CN108329346B - A kind of synthetic method of O, O- dialkyl sulfide substituted phosphorus oxychloride - Google Patents
A kind of synthetic method of O, O- dialkyl sulfide substituted phosphorus oxychloride Download PDFInfo
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- CN108329346B CN108329346B CN201810235512.4A CN201810235512A CN108329346B CN 108329346 B CN108329346 B CN 108329346B CN 201810235512 A CN201810235512 A CN 201810235512A CN 108329346 B CN108329346 B CN 108329346B
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- phosphorus oxychloride
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- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical class ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 32
- 125000000101 thioether group Chemical group 0.000 title claims abstract description 22
- 238000010189 synthetic method Methods 0.000 title claims abstract description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000460 chlorine Substances 0.000 claims abstract description 61
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 claims abstract description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005864 Sulphur Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 13
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 4
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 18
- 238000009833 condensation Methods 0.000 abstract description 10
- 230000005494 condensation Effects 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 6
- 238000004821 distillation Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000007796 conventional method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 description 17
- 238000009835 boiling Methods 0.000 description 8
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 4
- -1 chlopyrifos Chemical compound 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000000066 reactive distillation Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- CZGGKXNYNPJFAX-UHFFFAOYSA-N Dimethyldithiophosphate Chemical compound COP(S)(=S)OC CZGGKXNYNPJFAX-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- YASYVMFAVPKPKE-UHFFFAOYSA-N acephate Chemical compound COP(=O)(SC)NC(C)=O YASYVMFAVPKPKE-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 2
- IRDLUHRVLVEUHA-UHFFFAOYSA-N diethyl dithiophosphate Chemical compound CCOP(S)(=S)OCC IRDLUHRVLVEUHA-UHFFFAOYSA-N 0.000 description 2
- NBAUXRCSDWYKRP-UHFFFAOYSA-N dimethyl phosphorochloridothioate Chemical compound COP(Cl)(=O)SC NBAUXRCSDWYKRP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- XJFIKRXIJXAJGH-UHFFFAOYSA-N 5-chloro-1,3-dihydroimidazo[4,5-b]pyridin-2-one Chemical group ClC1=CC=C2NC(=O)NC2=N1 XJFIKRXIJXAJGH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000005945 Chlorpyrifos-methyl Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JHJOOSLFWRRSGU-UHFFFAOYSA-N Fenchlorphos Chemical compound COP(=S)(OC)OC1=CC(Cl)=C(Cl)C=C1Cl JHJOOSLFWRRSGU-UHFFFAOYSA-N 0.000 description 1
- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-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
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- 239000005924 Pirimiphos-methyl Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- CBWUNQZJGJFJLZ-UHFFFAOYSA-N [Cl].Cl Chemical compound [Cl].Cl CBWUNQZJGJFJLZ-UHFFFAOYSA-N 0.000 description 1
- MTRNILYVFSFMDV-UHFFFAOYSA-N [P].C(C)C1=NC=CC=N1 Chemical compound [P].C(C)C1=NC=CC=N1 MTRNILYVFSFMDV-UHFFFAOYSA-N 0.000 description 1
- ZSUFBRGARNXNBX-UHFFFAOYSA-N [P].C1=CC=NC=C1 Chemical compound [P].C1=CC=NC=C1 ZSUFBRGARNXNBX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 210000000436 anus Anatomy 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- SCKHCCSZFPSHGR-UHFFFAOYSA-N cyanophos Chemical compound COP(=S)(OC)OC1=CC=C(C#N)C=C1 SCKHCCSZFPSHGR-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- ATROHALUCMTWTB-OWBHPGMISA-N phoxim Chemical compound CCOP(=S)(OCC)O\N=C(\C#N)C1=CC=CC=C1 ATROHALUCMTWTB-OWBHPGMISA-N 0.000 description 1
- 229950001664 phoxim Drugs 0.000 description 1
- QHOQHJPRIBSPCY-UHFFFAOYSA-N pirimiphos-methyl Chemical group CCN(CC)C1=NC(C)=CC(OP(=S)(OC)OC)=N1 QHOQHJPRIBSPCY-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QYMMJNLHFKGANY-UHFFFAOYSA-N profenofos Chemical compound CCCSP(=O)(OCC)OC1=CC=C(Br)C=C1Cl QYMMJNLHFKGANY-UHFFFAOYSA-N 0.000 description 1
- JYQUHIFYBATCCY-UHFFFAOYSA-N quinalphos Chemical compound C1=CC=CC2=NC(OP(=S)(OCC)OCC)=CN=C21 JYQUHIFYBATCCY-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000010563 solid-state fermentation Methods 0.000 description 1
- YALHCTUQSQRCSX-UHFFFAOYSA-N sulfane sulfuric acid Chemical compound S.OS(O)(=O)=O YALHCTUQSQRCSX-UHFFFAOYSA-N 0.000 description 1
- XIUROWKZWPIAIB-UHFFFAOYSA-N sulfotep Chemical compound CCOP(=S)(OCC)OP(=S)(OCC)OCC XIUROWKZWPIAIB-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- AMFGTOFWMRQMEM-UHFFFAOYSA-N triazophos Chemical compound N1=C(OP(=S)(OCC)OCC)N=CN1C1=CC=CC=C1 AMFGTOFWMRQMEM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/20—Esters of thiophosphoric acids containing P-halide groups
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 O, the synthetic method of O- dialkyl sulfide substituted phosphorus oxychloride, in O, O- dialkyl group S- hydrogen-phosphorodithioate and chlorine carry out chlorination reaction and prepare O, in the reaction system of O- dialkyl sulfide substituted phosphorus oxychloride, it is passed through the sulphur that excessive chlorine generates reaction and is converted into disulphur dichloride, disulphur dichloride is then converted into sulfur dichloride；It is set as negative pressure state by the control of reaction temperature, and by reaction system, so that sulfur dichloride is passed through distillation condensation during the reaction and removes reaction system.This method is based on green chemical concept, realizes atom economy substantially；Raw material overall cost is far below conventional method, and quantity of three wastes is few, and is easily handled；Without traditional separation of solid and liquid, it is convenient for automated production, the safety and environmental protection grade of device improve；O, O- dialkyl sulfide substituted phosphorus oxychloride are not contacted with water, avoid the decomposition of product, and yield is up to 93%, and product content is up to 99%.
Description
Technical field
The invention belongs to the preparation technical field of pesticide intermediate more particularly to a kind of O, O- dialkyl sulfide substituted phosphorus oxychloride
Synthetic method.
Background technique
O, O- dialkyl sulfide substituted phosphorus oxychloride (abbreviation alkyl monochloride, similarly hereinafter) are the special of synthesis group thiophosphate pesticide
With intermediate, O is most representative in O- dialkyl sulfide substituted phosphorus oxychloride to have O, O- dimethyl thiophosphoryl chloride (abbreviation methyl one
Chloride, similarly hereinafter) and O, O- diethyl sulfo-phosphoryl chloride (abbreviation ethyl monochloride, similarly hereinafter).Methyl monochloride and ethyl
Monochloride can be used for preparing nearly 20 kinds efficient, middle less toxic organophosphorus pesticides, such as orthene, pirimiphos-methyl, methyl
Chlopyrifos, fenifrothion, tolelofos-methyl, Entex, Nankor, cynock, chlopyrifos, sulfotep, diazinon, Hostathion,
Profenofos, parathion, quinalphos and phoxim etc..Wherein diazinon, orthene, chlorpyrifos-methyl, chlopyrifos, methyl are phonetic
The kinds such as pyridine phosphorus, ethyl-pyrimidine phosphorus are the organic phosphorus species of high-efficiency low-toxicity that FAO (Food and Agriculture Organization of the United Nation) (FAO) is recommended to use.In recent years
Growing trend year by year is presented in demand of the pesticide market to alkyl monochloride.
The synthetic route of the alkyl monochloride of mainstream is to use phosphorus pentasulfide and alcohol for raw material both at home and abroad at present, is first closed
At O, O- dialkyl group S- hydrogen-phosphorodithioate (abbreviation alkyl sulfur compounds, similarly hereinafter), then alkyl monochloride is obtained through chlorination.
This route can avoid O well, and O, (compound can cause human anus to damage or be immunized suppression to O- trialkyl thiophosphate
System, be the impurity of FAO's strict control) generation.
Alkyl sulfur compounds obtains alkyl monochloride, sulphur and hydrogen chloride through chlorination, and wherein sulphur is dissolved in alkyl on a small quantity
Monochloride, most of sulphur exist in reaction solution in solid form, must be using filtering, after product rectifying also when post-processing
Sulphur can be precipitated；It is big in filtering middle ring packing pressure of slagging tap due to reaction solution acid gas-containing and alkyl monochloride facile hydrolysis, and
And obtained solid sulfur stink is larger, can only as Solid state fermentation (CN103304596, CN101293897,
CN104151351, CN106608889, CN106083921, CN104817588, CN104072536, CN102584892；Chemistry
Reagent, 2013,35 (1), 89-90；).
To solve the problems, such as to slag tap in filtering, environmental protection pressure caused by middle strong acidity gas is big, and Some Enterprises are used in chlorination
Sulphur is converted disulphur dichloride by the method for being passed through excessive chlorine in the process, then by reaction solution and akali sulphide reactant aqueous solution,
Sour gas is neutralized and disulphur dichloride is reduced to sulphur, is finally refiltered, and is reached sulphur and is separated with alkyl monochloride.
(modern, 14 (4), 2015,18-19)
Although this method solves filter process middle strong acidity gas problem, but disulphur dichloride and vulcanized sodium reaction process
Very exothermic, reaction temperature heating are very fast.Since alkyl monochloride stability is poor, alkyl is easily led to more than certain temperature
Monochloride is thermally decomposed, and slug or risk of explosion are generated.The solid sulfur stink being obtained by filtration is larger, can only be as at waste residue
Reason, and a large amount of sulfur-bearing, phosphorus foul smell waste water are generated after basic hydrolysis, the environmental protection pressure of wastewater treatment is huge.
Since the production of traditional alkyl monochloride faces the intractable problem of a large amount of three wastes, it is therefore necessary to be based on atom
Economics develops the new green synthesizing process of alkyl monochloride.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide a kind of O, O- dialkyl phosphinylidyne
The synthetic method of chlorine converts useful byproduct for the waste generated in current synthesis, after avoiding waste water from generating and simplify
Reason improves yield.
Invention thinking of the invention is added more in the chlorination process of alkyl sulfur compounds based on green chemical synthesis theory
Mostly excessive chlorine, is synthetically generated sulfur dichloride for disulphur dichloride, lower using its boiling point, obtains dichloride by distillation
Sulphur, sulfur dichloride can be used as key intermediate and vulcanizer of sulphur sulfate etc..This product obtained after reaction
Without washing, the hydrolysis of alkyl monochloride is also avoided.Synthetic method atom utilization is high, without separation of solid and liquid process, no
Stench sulphur and waste water are generated, is automated during easy to produce, and the higher sulfur dichloride of by-product value reduces alkyl
The production cost of monochloride.
But there are still following technical problems for the program: disulphur dichloride and chlorine reaction generation sulfur dichloride are one and balance
Reaction, and the chemical property of disulphur dichloride is more stable.
If reacting disulphur dichloride and sulfur dichloride meeting in late phase reaction liquid using the conventional method for being passed through excessive chlorine
In an equilibrium state, the purpose that disulphur dichloride is fully converted to sulfur dichloride in the technical program cannot achieve.
Applicant has found in early-stage study, 60 DEG C of sulfur dichloride boiling point, 138 DEG C of disulphur dichloride boiling point, and one chlorine of alkyl
The boiling point of compound is higher (132 DEG C of the boiling point of methyl monochloride, the boiling point of ethyl monochloride is higher).If using conventional essence
Can not also disulphur dichloride and alkyl monochloride be separated by evaporating mode.
Applicant thinks that the phase will generate before the reaction if using low vacuum reactive distillation mode during being passed through chlorine
Hydrogen chloride remove and system and absorbed to obtain by-product hydrochloric acid with water, the phase breaks disulphur dichloride after the reaction and chlorine generates dichloro
The chemical balance for changing sulphur will using the boiling point of sulfur dichloride far below the property of disulphur dichloride, the boiling point of alkyl monochloride
Continually distillation condensation removal system accelerates positive reaction to sulfur dichloride from reaction solution, and kettle liquid after reaction is essentially alkane
Base monochloride can be obtained purity using rectification under vacuum and reach 99% product, realizes the purpose of green syt.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of synthetic method of O, O- dialkyl sulfide substituted phosphorus oxychloride, in O, O- dialkyl group S- hydrogen-phosphorodithioate and chlorine
Gas carries out chlorination reaction and prepares O, in the reaction system of O- dialkyl sulfide substituted phosphorus oxychloride, is passed through excessive chlorine and reaction is generated
Sulphur be converted into disulphur dichloride, disulphur dichloride is then converted into sulfur dichloride；By the control of reaction temperature, and will
Reaction system is set as negative pressure state, so that sulfur dichloride is passed through distillation condensation during the reaction and removes reaction system.
Preferably, the integral molar quantity that chlorine is passed through be O, O- dialkyl group S- hydrogen-phosphorodithioate mole 2.15~
2.5 again.
Preferably, the negative pressure state, relative degree of vacuum are -0.04MPa~-0.05MPa.
Preferably, reaction temperature control is at 30~50 DEG C.
Preferably, the reaction time is 4~6h.
In some embodiments, chlorine is passed into O, O- dialkyl group S- hydrogen-phosphorodithioate and catalyst
Reaction system in, reaction early period obtain O, then reaction system is changed and is set by O- dialkyl sulfide substituted phosphorus oxychloride, sulphur and hydrogen chloride
For negative pressure state, continue to be passed through chlorine, obtains sulfur dichloride by distilling condensation.
Preferably, reacting the mole that early period, chlorine was passed through is O, O- dialkyl group S- hydrogen-phosphorodithioate mole
1.05~1.2 times.
Preferably, the hydrogen chloride generated in reaction process is absorbed with water.
Preferably, the catalyst is iron powder.
Preferably, the O, O- dialkyl group S- hydrogen-phosphorodithioate be O, O- dimethyl S- hydrogen-phosphorodithioate or
O, O- diethyl S- hydrogen-phosphorodithioate.
Compared with the prior art, the advantages of the present invention are as follows:
1) it is developed based on green chemical concept, no sulphur, phosphorus atoms waste realize atom economy, raw material are comprehensive substantially
Synthesis is originally far below conventional method；
2) without traditional separation of solid and liquid, it is convenient for automated production, improves the safety and environmental protection grade of device；
3) O, O- dialkyl sulfide substituted phosphorus oxychloride are not contacted with water, avoid the decomposition of product, and yield is greater than 93%, and product contains
It measures up to 99%；
4) quantity of three wastes is few, and is easily handled.
Specific embodiment
In certain specific embodiments of the invention, under certain temperature (preferably 30~50 DEG C), chlorine is slowly led to
Enter the O (due to exothermic heat of reaction), in the system of O- dialkyl group S- hydrogen-phosphorodithioate and catalyst, reaction obtains O, O- early period
Dialkyl sulfide substituted phosphorus oxychloride, sulphur and hydrogen chloride.The hydrogen chloride of generation can be absorbed to obtain byproduct hydrochloric acid with water.Preferably,
Reacting the mole that early period, chlorine was passed through is O, 1.05~1.2 times of O- dialkyl group S- hydrogen-phosphorodithioate mole.
Then, reaction system is changed to carry out reactive distillation under the conditions of certain low vacuum, maintaining reaction temperature is 30
~50 DEG C, continue to be passed through chlorine, by reactive distillation, condenser system constantly collects sulfur dichloride by-product.The low vacuum item
Part, relative degree of vacuum are preferably -0.04MPa~-0.05MPa.At the end of reaction, the moles total number that chlorine is passed through is preferably
2.15~2.5 times of O, O- dialkyl group S- hydrogen-phosphorodithioate mole.
After reaction, the O that purity reaches 99%, O- dialkyl phosphinylidyne can be obtained through high vacuum rectification in reaction solution
Chlorine, preferred relative degree of vacuum are -0.099MPa.
In the methods of the invention, used catalyst is iron powder, and dosage is preferably O, O- dialkyl group S- hydrogen-phosphordithiic acid
The 0.1%~0.3% of ester quality.
In following embodiments, methyl sulfide refers to that O, O- dimethyl S- hydrogen-phosphorodithioate, diethyl sulfide refer to O, O-
Diethyl S- hydrogen-phosphorodithioate.
Below in conjunction with specific preferred embodiment, the invention will be further described, but not thereby limiting the invention
Protection scope.
Embodiment 1:
To with long 10cm, Φ=23mm glass filler rectifying column, cooling tube, receiving bottle, chlorine tube, thermometer, stirring
500mL three-necked flask in 329.3g (2mol) methyl sulfide (96%) and 0.6g iron powder catalyst is added, at 40 DEG C of control
It is passed through chlorine, the hydrogen chloride of generation is absorbed with water.System gradually becomes cloudy, and generates yellow solid.When being passed through chlorine about 150g,
System is switched to 40 DEG C of maintaining reaction temperature simultaneously of pressure -0.04MPa, is faded away as chlorine is passed through yellow solid, rectifying,
Brownish red sulfur dichloride is collected in condensation.Chlorine is passed through 5h (being always passed through the time), collects when being passed through 319g (4.4mol, total intake)
Less than obvious liquid, stop reaction.It is collected into 210g sulfur dichloride altogether.Stop logical chlorine, the high vacuum rectification at -0.099MPa
Obtain 303.8g O, O- dimethyl thiophosphoryl chloride (purity 99%), yield 94.0%.
Embodiment 2:
To with long 10cm, Φ=23mm glass filler rectifying column, cooling tube, receiving bottle, chlorine tube, thermometer, stirring
500mL three-necked flask in 391.6g (2mol) diethyl sulfide (96%) and 1.0g iron powder catalyst is added, at 45 DEG C of control
It is passed through chlorine, the hydrogen chloride of generation is absorbed with water.System gradually becomes cloudy, and generates yellow solid.When being passed through chlorine about 160g,
System is switched to 45 DEG C of maintaining reaction temperature simultaneously of pressure -0.04MPa, is faded away as chlorine is passed through yellow solid, rectifying,
Brownish red sulfur dichloride is collected in condensation.Chlorine is passed through 4.5h, is collected when being passed through 306g (4.3mol) less than obvious liquid, stops anti-
It answers.It is collected into 205g sulfur dichloride altogether.Stop logical chlorine, high vacuum rectification obtains 355.7g O, O- diethyl at -0.099MPa
Base thiophosphoryl chloride (purity 99%), yield 93.4%.
Embodiment 3:
To with long 10cm, Φ=23mm glass filler rectifying column, cooling tube, receiving bottle, chlorine tube, thermometer, stirring
500mL three-necked flask in 329.3g (2mol) methyl sulfide (96%) and 0.4g iron powder catalyst is added, at 30 DEG C of control
It is passed through chlorine, the hydrogen chloride of generation is absorbed with water.System gradually becomes cloudy, and generates yellow solid.When being passed through chlorine about 170g,
System is switched to 30 DEG C of maintaining reaction temperature simultaneously of pressure -0.05MPa, is faded away as chlorine is passed through yellow solid, rectifying,
Brownish red sulfur dichloride is collected in condensation.Chlorine is passed through 5h, is collected when being passed through 355g (5.0mol) less than obvious liquid, stops anti-
It answers.It is collected into 207g sulfur dichloride altogether.Stop logical chlorine, high vacuum rectification obtains 302.6gO, O- diformazan at -0.099MPa
Base thiophosphoryl chloride (purity 99%), yield 93.6%.
Embodiment 4:
To with long 10cm, Φ=23mm glass filler rectifying column, cooling tube, receiving bottle, chlorine tube, thermometer, stirring
500mL three-necked flask in 329.3g (2mol) methyl sulfide (96%) and 0.8g iron powder catalyst is added, at 50 DEG C of control
It is passed through chlorine, the hydrogen chloride of generation is absorbed with water.System gradually becomes cloudy, and generates yellow solid.When being passed through chlorine about 150g,
System is switched to 50 DEG C of maintaining reaction temperature simultaneously of pressure -0.04MPa, is faded away as chlorine is passed through yellow solid, rectifying,
Brownish red sulfur dichloride is collected in condensation.Chlorine is passed through 6h, is collected when being passed through 305.3g (4.3mol) less than obvious liquid, stops anti-
It answers.It is collected into 213g sulfur dichloride altogether.Stop logical chlorine, high vacuum rectification obtains 304.7g O, O- diformazan at -0.099MPa
Base thiophosphoryl chloride (purity 99%), yield 94.3%.
Embodiment 5:
To with long 10cm, Φ=23mm glass filler rectifying column, cooling tube, receiving bottle, chlorine tube, thermometer, stirring
500mL three-necked flask in 391.6g (2mol) diethyl sulfide (96%) and 0.4g iron powder catalyst is added, at 35 DEG C of control
It is passed through chlorine, the hydrogen chloride of generation is absorbed with water.System gradually becomes cloudy, and generates yellow solid.When being passed through chlorine about 170g,
System is switched to 35 DEG C of maintaining reaction temperature simultaneously of pressure -0.05MPa, is faded away as chlorine is passed through yellow solid, rectifying,
Brownish red sulfur dichloride is collected in condensation.Chlorine is passed through 5h, is collected when being passed through 340.8g (4.8mol) less than obvious liquid, stops anti-
It answers.It is collected into 208g sulfur dichloride altogether.Stop logical chlorine, high vacuum rectification obtains 357.8g O, O- diethyl at -0.099MPa
Base thiophosphoryl chloride (purity 99%), yield 93.9%.
Embodiment 6:
To with long 10cm, Φ=23mm glass filler rectifying column, cooling tube, receiving bottle, chlorine tube, thermometer, stirring
500mL three-necked flask in 391.6g (2mol) diethyl sulfide (96%) and 1.2g iron powder catalyst is added, at 45 DEG C of control
It is passed through chlorine, the hydrogen chloride of generation is absorbed with water.System gradually becomes cloudy, and generates yellow solid.When being passed through chlorine about 150g,
System is switched to 45 DEG C of maintaining reaction temperature simultaneously of pressure -0.04MPa, is faded away as chlorine is passed through yellow solid, rectifying,
Brownish red sulfur dichloride is collected in condensation.Chlorine is passed through 4h, is collected when being passed through 319.5g (4.5mol) less than obvious liquid, stops anti-
It answers.It is collected into 213g sulfur dichloride altogether.Stop logical chlorine, high vacuum rectification obtains 365.2g O, O- diethyl at -0.099MPa
Base thiophosphoryl chloride (purity 99%), yield 95.8%.
Above-mentioned only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form.Although of the invention
It has been disclosed in a preferred embodiment above, however, it is not intended to limit the invention.Therefore, all without departing from technical solution of the present invention
Content, technical spirit any simple modifications, equivalents, and modifications made to the above embodiment, should all fall according to the present invention
In the range of technical solution of the present invention protection.
Claims (8)
1. the synthetic method of a kind of O, O- dialkyl sulfide substituted phosphorus oxychloride, it is characterised in that:
In O, O- dialkyl group S- hydrogen-phosphorodithioate and chlorine carry out chlorination reaction and prepare O, O- dialkyl sulfide substituted phosphorus oxychloride
In reaction system, it is passed through the sulphur that excessive chlorine generates reaction and is converted into disulphur dichloride, disulphur dichloride then turns
Turn to sulfur dichloride；It is set as negative pressure state at 30~50 DEG C, and by rectifying column by the control of reaction temperature, it is relatively true
Reciprocal of duty cycle is -0.04 MPa~-0.05MPa, so that sulfur dichloride is passed through rectifying during the reaction and removes reaction system.
2. the synthetic method of O according to claim 1, O- dialkyl sulfide substituted phosphorus oxychloride, which is characterized in that chlorine was passed through
Integral molar quantity is O, 2.15~2.5 times of O- dialkyl group S- hydrogen-phosphorodithioate mole.
3. the synthetic method of O according to claim 1, O- dialkyl sulfide substituted phosphorus oxychloride, which is characterized in that the reaction time is
4~6h.
4. the synthetic method of O according to claim 1 or 2, O- dialkyl sulfide substituted phosphorus oxychloride, which is characterized in that by chlorine
It is passed into O, in the reaction system of O- dialkyl group S- hydrogen-phosphorodithioate and catalyst, reaction obtains O, O- dialkyl group early period
Thiophosphoryl chloride, sulphur and hydrogen chloride, then rectifying column is changed be set as negative pressure state, is continued to be passed through chlorine, be obtained by rectifying
Sulfur dichloride.
5. the synthetic method of O according to claim 4, O- dialkyl sulfide substituted phosphorus oxychloride, which is characterized in that reaction chlorine early period
The mole that gas is passed through is O, 1.05~1.2 times of O- dialkyl group S- hydrogen-phosphorodithioate mole.
6. the synthetic method of O according to claim 4, O- dialkyl sulfide substituted phosphorus oxychloride, which is characterized in that by reaction process
The hydrogen chloride of middle generation is absorbed with water.
7. the synthetic method of O according to claim 4, O- dialkyl sulfide substituted phosphorus oxychloride, which is characterized in that the catalyst
For iron powder.
8. the synthetic method of O according to claim 1 or 2, O- dialkyl sulfide substituted phosphorus oxychloride, which is characterized in that the O,
O- dialkyl group S- hydrogen-phosphorodithioate is O, and O- dimethyl S- hydrogen-phosphorodithioate or O, O- diethyl S- hydrogen-two are thio
Phosphate.
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