CN113912645B - Preparation method of triphenylphosphine - Google Patents
Preparation method of triphenylphosphine Download PDFInfo
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- CN113912645B CN113912645B CN202111317553.6A CN202111317553A CN113912645B CN 113912645 B CN113912645 B CN 113912645B CN 202111317553 A CN202111317553 A CN 202111317553A CN 113912645 B CN113912645 B CN 113912645B
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- triphenylphosphine
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims abstract description 60
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910000104 sodium hydride Inorganic materials 0.000 claims abstract description 37
- 239000012312 sodium hydride Substances 0.000 claims abstract description 37
- 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 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 31
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims description 72
- 239000000243 solution Substances 0.000 claims description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- -1 trimethoxyborohydride-sodium Chemical compound 0.000 claims description 12
- 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 description 11
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 11
- 239000001119 stannous chloride Substances 0.000 claims description 11
- 235000011150 stannous chloride Nutrition 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical class [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 4
- 229940011051 isopropyl acetate Drugs 0.000 claims description 4
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 10
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 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 description 6
- 239000012280 lithium aluminium hydride Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 229910000085 borane Inorganic materials 0.000 description 4
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 4
- 239000005052 trichlorosilane Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 3
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 3
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 description 3
- 238000007239 Wittig reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- ZRDRRLQUBZPUOP-UHFFFAOYSA-N trichloro(hydroxy)silane Chemical compound O[Si](Cl)(Cl)Cl ZRDRRLQUBZPUOP-UHFFFAOYSA-N 0.000 description 1
- AVCVDUDESCZFHJ-UHFFFAOYSA-N triphenylphosphane;hydrochloride Chemical compound [Cl-].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 AVCVDUDESCZFHJ-UHFFFAOYSA-N 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
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
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- 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)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of triphenylphosphine, which comprises the following steps: the method comprises the following steps of (1) preparing trimethoxy monoboron sodium, and reacting the trimethoxy monoboron sodium with triphenylphosphine dichloride to obtain triphenylphosphine; further, reacting sodium hydride with trimethyl borate to obtain trimethoxy monoboron sodium reaction solution; dropwise adding the obtained trimethoxy monoboron sodium reaction solution into the first solution to react to obtain triphenylphosphine; the method provided by the invention can realize the advantages of high yield, high purity and more environmental protection of triphenylphosphine.
Description
Technical Field
The invention relates to the technical field of triphenylphosphine preparation, and particularly relates to a preparation method of triphenylphosphine.
Background
Triphenylphosphine is a chemical raw material with wide application, and is widely applied to wittig reaction process, catalyst ligand and the like in the industries of medicine, chemical engineering and the like. After the triphenylphosphine is used for wittig reaction, the triphenylphosphine becomes a byproduct triphenylphosphine oxide; if triphenylphosphine oxide is used as waste residue for treatment, the treatment cost is high, and the content of phosphorus in the three wastes is difficult to be treated below the environmental protection qualified standard. Therefore, the technology of reducing triphenylphosphine oxide to obtain triphenylphosphine has also been widely researched and applied.
1.2, at present, there are two main industrial methods for preparing triphenylphosphine by reducing triphenylphosphine oxide.
The first method is to directly reduce triphenylphosphine oxide using 1, 3-tetramethyldisiloxane, trichloromonohydroxysilane, or the like to obtain triphenylphosphine, wherein the chemical reaction equation is shown in formula (1):
the first method has the advantage of short process route. The disadvantages are that the market price of 1, 3-tetramethyl disiloxane is higher, a large amount of polydimethyl siloxane produced after the reaction needs to be properly treated, and the environmental protection cost is high. The trichlorosilane not only seriously corrodes equipment, but also has small proportion of effective reducing groups (hydrogen atoms) in molecules, so the total consumption is large, and the total cost of raw materials and equipment is high; a large amount of polydichlorosilane is also generated after the reaction, which needs to be properly treated, and the environmental protection cost is high.
The second method is that triphenylphosphine oxide is treated with oxalyl chloride to obtain triphenylphosphine dichloride; then reducing triphenylphosphine dichloride with lithium aluminum hydride, aluminum powder (flake) and the like to obtain triphenylphosphine; wherein, the chemical reaction equation is shown as chemical formula (2):
the second method has the advantages that the by-products in the first step are mainly oxalic acid, the by-products in the second step are mainly aluminum trichloride, lithium chloride, hydrochloric acid and the like, and the difficulty of environmental protection treatment is relatively small. The disadvantages are: if the reaction in the second step is reduced by lithium aluminum hydride, the raw material cost is high; if aluminum powder (flake) is used for reduction, although the cost is low, the conversion rate is high only if the aluminum powder (flake) needs to be excessive by more than 3 times, and the active aluminum powder (flake) has more residues, is difficult to recycle and apply and can only be treated by adding acid; the waste of active aluminum powder (sheet) is more, hydrogen is generated during acid adding post-treatment, the process danger is larger during enlarged production, and a great amount of aluminum salt is generated, so that the method is not environment-friendly.
Disclosure of Invention
The invention provides a preparation method of triphenylphosphine, which is used for improving the preparation process of the triphenylphosphine and adopts sodium hydride with lower price as an initial raw material to prepare trimethoxy sodium monohydroxyl, and then the trimethoxy sodium monohydroxyl reacts with triphenylphosphine dichloride under the action of catalytic amount of aluminum trichloride or stannous chloride to obtain the triphenylphosphine. The cost of raw materials is lower than that of the two methods, the main three wastes are only sodium chloride, and the solvent and the main auxiliary agent trimethyl borate can be recycled; the process is high in safety and more environment-friendly.
The invention provides a preparation method of triphenylphosphine, which comprises the following steps:
preparing the trimethoxy-boron monohydrogen sodium,
the triphenylphosphine is obtained by the reaction of trimethoxy monoboron sodium and triphenylphosphine dichloride.
Preferably, the method further comprises the following steps:
reacting sodium hydride with trimethyl borate to obtain trimethoxy monoboron sodium reaction solution;
dropwise adding the obtained trimethoxy monoboron sodium reaction solution into the first solution to obtain triphenylphosphine.
Preferably, the first solution is triphenylphosphine dichloride solution containing a catalytic amount of aluminum trichloride or stannous chloride.
Preferably, the method further comprises the following steps:
adding sodium hydride and a solvent A into the first reaction bottle; then, cooling to-50-10 ℃ under the protection of nitrogen, uniformly stirring at the temperature of-50-10 ℃, and then dropwise adding a second solution;
after the dropwise addition is finished, the mixture is continuously stirred for 1 to 5 hours at the temperature of between 50 ℃ below zero and 10 ℃ to generate trimethoxy sodium borohydride reaction liquid.
Preferably, the solvent A is one or a mixture of more of diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran and 1, 4-dioxane;
the dosage of the solvent A is 4-6 times of the mass ratio of sodium hydride;
the dosage of the trimethyl borate is 1.1 to 4.0 times of the equivalent of the sodium hydride;
the second solution is trimethyl borate, or a mixed solution of trimethyl borate and the solvent A.
Preferably, adding triphenylphosphine dichloride and the solution III into the reaction bottle II, and stirring uniformly under the protection of nitrogen at-50-10 ℃;
then adding a catalyst, and then dropwise adding trimethoxy monoboron sodium reaction solution;
after the dropwise addition is finished, the reaction is carried out for 3 to 15 hours at the temperature of minus 20 to 10 ℃;
filtering to remove insoluble substances generated in the reaction and obtain filtrate; wherein the insoluble substance is sodium chloride.
Preferably, the dosage of the triphenylphosphine dichloride is 0.4 to 0.45 time equivalent of the sodium hydride;
the third solution is a solvent A or a mixture of the solvent A and trimethyl borate; the mixing ratio of the solvent A and trimethyl borate is any ratio;
the dosage of the solution III is 4 to 8 times of the mass ratio of the triphenylphosphine dichloride;
the solvent A is one or a mixture of more of diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran and 1, 4-dioxane;
the catalyst is one or a mixture of stannous chloride and aluminum trichloride;
the dosage of the catalyst is 0.5 to 5 mass percent of the triphenylphosphine dichloride;
the temperature of the dropping of the trimethoxy monoboron sodium reaction liquid and the temperature of the heat preservation reaction after the dropping are both-20 to 10 ℃; the heat preservation reaction time after the dropwise addition is 3 to 15 hours;
the temperature for filtering and removing insoluble substances generated by the reaction is between-20 ℃ and room temperature.
Preferably, the filtrate is decompressed and concentrated, the azeotrope of trimethyl borate and the solvent A is recovered, and the concentrated residue is reserved;
adding a solvent B and dilute hydrochloric acid into the concentrated residues, and hydrolyzing and extracting;
carrying out liquid separation on the hydrolysis reaction product, washing the obtained organic layer with water to be neutral, and concentrating to remove the solvent B to obtain a crude product of the triphenylphosphine;
after purification and drying by a crystallization method, the high-purity triphenylphosphine is obtained.
Preferably, the solvent B is one or a mixture of more of benzene, toluene, xylene, chlorobenzene, anisole, tetrahydrofuran and methyltetrahydrofuran;
the dosage of the solvent B is 3-10 times of the mass ratio of the triphenylphosphine dichloride;
the dosage of the hydrochloric acid is 0.3 to 0.5 time equivalent of the sodium hydride;
in the water washing process, the water washing temperature is between 0 and 50 ℃;
the solvent used in the crystallization of the crude triphenylphosphine product can be ethanol, propanol, isopropanol, ethyl acetate, isopropyl acetate, toluene, petroleum ether, etc., or a mixture thereof;
the dosage of the crystallization solvent when the crude triphenylphosphine product is crystallized by a crystallization method is 3-10 times of the mass ratio of the crude triphenylphosphine product.
The invention has the following beneficial effects:
the method for preparing the triphenylphosphine by using the sodium hydride as the starting material to prepare the trimethoxy monoboron sodium and then using the trimethoxy monoboron sodium to reduce the triphenylphosphine dichloride to obtain the triphenylphosphine is not disclosed by related documents or technologies at present.
In the prior art, trimethoxy monoboron sodium can not exist stably at the temperature of more than 10 ℃; the reaction of disproportionation and decomposition is easy to occur, and further the reaction is converted into sodium methoxide and various byproducts, such as dimethoxy monohydroborane, methoxy dihydroborane and borane which escape in a gaseous state. In the process scheme for preparing sodium borohydride, due to the adoption of conditions such as excessive sodium hydride, a pressurized system, a reaction temperature of more than 200 ℃ and the like, trimethoxy monoborohydride sodium, dimethoxy monoborohydride, methoxy dihydroborane, borane and the like only exist as intermediates, and can continuously react with sodium hydride at a high temperature to finally obtain sodium borohydride, as shown in a chemical reaction formula (3):
the invention preferably selects another reaction condition, namely adopts a scheme that the temperature is lower than 10 ℃ and trimethyl borate is excessive, so that trimethoxy boron monohydroxyl sodium can be stably existed in the solution; and then directly used for the next reaction.
Further, trimethyl borate is preferably selected in the invention; when the temperature is below 10 ℃, only trimethyl borate can react with sodium hydride to obtain trimethoxy monoboron sodium; similar triethyl borate, tripropyl borate, tributyl borate, etc. do not react similarly.
Meanwhile, in the present invention, sodium hydride is used in a sufficient market, and the effective reducing group (hydrogen atom) has a large specific gravity in the molecule, and the unit cost thereof is lower than 1, 3-tetramethyldisiloxane, trichlorosilane, or lithium aluminum hydride, excess aluminum flakes (powder), etc. Compared with other existing industrial methods for preparing triphenylphosphine by using triphenylphosphine dichloride, the method has the advantages of lower raw material cost and higher process safety.
In addition, the method adopted by the invention does not generate a large amount of byproducts such as polysilicon, aluminum salt and the like which are difficult to treat, or dangerous active aluminum powder (flake) residues; the main auxiliary materials of trimethyl borate, the solvent A, the solvent B and the like can be recycled and reused; is more environment-friendly.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description.
The technical solution of the present invention is further described in detail by the following examples.
Detailed Description
The preferred embodiments of the present invention are described below, and it should be understood that the preferred embodiments described herein are only for illustrating and explaining the present invention and are not to be construed as limiting the present invention.
The embodiment of the invention provides a preparation method of triphenylphosphine, which comprises the following steps:
the trimethoxy monoboron sodium is prepared, and the trimethoxy monoboron sodium is reacted with triphenylphosphine dichloride to obtain triphenylphosphine.
Further comprising: reacting sodium hydride with trimethyl borate to obtain trimethoxy monoboron sodium reaction solution; dropwise adding the obtained trimethoxy monoboron sodium reaction solution into the first solution to react to obtain the triphenylphosphine. The first solution is triphenylphosphine dichloride solution containing a catalytic amount of aluminum trichloride or stannous chloride.
Further comprising: adding sodium hydride and a solvent A into the first reaction bottle; then, cooling to-50-10 ℃ under the protection of nitrogen, uniformly stirring at the temperature of-50-10 ℃, and then dropwise adding a second solution; after the dropwise addition is finished, the mixture is continuously stirred for 1 to 5 hours at the temperature of between 50 ℃ below zero and 10 ℃ to generate the trimethoxy monoboron sodium reaction solution.
The solvent A is one or a mixture of more of diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran and 1, 4-dioxane; the dosage of the solvent A is 4-6 times of the mass ratio of sodium hydride; the dosage of the trimethyl borate is 1.1 to 4.0 times of the equivalent of the sodium hydride; the second solution is trimethyl borate, or a mixed solution of trimethyl borate and the solvent A.
Further, adding triphenylphosphine dichloride and the solution III into the reaction bottle II, and stirring uniformly under the protection of nitrogen at-50-10 ℃; then adding a catalyst, and then dropwise adding trimethoxy monoboron sodium reaction solution; after the dropwise addition is finished, the reaction is carried out for 3 to 15 hours under the condition of the temperature of minus 20 to 10 ℃; filtering to remove insoluble substances generated in the reaction and obtain filtrate; wherein the insoluble substance is sodium chloride.
Wherein the dosage of the triphenylphosphine dichloride is 0.4 to 0.45 equivalent of the sodium hydride; the third solution is a solvent A or a mixture of the solvent A and trimethyl borate; the mixing ratio of the solvent A and trimethyl borate is any ratio; the dosage of the solution III is 4-8 times of the mass ratio of the triphenylphosphine dichloride; the solvent A is one or a mixture of more of diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran and 1, 4-dioxane; the catalyst is one or a mixture of stannous chloride and aluminum trichloride; the dosage of the catalyst is 0.5 to 5 mass percent of the triphenylphosphine dichloride; the temperature of the dropping of the trimethoxy monoboron sodium reaction liquid and the temperature of the heat preservation reaction after the dropping are both-20 to 10 ℃; the reaction time after the dropwise addition is 3 to 15 hours; the temperature for filtering and removing insoluble substances generated by the reaction is between-20 ℃ and room temperature.
Further, decompressing and concentrating the filtrate, recovering an azeotrope of trimethyl borate and the solvent A, and reserving a concentrated residue; adding a solvent B and dilute hydrochloric acid into the concentrated residues, and hydrolyzing and extracting; separating the hydrolyzed reactant, washing the obtained organic layer with water to neutrality, and concentrating to remove the solvent B to obtain a crude product of triphenylphosphine; after purification and drying by a crystallization method, the high-purity triphenylphosphine is obtained.
Wherein the solvent B is one or a mixture of benzene, toluene, xylene, chlorobenzene, anisole, tetrahydrofuran and methyltetrahydrofuran; the dosage of the solvent B is 3-10 times of the mass ratio of the triphenylphosphine dichloride; the dosage of the hydrochloric acid is 0.3 to 0.5 time equivalent of the sodium hydride; in the water washing process, the water washing temperature is between 0 and 50 ℃; the solvent used in the crystallization of the crude triphenylphosphine product can be ethanol, propanol, isopropanol, ethyl acetate, isopropyl acetate, toluene, petroleum ether, etc., or a mixture thereof; the dosage of the crystallization solvent when the triphenylphosphine crude product is crystallized by using a crystallization method is 3-10 times of the mass ratio of the triphenylphosphine crude product.
The preparation method comprises the following steps:
using a one-pot method; firstly, sodium hydride is used for reacting with trimethyl borate to prepare trimethoxy sodium borohydride; then the reaction liquid is dripped into the triphenylphosphine chloride solution containing the catalytic amount of aluminum trichloride (or stannous chloride), and the triphenylphosphine is obtained after the reaction. Byproducts are sodium chloride and trimethyl borate; wherein trimethyl borate can be recovered and reused together with the solvent, and the corresponding chemical reaction equation (4):
the specific operation steps are as follows:
step 1, adding sodium hydride and a solvent A into a reaction bottle I; then cooling to-50-10 ℃ under the protection of nitrogen, keeping the temperature at-50-10 ℃, stirring, and dropwise adding trimethyl borate (or the mixed solution of trimethyl borate and the solvent A). After the dropwise addition is finished, the mixture is continuously stirred for 1 to 5 hours at the temperature of between 50 ℃ below zero and 10 ℃ to generate the trimethoxy monoboron sodium reaction solution.
The solvent A can be one of diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran and 1, 4-dioxane, or a mixture of the diethyl ether, the tetrahydrofuran, the 2-methyltetrahydrofuran and the 1, 4-dioxane;
the dosage of the solvent A can be 4-6 times of the mass ratio of sodium hydride;
the dosage of the trimethyl borate can be 1.1 to 4.0 times of the equivalent of the sodium hydride;
the trimethyl borate (or the mixed solution of the trimethyl borate and the solvent A) can be pure trimethyl borate, or can be a solution of the trimethyl borate and the solvent A mixed in any proportion;
the dripping and heat preservation reaction temperature is between 50 ℃ below zero and 10 ℃;
the reaction time after the dropwise addition is kept at 1-5 hours.
And 2, adding triphenylphosphine dichloride and a solvent A (or a mixture of the solvent A and trimethyl borate) into the reaction bottle II, and keeping the temperature at-20-10 ℃ under the protection of nitrogen and stirring. Then adding a catalyst, and then dropwise adding trimethoxy monoboron sodium reaction solution. After the dropwise addition is finished, the temperature is kept between minus 20 ℃ and 10 ℃ for reaction for 3 to 15 hours. Insoluble matter (sodium chloride) produced by the reaction was then removed by filtration, and a filtrate was obtained.
The dosage of the triphenylphosphine dichloride can be 0.4 to 0.45 equivalent of the sodium hydride;
the solvent A can be one of diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran and 1, 4-dioxane, or a mixture of the diethyl ether, the tetrahydrofuran, the 2-methyltetrahydrofuran and the 1, 4-dioxane;
the solvent A and trimethyl borate are mixed in any proportion;
the dosage of the solvent A (or the mixture of the solvent A and trimethyl borate) can be 4 to 8 times of the mass ratio of triphenyl phosphine dichloride;
the catalyst can be stannous chloride, or aluminum trichloride, or a mixture of the stannous chloride and the aluminum trichloride;
the dosage of the catalyst can be 0.5 to 5 percent of the mass ratio of the triphenylphosphine dichloride;
the dripping operation time has no strict requirement, and the method is based on controlling the reaction heat release and ensuring the temperature of the reaction solution to be between 20 ℃ below zero and 10 ℃;
the temperature of the dropwise addition and the temperature of the reaction after the dropwise addition are both between-20 and 10 ℃;
the reaction time after the dropwise addition is kept at 3-15 hours.
The temperature during the filtration can be between-20 ℃ and room temperature.
And 3, carrying out reduced pressure concentration on the obtained filtrate, and recovering the azeotrope of the trimethyl borate and the solvent A. Adding solvent B and dilute hydrochloric acid into the concentrated residue, and hydrolyzing and extracting; and (3) separating the hydrolyzed reaction product, washing the obtained organic layer to be neutral by using water, and concentrating to remove the solvent B to obtain a crude product of the triphenylphosphine. Then purifying by a crystallization method and drying to obtain the high-purity triphenylphosphine.
The solvent B can be benzene, toluene, xylene, chlorobenzene, anisole, tetrahydrofuran, methyltetrahydrofuran, and the like, or a mixture of the benzene, the toluene, the xylene, the chlorobenzene, the anisole, the tetrahydrofuran, the methyltetrahydrofuran, and the like;
the dosage of the solvent B can be 3-10 times of the mass ratio of triphenylphosphine dichloride;
the concentration of the hydrochloric acid is not strictly required, and the dosage of the hydrochloric acid can be 0.3 to 0.5 time equivalent of that of sodium hydride;
the dosage of water and the washing times during washing have no strict requirements, and the washing is carried out until the water layer is neutral;
the temperature of the water washing is between 0 and 50 ℃;
the solvent used in the crystallization of the crude triphenylphosphine product can be ethanol, propanol, isopropanol, ethyl acetate, isopropyl acetate, toluene, petroleum ether, etc., or a mixture thereof;
the dosage of the solvent during the crystallization of the triphenylphosphine crude product can be 3-10 times of the mass ratio of the triphenylphosphine crude product;
the temperature and times of crystallization of the triphenylphosphine crude product are not strictly required, and the triphenylphosphine is purified to a satisfactory purity.
The invention adopts the scheme that the temperature is lower than 10 ℃ and trimethyl borate is excessive, so that the trimethoxy boron monohydrogen sodium can be kept stably in the solution; and then directly used for the next reaction. The situation that the trimethoxy monoboron sodium can not exist stably at the temperature of more than 10 ℃ in the prior art is reduced; and further reducing the unstable condition to cause the sodium trimethoxymonoborohydride to be easily subjected to disproportionation, decomposition and other reactions, and further converted into sodium methoxide and various byproducts, such as dimethoxy monohydroborane, methoxy dihydroborane and borane which escape in a gaseous state.
Further, trimethyl borate is preferably selected in the invention; when the temperature is below 10 ℃, only trimethyl borate can react with sodium hydride to obtain trimethoxy monoboron sodium; similar triethyl borate, tripropyl borate, tributyl borate, etc. do not react similarly.
Meanwhile, in the present invention, sodium hydride is used in a sufficient market supply, and the effective reducing group (hydrogen atom) has a large specific gravity in the molecule, and the unit cost thereof is lower than 1, 3-tetramethyldisiloxane, trichlorosilane, or lithium aluminum hydride, excess aluminum flakes (powder), etc. Compared with other existing industrial methods for preparing triphenylphosphine by using triphenylphosphine dichloride, the method has the advantages of lower raw material cost and higher process safety.
In addition, the method adopted by the invention does not generate a large amount of byproducts such as polysilicone, aluminum salt and the like which are difficult to treat or dangerous active aluminum powder (sheet) residues; the main auxiliary materials of trimethyl borate, the solvent A, the solvent B and the like can be recycled and reused; the environment is more friendly;
therefore, the method provided by the invention can realize the advantages of high yield, high purity and more environmental protection of triphenylphosphine.
Experimental example 1
1.1 to a 250ml reaction flask I, 20g (0.5 mol) of 60% sodium hydride and 80g of anhydrous tetrahydrofuran were added. Stirring and cooling to 0-10 ℃ under the protection of nitrogen. Then maintaining the protection of nitrogen, stirring and liquid temperature at 0-10 ℃, and dripping 57.2g (0.55 mol) of trimethyl borate; after the dripping is finished, the temperature is kept between 0 and 10 ℃ and the stirring is continued for 1 hour.
1.2 into another 1000ml reaction flask II, 74.9g (0.225 mol) of triphenylphosphine dichloride and 300g of tetrahydrofuran are added, and the temperature is controlled to be 0-10 ℃ under the protection of nitrogen and stirring. Then 0.375g of stannous chloride is added; then the temperature is controlled between 0 and 10 ℃, and the obtained reaction mixture is stirred and dropped by 4.1.1. After the dropwise addition, the temperature is kept between 0 and 10 ℃ for reaction for 15 hours. Then, the reaction mixture was filtered at room temperature to remove insoluble substances (sodium chloride) produced in the reaction.
1.3, carrying out reduced pressure concentration on the filtrate obtained in the step 1.2, and recovering the mixed solvent of trimethyl borate and tetrahydrofuran for use. 225g of toluene and 110g (0.15 mol) of 5% dilute hydrochloric acid were added to the concentrated residue, and after stirring at room temperature for 1 hour, liquid separation was performed; the organic layer was washed with water at 40-50 ℃ to neutrality and concentrated to remove toluene to give about 69g of residue as a crude triphenylphosphine. The crude product is crystallized for 2 times by using a mixed solvent of 2.8 times of ethanol and 0.2 time of toluene, and then dried to obtain 52.7g of triphenylphosphine, wherein the yield is 89.1%, and the purity of liquid chromatography is more than or equal to 99.7%.
Experimental example 2
2.1 to a 1000ml reaction flask I, 20g (0.5 mol) of 60% sodium hydride, and 120g of anhydrous 2-methyltetrahydrofuran were added. Stirring and cooling to-50 to-40 ℃ under the protection of nitrogen. Then maintaining the nitrogen protection, stirring and liquid temperature of-50 to-40 ℃, and dropwise adding a mixture of 208g (2 mol) of trimethyl borate and 200g of 2-methyltetrahydrofuran; after the dripping is finished, the mixture is kept at the temperature of between 50 ℃ below zero and 40 ℃ below zero and stirred for 5 hours.
2.2 into a second 2000ml reaction flask, 66.6g (0.2 mol) of triphenylphosphine dichloride and 533g of a mixture of 2-methyltetrahydrofuran/trimethyl borate are added, and the temperature is controlled to be-20 to-10 ℃ under the protection of nitrogen and stirring. Then 3.33g of anhydrous aluminum trichloride is added; then stirring and dripping the reaction mixture obtained by 4.2.1 at the temperature of minus 20 to minus 10 ℃. After the dropwise addition is finished, the temperature is kept for 3 hours at minus 20 to minus 10 ℃. Then filtering at-20-10 deg.C to remove insoluble substances (sodium chloride) generated by the reaction.
2.3, decompressing and concentrating the filtrate obtained in the step 2.2, and recovering the mixed solvent of trimethyl borate and 2-methyltetrahydrofuran for standby application. 666g of anisole and 91.3g (0.25 mol) of 10% dilute hydrochloric acid are added into the concentrated residue, and liquid separation is carried out after stirring for 1 hour at the temperature of 0-10 ℃; the organic layer is washed to neutrality by water at 0-10 ℃, and then concentrated to remove anisole, and about 57g of residue is obtained, which is a crude product of triphenylphosphine. The crude product is crystallized for 2 times by using a mixed solvent of 8 times of isopropanol and 2 times of petroleum ether, and then is dried in vacuum, 46.3g of triphenylphosphine is obtained, the yield is 88.3%, and the purity of liquid chromatography is more than or equal to 99.8%.
And (4) conclusion: as is obvious from experimental example 1 and experimental example 2, the yield of triphenylphosphine is at least more than or equal to 88.3%; the purity of liquid chromatogram is at least more than or equal to 99.7 percent.
Meanwhile, the invention adopts the scheme that the temperature is lower than 10 ℃ and trimethyl borate is excessive, so that the trimethoxy boron-hydrogen sodium can be stably kept in the solution; and then directly used for the next reaction. The situation that the trimethoxy monoboron sodium can not exist stably at the temperature of more than 10 ℃ in the prior art is reduced; and further reducing the unstable condition to cause the sodium trimethoxymonoborohydride to be easily subjected to disproportionation, decomposition and other reactions, and further converted into sodium methoxide and various byproducts, such as dimethoxy monohydroborane, methoxy dihydroborane and borane which escape in a gaseous state.
Further, trimethyl borate is preferably selected in the invention; when the temperature is below 10 ℃, only trimethyl borate can react with sodium hydride to obtain trimethoxy monoboron sodium; similar triethyl borate, tripropyl borate, tributyl borate, etc. do not react similarly.
Meanwhile, in the present invention, sodium hydride is used in a sufficient market supply, and the effective reducing group (hydrogen atom) has a large specific gravity in the molecule, and the unit cost thereof is lower than 1, 3-tetramethyldisiloxane, trichlorosilane, or lithium aluminum hydride, excess aluminum flakes (powder), etc. Compared with other existing industrial methods for preparing triphenylphosphine by using triphenylphosphine dichloride, the method has the advantages of lower raw material cost and higher process safety.
In addition, the method adopted by the invention does not generate a large amount of byproducts such as polysilicone, aluminum salt and the like which are difficult to treat or dangerous active aluminum powder (sheet) residues; the main auxiliary materials of trimethyl borate, the solvent A, the solvent B and the like can be recycled and reused; the environment is more friendly;
therefore, the method provided by the invention can realize the advantages of high yield, high purity and more environmental protection of triphenylphosphine.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (4)
1. The preparation method of triphenylphosphine is characterized by comprising the following steps:
preparing the trimethoxy-boron monohydrogen sodium,
reacting trimethoxy monoboron sodium with triphenylphosphine dichloride to obtain triphenylphosphine;
wherein, the preparation method further comprises the following steps:
reacting sodium hydride with trimethyl borate to obtain trimethoxy sodium borohydride reaction liquid;
dropwise adding the obtained trimethoxy-boron monohydrogen sodium reaction solution into the first solution to obtain triphenylphosphine;
the first solution is a triphenylphosphine dichloride solution containing a catalytic amount of aluminum trichloride or stannous chloride;
wherein, the preparation method further comprises the following steps:
adding sodium hydride and a solvent A into the first reaction bottle; then, cooling to-50 to 10 ℃ under the protection of nitrogen, keeping the temperature at-50 to 10 ℃, uniformly stirring, and then dropwise adding a second solution;
after the dropwise addition is finished, continuously keeping the temperature for 1 to 5 hours at-50 to 10 ℃ to generate trimethoxy boron-hydrogen-based sodium reaction liquid; the second solution is trimethyl borate, or a mixed solution of trimethyl borate and the solvent A;
wherein the solvent A is one or a mixture of more of diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran and 1, 4-dioxane;
the using amount of the solvent A is 4-6 times of the mass ratio of sodium hydride;
the dosage of the trimethyl borate is 1.1 to 4.0 times of the equivalent of the sodium hydride;
the second solution is trimethyl borate, or a solution formed by mixing trimethyl borate and the solvent A.
2. The preparation method of triphenylphosphine according to claim 1, wherein triphenylphosphine dichloride and the solution III are added into a second reaction bottle, and the mixture is stirred uniformly under the protection of nitrogen at-50 to 10 ℃;
then adding a catalytic amount of aluminum trichloride or stannous chloride as a catalyst to obtain a first solution, and then dropwise adding a trimethoxy monoboron sodium reaction solution;
after the dropwise addition is finished, carrying out heat preservation reaction for 3 to 15 hours under the conditions of minus 20 to 10 ℃;
filtering to remove insoluble substances generated in the reaction and obtain filtrate; wherein the insoluble substance is sodium chloride;
wherein the dosage of the triphenylphosphine dichloride is 0.4 to 0.45 equivalent of the sodium hydride;
the third solution is a solvent A or a mixture of the solvent A and trimethyl borate; the mixing ratio of the solvent A and trimethyl borate is any ratio;
the dosage of the solution III is 4 to 8 times of the mass ratio of triphenylphosphine dichloride;
the dosage of the catalyst is 0.5 to 5 mass percent of the triphenylphosphine dichloride;
the temperature of the dropping of the trimethoxyborohydride-sodium reaction liquid and the temperature of the heat preservation reaction after the dropping are both-20 to 10 ℃; the reaction time after the dropwise addition is 3 to 15 hours;
the temperature for filtering and removing insoluble substances generated by the reaction is-20 ℃ to room temperature.
3. The process according to claim 2, wherein the triphenylphosphine,
decompressing and concentrating the filtrate, recovering an azeotrope of trimethyl borate and the solvent A, and reserving a concentrated residue;
adding a solvent B and dilute hydrochloric acid into the concentrated residues, and hydrolyzing and extracting;
separating the hydrolyzed reactant, washing the obtained organic layer with water to neutrality, and concentrating to remove the solvent B to obtain a crude product of triphenylphosphine;
purifying by a crystallization method, and drying to obtain the triphenylphosphine.
4. The method for preparing triphenylphosphine as claimed in claim 3, wherein the solvent B is one or more of benzene, toluene, xylene, chlorobenzene, anisole, tetrahydrofuran, and methyltetrahydrofuran;
the dosage of the solvent B is 3 to 10 times of the mass ratio of triphenylphosphine dichloride;
the dosage of the hydrochloric acid is 0.3 to 0.5 equivalent times of the sodium hydride;
in the water washing process, the water washing temperature is 0-50 ℃;
the solvent used for crystallizing the crude triphenylphosphine product is ethanol, propanol, isopropanol, ethyl acetate, isopropyl acetate, toluene or petroleum ether, or a mixture thereof;
the dosage of a crystallization solvent for crystallizing the crude triphenylphosphine product by using a crystallization method is 3-10 times of the mass ratio of the crude triphenylphosphine product.
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