CN110218226A - A kind of synthetic method of diphenyl phosphine chloride - Google Patents
A kind of synthetic method of diphenyl phosphine chloride Download PDFInfo
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- CN110218226A CN110218226A CN201910599557.4A CN201910599557A CN110218226A CN 110218226 A CN110218226 A CN 110218226A CN 201910599557 A CN201910599557 A CN 201910599557A CN 110218226 A CN110218226 A CN 110218226A
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- diphenyl phosphine
- phosphine chloride
- reaction
- synthetic method
- complexing agent
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- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000010189 synthetic method Methods 0.000 title claims abstract description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008139 complexing agent Substances 0.000 claims abstract description 27
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000003039 volatile agent Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 238000004821 distillation Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000010792 warming Methods 0.000 claims abstract description 7
- 230000006837 decompression Effects 0.000 claims abstract description 6
- 238000004090 dissolution Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002608 ionic liquid Substances 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002841 Lewis acid Substances 0.000 claims description 6
- 150000007517 lewis acids Chemical class 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- -1 stirring is opened Chemical compound 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 description 22
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 description 11
- 238000004587 chromatography analysis Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- 238000012805 post-processing Methods 0.000 description 7
- 238000005292 vacuum distillation Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 2
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 2
- PHLJWFAYUAZPJR-UHFFFAOYSA-M P.[Cl-].C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound P.[Cl-].C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 PHLJWFAYUAZPJR-UHFFFAOYSA-M 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ZFJMTDFOGDGPTF-UHFFFAOYSA-N phosphanium;chloride;hydrochloride Chemical compound P.Cl.Cl ZFJMTDFOGDGPTF-UHFFFAOYSA-N 0.000 description 1
- BZCGWAXQDLXLQM-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O.ClP(Cl)(Cl)=O BZCGWAXQDLXLQM-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material 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
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 kind of synthetic methods of diphenyl phosphine chloride; belong to chemosynthesis technical field; it solves and existing prepares the problems such as diphenyl phosphorus chloride product yield is low; a kind of synthetic method of diphenyl phosphine chloride, which comprises the following steps: under the protection of dry nitrogen; open stirring; benzene, phosphorus trichloride and catalyst are added into reactor, is warming up to 50-80 DEG C, the back flow reaction 2-3h at 50-80 DEG C；Step S01 is continuously heating to 85-200 DEG C after the reaction was completed, and back flow reaction is carried out at 85-200 DEG C；Step S02 reaction terminates to add benzene into reactor after reactor cooling, adds de-complexing agent, distillation removing solvent benzol, then carries out vacuum decompression distillation, obtain front-end volatiles and tails after stirring to de-complexing agent dissolution.The present invention has many advantages, such as that product yield is high.
Description
Technical field
The invention belongs to chemosynthesis technical field, in particular to a kind of synthetic method of diphenyl phosphine chloride.
Background technique
Diphenyl phosphine chloride is a kind of important organic phosphorus chemical product, its own Ph contained2P group can be used as transition
Metal and metal carbonyl ligand, are widely used as the catalyst of a variety of reactions such as catalytic hydrogenation, carbonylation, oligomerisation, in addition to this, two
Tetraphenylphosphonium chloride phosphine is the intermediate for producing important organic phosphorus products such as fire retardant, insecticide, antioxidant, photoinitiator.
" two-step method " synthesis is the conventional method for preparing diphenyl phosphine chloride, first by benzene, phosphorus trichloride through excessive trichlorine
Change aluminium catalysis reaction and obtains PhPCl2, then PhPCl2It is disproportionated to obtain Ph through aluminum trichloride (anhydrous) high temperature2PCl, but the method is received
Rate is low, and severe reaction conditions.
It is different from traditional synthetic method there are also some, such as with Ph3P and PCl3It is anti-through 320-700 DEG C of high temperature for raw material
Ying Hou obtains Ph2The yield of PCl is 20%-50%；It is anti-at 400 DEG C or using diphenyl time phosphoryl chloride phosphorus oxychloride and triphenyl phosphorus as raw material
20h or more is answered, Ph is obtained2The yield of PCl is 30%；Also it has had been reported that a kind of using diphenyl phosphine oxide and phosphorus trichloride as raw material system
Standby Ph2The method of PCl, but diphenyl phosphine oxide is difficult to produce, and can not obtain reaction raw materials easily.It is prepared using these methods
Ph2PCl with the low defect of high production cost, severe reaction conditions, product yield, and is unable to reach environmental requirement.
Summary of the invention
The purpose of the present invention is being directed to the above-mentioned problems in the prior art, a kind of conjunction of diphenyl phosphine chloride is provided
At method.
Object of the invention can be realized by the following technical scheme: a kind of synthetic method of diphenyl phosphine chloride, special
Sign is, comprising the following steps:
S01: under the protection of dry nitrogen, opening stirring, and benzene, phosphorus trichloride and catalyst, heating are added into reactor
To 50-80 DEG C, the back flow reaction 2-3h at 50-80 DEG C；
S02: step S01 is continuously heating to 85-200 DEG C after the reaction was completed, and back flow reaction is carried out at 85-200 DEG C；
S03: step S02 reaction terminates to add benzene into reactor after reactor cooling, add de-complexing agent, stir
Distillation removing solvent benzol, then carries out vacuum decompression distillation, obtains front-end volatiles and tails after to de-complexing agent dissolution.
Preferably, the catalyst includes aluminum trichloride (anhydrous), anhydrous ferric trichloride, anhydrous tri-chlorination zinc, anhydrous four
One of titanium chloride or any combination.
Preferably, the catalyst is aluminum trichloride (anhydrous).
Preferably, the amount proportion of the substance of the phosphorus trichloride, benzene and catalyst is 1:(2-10): (1-3).
Preferably, the de-complexing agent includes one or both of triphenylphosphine oxide, lewis acid ionic liquid at room temperature
Combination.
Preferably, the de-complexing agent is triphenylphosphine oxide.
Preferably, the de-complexing agent dosage and the proportion of catalyst amount are (0.75-1.5): 1.
Preferably, in step S02, when reacting under normal pressure, the back flow reaction 8-24h at 100-140 DEG C.
Preferably, in step S02, lower reaction of pressurizeing is forced into 0.05-1MPa, the back flow reaction 0.5- at 85-200 DEG C
10h。
Preferably, the de-complexing agent lewis acid ionic liquid at room temperature includes triethylamine hydrochloride-AlCl3Ionic liquid
Body, chlorination N- alkyl pyridine-AlCl3Ionic liquid, 1- methyl -3- alkyl imidazole-AlCl3One of ionic liquid is any
Combination.
Preferably, in step S01 and step S02, the reactor carries out oil bath heating.
The working principle of the invention: benzene and phosphorus trichloride of the invention reacts under the catalysis of catalyst aluminum trichloride (anhydrous)
Phenylphosphonic dichloride is first generated, reaction temperature is 50-80 DEG C, reaction time 2-3h.When reaction temperature increases, anhydrous three
Under the catalysis of aluminium chloride, the reaction was continued generates diphenyl phosphine chloride for phenylphosphonic dichloride and benzene, and reaction temperature is 100- under normal pressure
140 DEG C, reflux time 8-24h；If the lower reaction of pressurization, is forced into 0.05-1MPa, the back flow reaction at 85-200 DEG C
0.5-10h。
It needs first to add solvent benzol after reactor is cooled to room temperature, adding benzene is to be conducive to solve to dissolve de-complexing agent
Network is thorough, if not adding benzene, solvent is few, slow so as to cause decomplexing and decomplexing is not thorough.Then de-complexing agent, decomplexing are added
Agent is used to release the complexing of diphenyl phosphine chloride and catalyst alchlor.Because diphenyl phosphine chloride is easy and alchlor hair
Raw complex reaction generates complex compound, if reacting without decomplexing, causes the yield of diphenyl phosphine chloride low, therefore needs to add solution
Network agent carries out decomplexing, after the completion of decomplexing, distillation removing solvent benzol, then vacuum decompression distillation is carried out, front-end volatiles and tails are obtained,
Main component in front-end volatiles is by-product phenylphosphonic dichloride, and the main component of tails is product diphenyl phosphine chloride, benzene
By-product of the base dichloride phosphine as reaction can be sold in addition, can also be covered and be used in next group synthesis material, continue to be converted into two
Tetraphenylphosphonium chloride phosphine.And it is of the invention only generate a small amount of by-product phenylphosphonic dichloride amount, diphenyl phosphine chloride yield is high, significantly
The yield of product diphenyl phosphine chloride is improved, and is distilled by vacuum decompression, front-end volatiles and tails are separately collected,
Easy to separate and purify, obtained product purity is high.
Compared with prior art, the invention has the following advantages that
1. after reaction of the invention generates diphenyl phosphine chloride, de-complexing agent decomplexing is added, then carry out diphenyl phosphine chloride
Recycling, substantially increases the yield of diphenyl phosphine chloride, improves the purity of product, and de-complexing agent releases diphenyl phosphine chloride and urges
The complexing of agent alchlor, substantially increases product yield.
2. de-complexing agent triphenylphosphine oxide decomplexing effect of the invention is good, decomplexing is thorough, can unlock diphenyl at room temperature
Complexing between phosphonium chloride and alchlor is compared and traditional de-complexing agent such as sodium chloride and potassium chloride, sodium chloride and chlorination
Potassium is difficult to recycle as de-complexing agent, and required temperature height is reacted in decomplexing, and de-complexing agent triphenylphosphine oxide of the invention is easy
Recycling, and decomplexing reaction is carried out at room temperature.
3. reaction raw materials of the invention are economical and easily available, benzene, phosphorus trichloride and alchlor are all normal in modern organic chemical industry
Raw material.
4. reaction condition of the present invention is mild, without extraordinary production equipment, it is not necessarily to high temperature and pressure, technological operation is simple and easy to control,
It is high income, at low cost without a large amount of waste residues, it is easy to implement industrialized production.
5. product diphenyl phosphine chloride high income of the invention, by-product is less, easy to separate and purify, and product purity is high.
6. element utilization rate of the invention is high, the by-product dichlorophenyl phosphine of generation can other than sell, can also cover use it is next
It criticizes in synthesis material, continues to be converted into diphenyl phosphine chloride.
Specific embodiment
The following is specific embodiments of the present invention, and technical scheme of the present invention will be further described, but the present invention is simultaneously
It is not limited to these embodiments.
Embodiment 1
Synthetic reaction: being continually fed into drying nitrogen into the three-necked flask of dry 1000mL, opens stirring, protects in nitrogen
Shield is lower to be added benzene 117g (1.5mol), and alchlor 80g (0.6mol), phosphorus trichloride 68.7g (0.5mol) are warming up to 60 DEG C,
Oil bath temperature is set as 120 DEG C again after back flow reaction 2h, is condensed back 12h, synthetic reaction terminates.
Post-processing: adding benzene 500mL after being cooled to room temperature, be added de-complexing agent triphenylphosphine oxide 168g (0.6mol), stirring
Continue to stir 1h after to triphenylphosphine oxide all dissolution, decomplexing is completed.Solution after decomplexing is transferred in single-necked flask, often first
Using water ring vacuum pump vacuum distillation removing solvent benzol after pressure distillation, it is then switched to vacuum oil pump vacuum distillation product, is collected
To front-end volatiles 6g, gas chromatographic analysis, phenylphosphonic dichloride content >=98% in front-end volatiles are carried out；It is collected into tails 92g, into
Promoting the circulation of qi analysis of hplc, diphenyl phosphine chloride content >=98% in tails, product yield is 83.4% in terms of phosphorus trichloride.
Embodiment 2
Synthetic reaction: being continually fed into drying nitrogen into the three-necked flask of dry 1000mL, opens stirring, protects in nitrogen
Shield is lower to be added benzene 117g (1.5mol), and alchlor 80g (0.6mol), phosphorus trichloride 68.7g (0.5mol) are warming up to 80 DEG C,
Oil bath temperature is set as 120 DEG C again after back flow reaction 2h, is condensed back 12h, reaction terminates.
2) post-process: post-processing approach is same as Example 1, is collected into front-end volatiles 5.7g, carries out gas chromatographic analysis, preceding
Phenylphosphonic dichloride content >=98% in fraction；It is collected into tails 91.6g, carries out gas chromatographic analysis, hexichol in tails
Base phosphonium chloride content >=98%, product yield is 83.0% in terms of phosphorus trichloride.
Embodiment 3
Synthetic reaction: being continually fed into drying nitrogen into the three-necked flask of dry 1000mL, opens stirring, protects in nitrogen
Shield is lower to be added benzene 101.4g (1.3mol), and alchlor 80g (0.6mol), phosphorus trichloride 68.7g (0.5mol) are warming up to 60
DEG C, oil bath temperature is set as 120 DEG C again after back flow reaction 2h, is condensed back 12h, reaction terminates.
Post-processing: post-processing approach is same as Example 1, is collected into front-end volatiles 10.5g, carries out gas chromatographic analysis, preceding
Phenylphosphonic dichloride content >=98% in fraction；It is collected into tails 83.9g, carries out gas chromatographic analysis, hexichol in tails
Base phosphonium chloride content >=98%, product yield is 76.0% in terms of phosphorus trichloride.
Embodiment 4
Synthetic reaction: being continually fed into drying nitrogen into the three-necked flask of dry 1000mL, opens stirring, protects in nitrogen
Shield is lower to be added benzene 117g (1.5mol), and alchlor 100g (0.75mol), phosphorus trichloride 68.7g (0.5mol) are warming up to 60
DEG C, oil bath temperature is set as 120 DEG C again after back flow reaction 2h, is condensed back 12h, reaction terminates.
Post-processing: benzene 600mL is added after being cooled to room temperature, is added de-complexing agent triphenylphosphine oxide 208g (0.75mol), stirs
Continue to stir 1h after mixing to triphenylphosphine oxide all dissolution, decomplexing is completed.Solution after decomplexing is transferred in single-necked flask, first
Using water ring vacuum pump vacuum distillation removing solvent benzol after air-distillation, it is then switched to vacuum oil pump vacuum distillation product, is received
Collect front-end volatiles 6.4g, carries out gas chromatographic analysis, phenylphosphonic dichloride content >=98% in front-end volatiles；It is collected into tails
92.5g carries out gas chromatographic analysis, and diphenyl phosphine chloride content >=98% in tails, product yield is in terms of phosphorus trichloride
83.8%.
Embodiment 5
Synthetic reaction: being continually fed into drying nitrogen into the three-necked flask of dry 500mL, opens stirring, protects in nitrogen
Shield is lower to be added benzene 117g (1.5mol), and alchlor 80g (0.6mol), phosphorus trichloride 68.7g (0.5mol) are warming up to 60 DEG C,
Reaction solution is moved in 500mL autoclave after back flow reaction 2h, is forced into 0.17-0.18Mpa, 116-120 DEG C of reaction 5h, is stopped
Reaction.
Post-processing: moving into reaction solution in dry 1000mL three-necked flask after being cooled to room temperature, lead to drying nitrogen protection,
Benzene 500mL is added, is added de-complexing agent triphenylphosphine oxide 168g (0.6mol), stirring to triphenylphosphine oxide continues to stir after all dissolving
1h is mixed, decomplexing is completed.Solution after decomplexing is transferred in single-necked flask, is steamed after first air-distillation using water ring vacuum pump decompression
Removing solvent benzol is evaporated, vacuum oil pump vacuum distillation product is then switched to, is collected into front-end volatiles 3.6g, carries out gas-chromatography point
It analyses, phenylphosphonic dichloride content >=98% in front-end volatiles；It is collected into tails 98.5g, carries out gas chromatographic analysis, in tails
Diphenyl phosphine chloride content >=98%, product yield is 89.3% in terms of phosphorus trichloride.
Embodiment 6
Synthetic reaction: synthetic reaction is the same as embodiment 1.
Post-processing: benzene 500mL is added after being cooled to room temperature, de-complexing agent triethylamine hydrochloride-AlCl is added3Ionic liquid
202.6g (0.6mol) stirs 1h.Solution after decomplexing is transferred in single-necked flask, Water-ring vacuum is utilized after first air-distillation
Pump vacuum distillation removing solvent benzol, is then switched to vacuum oil pump vacuum distillation product, is collected into front-end volatiles 5.4g, carries out gas phase
Chromatography, phenylphosphonic dichloride content >=98% in front-end volatiles；Be collected into tails 67g, carry out gas chromatographic analysis, after evaporate
Diphenyl phosphine chloride content >=98% in point, product yield is 60.7% in terms of phosphorus trichloride.
In 1-6 of the embodiment of the present invention, magnetic agitation is can be used in stirring.
Conclusion: obtaining from embodiment 1-6, and the product purity of method of the invention arrived is high, the diphenyl in tails
Phosphonium chloride content >=98%, by-product phenylphosphonic dichloride content >=98% in front-end volatiles, the by-product phenyl dichloro of generation
Phosphine can be sold in addition, can also be covered and be used in next group synthesis material, continue to be converted into diphenyl phosphine chloride.Come relative to product
It says, the by-product that the present invention generates is few, and high income of the invention (in terms of phosphorus trichloride).De-complexing agent triphenyl oxygen of the present invention
Phosphine and lewis acid ionic liquid at room temperature can improve yield, but the two compares, and use triphenylphosphine oxide as de-complexing agent, produce
The yield of object is higher, therefore the decomplexing effect of triphenylphosphine oxide is more preferable, and decomplexing is more thorough.
According to embodiment 5 it is found that under normal pressure, after 60 DEG C of reaction 2h, moving into autoclave, being forced into 0.17-
0.18Mpa, 116-120 DEG C of reaction 5h, the yield (in terms of phosphorus trichloride) of end product are 89.3%.The lower reaction of pressurization is not only contracted
The short reaction time, and improve the yield of reaction.
Specific embodiment described herein is only an example for the spirit of the invention.The neck of technology belonging to the present invention
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
Claims (10)
1. a kind of synthetic method of diphenyl phosphine chloride, which comprises the following steps:
S01: under the protection of dry nitrogen, stirring is opened, benzene, phosphorus trichloride and catalyst is added into reactor, is warming up to 50-
80 DEG C, the back flow reaction 2-3h at 50-80 DEG C；
S02: step S01 is continuously heating to 85-200 DEG C after the reaction was completed, and back flow reaction is carried out at 85-200 DEG C；
S03: step S02 reaction terminates to add benzene into reactor after reactor cooling, adds de-complexing agent, stirring extremely solves
Distillation removing solvent benzol, then carries out vacuum decompression distillation, obtains front-end volatiles and tails after network agent dissolution.
2. a kind of synthetic method of diphenyl phosphine chloride according to claim 1, which is characterized in that the catalyst packet
Include one of aluminum trichloride (anhydrous), anhydrous ferric trichloride, anhydrous tri-chlorination zinc, anhydrous titanium tetrachloride or any combination.
3. a kind of synthetic method of diphenyl phosphine chloride according to claim 2, which is characterized in that the catalyst is
Aluminum trichloride (anhydrous).
4. a kind of synthetic method of diphenyl phosphine chloride according to claim 1, which is characterized in that the tri-chlorination
The amount proportion of the substance of phosphorus, benzene and catalyst is 1:(2-10): (1-3).
5. a kind of synthetic method of diphenyl phosphine chloride according to claim 1, which is characterized in that the de-complexing agent packet
It is combined containing one or both of triphenylphosphine oxide, lewis acid ionic liquid at room temperature.
6. a kind of synthetic method of diphenyl phosphine chloride according to claim 1, which is characterized in that the de-complexing agent is
Triphenylphosphine oxide.
7. a kind of synthetic method of diphenyl phosphine chloride according to claim 1, which is characterized in that the de-complexing agent dosage
Proportion with catalyst amount is (0.75-1.5): 1.
8. a kind of synthetic method of diphenyl phosphine chloride according to claim 1, which is characterized in that in step S02, normal pressure
When lower reaction, the back flow reaction 8-24h at 100-140 DEG C.
9. a kind of synthetic method of diphenyl phosphine chloride according to claim 1, which is characterized in that in step S02, pressurization
Lower reaction, is forced into 0.05-1MPa, the back flow reaction 0.5-10h at 85-200 DEG C.
10. a kind of synthetic method of diphenyl phosphine chloride according to claim 5, which is characterized in that the de-complexing agent
For lewis acid ionic liquid at room temperature, lewis acid ionic liquid at room temperature includes triethylamine hydrochloride-AlCl3Ionic liquid, chlorine
Change N- alkyl pyridine-AlCl3Ionic liquid, 1- methyl -3- alkyl imidazole-AlCl3One of ionic liquid or any combination.
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| CN110684047B (en) * | 2019-11-18 | 2022-07-29 | 怀化泰通新材料科技有限公司 | Joint production method of phenyl phosphine dichloride and diphenyl phosphine chloride |
| CN110922428A (en) * | 2019-12-04 | 2020-03-27 | 浙江扬帆新材料股份有限公司 | Synthesis method of chlorophosphine compound |
| CN110922428B (en) * | 2019-12-04 | 2022-03-04 | 浙江扬帆新材料股份有限公司 | Synthesis method of chlorophosphine compound |
| CN114149327A (en) * | 2021-11-04 | 2022-03-08 | 安徽东至广信农化有限公司 | Method for synthesizing o-phenylenediamine through continuous ammoniation |
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