CN110240614A - A kind of chemical synthesis process of diphenyl phosphate chloride - Google Patents
A kind of chemical synthesis process of diphenyl phosphate chloride Download PDFInfo
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- CN110240614A CN110240614A CN201910473644.5A CN201910473644A CN110240614A CN 110240614 A CN110240614 A CN 110240614A CN 201910473644 A CN201910473644 A CN 201910473644A CN 110240614 A CN110240614 A CN 110240614A
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- diphenyl phosphate
- chloride
- chemical synthesis
- synthesis process
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- HXBZCHYDLURWIZ-UHFFFAOYSA-N diphenyl hydrogen phosphate;hydrochloride Chemical compound Cl.C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 HXBZCHYDLURWIZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 title claims description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims abstract description 13
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 12
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical class C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000010189 synthetic method Methods 0.000 claims abstract description 5
- 239000006227 byproduct Substances 0.000 claims abstract description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000001103 potassium chloride Substances 0.000 claims abstract description 3
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 3
- FVOMJWZIGNBHOA-UHFFFAOYSA-M sodium;diphenyl phosphate Chemical compound [Na+].C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 FVOMJWZIGNBHOA-UHFFFAOYSA-M 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- -1 di(2-ethylhexyl)phosphate Phenyl ester Chemical class 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000004816 dichlorobenzenes Chemical class 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229950002366 nafoxidine Drugs 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 238000005265 energy consumption Methods 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004821 distillation Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 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 1
- YAHANRGTYRBKTL-UHFFFAOYSA-N C1=CC=C(C=C1)C2=CC=C(C=C2)OOP(=O)(OC3=CC=CC=C3)OC4=CC=CC=C4 Chemical compound C1=CC=C(C=C1)C2=CC=C(C=C2)OOP(=O)(OC3=CC=CC=C3)OC4=CC=CC=C4 YAHANRGTYRBKTL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- DMJNNHOOLUXYBV-PQTSNVLCSA-N meropenem Chemical compound C=1([C@H](C)[C@@H]2[C@H](C(N2C=1C(O)=O)=O)[C@H](O)C)S[C@@H]1CN[C@H](C(=O)N(C)C)C1 DMJNNHOOLUXYBV-PQTSNVLCSA-N 0.000 description 1
- 229960002260 meropenem Drugs 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
- NZMAJUHVSZBJHL-UHFFFAOYSA-N n,n-dibutylformamide Chemical compound CCCCN(C=O)CCCC NZMAJUHVSZBJHL-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
- C07F9/1406—Esters of phosphoric acids containing P(=O)-halide groups containing the structure Hal-P(=O)-O-aryl
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 present invention relates to a kind of synthetic methods of diphenyl phosphate chloride, the following steps are included: using a certain amount of organic amine as catalyst, 1-10h is reacted in organic solvent with a certain amount of two (trichloromethyl) carbonic esters after one of a certain amount of diphenyl phosphate or diphenyl phosphate salt or two kinds are mixed with arbitrary proportion, the reaction temperature is 0-60 DEG C, and the diphenyl phosphate salt is any one of diphenyl phosphate sodium salt or diphenyl phosphate sylvite；To above-mentioned steps 1) in after reaction, by product cooling washing, dry, normal pressure or solvent is recovered under reduced pressure, cooling is filtered to remove insoluble matter and diphenyl phosphate chloride is made.It is simple that the beneficial effects of the invention are as follows process routes, and reaction condition is mild, and post-processing energy consumption is small, and without high vacuum, high temperature distillation, production cost is low, product yield and all higher advantage of quality, and avoids lead to the problem of a large amount of phosphorus-containing wastewaters and solid waste simultaneously.
Description
Technical field
The present invention relates to chemical technology field more particularly to a kind of chemical synthesis process of diphenyl phosphate chloride.
Background technique
Diphenyl phosphate chloride is for synthesizing penem-like pharmaceutical, phosphonium flame retardant and the important intermediate of liquid crystal material, such as
Drug Meropenem and 4- biphenylyloxy diphenyl phosphate etc. are produced with it.
Before the present invention provides, the chemical synthesis process of diphenyl phosphate chloride is mostly with phosphorus oxychloride and benzene in the prior art
Phenol is raw material, is synthesized under Louis acid catalysis.
Synthetic route is as follows:
What is such as: chemical research 2012,23(6) proposed is warming up to 60 DEG C with 0.8g aluminum trichloride (anhydrous) and 15.3g phosphorus oxychloride, to
The mixed liquor of 10ml dichloroethanes and 18.8g phenol is added dropwise in reaction system, 70 DEG C of temperature control is added dropwise hereinafter, drop, which finishes, is warming up to 70
DEG C, insulation reaction 15 hours, suitable quantity of water is added dropwise, filtering, low boilers are evaporated off in filtrate elder generation normal pressure, then are evaporated under reduced pressure, collection 140~
160 DEG C/3mmHg fraction.
The process has used phosphorus oxychloride, severe corrosion to equipment, and a large amount of high phosphorus waste water are difficult to handle, and pollution is tight
Weight；The process byproducts are more simultaneously, need high vacuum high temperature distillation product, energy consumption is high, bottoms generate a large amount of solid wastes.
The problems such as this method the problems such as there are high corrosion, high energy consumption, high pollutions, yield is low, high production cost, is badly in need of solving.
Summary of the invention
In view of the deficiencies of the prior art, the present invention relates to a kind of chemical synthesis process of diphenyl phosphate chloride, this method tools
Standby simple process, the feature of working condition mildly, in high yield, inexpensive, the three wastes are few.
To achieve the above object, the invention provides the following technical scheme:
A kind of synthetic method of diphenyl phosphate chloride, which comprises the following steps:
1) using a certain amount of organic amine as catalyst, by one of a certain amount of diphenyl phosphate or diphenyl phosphate salt or
Two kinds mixed with arbitrary proportion after with a certain amount of two (trichloromethyl) carbonic esters react 1-10h in organic solvent, it is described
Reaction temperature is 0-60 DEG C, and the diphenyl phosphate salt is any in diphenyl phosphate sodium salt or diphenyl phosphate sylvite
Kind；
2) to above-mentioned steps 1) in after reaction, by product cooling washing, dry, normal pressure or solvent is recovered under reduced pressure, cools down
It is filtered to remove insoluble matter and diphenyl phosphate chloride is made.
Its reaction equation is as follows:
Or
Wherein, M=sodium or potassium
The step 1) is by one of a certain amount of diphenyl phosphate or diphenyl phosphate salt or two kinds with arbitrary proportion
3-6h is reacted in organic solvent with a certain amount of two (trichloromethyl) carbonic esters after mixing.
Product described in the step 2) is cooled to 10 DEG C or less and is washed, dried, normal pressure or is recovered under reduced pressure
Solvent, cooling are filtered to remove insoluble matter and diphenyl phosphate chloride are made.
The diphenyl phosphate (or diphenyl phosphate salt): two (trichloromethyl) carbonic esters: the object of organic amine catalyst
The amount ratio of matter is 1:0.35-1.0:0.01-1.5.
The diphenyl phosphate (or diphenyl phosphate salt): two (trichloromethyl) carbonic esters: the object of organic amine catalyst
The amount ratio of matter is 1:0.35-0.5:0.1-0.5.
The organic amine catalyst is one of following or more than one arbitrary proportion mixtures: triethylamine, diisopropyl
Ethamine, pyridine, morpholine, imidazoles, 2-methylimidazole, tetramethylguanidine, tetramethylurea, n,N-Dimethylformamide, N, N- dimethyl
Acetamide, N, N- dibutyl formamide, N- methylpyrrole, N- methyl nafoxidine.
The organic amine catalyst is n,N-Dimethylformamide.
The organic solvent is one of following or more than one arbitrary proportion mixtures: benzene,toluene,xylene, chlorobenzene,
Dichloro-benzenes, n-hexane, hexamethylene, Di Iso Propyl Ether, dibutyl ethers, tetrahydrofuran, ethyl acetate, methylene chloride, chloroform
Or dichloroethanes.
The organic solvent is methylene chloride.
The consumption of organic solvent is 3-8 times of diphenyl phosphate or diphenyl phosphate salt quality, is lower than this dosage object
Material reaction is insufficient, will cause increased costs, reaction efficiency decline higher than this dosage.
Compared with prior art, the beneficial effects of the present invention are: with diphenyl phosphate (or diphenyl phosphate salt) and two (three
Chloromethyl) carbonic ester is raw material, synthesize diphenyl phosphate chloride under organic amine catalysis, this programme instead of it is existing with phenol and
Phosphorus oxychloride is the synthetic method of raw material, is compared compared with scheme, and technical solution used herein has process route letter
Single, reaction condition is mild, and post-processing energy consumption is small, and without high vacuum, high temperature distillation, production cost is low, and product yield and quality are all
Higher advantage, and avoid lead to the problem of a large amount of phosphorus-containing wastewaters and solid waste simultaneously, the synthetic method of the diphenyl phosphate chloride
With biggish economic value and the value of environmental protection.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
120g methylene chloride, 7.3g are put into equipped with tetra- mouthfuls of thermometer, reflux condensing tube and churned mechanically 500ml reaction flasks
N,N-Dimethylformamide, stirring 10 DEG C of temperature control hereinafter, investment 28g bis- (trichloromethyl) carbonic ester, stream be added 50g di(2-ethylhexyl)phosphate
The solution of phenyl ester and 120g methylene chloride, finishes, and reacts 3 hours, and after reaction, 10 DEG C of temperature control hereinafter, be slowly added to for detection
Water 20g, stirs liquid separation, and organic phase is dry with anhydrous sodium sulfate；It is filtered to remove desiccant, methylene chloride is evaporated off in filtrate normal pressure, drop
Temperature is filtered to remove insoluble matter to 0 DEG C, obtains diphenyl phosphate chloride 48.9g, and GC detects purity 99.2%, yield 90.3%.
Embodiment 2
120g methylene chloride, 3.6g are put into equipped with tetra- mouthfuls of thermometer, reflux condensing tube and churned mechanically 500ml reaction flasks
N,N-Dimethylformamide, stirring 10 DEG C of temperature control hereinafter, investment 28g bis- (trichloromethyl) carbonic ester, stream be added 50g di(2-ethylhexyl)phosphate
The solution of phenyl ester and 120g methylene chloride, finishes, and reacts 3 hours, and after reaction, 10 DEG C of temperature control hereinafter, be slowly added to for detection
Water 20g, stirs liquid separation, and organic phase is dry with anhydrous sodium sulfate；It is filtered to remove desiccant, methylene chloride is evaporated off in filtrate normal pressure, drop
Temperature is filtered to remove insoluble matter to 0 DEG C, obtains diphenyl phosphate chloride 47.2g, and GC detects purity 98.1%, yield 86.2%.
Embodiment 3
330g methylene chloride, 7.3g are put into equipped with tetra- mouthfuls of thermometer, reflux condensing tube and churned mechanically 500ml reaction flasks
N,N-Dimethylformamide, stirring 10 DEG C of temperature control hereinafter, investment 28g bis- (trichloromethyl) carbonic ester, 55g phosphoric acid is added portionwise
Hexichol ester sodium salt, finishes, and reacts 5 hours, and after reaction, 10 DEG C of temperature control stirs liquid separation hereinafter, be slowly added to water 20g for detection,
Organic phase is dry with anhydrous sodium sulfate；It is filtered to remove desiccant, methylene chloride is evaporated off in filtrate normal pressure, is cooled to 0 DEG C, is filtered to remove
Insoluble matter, obtains diphenyl phosphate chloride 47.5g, and GC detects purity 99.3%, yield 87.8%.
It should also be noted that, the terms "include", "comprise" or its any other variant are intended to nonexcludability
It include so that the process, method, commodity or the equipment that include a series of elements not only include those elements, but also to wrap
Include other elements that are not explicitly listed, or further include for this process, method, commodity or equipment intrinsic want
Element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that including element
There is also other identical elements in process, method, commodity or equipment.
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art,
It is still possible to modify the technical solutions described in the foregoing embodiments, or part of technical characteristic is carried out etc.
With replacement, all within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in this
Within the protection scope of invention.
Claims (10)
1. a kind of synthetic method of diphenyl phosphate chloride, which comprises the following steps:
1) using a certain amount of organic amine as catalyst, by one of a certain amount of diphenyl phosphate or diphenyl phosphate salt or
Two kinds mixed with arbitrary proportion after with a certain amount of two (trichloromethyl) carbonic esters react 1-10h in organic solvent, it is described
Reaction temperature is 0-60 DEG C, and the diphenyl phosphate salt is any in diphenyl phosphate sodium salt or diphenyl phosphate sylvite
Kind；
2) to above-mentioned steps 1) in after reaction, by product cooling washing, dry, normal pressure or solvent is recovered under reduced pressure, cools down
It is filtered to remove insoluble matter and diphenyl phosphate chloride is made.
2. a kind of chemical synthesis process of diphenyl phosphate chloride as described in claim 1, it is characterised in that the step 1)
After one of a certain amount of diphenyl phosphate or diphenyl phosphate salt or two kinds are mixed with arbitrary proportion with it is a certain amount of
Two (trichloromethyl) carbonic esters react 3-6h in organic solvent.
3. a kind of chemical synthesis process of diphenyl phosphate chloride as described in claim 1, it is characterised in that the step 2)
Described in product be cooled to 10 DEG C or less and washed, dried, normal pressure or solvent being recovered under reduced pressure, cooling is filtered to remove insoluble
Diphenyl phosphate chloride is made in object.
4. a kind of chemical synthesis process of diphenyl phosphate chloride as described in claim 1, it is characterised in that the di(2-ethylhexyl)phosphate
Phenyl ester (or diphenyl phosphate salt): two (trichloromethyl) carbonic esters: the mass ratio of the material of organic amine catalyst is 1:0.35-1.0:
0.01-1.5。
5. a kind of chemical synthesis process of diphenyl phosphate chloride as claimed in claim 4, it is characterised in that the di(2-ethylhexyl)phosphate
Phenyl ester (or diphenyl phosphate salt): two (trichloromethyl) carbonic esters: the mass ratio of the material of organic amine catalyst is 1:0.35-0.5:
0.1-0.5。
6. a kind of chemical synthesis process of diphenyl phosphate chloride as described in claim 1, it is characterised in that the organic amine
Catalyst is one of following or more than one arbitrary proportion mixtures: triethylamine, diisopropylethylamine, pyridine, morpholine, imidazoles,
2-methylimidazole, tetramethylguanidine, tetramethylurea, n,N-Dimethylformamide, n,N-dimethylacetamide, N, N- dibutyl formyl
Amine, N- methylpyrrole, N- methyl nafoxidine.
7. a kind of chemical synthesis process of diphenyl phosphate chloride as claimed in claim 6, it is characterised in that the organic amine
Catalyst is n,N-Dimethylformamide.
8. a kind of chemical synthesis process of diphenyl phosphate chloride as described in claim 1, it is characterised in that described is organic molten
Agent is one of following or more than one arbitrary proportion mixtures: benzene,toluene,xylene, chlorobenzene, dichloro-benzenes, n-hexane, hexamethylene
Alkane, Di Iso Propyl Ether, dibutyl ethers, tetrahydrofuran, ethyl acetate, methylene chloride, chloroform or dichloroethanes.
9. a kind of chemical synthesis process of diphenyl phosphate chloride as claimed in claim 8, it is characterised in that described is organic molten
Agent is methylene chloride.
10. a kind of chemical synthesis process of diphenyl phosphate chloride as described in any one of claim 1-9, it is characterised in that
The consumption of organic solvent is 3-8 times of diphenyl phosphate or diphenyl phosphate salt quality.
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| WO2020244162A1 (en) * | 2019-06-01 | 2020-12-10 | 菏泽帝捷化工股份有限公司 | Chemical synthesis method of diphenyl chlorophosphate |
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| CN102408364A (en) * | 2010-09-26 | 2012-04-11 | 中化蓝天集团有限公司 | Method for preparing paratoluensulfonyl chloride |
| JP5212665B2 (en) * | 2008-03-11 | 2013-06-19 | 国立大学法人 奈良先端科学技術大学院大学 | Photolabile protecting group |
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| IL147490A0 (en) * | 2002-01-06 | 2002-08-14 | Bromine Compounds Ltd | Preparation of phenylphosphate esters of 4,4'-biphenol |
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| CN105037419B (en) * | 2015-09-10 | 2017-08-25 | 巨野帝捷化工有限公司 | A kind of preparation method of chlorination diphenyl phosphate |
| CN110240614A (en) * | 2019-06-01 | 2019-09-17 | 菏泽帝捷化工股份有限公司 | A kind of chemical synthesis process of diphenyl phosphate chloride |
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