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
The starting complexes [ organophosphine-aluminum trichloride ] mentioned in the examples below can all be prepared by the prior art, i.e. alkane or arene reacted with phosphorus trichloride under the catalysis of aluminum trichloride.
Example 1
The preparation method of the organic phosphine compound of this example comprises the following steps:
(1) 267g (1 mol) of [ methyl phosphine dichloride-aluminum trichloride ] complex is added into a 2L flask, 534g of chlorinated paraffin-42 is added, the mixture is stirred uniformly at a high speed and is heated to 45+/-2 ℃, chlorine gas is introduced, the temperature in the flask is kept between 50 ℃ and 55 ℃ in the process of introducing the chlorine gas, and the reaction is finished when the chlorine gas is not absorbed any more.
After the temperature of the materials in the flask is cooled to below 35 ℃, pouring the materials into a 1L measuring cylinder, standing and layering, separating out the upper chlorinated paraffin-42, wherein the lower layer is a mixture of methyl phosphine tetrachloride and aluminum trichloride, and the methyl phosphine tetrachloride and the aluminum trichloride are not complexed.
The [ methyl phosphine dichloride-aluminum trichloride ] complex is an aluminum trichloride complex of methyl phosphine dichloride obtained by reacting methane and phosphorus trichloride under the catalysis of aluminum trichloride, and the [ methyl phosphine dichloride-aluminum trichloride ] complex is obtained by purifying after the reaction is finished.
(2) Transferring the lower layer mixture obtained in the step (1) into a 1L beaker, adding 0.5L of chloroform and 133.5 g of phosphorus trichloride, uniformly stirring, and standing for layering; the upper layer is a mixture of methyl phosphine tetrachloride and phosphorus trichloride, and the lower layer is a mixture of chloroform and aluminum trichloride.
(3) Transferring the mixture of the upper layer methyl phosphine tetrachloride and phosphorus trichloride obtained in the step (2) into a flask, adding 30g of yellow phosphorus particles under stirring at 50 ℃ for half an hour, performing atmospheric distillation, collecting fraction phosphorus trichloride before 81 ℃, collecting fraction methyl phosphine dichloride at 81-82 ℃, and collecting 105.9 g of methyl phosphine dichloride to obtain 90.5% yield and 99.4% GC purity; the distillation residue was mixed into the next batch and added before the yellow phosphorus was added.
(4) And (3) distilling the lower chloroform and aluminum trichloride mixture obtained in the step (2) after layering to remove chloroform to obtain aluminum trichloride, and further performing activating treatment and recycling.
The method is the same as above for other [ alkyl phosphine dichloride-aluminum trichloride ] complexes, [ dialkyl phosphine chloride-aluminum trichloride ] complexes, from which the target product alkyl phosphine dichloride is released.
Example 2
The preparation method of the organic phosphine compound of this example is the same as that of example 1 except that: in the step (2), the lower layer mixture in the step (1) is transferred into a 1L beaker, 0.5L of trichloroethyl phosphate and 133.5 g of phosphorus trichloride are added, and after uniform stirring, standing and layering are carried out: the upper layer is a mixture of methyl phosphine tetrachloride and phosphorus trichloride, and the lower layer is a mixture of trichloroethyl phosphate and aluminum trichloride.
In the step (3), the mixture of the upper layer methyl phosphine tetrachloride and phosphorus trichloride obtained after layering in the step (2) is transferred into a flask, 30g of yellow phosphorus particles are added under stirring at 50 ℃, after stirring for half an hour, normal pressure distillation is carried out, phosphorus trichloride is used before the boiling point of 81 ℃, and the fraction at the temperature of 81-82 ℃ is collected to obtain 107.1 g of methyl phosphine dichloride, the yield is 91.5%, and the GC purity is 99.6%.
In the step (4), adding 0.5L of chloroform into the mixture of the lower trichloroethyl phosphate and the aluminum trichloride obtained after layering in the step (2), and standing after uniformly stirring to obtain a liquid-solid two-phase; filtering to obtain aluminum trichloride, and further activating and recycling; the filtrate is a mixture of trichloroethyl phosphate and chloroform, and the trichloroethyl phosphate is recovered after the chloroform is distilled off at 61-65 ℃.
The trichloroethyl phosphate in this example may be replaced with trichloropropyl phosphate.
Example 3
The preparation method of the organic phosphine compound of this example comprises the following steps:
(1) 329g (1 mol) of [ phenyl phosphine dichloride-aluminum trichloride ] complex is added into a 2L flask, 658g of chlorinated paraffin-42 is added, the mixture is stirred uniformly at a high speed and is heated to 45 ℃, chlorine gas is introduced, the temperature in the flask is kept between 78 ℃ and 85 ℃ in the process of introducing the chlorine gas, and the reaction is finished when the chlorine gas is not absorbed any more.
Keeping the temperature of the materials at 80 ℃, pouring the materials into a 2L measuring cylinder, standing and layering, separating the upper chlorinated paraffin-42, and the lower layer is a mixture of phenyl phosphine tetrachloride and aluminum trichloride.
The [ phenyl phosphine dichloride and aluminum trichloride ] complex is obtained by reacting benzene and phosphorus trichloride under the catalysis of aluminum trichloride to obtain the aluminum trichloride complex of phenyl phosphine dichloride, purifying after the reaction is finished, and removing unreacted raw materials.
(2) Transferring the mixture of the lower-layer phenyl phosphine tetrachloride and aluminum trichloride obtained in the step (1) into a 2L beaker, heating to 80 ℃, adding 0.5L of chlorobenzene and 164.5g of phosphorus trichloride into the mixture, stirring at 70 ℃, standing and layering after stirring uniformly: the upper layer is a mixture of chlorobenzene and aluminum trichloride, and the lower layer is a mixture of phenyl phosphine tetrachloride and phosphorus trichloride.
(3) Transferring the mixture of the lower-layer phenyl phosphine tetrachloride and phosphorus trichloride obtained in the step (2) into a flask, adding 30g of yellow phosphorus particles under stirring at 70 ℃, stirring for half an hour, performing normal pressure distillation, and collecting fraction phosphorus trichloride at the temperature of 81 ℃; then the mixture is converted into vacuum distillation, the pressure is 0.085MPa, and the fraction phenyl phosphine dichloride between 90 ℃ and 100 ℃ is collected to obtain 163.4 g of phenyl phosphine dichloride, the yield is 91.3 percent, and the GC purity is 99.2 percent; the distillation residue was mixed into the next batch and added before the yellow phosphorus was added.
(4) And (3) distilling the upper chlorobenzene and aluminum trichloride mixture obtained in the step (2) at 132 ℃ to remove chlorobenzene and obtain aluminum trichloride, and further performing activation treatment and recycling.
Example 4
The preparation method of the organic phosphine compound of this example is the same as that of example 3 except that:
in the step (2), transferring the mixture of the lower layer phenyl phosphine tetrachloride and aluminum trichloride obtained in the step (1) into a 2L beaker, heating to 80 ℃, then adding 0.5L of trichloroethyl phosphate and 164.5g g of phosphorus trichloride into the mixture, stirring at 70 ℃, and standing for layering after stirring uniformly: the upper layer is a mixture of trichloroethyl phosphate and aluminum trichloride, and the lower layer is a mixture of phenyl phosphine tetrachloride and phosphorus trichloride.
165.6 g of phenyl phosphine dichloride is obtained in the step (3) in the same way as in the example 3, the yield is 92.5%, and the GC purity is 99.3%.
In the step (4), chlorobenzene 0.5L is added into the mixture of the upper trichloroethyl phosphate and the aluminum trichloride obtained after layering in the step (2), and after uniform stirring, the mixture is left to stand, so that liquid-solid two phases are obtained: filtering to obtain aluminum trichloride, and further activating and recycling; the filtrate was a mixture of trichloroethyl phosphate and chlorobenzene, and the chlorobenzene was distilled off at 132℃to recover trichloroethyl phosphate.
The trichloroethyl phosphate in this example may be replaced with trichloropropyl phosphate.
Example 5
The preparation method of the organic phosphine compound of this example was the same as in example 4 except that:
in the step (3), transferring the mixture of the lower layer phenyl phosphine tetrachloride and phosphorus trichloride obtained after layering in the step (2) into a flask, adding 10 g of anhydrous stannous chloride and 120 g of tin powder under stirring at 70 ℃, stirring for half an hour, performing normal pressure distillation, and collecting fraction phosphorus trichloride at the temperature of 81 ℃; then the mixture is converted into vacuum distillation, the pressure is 0.085MPa, and fraction phenyl phosphine dichloride between 90 ℃ and 100 ℃ is collected to obtain 161.3 g of phenyl phosphine dichloride, the yield is 90.1 percent, and the GC purity is 99.1 percent; the distillation residue is treated as solid waste.
Example 6
The preparation method of the organic phosphine compound of this example comprises the following steps:
(1) 370 g (1 mol) of [ diphenylphosphine chloride aluminum trichloride ] complex is added into a 2L flask, 740 g of chlorinated paraffin-42 is added, the mixture is stirred uniformly at a high speed and heated to 45 ℃, chlorine gas is introduced, the temperature is gradually increased to 200 ℃ in the process of introducing the chlorine gas, and the reaction is finished when the chlorine gas is not absorbed any more.
Keeping the temperature of the materials at 200 ℃, pouring the materials into a 2L measuring cylinder, standing and layering, separating the upper chlorinated paraffin-42, and the lower layer is a mixture of diphenyl phosphine trichloride and aluminum trichloride.
The [ diphenylphosphine chloride-aluminum trichloride ] complex is prepared by firstly preparing the [ diphenylphosphine dichloride-aluminum trichloride ] complex and then performing disproportionation reaction to prepare the [ diphenylphosphine chloride-aluminum trichloride ] complex.
(2) Transferring the mixture of the lower diphenyl phosphine trichloride and the aluminum trichloride obtained in the step (1) into a 2L beaker, heating to 200 ℃, adding dichlorobenzene 1L into the mixture, keeping the temperature of 200 ℃ for stirring, and standing for layering after stirring uniformly: the upper layer is a mixture of dichlorobenzene and aluminum trichloride, and the lower layer (2) is diphenyl phosphine trichloride.
(3) Transferring the diphenyl phosphine trichloride obtained in the step (2) into a flask, adding 740 g of chlorinated paraffin-42 at 200 ℃, stirring uniformly, slowly adding 10 g of anhydrous stannous chloride and 120 g of tin powder, stirring for half an hour, performing vacuum distillation under the pressure of 0.085MPa, and collecting 220-240 ℃ fraction diphenyl phosphine chloride to obtain 156.6 g, wherein the yield is 87.5%, and the GC purity is 99.6%; the distillation residue is treated as solid waste.
(4) And (3) vacuum distilling the upper dichlorobenzene and aluminum trichloride mixture obtained in the step (2) for removing dichlorobenzene to obtain aluminum trichloride, and further performing activation treatment for recycling.
Example 7
The preparation method of the organic phosphine compound of this example comprises the following steps:
(1) 274.6g (1 mol) of [ diethyl phosphine chloride-aluminum trichloride ] complex is added into a 2L flask, 549g of chlorinated paraffin-42 is added, the mixture is stirred uniformly at a high speed and is heated to 45+/-2 ℃, chlorine gas is introduced, the temperature in the flask is kept between 50 ℃ and 55 ℃ in the process of introducing the chlorine gas, and the reaction is finished when the chlorine gas is not absorbed any more.
And after the temperature of the materials in the flask is cooled to below 35 ℃, pouring the materials into a 1L measuring cylinder, standing and layering, separating out the upper chlorinated paraffin-42, wherein the lower layer is a mixture of diethyl phosphine trichloride and aluminum trichloride, and at the moment, the diethyl phosphine trichloride and the aluminum trichloride are not complexed.
The [ diethyl phosphine trichloride and aluminum trichloride ] complex is an aluminum trichloride complex of diethyl phosphine trichloride obtained by reacting ethane and phosphorus trichloride under the catalysis of aluminum trichloride, and the [ diethyl phosphine trichloride and aluminum trichloride ] complex is obtained by purifying after the reaction is finished.
(2) Transferring the lower layer mixture obtained in the step (1) into a 1L beaker, adding 0.5L of chlorobenzene and 123 g of phosphorus trichloride, uniformly stirring, and standing for layering; the upper layer is a mixture of diethyl phosphine trichloride and phosphorus trichloride, and the lower layer is a mixture of chlorobenzene and aluminum trichloride.
(3) Transferring the mixture of the upper layer diethyl phosphine trichloride and phosphorus trichloride obtained after layering in the step (2) into a flask, adding 10 g of anhydrous stannous chloride and 120 g of tin powder under stirring at 50 ℃, stirring for half an hour, performing vacuum distillation under the pressure of 0.085MPa, and collecting the fraction diethyl phosphine chloride at 132-135 ℃ to obtain 112.8 g, wherein the yield is 90.5%, and the GC purity is 99.1%; the distillation residue is treated as solid waste.
(4) And (3) distilling the mixture of the lower chlorobenzene and aluminum trichloride obtained in the step (2) after layering to remove chlorobenzene to obtain aluminum trichloride, and further performing activating treatment and recycling.
Claims (8)
1. A method for producing an organic phosphine compound, characterized by comprising the steps of:
(1) reacting an [ organic phosphine-aluminum trichloride ] complex obtained by reacting alkane or arene catalyzed by aluminum trichloride with phosphorus trichloride with chlorine, adding the [ organic phosphine-aluminum trichloride ] complex into a reaction vessel, adding chlorinated paraffin into the reaction vessel, uniformly stirring and heating to 45+/-2 ℃, starting to introduce the chlorine, and ending the reaction when the chlorine is not absorbed any more; standing for layering after the reaction is finished, separating the upper chlorinated paraffin, wherein the lower layer is a mixture of a polychlorinated organic phosphine intermediate and aluminum trichloride;
the organic phosphine in the [ organic phosphine-aluminum trichloride ] complex is alkyl phosphine dichloride, dialkyl phosphine chloride, phenyl phosphine dichloride or diphenyl phosphine chloride;
(2) adding a solvent into the mixture of the polychlorinated organic phosphine intermediate and aluminum trichloride obtained in the step (1), stirring and layering, wherein the polychlorinated organic phosphine intermediate and the aluminum trichloride are positioned on different layers;
(3) and (3) reacting the polychlorinated organic phosphine intermediate obtained in the step (2) with yellow phosphorus or stannous chloride and tin powder to obtain the target product organic phosphine.
2. The method for producing an organic phosphine compound according to claim 1, wherein: for the [ alkyl phosphine dichloride-aluminum trichloride ] complex or the [ dialkyl phosphine chloride-aluminum trichloride ] complex, maintaining the temperature in a reaction vessel between 50 ℃ and 55 ℃ in the chlorine gas introducing process; for the [ phenyl phosphine dichloride-aluminum trichloride ] complex, maintaining the temperature in a reaction vessel at 78-85 ℃ in the chlorine gas introducing process; for the [ diphenylphosphine chloride-aluminum trichloride ] complex, the temperature in the reaction vessel was kept gradually rising to 200℃during the chlorine gas introduction.
3. The method for producing an organic phosphine compound according to claim 1, wherein: in the step (2), the step of (C),
adding chloralkane and phosphorus trichloride or phosphate and phosphorus trichloride into a mixture of polychlorinated organic phosphine intermediate and aluminum trichloride, which is obtained by reacting an [ alkyl phosphine dichloride-aluminum trichloride ] complex with chlorine, stirring uniformly, and standing for layering; the upper layer is a mixture of alkyl phosphine tetrachloride and phosphorus trichloride, and the lower layer is a mixture of chloralkane and aluminum trichloride, or a mixture of phosphate and aluminum trichloride; the phosphate is trichloroethyl phosphate or trichloropropyl phosphate;
adding chloralkane and phosphorus trichloride or phosphate and phosphorus trichloride into a mixture of polychlorinated organic phosphine intermediate and aluminum trichloride, which is obtained by reacting a [ dialkylphosphine chloride-aluminum trichloride ] complex with chlorine, stirring uniformly, and standing for layering; the upper layer is a mixture of dialkyl phosphine trichloride and phosphorus trichloride, and the lower layer is a mixture of chloralkane and aluminum trichloride or a mixture of phosphate and aluminum trichloride; the phosphate is trichloroethyl phosphate or trichloropropyl phosphate;
adding chlorinated aromatic hydrocarbon and phosphorus trichloride or phosphate and phosphorus trichloride into a mixture of polychlorinated organic phosphine intermediate and aluminum trichloride obtained by reacting a [ phenyl phosphine dichloride-aluminum trichloride ] complex with chlorine, uniformly stirring, standing and layering, wherein the upper layer is a mixture of chlorinated aromatic hydrocarbon and aluminum trichloride or a mixture of phosphate and aluminum trichloride, and the lower layer is a mixture of phenyl phosphine tetrachloride and phosphorus trichloride; the phosphate is trichloroethyl phosphate or trichloropropyl phosphate;
and adding chlorinated aromatic hydrocarbon into the mixture of the polychlorinated organic phosphine intermediate and aluminum trichloride, which is obtained by reacting the [ diphenyl phosphine chloride-aluminum trichloride ] complex with chlorine, stirring uniformly, standing and layering, wherein the upper layer is the mixture of the chlorinated aromatic hydrocarbon and the aluminum trichloride, and the lower layer is diphenyl phosphine trichloride.
4. A process for producing an organic phosphine compound according to claim 3, wherein:
in the step (3), the mixture of the upper alkyl phosphine tetrachloride and phosphorus trichloride obtained after layering in the step (2), or the mixture of the dialkyl phosphine trichloride and phosphorus trichloride is transferred into a flask, yellow phosphorus or stannous chloride and tin powder are added for reaction, and then normal pressure distillation is carried out, and fractions between corresponding distillation ranges of the alkyl phosphine dichloride or the dialkyl phosphine trichloride are collected.
5. The process for producing an organic phosphine compound according to claim 4, wherein: when chloralkane and phosphorus trichloride are added in the step (2), the chloralkane is distilled off from the mixture of the lower chloralkane and the aluminum trichloride obtained after layering in the step (2), and the aluminum trichloride is recovered.
6. The process for producing an organic phosphine compound according to claim 4, wherein: when adding phosphate and phosphorus trichloride, adding chlorinated alkane or chlorinated aromatic hydrocarbon into the mixture of the phosphate and the aluminum trichloride obtained after layering in the step (2), stirring uniformly, and standing to obtain liquid-solid two phases; filtering to obtain aluminum trichloride; the filtrate is a mixture of phosphate and chlorinated alkane or chlorinated aromatic hydrocarbon, and the phosphate is recovered after the chlorinated alkane or chlorinated aromatic hydrocarbon is distilled off.
7. A process for producing an organic phosphine compound according to claim 3, wherein:
in the step (3), the mixture of the lower layer phenyl phosphine tetrachloride and phosphorus trichloride obtained after layering in the step (2) is transferred into a flask, yellow phosphorus or stannous chloride and tin powder are added for reaction, the phosphorus trichloride is removed by normal pressure distillation, and then the phenyl phosphine dichloride is collected by vacuum distillation.
8. A process for producing an organic phosphine compound according to claim 3, wherein: and (3) transferring the lower diphenyl phosphine trichloride obtained after layering in the step (2) into a flask, adding chlorinated paraffin, stirring uniformly, slowly adding anhydrous stannous chloride and tin powder for reaction, and then carrying out vacuum distillation to collect the diphenyl phosphine chloride.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB707961A (en) * | 1948-04-30 | 1954-04-28 | Nat Res Dev | Improvements in or relating to the production of organic phosphorus compounds |
| US3840576A (en) * | 1951-08-09 | 1974-10-08 | Mini Of Supply | Preparation of complex aluminum compounds and alkyl phosphorus halides |
| CN108558943A (en) * | 2018-05-10 | 2018-09-21 | 四川福思达生物技术开发有限责任公司 | A method of dissociation dichloromethylphosphine and aluminum chloride complex |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB707961A (en) * | 1948-04-30 | 1954-04-28 | Nat Res Dev | Improvements in or relating to the production of organic phosphorus compounds |
| US3840576A (en) * | 1951-08-09 | 1974-10-08 | Mini Of Supply | Preparation of complex aluminum compounds and alkyl phosphorus halides |
| CN108558943A (en) * | 2018-05-10 | 2018-09-21 | 四川福思达生物技术开发有限责任公司 | A method of dissociation dichloromethylphosphine and aluminum chloride complex |
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| "Two Independent Orthogonal Stereomutations at a Single Asymmetric Center: A Narcissistic Couple";Malachi W. Gillick-Healy等;《Chem. Eur. J.》;第23卷;第2332 –2339页 * |
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