CN110330526B - 一种硫代次磷酸酯的绿色合成方法 - Google Patents
一种硫代次磷酸酯的绿色合成方法 Download PDFInfo
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- CN110330526B CN110330526B CN201910680014.5A CN201910680014A CN110330526B CN 110330526 B CN110330526 B CN 110330526B CN 201910680014 A CN201910680014 A CN 201910680014A CN 110330526 B CN110330526 B CN 110330526B
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- Prior art keywords
- phenyl
- water
- methoxyphenyl
- methylphenyl
- phosphine oxide
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical group 0.000 claims abstract description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 4
- 238000010189 synthetic method Methods 0.000 claims abstract description 4
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 3
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 3
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004076 pyridyl group Chemical group 0.000 claims abstract description 3
- -1 2, 4-dimethylphenyl Chemical group 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 11
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 claims 2
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 claims 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 2
- 239000002994 raw material Substances 0.000 claims 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims 1
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims 1
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 claims 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 claims 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical compound [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 44
- 150000001875 compounds Chemical class 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 23
- 238000005160 1H NMR spectroscopy Methods 0.000 description 22
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 15
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- RCHBKQDIZMPNEQ-UHFFFAOYSA-N 2-phenyl-3-sulfanylideneisoindol-1-one Chemical compound S=C1C2=CC=CC=C2C(=O)N1C1=CC=CC=C1 RCHBKQDIZMPNEQ-UHFFFAOYSA-N 0.000 description 11
- 238000010168 coupling process Methods 0.000 description 7
- 238000005859 coupling reaction Methods 0.000 description 7
- 230000008878 coupling Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- HBQLLMHESKCGLQ-UHFFFAOYSA-N 1-[(3,5-dimethylphenyl)-phenylsulfanylphosphoryl]-3,5-dimethylbenzene Chemical compound CC=1C=C(C=C(C=1)C)P(SC1=CC=CC=C1)(=O)C1=CC(=CC(=C1)C)C HBQLLMHESKCGLQ-UHFFFAOYSA-N 0.000 description 2
- VOQSHJCVOFORGO-UHFFFAOYSA-N 1-chloro-4-diphenylphosphorylsulfanylbenzene Chemical compound C1=CC(Cl)=CC=C1SP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VOQSHJCVOFORGO-UHFFFAOYSA-N 0.000 description 2
- KTMYPUKQOWILJZ-UHFFFAOYSA-N 1-diphenylphosphorylsulfanyl-2-methylbenzene Chemical compound CC1=C(C=CC=C1)SP(C1=CC=CC=C1)(C1=CC=CC=C1)=O KTMYPUKQOWILJZ-UHFFFAOYSA-N 0.000 description 2
- YIJIPBKAJAHNAG-UHFFFAOYSA-N 1-diphenylphosphorylsulfanyl-3-methoxybenzene Chemical compound COc1cccc(SP(=O)(c2ccccc2)c2ccccc2)c1 YIJIPBKAJAHNAG-UHFFFAOYSA-N 0.000 description 2
- PJYGOSAFXFSGGG-UHFFFAOYSA-N 1-methyl-4-[(4-methylphenyl)-phenylsulfanylphosphoryl]benzene Chemical compound Cc1ccc(cc1)P(=O)(Sc1ccccc1)c1ccc(C)cc1 PJYGOSAFXFSGGG-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 2
- KEKMRZXUTZRTOE-UHFFFAOYSA-N [phenyl(phenylsulfanyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)SC1=CC=CC=C1 KEKMRZXUTZRTOE-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- UAJKMIKQRPIARP-UHFFFAOYSA-N dicyclohexylphosphorylsulfanylbenzene Chemical compound C1(=CC=CC=C1)SP(=O)(C1CCCCC1)C1CCCCC1 UAJKMIKQRPIARP-UHFFFAOYSA-N 0.000 description 2
- VVWVVPIOLIUWSN-UHFFFAOYSA-N ditert-butylphosphorylsulfanylbenzene Chemical compound CC(C)(C)P(=O)(C(C)(C)C)SC1=CC=CC=C1 VVWVVPIOLIUWSN-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- MXTFDZDZNYMXEH-UHFFFAOYSA-N 1-(2,4-dimethoxyphenyl)phosphonoyl-2,4-dimethoxybenzene Chemical compound COC1=CC(OC)=CC=C1P(=O)C1=CC=C(OC)C=C1OC MXTFDZDZNYMXEH-UHFFFAOYSA-N 0.000 description 1
- IBDGJWBORVHALW-UHFFFAOYSA-N 1-bromo-4-diphenylphosphorylsulfanylbenzene Chemical compound C1=CC(Br)=CC=C1SP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 IBDGJWBORVHALW-UHFFFAOYSA-N 0.000 description 1
- NNODRUWXPNWCKO-UHFFFAOYSA-N 2-(2-fluorophenyl)sulfanylisoindole-1,3-dione Chemical compound FC1=C(C=CC=C1)SN1C(C=2C(C1=O)=CC=CC2)=O NNODRUWXPNWCKO-UHFFFAOYSA-N 0.000 description 1
- KPYGHQALDAITMY-UHFFFAOYSA-N 2-(2-methylphenyl)isoindole-1,3-dione Chemical compound CC1=CC=CC=C1N1C(=O)C2=CC=CC=C2C1=O KPYGHQALDAITMY-UHFFFAOYSA-N 0.000 description 1
- UTDBCWSLBSPUPK-UHFFFAOYSA-N 2-(3-methoxyphenyl)isoindole-1,3-dione Chemical compound COC1=CC=CC(N2C(C3=CC=CC=C3C2=O)=O)=C1 UTDBCWSLBSPUPK-UHFFFAOYSA-N 0.000 description 1
- MHNWGALOHVYLDZ-UHFFFAOYSA-N 2-(4-chlorophenyl)sulfanylisoindole-1,3-dione Chemical compound C1=CC(Cl)=CC=C1SN1C(=O)C2=CC=CC=C2C1=O MHNWGALOHVYLDZ-UHFFFAOYSA-N 0.000 description 1
- MMWQKFNXBPPXIP-UHFFFAOYSA-N 2-benzyl-3-sulfanylideneisoindol-1-one Chemical compound S=C1C2=CC=CC=C2C(=O)N1CC1=CC=CC=C1 MMWQKFNXBPPXIP-UHFFFAOYSA-N 0.000 description 1
- KAGAVUGKKXTQSJ-UHFFFAOYSA-N 2-pyridin-2-ylsulfanylisoindole-1,3-dione Chemical compound O=C1C2=CC=CC=C2C(=O)N1SC1=CC=CC=N1 KAGAVUGKKXTQSJ-UHFFFAOYSA-N 0.000 description 1
- CWPKTBMRVATCBL-UHFFFAOYSA-N 3-[1-[1-[(2-methylphenyl)methyl]piperidin-4-yl]piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound CC1=CC=CC=C1CN1CCC(N2CCC(CC2)N2C(NC3=CC=CC=C32)=O)CC1 CWPKTBMRVATCBL-UHFFFAOYSA-N 0.000 description 1
- SEXMAJCJOIWOKW-UHFFFAOYSA-N 3-prop-2-enylphosphonoylprop-1-ene Chemical compound C(C=C)P(CC=C)=O SEXMAJCJOIWOKW-UHFFFAOYSA-N 0.000 description 1
- IGHOSNRNSSBYGF-UHFFFAOYSA-N C(#CCCCC)P(C#CCCCC)=O Chemical compound C(#CCCCC)P(C#CCCCC)=O IGHOSNRNSSBYGF-UHFFFAOYSA-N 0.000 description 1
- VUKPOADSGHRVJW-UHFFFAOYSA-N C1=CC=C2C(=C1)C(=O)N(C2=S)C3=CC=C(C=C3)Br Chemical compound C1=CC=C2C(=C1)C(=O)N(C2=S)C3=CC=C(C=C3)Br VUKPOADSGHRVJW-UHFFFAOYSA-N 0.000 description 1
- NHEULQMXMXIOJY-UHFFFAOYSA-N Cl[PH2]=O Chemical compound Cl[PH2]=O NHEULQMXMXIOJY-UHFFFAOYSA-N 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000001484 Trigonella foenum graecum Nutrition 0.000 description 1
- 244000250129 Trigonella foenum graecum Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- MWYXORYWUKRJEX-UHFFFAOYSA-N bis(2-methoxyphenyl)-oxophosphanium Chemical compound COC1=CC=CC=C1[P+](=O)C1=CC=CC=C1OC MWYXORYWUKRJEX-UHFFFAOYSA-N 0.000 description 1
- LMXRTXPFJNGAAX-UHFFFAOYSA-N bis(3,5-dimethylphenyl)-oxophosphanium Chemical compound CC1=CC(C)=CC([P+](=O)C=2C=C(C)C=C(C)C=2)=C1 LMXRTXPFJNGAAX-UHFFFAOYSA-N 0.000 description 1
- ZHIPXAFNKGZMSC-UHFFFAOYSA-N bis(4-methylphenyl)-oxophosphanium Chemical compound C1=CC(C)=CC=C1[P+](=O)C1=CC=C(C)C=C1 ZHIPXAFNKGZMSC-UHFFFAOYSA-N 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HJPHBJYOODQSLK-UHFFFAOYSA-N dicyclohexyl(oxo)phosphanium Chemical compound C1CCCCC1[P+](=O)C1CCCCC1 HJPHBJYOODQSLK-UHFFFAOYSA-N 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- DAPZRBJQPPDZGH-UHFFFAOYSA-N diphenylphosphanyl(diphenyl)phosphane Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)P(C=1C=CC=CC=1)C1=CC=CC=C1 DAPZRBJQPPDZGH-UHFFFAOYSA-N 0.000 description 1
- JIKVJUUIMIGAAO-UHFFFAOYSA-N diphenylphosphinous acid Chemical compound C=1C=CC=CC=1P(O)C1=CC=CC=C1 JIKVJUUIMIGAAO-UHFFFAOYSA-N 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- QQSIRURWBGEHFS-UHFFFAOYSA-N ditert-butyl(oxo)phosphanium Chemical compound CC(C)(C)[P+](=O)C(C)(C)C QQSIRURWBGEHFS-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- UHFIMVQOGRRZRM-UHFFFAOYSA-N hydroxy-diphenyl-sulfanylidene-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(=S)(O)C1=CC=CC=C1 UHFIMVQOGRRZRM-UHFFFAOYSA-N 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 201000004792 malaria Diseases 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical class OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VEMKTZHHVJILDY-UHFFFAOYSA-N resmethrin Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000006863 thiophosphorylation reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 235000001019 trigonella foenum-graecum Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3211—Esters of acyclic saturated acids which can have 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3217—Esters of acyclic unsaturated acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3223—Esters of cycloaliphatic acids
-
- 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
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Abstract
一种如下式I所示硫代次磷酸酯的绿色合成方法，
其中，R1为苯基、不超过三个甲基或三个甲氧基或三个卤素取代的苯基、不超过六个碳原子的直链或支链烷基、不超过六个碳原子的直链或支链烯基、不超过六个碳原子的直链或支链炔基、3‑8元脂环族基团；R2为苯基、不超过三个甲基或三个甲氧基或三个卤素取代的苯基、吡啶基、苄基、萘基、3‑8元脂环族基团；该合成方法是N‑R2硫基邻苯二甲酰亚胺与二R1基氧化膦以水作溶剂进行反应，直接得到产物硫代次磷酸酯。
Description
技术领域
本发明涉及一种硫代次磷酸酯的合成方法，该方法只需用水作溶剂，不需要添加任何催化剂或碱，相较以往文献报道的方法更加绿色环保。所得到的硫代次磷酸酯在医药、农药、化工等领域有重要应用。
背景技术
随着全球经济的快速发展，环境问题越来越受到重视。在过去的几十年里，以减少化学过程中有毒或污染废物为目标的绿色化学受到了越来越广泛的关注(参见Anastas,P.；Eghbali,N.,Green chemistry:principles and practice.Chemical SocietyReviews 2010,39,301-312)。一般来说，反应体系中的化学污染主要来自有机溶剂和金属催化剂的使用。因此，对环境友好反应体系的研究已成为化学研究中最引人注目的领域之一(参见Bhunia,A.；Yetra,S.R.；Biju,A.T.,Recent advances in transition-metal-free carbon-carbon and carbon–heteroatom bond-forming reactions usingarynes.Chemical Society Reviews 2012,41,3140-3152)。就溶剂而言，与普通有机溶剂相比，水是我们生态系统中最常见和最友好的溶剂。它是一种廉价、无毒、高度稳定、不易燃、易于操作和“绿色”的溶剂(参见Butler,R.N.；Coyne,A.G.,Water:Nature’s ReactionEnforcer,Comparative Effects for Organic Synthesis“In-Water”and“On-Water”.Chemical reviews 2010,110,6302-6337)。已有研究表明水可以加速反应(参见Han,M.-Y.；Lin,J.；Li,W.；Luan,W.-Y.；Mai,P.-L.；Zhang,Y.,Catalyst-free nucleophilicaddition reactions of silyl glyoxylates in water.Green chemistry 2018,20,1228-1232)。尽管许多有机反应物的水溶性较差，但自Breslow的开创性工作以来，水已被广泛用作化学合成中的溶剂(参见Rideout,D.C.；Breslow,R.,Hydrophobic accelerationof Diels-Alder reactions.Journal of the American Chemical Society 1980,102,7816-7817)。
含硫有机磷化合物由于其具有广阔的生物活性和防治虫害等应用前景，60多年来一直受到极大的关注(参见Melnikov,N.N.,Chemistry of pesticides.SpringerScience&Business Media:2012)。因此，这些化合物的合成研究非常广泛，特别是对二烷基(或二芳基)亚磷酸酯的硫代酯类化合物而言，有些有机磷杀虫剂就是这类化合物，比如砜吸磷和iproenfos(参见Wang,J.；Huang,X.；Ni,Z.；Wang,S.；Wu,J.；Pan,Y.,TBPB-promotedmetal-free synthesis of thiophosphinate/phosphonothioate by direct P–S bondcoupling.Green Chemistry 2015,17,314-319)。Yokomatsu等人最近报道了CuI催化亚磷酸二乙酯与苯乙醇偶联合成硫代磷酸酯的工艺(参见Kaboudin,B.；Abedi,Y.；Kato,J.-y.；Yokomatsu,T.,Copper(I)iodide catalyzed synthesis of thiophosphates bycoupling of H-phosphonates with benzenethiols.Synthesis 2013,45,2323-2327)。Li等人发现NCS可以促进硫醇与亚磷酸酯之间的磷硫化反应(参见Liu,Y.-C.；Lee,C.-F.,N-Chlorosuccinimide-promoted synthesis of thiophosphates from thiols andphosphonates under mild conditions.Green Chemistry 2014,16,357-364)。基于二烷基(或二芳基)亚磷酸酯的磷硫代酸酯的合成已得到广泛的研究，但对H-硫代膦氧化物或H-次磷酸酯类化合物的研究较少，它们是某些农药的核心结构，如乙苯稻瘟净(或叫枯瘟净)(参见Yuan,C.；Feng,H.,Studies on organophosphorus compounds XL.An one-potprocedure for the mono-o-alkylation of phosphonic acid:a facile synthesis ofalkyl hydrogen p-substituted phenylphosphonates.Synthesis 1990,1990,140-141)。这类化合物还可用作有机合成中的磷转移试剂。常规合成硫代次膦酸酯通常是通过次磷酰氯与硫醇之间的反应进行的(参见Carta,P.；Puljic,N.；Robert,C.；Dhimane,A.-L.；Fensterbank,L.；
E.；Malacria,M.,Generation of phosphorus-centeredradicals via homolytic substitution at sulfur.Organic letters 2007,9,1061-1063)。Haynes报告了H-膦氧化物与硫酚在NBS和碱存在下的偶联合成策略(参见Au-Yeung,T.-L.；Chan,K.-Y.；Chan,W.-K.；Haynes,R.K.；Williams,I.D.；Yeung,L.L.,Reactions of(RP)-and(SP)-tert-butylphenylphosphinobromidates and tert-butylphenylthionophosphino-chloridates with heteroatom nucleophiles；preparation of P-chiral binol phosphinates and related compounds.TetrahedronLetters 2001,42,453-456)。Yamaguchi等人报告了一种硫代次膦酸酯的合成方案，方法是在铑催化条件下将四苯基二膦二氧化物与二硫化合物偶合(参见Arisawa,M.；Ono,T.；Yamaguchi,M.,Rhodium-catalyzed thiophosphinylation and phosphinylationreactions of disulfides and diselenides.Tetrahedron letters 2005,46,5669-5671)。然而，诸如使用有毒的次膦酰氯、强碱或Lewis酸、复杂的多步反应以及昂贵的过渡金属等缺陷限制了这一方法的广泛应用。Wang等人报道了用过氧化物(TBPB)促进P-S键直接偶联来合成硫代次膦酸酯/硫代亚膦酸酯的方法(参见Wang,J.；Huang,X.；Ni,Z.；Wang,S.；Wu,J.；Pan,Y.,TBPB-promoted metal-free synthesis of thiophosphinate/phosphonothioate by direct P–S bond coupling.Green Chemistry 2015,17,314-319)。
发明概述
而我们研发出一种如下式I所示硫代次磷酸酯的绿色合成方法，
其中，R1为苯基、不超过三个甲基或三个甲氧基或三个卤素取代的苯基、不超过六个碳原子的直链或支链烷基、不超过六个碳原子的直链或支链烯基、不超过六个碳原子的直链或支链炔基、3-8元脂环族基团；R2为苯基、不超过三个甲基或三个甲氧基或三个卤素取代的苯基、吡啶基、苄基、萘基、3-8元脂环族基团。该合成方法是N-R2硫基邻苯二甲酰亚胺与二R1基氧化膦以水作溶剂进行反应，直接得到产物硫代次磷酸酯，反应方程式如下所示：
我们所研发的硫代次磷酸酯的合成方法，只需要以水作为溶剂，不需要添加任何催化剂和/或碱，包括有机碱和无机碱。相比此前报道过的以有机溶剂作为反应溶剂，多数情况都需要添加碱或各类金属催化剂的方法，我们所开发的方法更绿色环保，有更大的潜在应用价值。
具体实施方式
实施例1：二苯基硫代次膦酸-S-苯酯的制备(化合物编号1)
将N-苯硫基邻苯二甲酰亚胺(207mg，1.0mmol)和二苯基氧化膦(202mg，1.0mmol)加入5mL水中，40℃下搅拌反应3h，过滤，水洗，鼓风干燥，得二苯基硫代次膦酸-S-苯酯245mg(收率：79％)。
1H NMR(400MHz,CDCl3):δ7.79-7.72(m,4H),7.55-7.50(m,6H),7.38-7.34(m,2H),7.28-7.22(m,3H)；LC/MS(M+1)+＝311.1。
实施例2：二(4-甲基苯基)硫代次膦酸-S-苯酯的制备(化合物编号2)
将N-苯硫基邻苯二甲酰亚胺(207mg，1.0mmol)和二(4-甲基苯基)氧化膦(230mg，1.0mmol)加入5mL水中，40℃下搅拌反应2h，过滤，水洗，鼓风干燥，得二(4-甲基苯基)硫代次膦酸-S-苯酯284mg(收率：84％)。
1H NMR(400MHz,CDCl3):δ7.76-7.72(m,4H),7.54-7.49(m,6H),7.27-7.22(m,3H),2.39(s,6H)；LC/MS(M+1)+＝339.1。
实施例3：二(3,5-二甲基苯基)硫代次膦酸-S-苯酯的制备(化合物编号3)
将N-苯硫基邻苯二甲酰亚胺(207mg，1.0mmol)和二(3,5-二甲基苯基)氧化膦(258mg，1.0mmol)加入5mL水中，40℃下搅拌反应2h，过滤，水洗，鼓风干燥，得二(3,5-二甲基苯基)硫代次膦酸-S-苯酯315mg(收率：86％)。
1H NMR(400MHz,CDCl3):δ7.61-7.55(m,6H),7.39-7.36(m,2H),7.27-7.23(m,3H),2.39(s,6H),2.35(s,6H)；LC/MS(M+1)+＝367.2。
实施例4：二(2-甲氧基苯基)硫代次膦酸-S-苯酯的制备(化合物编号4)
将N-苯硫基邻苯二甲酰亚胺(207mg，1.0mmol)和二(2-甲氧基苯基)氧化膦(262mg，1.0mmol)加入5mL水中，40℃下搅拌反应2h，过滤，水洗，鼓风干燥，得二(2-甲氧基苯基)硫代次膦酸-S-苯酯326mg(收率：88％)。
1H NMR(400MHz,CDCl3):δ7.76(m,2H),7.65(m,2H),7.36(m,2H),7.27-7.23(m,3H),7.20-7.16(m,4H),3.85(s,6H)；LC/MS(M+1)+＝371.2。
实施例5：二(2,4-二甲氧基苯基)硫代次膦酸-S-苯酯的制备(化合物编号5)
将N-苯硫基邻苯二甲酰亚胺(207mg，1.0mmol)和二(2,4-二甲氧基苯基)氧化膦(322mg，1.0mmol)加入5mL水中，40℃下搅拌反应2h，过滤，水洗，鼓风干燥，得二(2,4-二甲氧基苯基)硫代次膦酸-S-苯酯366mg(收率：85％)。
1H NMR(400MHz,CDCl3):δ7.43(m,2H),7.39(m,2H),7.28-7.23(m,5H),7.20-7.16(m,2H),3.88(s,6H),3.84(s,6H)；LC/MS(M+1)+＝431.1。
实施例6：二(2-甲基戊基)硫代次膦酸-S-苯酯的制备(化合物编号6)
将N-苯硫基邻苯二甲酰亚胺(207mg，1.0mmol)和二(2-甲基戊基)氧化膦(218mg，1.0mmol)加入5mL水中，室温下搅拌反应4h，过滤，水洗，鼓风干燥，得二(2-甲基戊基)硫代次膦酸-S-苯酯235mg(收率：72％)。
1H NMR(400MHz,CDCl3):δ7.38(m,2H),7.27-7.23(m,3H),1.76-1.72(m,2H),1.52-1.47(m,4H),1.33-1.29(m,4H),1.22-1.18(m,4H),0.99-0.85(m,12H)；LC/MS(M+1)+＝327.2。
实施例7：二烯丙基硫代次膦酸-S-苯酯的制备(化合物编号7)
将N-苯硫基邻苯二甲酰亚胺(207mg，1.0mmol)和二烯丙基氧化膦(130mg，1.0mmol)加入5mL水中，室温下搅拌反应4h，过滤，水洗，鼓风干燥，得二烯丙基硫代次膦酸-S-苯酯159.6mg(收率：67％)。
1H NMR(400MHz,CDCl3):δ7.38(m,2H),7.27-7.23(m,3H),5.72(m,2H),5.30(dd,J＝10.2,5.8Hz,6H),5.04(dd,J＝10.1,5.6Hz,6H)；LC/MS(M+1)+＝239.1。
实施例8：二(2-甲基-1-戊烯基)硫代次膦酸-S-苯酯的制备(化合物编号8)
将N-苯硫基邻苯二甲酰亚胺(207mg，1.0mmol)和二(2-甲基-1-戊烯基)氧化膦(214mg，1.0mmol)加入5mL水中，室温下搅拌反应5h，过滤，水洗，鼓风干燥，得二(2-甲基-1-戊烯基)硫代次膦酸-S-苯酯200mg(收率：62％)。
1H NMR(400MHz,CDCl3):δ7.37(m,2H),7.27-7.23(m,3H),4.78-4.74(m,2H),2.21-2.16(m,4H),1.81(s,6H),1.35-1.29(m,4H),0.99(t,J＝7.2Hz,6H)；LC/MS(M+1)+＝323.2。
实施例9：二(1-己炔基)硫代次膦酸-S-苯酯的制备(化合物编号9)
将N-苯硫基邻苯二甲酰亚胺(207mg，1.0mmol)和二(1-己炔基)氧化膦(210mg，1.0mmol)加入5mL水中，室温下搅拌反应4h，过滤，水洗，鼓风干燥，得二(1-己炔基)硫代次膦酸-S-苯酯207mg(收率：65％)。
1H NMR(400MHz,CDCl3):δ7.38(m,2H),7.27-7.23(m,3H),2.48-2.42(m,4H),1.47-1.43(m,4H),1.33-1.28(m,4H),0.93-0.87(m,6H)；LC/MS(M+1)+＝319.2。
实施例10：二环己基硫代次膦酸-S-苯酯的制备(化合物编号10)
将N-苯硫基邻苯二甲酰亚胺(207mg，1.0mmol)和二环己基氧化膦(214mg，1.0mmol)加入5mL水中，40℃下搅拌反应2h，过滤，水洗，鼓风干燥，得二环己基硫代次膦酸-S-苯酯242mg(收率：75％)。
1H NMR(400MHz,CDCl3):δ7.37(m,2H),7.26-7.23(m,3H),1.80-1.76(m,4H),1.56-1.35(m,18H)；LC/MS(M+1)+＝323.2。
实施例11：二叔丁基硫代次膦酸-S-苯酯的制备(化合物编号11)
将N-苯硫基邻苯二甲酰亚胺(207mg，1.0mmol)和二叔丁基氧化膦(162mg，1.0mmol)加入5mL水中，40℃下搅拌反应3h，过滤，水洗，鼓风干燥，得二叔丁基硫代次膦酸-S-苯酯208mg(收率：77％)。
1H NMR(400MHz,CDCl3):δ7.36(m,2H),7.27-7.24(m,3H),1.18(s,18H)；LC/MS(M+1)+＝271.2。
实施例12：二苯基硫代次膦酸-S-2-甲基苯酯的制备(化合物编号12)
将N-2-甲基苯硫基邻苯二甲酰亚胺(221mg，1.0mmol)和二苯基氧化膦(202mg，1.0mmol)加入5mL水中，40℃下搅拌反应2h，过滤，水洗，鼓风干燥，得二苯基硫代次膦酸-S-2-甲基苯酯269mg(收率：83％)。
1H NMR(400MHz,CDCl3):δ7.75-7.71(m,4H),7.52-7.46(m,10H),7.32(m,1H),7.19(m,1H),2.37(s,3H)；LC/MS(M+1)+＝325.1。
实施例13：二苯基硫代次膦酸-S-2,4-二甲基苯酯的制备(化合物编号13)
将N-2,4-二甲基苯硫基邻苯二甲酰亚胺(235mg，1.0mmol)和二苯基氧化膦(202mg，1.0mmol)加入5mL水中，40℃下搅拌反应2h，过滤，水洗，鼓风干燥，得二苯基硫代次膦酸-S-2,4-二甲基苯酯277mg(收率：82％)。
1H NMR(400MHz,CDCl3):δ7.75-7.71(m,4H),7.53-7.49(m,6H),7.28(m,1H),6.95-6.93(m,2H),2.33(s,3H),2.30(s,3H)；LC/MS(M+1)+＝339.1。
实施例14：二苯基硫代次膦酸-S-3-甲氧基苯酯的制备(化合物编号14)
将N-3-甲氧基苯硫基邻苯二甲酰亚胺(237mg，1.0mmol)和二苯基氧化膦(202mg，1.0mmol)加入5mL水中，40℃下搅拌反应2h，过滤，水洗，鼓风干燥，得二苯基硫代次膦酸-S-3-甲氧基苯酯265mg(收率：78％)。
1H NMR(400MHz,CDCl3):δ7.74-7.70(m,4H),7.53-7.49(m,6H),7.20(m,1H),7.07(m,1H),6.70(m,1H),6.59(m,1H),3.78(s,3H)；LC/MS(M+1)+＝341.1。
实施例15：二苯基硫代次膦酸-S-3,5-二甲氧基苯酯的制备(化合物编号15)
将N-3,5-二甲氧基苯硫基邻苯二甲酰亚胺(267mg，1.0mmol)和二苯基氧化膦(202mg，1.0mmol)加入5mL水中，40℃下搅拌反应2h，过滤，水洗，鼓风干燥，得二苯基硫代次膦酸-S-3,5-二甲氧基苯酯270mg(收率：73％)。
1H NMR(400MHz,CDCl3):δ7.73-7.68(m,4H),7.52-7.48(m,6H),6.28(m,2H),6.19(m,1H),3.76(s,6H)；LC/MS(M+1)+＝371.1。
实施例16：二苯基硫代次膦酸-S-2-氟苯酯的制备(化合物编号16)
将N-2-氟苯硫基邻苯二甲酰亚胺(225mg，1.0mmol)和二苯基氧化膦(202mg，1.0mmol)加入5mL水中，40℃下搅拌反应2h，过滤，水洗，鼓风干燥，得二苯基硫代次膦酸-S-2-氟苯酯263mg(收率：80％)。
1H NMR(400MHz,CDCl3):δ7.75-7.70(m,4H),7.54-7.50(m,6H),7.42(m,1H),7.37(m,1H),7.08(m,2H)；LC/MS(M+1)+＝329.1。
实施例17：二苯基硫代次膦酸-S-4-氯苯酯的制备(化合物编号17)
将N-4-氯苯硫基邻苯二甲酰亚胺(241.7mg，1.0mmol)和二苯基氧化膦(202mg，1.0mmol)加入5mL水中，40℃下搅拌反应2h，过滤，水洗，鼓风干燥，得二苯基硫代次膦酸-S-4-氯苯酯279mg(收率：81％)。
1H NMR(400MHz,CDCl3):δ7.74-7.70(m,4H),7.53-7.49(m,6H),7.31-7.28(m,4H)；LC/MS(M+1)+＝345.1。
实施例18：二苯基硫代次膦酸-S-4-溴苯酯的制备(化合物编号18)
将N-4-溴苯硫基邻苯二甲酰亚胺(286mg，1.0mmol)和二苯基氧化膦(202mg，1.0mmol)加入5mL水中，40℃下搅拌反应2h，过滤，水洗，鼓风干燥，得二苯基硫代次膦酸-S-4-溴苯酯296mg(收率：76％)。
1H NMR(400MHz,CDCl3):δ7.76-7.72(m,6H),7.55-7.51(m,6H),7.27(m,2H)；LC/MS(M+1)+＝389.0,391.0。
实施例19：二苯基硫代次膦酸-S-萘-1-酯的制备(化合物编号19)
将N--萘-1-硫基邻苯二甲酰亚胺(257mg，1.0mmol)和二苯基氧化膦(202mg，1.0mmol)加入5mL水中，40℃下搅拌反应2h，过滤，水洗，鼓风干燥，得二苯基硫代次膦酸-S-萘-1-酯256mg(收率：71％)。
1H NMR(400MHz,CDCl3):δ8.17(m,1H),8.15(m,1H),7.95(m,1H),7.75-7.72(m,4H),7.61(m,1H),7.55-7.48(m,8H),7.38(m,1H)；LC/MS(M+1)+＝361.1。
实施例20：二苯基硫代次膦酸-S-吡啶-2-酯的制备(化合物编号20)
将N-吡啶-2-硫基邻苯二甲酰亚胺(208mg，1.0mmol)和二苯基氧化膦(202mg，1.0mmol)加入5mL水中，室温下搅拌反应2h，过滤，水洗，鼓风干燥，得二苯基硫代次膦酸-S-吡啶-2-酯212mg(收率：68％)。
1H NMR(400MHz,CDCl3):δ8.29(m,1H),7.73-7.70(m,4H),7.65(m,1H),7.55-7.48(m,6H),7.41(m,1H),7.23(m,1H)；LC/MS(M+1)+＝312.1。
实施例21：二苯基硫代次膦酸-S-苄酯的制备(化合物编号21)
将N-苄硫基邻苯二甲酰亚胺(221mg，1.0mmol)和二苯基氧化膦(202mg，1.0mmol)加入5mL水中，40℃下搅拌反应3h，过滤，水洗，鼓风干燥，得二苯基硫代次膦酸-S-苄酯240mg(收率：74％)。
1H NMR(400MHz,CDCl3):δ7.74-7.70(m,4H),7.54-7.49(m,6H),7.37(m,2H),7.26(m,2H),7.22(m,1H),3.77(s,2H)；LC/MS(M+1)+＝325.1。
实施例22：二苯基硫代次膦酸-S-环戊酯的制备(化合物编号22)
将N-环戊基-1-硫基邻苯二甲酰亚胺(199mg，1.0mmol)和二苯基氧化膦(202mg，1.0mmol)加入5mL水中，40℃下搅拌反应3h，过滤，水洗，鼓风干燥，得二苯基硫代次膦酸-S-环戊酯200mg(收率：66％)。
1H NMR(400MHz,CDCl3):δ7.75-7.70(m,4H),7.55-7.50(m,6H),2.58(m,1H),1.92-1.65(m,8H)；LC/MS(M+1)+＝303.1。
其他合成过的符合式I所示的硫代次磷酸酯，其合成过程就不一一列举了，部分结构式如下表所示：
Claims (5)
1.一种如下式I所示硫代次磷酸酯的合成方法，
其中，R1为苯基、不超过三个甲基或三个甲氧基或三个卤素取代的苯基、不超过六个碳原子的直链或支链烷基、不超过六个碳原子的直链或支链烯基、不超过六个碳原子的直链或支链炔基、3-8元脂环族基团；R2为苯基、不超过三个甲基或三个甲氧基或三个卤素取代的苯基、吡啶基、苄基、萘基、3-8元脂环族基团；该合成方法是N-R2硫基邻苯二甲酰亚胺与二R1基氧化膦以水作溶剂进行反应，直接得到产物硫代次磷酸酯，反应方程式如下所示：
2.依据权利要求1所述的一种如式I所示硫代次磷酸酯的合成方法，式I中R1为苯基、2-甲基苯基、3-甲基苯基、4-甲基苯基、2-甲氧基苯基、3-甲氧基苯基、4-甲氧基苯基、2,4-二甲基苯基、3,5-二甲基苯基、2,4-二甲氧基苯基、3,5-二甲氧基苯基、二叔丁基；R2为苯基、2-甲基苯基、3-甲基苯基、4-甲基苯基、2-甲氧基苯基、3-甲氧基苯基、4-甲氧基苯基、2,4-二甲基苯基、3,5-二甲基苯基、2,4-二甲氧基苯基、3,5-二甲氧基苯基、2-氟苯基、3-氟苯基、4-氟苯基、4-氯苯基、4-溴苯基、萘-1-基、萘-2-基、吡啶-2-基、吡啶-3-基、吡啶-4-基、苄基、环己基、环戊基。
3.依据权利要求1所述的硫代次磷酸酯的合成方法，其原料配比和反应条件为：以二R1基氧化膦为1当量，则N-R2硫基邻苯二甲酰亚胺为0.8-1.2当量，溶剂水与二R1基氧化膦的质量比为1:5至1:100，反应温度为0℃-100℃。
4.依据权利要求1所述的硫代次磷酸酯的合成方法，其原料配比和反应条件为：二R1基氧化膦与N-R2硫基邻苯二甲酰亚胺等当量反应，溶剂水与二R1基氧化膦的质量比为1:10至1:50，反应温度为30℃-50℃。
5.依据权利要求1所述的硫代次磷酸酯的合成方法，其特征为以水作溶剂，不添加任何催化剂和/或碱。
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| US4298738A (en) * | 1979-03-14 | 1981-11-03 | Basf Aktiengesellschaft | Acylphosphine oxide compounds their preparation and use |
| CN1089614A (zh) * | 1992-10-28 | 1994-07-20 | E.R.斯奎布父子公司 | α-膦酰基磺酸酯角鲨烯合成酶抑制剂及方法 |
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| US4298738A (en) * | 1979-03-14 | 1981-11-03 | Basf Aktiengesellschaft | Acylphosphine oxide compounds their preparation and use |
| CN1089614A (zh) * | 1992-10-28 | 1994-07-20 | E.R.斯奎布父子公司 | α-膦酰基磺酸酯角鲨烯合成酶抑制剂及方法 |
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| Title |
|---|
| Benign synthesis of thiophosphates, thiophosphinates and selenophosphates in neat condition using N-chalcogenoimides as the source of electrophilic sulfur/selenium;Manas Mondal 等;《Tetrahedron Letters》;20190720;第60卷;150965（1-4） * |
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