CN111116645A - Synthesis method of thiophosphate compound - Google Patents
Synthesis method of thiophosphate compound Download PDFInfo
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- CN111116645A CN111116645A CN201911291209.7A CN201911291209A CN111116645A CN 111116645 A CN111116645 A CN 111116645A CN 201911291209 A CN201911291209 A CN 201911291209A CN 111116645 A CN111116645 A CN 111116645A
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- -1 thiophosphate compound Chemical class 0.000 title claims abstract description 53
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims abstract description 33
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 84
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 78
- 229910052760 oxygen Inorganic materials 0.000 claims description 59
- 239000002904 solvent Substances 0.000 claims description 54
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 52
- 239000003480 eluent Substances 0.000 claims description 52
- 238000001704 evaporation Methods 0.000 claims description 52
- 238000000926 separation method Methods 0.000 claims description 42
- 229950009390 symclosene Drugs 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 28
- 238000004440 column chromatography Methods 0.000 claims description 26
- 239000000706 filtrate Substances 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 26
- 239000003208 petroleum Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
- 125000001624 naphthyl group Chemical group 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 description 30
- 238000003756 stirring Methods 0.000 description 23
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 21
- 239000002994 raw material Substances 0.000 description 7
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 4
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- AMNLXDDJGGTIPL-UHFFFAOYSA-N 2,4-dimethylbenzenethiol Chemical compound CC1=CC=C(S)C(C)=C1 AMNLXDDJGGTIPL-UHFFFAOYSA-N 0.000 description 1
- KOQGXYGQUONZGY-UHFFFAOYSA-N 2-(2-methylphenyl)benzenethiol Chemical compound CC1=CC=CC=C1C1=CC=CC=C1S KOQGXYGQUONZGY-UHFFFAOYSA-N 0.000 description 1
- DSCJETUEDFKYGN-UHFFFAOYSA-N 2-Methoxybenzenethiol Chemical compound COC1=CC=CC=C1S DSCJETUEDFKYGN-UHFFFAOYSA-N 0.000 description 1
- WGQKBCSACFQGQY-UHFFFAOYSA-N 2-Methyl-1-butanethiol Chemical compound CCC(C)CS WGQKBCSACFQGQY-UHFFFAOYSA-N 0.000 description 1
- PWOBDMNCYMQTCE-UHFFFAOYSA-N 2-chlorobenzenethiol Chemical compound SC1=CC=CC=C1Cl PWOBDMNCYMQTCE-UHFFFAOYSA-N 0.000 description 1
- IYAMNWOKPYKULR-UHFFFAOYSA-N 3-(2-methylphenyl)benzenethiol Chemical compound CC1=CC=CC=C1C1=CC=CC(S)=C1 IYAMNWOKPYKULR-UHFFFAOYSA-N 0.000 description 1
- CQJDYPZUDYXHLM-UHFFFAOYSA-N 3-chlorobenzenethiol Chemical compound SC1=CC=CC(Cl)=C1 CQJDYPZUDYXHLM-UHFFFAOYSA-N 0.000 description 1
- FTBCOQFMQSTCQQ-UHFFFAOYSA-N 4-bromobenzenethiol Chemical compound SC1=CC=C(Br)C=C1 FTBCOQFMQSTCQQ-UHFFFAOYSA-N 0.000 description 1
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 1
- NIFAOMSJMGEFTQ-UHFFFAOYSA-N 4-methoxybenzenethiol Chemical compound COC1=CC=C(S)C=C1 NIFAOMSJMGEFTQ-UHFFFAOYSA-N 0.000 description 1
- APDUDRFJNCIWAG-UHFFFAOYSA-N 4-propan-2-ylbenzenethiol Chemical compound CC(C)C1=CC=C(S)C=C1 APDUDRFJNCIWAG-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- CIWAIBDMLJSIBX-UHFFFAOYSA-N C=1C=CSC=1.OC1=CC=CS1 Chemical compound C=1C=CSC=1.OC1=CC=CS1 CIWAIBDMLJSIBX-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NUALMQRIQGQOFG-UHFFFAOYSA-N S1C(=CC=C1)O.C1=CC=CC2=CC=CC=C12 Chemical compound S1C(=CC=C1)O.C1=CC=CC2=CC=CC=C12 NUALMQRIQGQOFG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 1
- 150000001504 aryl thiols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- CMKBCTPCXZNQKX-UHFFFAOYSA-N cyclohexanethiol Chemical compound SC1CCCCC1 CMKBCTPCXZNQKX-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XFMJUIKWKVJNDY-UHFFFAOYSA-N diethoxyphosphorylsulfanylmethylbenzene Chemical compound CCOP(=O)(OCC)SCC1=CC=CC=C1 XFMJUIKWKVJNDY-UHFFFAOYSA-N 0.000 description 1
- FOBPTJZYDGNHLR-UHFFFAOYSA-N diphosphorus Chemical compound P#P FOBPTJZYDGNHLR-UHFFFAOYSA-N 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
-
- 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
- C07F9/1653—Esters of thiophosphoric acids with arylalkanols
-
- 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
- C07F9/17—Esters of thiophosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
-
- 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
- C07F9/177—Esters of thiophosphoric acids with cycloaliphatic alcohols
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
- C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses a synthesis method of a thiophosphate compound, which comprises the steps of taking mercaptan as a reaction substrate, taking trichloroisocyanuric acid (TCCA) as an accelerant, reacting the reaction substrate and the accelerant in an organic solvent for 10-20 min under the conditions of normal temperature and normal pressure, then adding phosphite triester, continuing to react for 10-20 min, and separating after the reaction is finished to obtain the thiophosphate compound. The synthesis method of the invention has the advantages that the reaction is carried out at normal temperature and normal pressure, and no special requirements are required; the reaction time is short; the reaction substrate has good universality.
Description
Technical Field
The invention relates to a synthetic method of a thiophosphate compound.
Background
The organic compound containing phosphorus and sulfur has special properties and wide application. Thiophosphate compounds are important in sulfur-phosphorus-containing organic compounds, and the compounds have wide application in various fields such as medicines, pesticides, biology, materials and the like. The conventional synthesis of these compounds is carried out by reacting halogenated phosphates with thiols, but with halogenated phosphorusThe preparation method of the acid ester compound is complex and inconvenient to operate. In recent years, the use of diphosphorous acid diesters (H-P (O) (OR))2) The synthesis of phosphorothioate compounds by cross-dehydrocoupling (CDC) reaction with thiols has been developed. In 2013, the literature reports that CuI can catalyze the reaction of hydrogen phosphorous acid diester and aryl mercaptan to synthesize phosphorothioate compounds in the presence of triethylamine (Synthesis2013, 45, 2323); in 2014, the literature reports the reaction for preparing the thiophosphate compound by taking hydrogen phosphorous acid diester and thiol promoted by NCS as raw materials (Green chem.2014, 16, 357); in 2016, a reaction for preparing a thiophosphate compound by taking Pd-catalyzed diphosphorous acid diester and mercaptan as raw materials is reported (J.Am.chem.Soc.2016, 138, 5825); in 2017, Cs is reported in literature2CO3A reaction for preparing a thiophosphate compound by using catalytic diphosphorous diester and mercaptan as raw materials (Angew. chem. int. Ed.2017, 56, 2487); the NHCs catalyst can catalyze the reaction of the diphosphorus acid diester and the disulfide to synthesize the thiophosphate compound (chem.Eur.J.2017, 23, 6259).
The phosphite triester compound has low price and strong nucleophilic ability. Therefore, K has been reported2CO3The reaction for preparing the thiophosphate compound by taking the phosphite triester and the mercaptan as raw materials is promoted, and the reaction time is generally 5-12h (RSCAdv.2017, 7, 45416). However, this reaction is only applicable to aryl thiols, and aliphatic thiols are not. Chinese patent CN10884260 reports a method for preparing thiophosphate compounds by reacting phosphite triester and disulfide, and the reaction does not need catalyst or promoter. However, this reaction is only applicable to diaryl disulfides, and it is well known that disulfide compounds still need to be prepared from thiols. The above methods have advantages but disadvantages, such as the use of a transition metal catalyst in some methods, limited substrate in some methods, relatively high raw material cost in some methods, and long reaction time in some methods.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing a thiophosphate compound at room temperature by using phosphite triester and mercaptan as raw materials.
In order to achieve the purpose, the invention adopts the following technical scheme: a method for synthesizing a thiophosphate compound comprises the steps of taking mercaptan as a reaction substrate, taking trichloroisocyanuric acid (TCCA) as an accelerant, reacting the reaction substrate and the accelerant in an organic solvent for 10-20 min under the conditions of normal temperature and normal pressure, then adding phosphite triester, continuing to react for 10-20 min, and separating after the reaction is finished to obtain the thiophosphate compound.
The structural formula of the phosphite triester compound is shown as a formula (II), the structure of the thiol compound is shown as a formula (III), and the structural formula of the corresponding obtained thiophosphate compound is shown as a formula (I);
in the formula (I) or formula (II), R1Is C1-C8 alkyl, preferably methyl, ethyl, isopropyl or n-butyl.
In the formula (I) or formula (III), R2Is C1-C12 alkyl, benzyl, substituted benzyl, phenyl, substituted phenyl, heteroaryl, substituted heteroaryl, naphthyl or substituted naphthyl. The heteroaryl group may be an aromatic group containing a heteroatom such as N, O, S in the ring. The substituted benzyl, substituted phenyl, substituted heteroaromatic group and substituted naphthyl refer to that hydrogen on a benzene ring, a heteroaromatic ring or a naphthalene ring is substituted by one or more substituents, and each substituent is independently selected from one of the following groups: halogen, alkyl of C1-C4, alkoxy of C1-C4, amino and hydroxyl. Preferably R2Cyclohexyl, 2-methylbutyl, dodecyl, benzyl, halogenated phenyl, alkyl substituted phenyl, alkoxy substituted phenyl, amino substituted phenyl, naphthyl or thienyl.
In the invention, the quantity ratio of the mercaptan compound to the substances of the phosphite triester and TCCA is 100: 90-250: 30-60, preferably 100: 100-200: 33 to 50.
In the invention, the organic solvent is dichloromethane, tetrahydrofuran, N-dimethylformamide, toluene and acetonitrile, preferably acetonitrile or N, N-dimethylformamide; the mass usage of the solvent is recommended to be 7-30 times of that of the thiol compound.
The post-treatment method of the reaction liquid comprises the following steps: after the reaction is finished, filtering, evaporating the filtrate under reduced pressure to remove the solvent, and then performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting the eluent containing the target compound, and evaporating the solvent to obtain the product, i.e. the thiophosphate compound.
The invention specifically recommends that the method for synthesizing the thiophosphate compound by taking the phosphite triester and the mercaptan as raw materials is carried out according to the following steps: adding mercaptan and TCCA into an organic solvent, reacting for 10-20 min at normal temperature and normal pressure, adding phosphite triester into a reaction system, continuing to react for 10-20 min, filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether to ethyl acetate is 20: 1 as eluent, collecting the eluent containing the target compound, and evaporating the solvent to obtain the product, i.e. the thiophosphate compound. The organic solvent is acetonitrile or N, N-dimethylformamide; the quantity ratio of the mercaptan compound to the substances of the phosphite triester and TCCA is 100: 100-200: 33 to 50.
The synthesis method has the beneficial effects that:
(1) the reaction is carried out at normal temperature and normal pressure, and has no special requirement.
(2) The reaction time is short.
(3) The reaction substrate has good universality.
Detailed Description
The invention is further illustrated by the following specific examples, without limiting the scope of the invention thereto.
The following examples show the structural formulas of the phosphorothioate compounds shown in formulas (1) to (23), respectively:
example 1: preparation of O, O-diethyl-S-p-tolylthiophosphate (formula (1))
In a 15mL reaction tube equipped with a magnetic stirrer, p-toluenesulphonol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL acetonitrile were added, and the reaction was stirred at room temperature for 10min, then triethyl phosphite (1.2mmol) was added, and stirring was continued at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting eluent containing target compound, evaporating solvent to obtain product O, O-diethyl-S-p-tolyl thiophosphate with separation yield of 94%.
Example 2: preparation of O, O-diethyl-S-p-tolylthiophosphate (formula (1))
The reaction procedure was as in example 1, except that the reaction solvent was changed to methylene chloride and the isolated yield of O, O-diethyl-S-p-tolylthiophosphate was 67%.
Example 3: preparation of O, O-diethyl-S-p-tolylthiophosphate (formula (1))
The procedure was as in example 1, except that the reaction solvent was changed to tetrahydrofuran, and the isolated yield of O, O-diethyl-S-p-tolylthiophosphate was 83%.
Example 4: preparation of O, O-diethyl-S-p-tolylthiophosphate (formula (1))
The reaction procedure was as in example 1, except that the reaction solvent was changed to N, N-dimethylformamide, and the isolated yield of O, O-diethyl-S-p-tolylthiophosphate was 93%.
Example 5: preparation of O, O-diethyl-S-p-tolylthiophosphate (formula (1))
The reaction procedure was as in example 1, except that the reaction solvent was changed to toluene, and O, O-diethyl-S-p-tolylthiophosphate was isolated in a yield of 50%.
Example 6: preparation of O, O-diethyl-S-p-tolylthiophosphate (formula (1))
The reaction procedure was as in example 1, except that the amount of trichloroisocyanuric acid was changed to 0.33mmol, and the isolated yield of O, O-diethyl-S-p-tolylthiophosphate was 90%.
Example 7: preparation of O, O-diethyl-S-m-tolyl phosphorothioate (formula (2))
In a 15mL reaction tube equipped with a magnetic stirrer, m-tolylthiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL of acetonitrile were added, and the reaction was stirred at room temperature for 10min, then triethyl phosphite (1.2mmol) was added, and stirring was continued at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting eluent containing target compound, evaporating solvent to obtain product O, O-diethyl-S-m-tolyl thiophosphate with separation yield of 75%.
Example 8: preparation of O, O-diethyl-S-O-tolylthiophosphate (formula (3))
In a 15mL reaction tube equipped with a magnetic stirrer, o-tolylthiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL of acetonitrile were added, and the reaction was stirred at room temperature for 10min, then triethyl phosphite (1.2mmol) was added, and stirring was continued at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting eluent containing target compound, evaporating solvent to obtain product O, O-diethyl-S-O-tolyl thiophosphate with separation yield of 60%.
Example 9: preparation of O, O-diethyl-S-p-isopropylphenyl phosphorothioate (formula (4))
In a 15mL reaction tube equipped with a magnetic stirrer, p-isopropylthiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL of acetonitrile were added, and the reaction was stirred at room temperature for 10min, then triethyl phosphite (1.2mmol) was added, and stirring was continued at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product O, O-diethyl-S-p-isopropylphenyl thiophosphate, with the separation yield of 80%.
Example 10: preparation of O, O-diethyl-S-p-tert-butylphenyl thiophosphate (formula (5))
To a 15mL reaction tube equipped with a magnetic stirrer, p-tert-butylphenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL acetonitrile were added, and the reaction was stirred at room temperature for 10min, followed by the addition of triethyl phosphite (1.2mmol) and continued stirring at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product O, O-diethyl-S-p-tert-butylphenyl thiophosphate, with a separation yield of 84%.
Example 11: preparation of O, O-diethyl-S-p-methoxyphenyl phosphorothioate (formula (6))
A15 mL reaction tube equipped with a magnetic stirrer was charged with p-methoxythiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL acetonitrile, stirred at room temperature for 10min, then triethyl phosphite (1.2mmol) was added, and stirring was continued at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting eluent containing target compound, evaporating solvent to obtain product O, O-diethyl-S-p-methoxyphenyl thiophosphate, and separating yield is 85%.
Example 12: preparation of O, O-diethyl-S-O-methoxyphenyl phosphorothioate (formula (7))
In a 15mL reaction tube equipped with a magnetic stirrer, o-methoxythiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL acetonitrile were added, and the reaction was stirred at room temperature for 10min, then triethyl phosphite (1.2mmol) was added, and stirring was continued at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product O, O-diethyl-S-O-methoxyphenyl thiophosphate, wherein the separation yield is 72 percent.
Example 13: preparation of O, O-diethyl-S- (2, 4-dimethylphenyl) thiophosphate (formula (8))
2, 4-Dimethylthiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL acetonitrile were added to a 15mL reaction tube equipped with a magnetic stirrer, and the reaction was stirred at room temperature for 10min, followed by the addition of triethyl phosphite (1.2mmol) and continued stirring at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting eluent containing target compound, evaporating solvent to obtain O, O-diethyl-S- (2, 4-dimethylphenyl) thiophosphate, and separating yield is 72%.
Example 14: preparation of O, O-diethyl-S-p-chlorophenyl thiophosphate (formula (9))
P-chlorothiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL acetonitrile were added to a 15mL reaction tube equipped with a magnetic stirrer, and the reaction was stirred at room temperature for 10min, followed by the addition of triethyl phosphite (1.2mmol) and continued stirring at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product O, O-diethyl-S-p-chlorophenyl thiophosphate, with the separation yield of 93%.
Example 15: preparation of O, O-diethyl-S-m-chlorophenyl phosphorothioate (formula (10))
In a 15mL reaction tube equipped with a magnetic stirrer, m-chlorothiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL acetonitrile were added, and the reaction was stirred at room temperature for 10min, then triethyl phosphite (1.2mmol) was added and stirring was continued at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product O, O-diethyl-S-m-chlorophenyl thiophosphate, wherein the separation yield is 87%.
Example 16: preparation of O, O-diethyl-S-O-chlorophenyl thiophosphate (formula (11))
To a 15mL reaction tube equipped with a magnetic stirrer, o-chlorothiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL acetonitrile were added, and the reaction was stirred at room temperature for 10min, followed by the addition of triethyl phosphite (1.2mmol) and continued stirring at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product O, O-diethyl-S-O-chlorophenyl thiophosphate, wherein the separation yield is 90%.
Example 17: preparation of O, O-diethyl-S-p-bromophenyl phosphorothioate (formula (12))
In a 15mL reaction tube equipped with a magnetic stirrer, p-bromothiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL acetonitrile were added, and the reaction was stirred at room temperature for 10min, then triethyl phosphite (1.2mmol) was added, and stirring was continued at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting eluent containing target compound, evaporating solvent to obtain O, O-diethyl-S-p-bromophenyl thiophosphate, and separating yield is 82%.
Example 18: preparation of O, O-diethyl-S-p-fluorophenyl phosphorothioate (formula (13))
P-fluorophenylthiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL of acetonitrile were added to a 15mL reaction tube equipped with a magnetic stirrer, and the reaction was stirred at room temperature for 10min, followed by addition of triethyl phosphite (1.2mmol) and further stirring at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting eluent containing target compound, evaporating solvent to obtain product O, O-diethyl-S-p-fluorophenyl thiophosphate, and separating yield is 88%.
Example 19: preparation of O, O-diethyl-S-p-aminophenyl phosphorothioate (formula (14))
In a 15mL reaction tube equipped with a magnetic stirrer, p-aminophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL of acetonitrile were added, and the reaction was stirred at room temperature for 10min, then triethyl phosphite (1.2mmol) was added, and stirring was continued at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product O, O-diethyl-S-p-aminophenyl thiophosphate, wherein the separation yield is 48%.
Example 20: preparation of O, O-diethyl-S- (thien-2-yl) thiophosphate (formula (15))
Thiophene-2-thiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL acetonitrile were added to a 15mL reaction tube equipped with a magnetic stirrer, and the reaction was stirred at room temperature for 10min, followed by the addition of triethyl phosphite (1.2mmol) and continued stirring at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting eluent containing target compound, evaporating solvent to obtain O, O-diethyl-S- (thiophene-2-yl) thiophosphate with separation yield of 50%.
Example 21: preparation of O, O-diethyl-S- (naphthalen-2-yl) thiophosphate (formula (16))
Naphthalene-2-thiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL acetonitrile were added to a 15mL reaction tube equipped with a magnetic stirrer, and the reaction was stirred at room temperature for 10min, followed by the addition of triethyl phosphite (1.2mmol) and continued stirring at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting eluent containing target compound, evaporating solvent to obtain O, O-diethyl-S- (naphthalene-2-yl) thiophosphate with separation yield of 56%.
Example 22: preparation of O, O-diethyl-S-benzylthiophosphate (formula (17))
To a 15mL reaction tube equipped with a magnetic stirrer, benzylthiol (1mmol), trichloroisocyanuric acid (0.5mmol) and 2mL acetonitrile were added, and the reaction was stirred at room temperature for 10min, followed by the addition of triethyl phosphite (2mmol) and continued stirring at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting eluent containing target compound, evaporating solvent to obtain O, O-diethyl-S- (naphthalene-2-yl) thiophosphate with separation yield of 74%.
Example 23: preparation of O, O-diethyl-S- (2-methylbutyl) thiophosphate (formula (18))
2-Methylbutanethiol (1mmol), trichloroisocyanuric acid (0.5mmol) and 2mL acetonitrile were added to a 15mL reaction tube equipped with a magnetic stirrer, and the reaction was stirred at room temperature for 10min, followed by the addition of triethyl phosphite (2mmol) and continued stirring at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting eluent containing target compound, evaporating solvent to obtain product O, O-diethyl-S- (2-methylbutyl) thiophosphate, and separating yield is 70%.
Example 24: preparation of O, O-diethyl-S-cyclohexyl thiophosphate (formula (19))
A15 mL reaction tube equipped with a magnetic stirrer was charged with cyclohexyl thiol (1mmol), trichloroisocyanuric acid (0.5mmol) and 2mL acetonitrile, stirred at room temperature for 10min, then triethyl phosphite (2mmol) was added, and stirring was continued at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting eluent containing target compound, evaporating solvent to obtain product O, O-diethyl-S-cyclohexyl thiophosphate, and separating yield is 72%.
Example 25: preparation of O, O-diethyl-S-dodecylthiophosphate (formula (20))
A15 mL reaction tube equipped with a magnetic stirrer was charged with dodecylmercaptan (1mmol), trichloroisocyanuric acid (0.5mmol) and 2mL acetonitrile, stirred at room temperature for 10min, then triethyl phosphite (2mmol) was added, and stirring was continued at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting the eluent containing the target compound, evaporating the solvent to obtain the product O, O-diethyl-S-dodecyl thiophosphate, wherein the separation yield is 64%.
Example 26: preparation of O, O-diethyl-S-dodecylthiophosphate (formula (20))
The reaction procedure was as in example 26 except that dodecylmercaptan and trichloroisocyanuric acid were stirred at room temperature for 20min and then stirred at room temperature for 20min after triethyl phosphite was added, and the isolation yield of O, O-diethyl-S-dodecylthiophosphate was 80%.
Example 26: preparation of O, O-dimethyl-S-p-tolylthiophosphate (formula (21))
P-methylthiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL acetonitrile were added to a 15mL reaction tube equipped with a magnetic stirrer, and the reaction was stirred at room temperature for 10min, followed by the addition of trimethyl phosphite (1.2mmol) and continued stirring at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting eluent containing target compound, evaporating solvent to obtain product O, O-dimethyl-S-p-tolyl thiophosphate, with separation yield of 95%.
Example 27: preparation of O, O-diisopropyl-S-p-tolylthiophosphate (formula (22))
P-methylthiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL of acetonitrile were added to a 15mL reaction tube equipped with a magnetic stirrer, and the reaction was stirred at room temperature for 10min, followed by the addition of triisopropyl phosphite (1.2mmol) and further stirring at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting eluent containing target compound, evaporating solvent to obtain product O, O-diisopropyl-S-p-tolyl thiophosphate, and separating yield is 86%.
Example 28: preparation of O, O-di-n-butyl-S-p-tolylthiophosphate (formula (23))
In a 15mL reaction tube equipped with a magnetic stirrer, p-methylthiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL acetonitrile were added, and the reaction was stirred at room temperature for 10min, then tri-n-butyl phosphite (1.2mmol) was added, and the stirring was continued at room temperature for 10 min. Filtering, evaporating the filtrate under reduced pressure to remove the solvent, and performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting eluent containing target compound, evaporating solvent to obtain product O, O-di-n-butyl-S-p-tolyl thiophosphate with separation yield of 86%.
Claims (5)
1. A synthetic method of a thiophosphate compound is characterized in that: using mercaptan as a reaction substrate, using trichloroisocyanuric acid as an accelerant, reacting the reaction substrate and the accelerant in an organic solvent for 10-20 min under the conditions of normal temperature and normal pressure, then adding phosphite triester, continuing to react for 10-20 min, and separating after the reaction is finished to obtain the thiophosphate compound;
the structural formula of the phosphite triester compound is shown as a formula (II), the structural formula of the thiol compound is shown as a formula (III), and the structural formula of the obtained thiophosphate compound is shown as a formula (I);
in the formula (I) or formula (II), R1Is C1-C8 alkyl; in the formula (I) or formula (III), R2Is C1-C12 alkyl, benzyl, substituted benzyl, phenyl, substituted phenyl, heteroaromatic group, substituted heteroaromatic group, naphthyl or substituted naphthyl, the heteroaromatic group can be an aromatic group containing N, O, S and other heteroatoms in the ring, the substituted benzyl, substituted phenyl, substituted heteroaromatic group and substituted naphthyl refer to that hydrogen on the benzene ring, heteroaromatic ring or naphthalene ring is substituted by one or more substituents, and the substituents are independently selected from one of the following groups: halogen, alkyl of C1-C4, alkoxy of C1-C4, amino and hydroxyl.
2. The method of claim 1, wherein: preferably R1Is methyl, ethyl, isopropyl or n-butyl; preferably R2Is cyclohexyl, 2-methylbutyl, dodecyl, benzyl, halogenated phenyl, alkyl-substituted phenyl, alkoxy-substituted phenyl, amino-substituted phenyl, naphthyl or thiaA thienyl group.
3. The method of claim 2, wherein: the mass ratio of the mercaptan compounds to the substances of the phosphite triester and the trichloroisocyanuric acid is 100: 90-250: 30-60, preferably 100: 100-200: 33 to 50; the organic solvent is dichloromethane, tetrahydrofuran, N-dimethylformamide, toluene and acetonitrile, and the mass amount of the solvent is 7-30 times of that of the thiol compound.
4. The method of claim 3, wherein: the mass ratio of the mercaptan compounds to the substances of the phosphite triester and the trichloroisocyanuric acid is 100: 100-200: 33 to 50; the organic solvent is preferably acetonitrile or N, N-dimethylformamide.
5. The method of claim 4, wherein: the post-treatment method of the reaction liquid comprises the following steps: after the reaction is finished, filtering, evaporating the filtrate under reduced pressure to remove the solvent, and then performing column chromatography separation, wherein the volume ratio of petroleum ether/ethyl acetate is 20: 1 as eluent, collecting the eluent containing the target compound, and evaporating the solvent to obtain the product, i.e. the thiophosphate compound.
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CN1445231A (en) * | 2002-07-23 | 2003-10-01 | 浙江新安化工集团股份有限公司 | Technique of combination processing organic phosphorus and organosilicon monomer |
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CN108774260A (en) * | 2018-06-26 | 2018-11-09 | 广东工业大学 | A kind of synthetic method of group thiophosphate compound |
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CN1445231A (en) * | 2002-07-23 | 2003-10-01 | 浙江新安化工集团股份有限公司 | Technique of combination processing organic phosphorus and organosilicon monomer |
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CN106905361A (en) * | 2017-01-26 | 2017-06-30 | 北京大学 | A kind of application of the synthetic method and the method for group thiophosphate compound in multi-medicament synthesis |
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