CN111606945A - Preparation method of compound containing P-O bond or P-S bond - Google Patents
Preparation method of compound containing P-O bond or P-S bond Download PDFInfo
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- CN111606945A CN111606945A CN202010532469.5A CN202010532469A CN111606945A CN 111606945 A CN111606945 A CN 111606945A CN 202010532469 A CN202010532469 A CN 202010532469A CN 111606945 A CN111606945 A CN 111606945A
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- Prior art keywords
- reaction
- cdcl
- phosphorus
- dimethyl sulfoxide
- added
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 388
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 174
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 claims abstract description 164
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 64
- 239000011574 phosphorus Substances 0.000 claims abstract description 64
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 35
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000007858 starting material Substances 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 129
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 75
- -1 4-chlorobutyl Chemical group 0.000 claims description 49
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 8
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims description 8
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 7
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 7
- 150000003573 thiols Chemical class 0.000 claims description 7
- NIFAOMSJMGEFTQ-UHFFFAOYSA-N 4-methoxybenzenethiol Chemical compound COC1=CC=C(S)C=C1 NIFAOMSJMGEFTQ-UHFFFAOYSA-N 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 6
- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-UHFFFAOYSA-N 0.000 claims description 5
- GNXBFFHXJDZGEK-UHFFFAOYSA-N 4-tert-butylbenzenethiol Chemical compound CC(C)(C)C1=CC=C(S)C=C1 GNXBFFHXJDZGEK-UHFFFAOYSA-N 0.000 claims description 5
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 claims description 5
- 229950011260 betanaphthol Drugs 0.000 claims description 5
- CMKBCTPCXZNQKX-UHFFFAOYSA-N cyclohexanethiol Chemical compound SC1CCCCC1 CMKBCTPCXZNQKX-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- PTHGDVCPCZKZKR-UHFFFAOYSA-N (4-chlorophenyl)methanol Chemical compound OCC1=CC=C(Cl)C=C1 PTHGDVCPCZKZKR-UHFFFAOYSA-N 0.000 claims description 4
- GEZMEIHVFSWOCA-UHFFFAOYSA-N (4-fluorophenyl)methanol Chemical compound OCC1=CC=C(F)C=C1 GEZMEIHVFSWOCA-UHFFFAOYSA-N 0.000 claims description 4
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 claims description 4
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 claims description 4
- 229940061334 2-phenylphenol Drugs 0.000 claims description 4
- IWJGMJHAIUBWKT-UHFFFAOYSA-N 4-bromo-2-methylphenol Chemical compound CC1=CC(Br)=CC=C1O IWJGMJHAIUBWKT-UHFFFAOYSA-N 0.000 claims description 4
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 claims description 4
- HXHGULXINZUGJX-UHFFFAOYSA-N 4-chlorobutanol Chemical compound OCCCCCl HXHGULXINZUGJX-UHFFFAOYSA-N 0.000 claims description 4
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 4
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 claims description 4
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 4
- XXSCONYSQQLHTH-UHFFFAOYSA-N 9h-fluoren-9-ylmethanol Chemical compound C1=CC=C2C(CO)C3=CC=CC=C3C2=C1 XXSCONYSQQLHTH-UHFFFAOYSA-N 0.000 claims description 4
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 4
- GUDMZGLFZNLYEY-UHFFFAOYSA-N cyclopropylmethanol Chemical compound OCC1CC1 GUDMZGLFZNLYEY-UHFFFAOYSA-N 0.000 claims description 4
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 claims description 4
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 4
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 4
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 claims description 4
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 claims description 4
- 235000010292 orthophenyl phenol Nutrition 0.000 claims description 4
- 229950009195 phenylpropanol Drugs 0.000 claims description 4
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 4
- RFCQDOVPMUSZMN-UHFFFAOYSA-N 2-Naphthalenethiol Chemical compound C1=CC=CC2=CC(S)=CC=C21 RFCQDOVPMUSZMN-UHFFFAOYSA-N 0.000 claims description 3
- SGHBRHKBCLLVCI-UHFFFAOYSA-N 3-hydroxybenzonitrile Chemical compound OC1=CC=CC(C#N)=C1 SGHBRHKBCLLVCI-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- PBLNHHSDYFYZNC-UHFFFAOYSA-N (1-naphthyl)methanol Chemical compound C1=CC=C2C(CO)=CC=CC2=C1 PBLNHHSDYFYZNC-UHFFFAOYSA-N 0.000 claims description 2
- QETISSZVCNFQBN-UHFFFAOYSA-N cyclopentane;cyclopentylmethanol;iron Chemical compound [Fe].[CH]1[CH][CH][CH][CH]1.OC[C]1[CH][CH][CH][CH]1 QETISSZVCNFQBN-UHFFFAOYSA-N 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
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- BMPBPTNLNBRGOT-UHFFFAOYSA-N tris(4-ethylphenyl) phosphate Chemical compound C1=CC(CC)=CC=C1OP(=O)(OC=1C=CC(CC)=CC=1)OC1=CC=C(CC)C=C1 BMPBPTNLNBRGOT-UHFFFAOYSA-N 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims 5
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 4
- 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 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 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 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 claims 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 claims 1
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 claims 1
- 125000004176 4-fluorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1F)C([H])([H])* 0.000 claims 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 claims 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 claims 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 231100000086 high toxicity Toxicity 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 248
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 231
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 115
- 239000000047 product Substances 0.000 description 74
- 239000002994 raw material Substances 0.000 description 67
- 238000004440 column chromatography Methods 0.000 description 63
- 238000005160 1H NMR spectroscopy Methods 0.000 description 60
- 238000004679 31P NMR spectroscopy Methods 0.000 description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 60
- 229910001873 dinitrogen Inorganic materials 0.000 description 60
- 239000000243 solution Substances 0.000 description 60
- 239000003208 petroleum Substances 0.000 description 56
- VWBYXJRDIQCSLW-UHFFFAOYSA-N O=[P](c1ccccc1)c1ccccc1 Chemical compound O=[P](c1ccccc1)c1ccccc1 VWBYXJRDIQCSLW-UHFFFAOYSA-N 0.000 description 54
- 239000003480 eluent Substances 0.000 description 53
- 239000011259 mixed solution Substances 0.000 description 53
- 239000012074 organic phase Substances 0.000 description 36
- 238000000926 separation method Methods 0.000 description 28
- 239000011541 reaction mixture Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 238000010791 quenching Methods 0.000 description 24
- 230000000171 quenching effect Effects 0.000 description 24
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 24
- 238000000605 extraction Methods 0.000 description 23
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 22
- 239000000758 substrate Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- MFGWMAAZYZSWMY-UHFFFAOYSA-N (2-naphthyl)methanol Chemical compound C1=CC=CC2=CC(CO)=CC=C21 MFGWMAAZYZSWMY-UHFFFAOYSA-N 0.000 description 4
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 description 4
- 238000004293 19F NMR spectroscopy Methods 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 3
- CRTMHFYHYMQVSB-UHFFFAOYSA-N CC=1C=C(C=C(C1)C)[P](C1=CC(=CC(=C1)C)C)=O Chemical compound CC=1C=C(C=C(C1)C)[P](C1=CC(=CC(=C1)C)C)=O CRTMHFYHYMQVSB-UHFFFAOYSA-N 0.000 description 3
- DTQFYZAIOBOXCO-UHFFFAOYSA-N COc1ccc(cc1)[P](=O)c1ccc(OC)cc1 Chemical compound COc1ccc(cc1)[P](=O)c1ccc(OC)cc1 DTQFYZAIOBOXCO-UHFFFAOYSA-N 0.000 description 3
- ICYMNRZVLLTNSE-UHFFFAOYSA-N Cc1ccc(cc1)[P](=O)c1ccc(C)cc1 Chemical compound Cc1ccc(cc1)[P](=O)c1ccc(C)cc1 ICYMNRZVLLTNSE-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 150000008301 phosphite esters Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- RMKPWTRWUXMDFF-UHFFFAOYSA-N 1-diphenylphosphorylsulfanyl-4-methoxybenzene Chemical compound C1=CC(OC)=CC=C1SP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 RMKPWTRWUXMDFF-UHFFFAOYSA-N 0.000 description 2
- TUBWQKVQNGIYDH-UHFFFAOYSA-N 1-diphenylphosphorylsulfanyl-4-methylbenzene Chemical compound C1=CC(C)=CC=C1SP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 TUBWQKVQNGIYDH-UHFFFAOYSA-N 0.000 description 2
- SZEGCMLXRGJJSP-UHFFFAOYSA-N 1-tert-butyl-4-diphenylphosphorylsulfanylbenzene Chemical compound CC(C)(C)c1ccc(SP(=O)(c2ccccc2)c2ccccc2)cc1 SZEGCMLXRGJJSP-UHFFFAOYSA-N 0.000 description 2
- CQJDYPZUDYXHLM-UHFFFAOYSA-N 3-chlorobenzenethiol Chemical compound SC1=CC=CC(Cl)=C1 CQJDYPZUDYXHLM-UHFFFAOYSA-N 0.000 description 2
- FTBCOQFMQSTCQQ-UHFFFAOYSA-N 4-bromobenzenethiol Chemical compound SC1=CC=C(Br)C=C1 FTBCOQFMQSTCQQ-UHFFFAOYSA-N 0.000 description 2
- ZKHQWZAMYRWXGA-KQYNXXCUSA-J ATP(4-) Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O)[C@@H](O)[C@H]1O ZKHQWZAMYRWXGA-KQYNXXCUSA-J 0.000 description 2
- ZKHQWZAMYRWXGA-UHFFFAOYSA-N Adenosine triphosphate Natural products C1=NC=2C(N)=NC=NC=2N1C1OC(COP(O)(=O)OP(O)(=O)OP(O)(O)=O)C(O)C1O ZKHQWZAMYRWXGA-UHFFFAOYSA-N 0.000 description 2
- 238000003383 Atherton-Todd reaction Methods 0.000 description 2
- ICYMWVUJWFAKOL-UHFFFAOYSA-N C(CCC)[P](C1=CC=CC=C1)=O Chemical compound C(CCC)[P](C1=CC=CC=C1)=O ICYMWVUJWFAKOL-UHFFFAOYSA-N 0.000 description 2
- MGYJFVVDKRKQDE-UHFFFAOYSA-N CC(C)(C)c1ccc(cc1)[P](=O)c1ccc(cc1)C(C)(C)C Chemical compound CC(C)(C)c1ccc(cc1)[P](=O)c1ccc(cc1)C(C)(C)C MGYJFVVDKRKQDE-UHFFFAOYSA-N 0.000 description 2
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- LMJGFWVFXNGHPB-UHFFFAOYSA-N 2-diphenylphosphorylsulfanylnaphthalene Chemical compound O=P(Sc1ccc2ccccc2c1)(c1ccccc1)c1ccccc1 LMJGFWVFXNGHPB-UHFFFAOYSA-N 0.000 description 1
- CDTBLEQRZSUIPV-UHFFFAOYSA-N 2-hydroxyethyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCO)OC1=CC=CC=C1 CDTBLEQRZSUIPV-UHFFFAOYSA-N 0.000 description 1
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- 201000011040 acute kidney failure Diseases 0.000 description 1
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- JELQNFAUSQUEGV-UHFFFAOYSA-N benzyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OCC1=CC=CC=C1 JELQNFAUSQUEGV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QYGNFNURXBPNIB-UHFFFAOYSA-N butylphosphonoylbenzene Chemical compound CCCCP(=O)C1=CC=CC=C1 QYGNFNURXBPNIB-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- CPKKNIYMTSBFIQ-UHFFFAOYSA-N cyclohexyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1CCCCC1 CPKKNIYMTSBFIQ-UHFFFAOYSA-N 0.000 description 1
- UZGIIDUEYHMUHR-UHFFFAOYSA-N diphenyl 2,2,2-trifluoroethyl phosphate Chemical compound P(=O)(OCC(F)(F)F)(OC1=CC=CC=C1)OC1=CC=CC=C1 UZGIIDUEYHMUHR-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- VPWBLJIHTCFTQH-UHFFFAOYSA-N diphenyl prop-2-ynyl phosphate Chemical compound C=1C=CC=CC=1OP(OCC#C)(=O)OC1=CC=CC=C1 VPWBLJIHTCFTQH-UHFFFAOYSA-N 0.000 description 1
- YDICVVYPXSZSFA-UHFFFAOYSA-N diphenyl propan-2-yl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OC(C)C)OC1=CC=CC=C1 YDICVVYPXSZSFA-UHFFFAOYSA-N 0.000 description 1
- XQKSZQAETWILLX-UHFFFAOYSA-N diphenyl(phosphoroso)phosphane Chemical compound P(=O)#P(C1=CC=CC=C1)C1=CC=CC=C1 XQKSZQAETWILLX-UHFFFAOYSA-N 0.000 description 1
- JWIKEUPJOCUJPL-UHFFFAOYSA-N diphenylphosphorylsulfanylmethylbenzene Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)SCC1=CC=CC=C1 JWIKEUPJOCUJPL-UHFFFAOYSA-N 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- JSPBAVGTJNAVBJ-UHFFFAOYSA-N ethyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCC)OC1=CC=CC=C1 JSPBAVGTJNAVBJ-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 208000010710 hepatitis C virus infection Diseases 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- FCOAHACKGGIURQ-UHFFFAOYSA-N iprobenfos Chemical compound CC(C)OP(=O)(OC(C)C)SCC1=CC=CC=C1 FCOAHACKGGIURQ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JSJUBNHZCFKUKY-UHFFFAOYSA-N naphthalen-2-yl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C2C=CC=CC2=CC=1)(=O)OC1=CC=CC=C1 JSJUBNHZCFKUKY-UHFFFAOYSA-N 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-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
- C07F9/28—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
- C07F9/3229—Esters of aromatic acids (P-C aromatic linkage)
-
- 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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- 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
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/327—Esters with unsaturated acyclic 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
- C07F9/28—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
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3276—Esters 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
- C07F9/28—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
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3282—Esters 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
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- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3288—Esters 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4021—Esters of aromatic acids (P-C aromatic linkage)
-
- 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
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- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4084—Esters 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
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Abstract
The invention discloses a preparation method of a compound containing a P-O bond or a P-S bond. The method takes a compound containing hydroxyl or sulfhydryl and a phosphorus reagent as starting materials, and then the starting materials are put into trifluoromethane sulfonic anhydride (Tf) in an inert gas atmosphere2O) and dimethyl sulfoxide (DMSO) according to a molar ratio, wherein the hydroxyl-containing or sulfhydryl-containing compound comprises: phosphorus reagent: reacting trifluoromethane sulfonic anhydride and dimethyl sulfoxide in a ratio of 1-5: 1-2.5: 2-3: 2 in an organic solvent at a reaction temperature of 25-100 ℃ for 6-20 hours to obtain the compound with the structural general formula (I). The reagent used in the invention is low in toxicity, green and environment-friendly, and avoids the use of noble metal catalysts with high price and high toxicity; reagent trifluoromethane sulfonic anhydride (Tf) used in the present invention2O) and dimethyl sulfoxide (DMSO) not only have low toxicity, but also have very low cost, so that the invention is environment-friendly, has high economical efficiency and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of a compound containing a P-O bond or a P-S bond.
Background
Compounds containing a P-O bond or a P-S bond are important organic molecules, which are not only essential substances for maintaining normal existence of a living body, but also are widely used in various research fields such as agricultural chemistry, life science, pharmaceutical chemistry, and material science. For example, in the field of life sciences, Adenosine Triphosphate (ATP) is a compound containing a P — O bond present in a living body, which ensures energy supply for various vital activities of cells; in the field of medicinal chemistry, Sofosbuvir (Sofosbuvir) is a drug molecule containing a P-O bond, which has a specific therapeutic effect in treating chronic hepatitis c diseases (Han, m.z.final.in.j.pharm, 2019,50, 1393); in the field of agricultural science, iprobenfos is an organophosphorus pesticide containing a P-S bond (Zhangixin. pesticide, 1989,28, 18); in the field of material science, DOPO-ACA is a highly effective flame retardant containing a P-O bond (Kangxinglong et al, proceedings of Henan university, 2019,49, 567).
Among the methods for preparing compounds having P-O bond/P-S bond which have been developed so far, the coupling reaction of phosphoryl chloride with active hydrogen-containing compounds developed earlier and some conventional synthetic methods such as Atherton-Todd reaction are still dominant. However, these conventional syntheses all have great limitations and certain disadvantages: for example, phosphoryl chloride reagents are unstable, extremely deliquescent, and require prior pre-preparation by chlorination or other synthetic steps; as another example, carbon tetrachloride, which is used as both a reagent and a solvent in most Atherton-Todd reactions, is highly volatile and toxic, and can cause symptoms such as paralysis of the nervous system or acute renal failure after inhalation by the operator. Therefore, the above-mentioned drawbacks of the conventional synthesis methods have greatly limited the mass production and application of the P-O bond/P-S bond-containing compounds. Although novel syntheses such as transition metal promoted coupling reaction ([1] Arisawa, M.et al. tetrahedron Lett.,2005,46, 5669; [2] Kaboudin, B.et al. Synthesis,2013,2323) and radical reaction ([1] Zhang, X.H.et al. J.org.chem.2018,83,1532; [2] Huang, H.et al. org.biomol.chem.,2018,16,4236) have been developed in recent years, these reactions require the addition of noble metal reagents as well as a large amount of additives, which makes them less economical, and the generation of a large amount of metal salt waste is serious to the environment.
It should be noted that all the developed synthetic methods have poor universality, and none of them can simultaneously react with phosphorus reagents such as alcohol, phenol, thiol, thiophenol and aryl phosphorus reagent, phosphite, etc. Therefore, the economic, green and high-universality synthesis method is developed, and the compound containing the P-O bond/P-S bond is efficiently prepared by using cheap, easily-obtained, low-toxicity and harmless chemical reagents, so that the compound has a good application prospect in the field of actual production or scientific research.
Disclosure of Invention
One of the purposes of the invention is to provide a synthesis method for preparing a compound containing a P-O bond or a P-S bond, the method has mild reaction conditions, cheap and easily available starting materials, convenient operation and very wide applicability of reaction substrates, various alcohols, phenols, thiols and thiophenols can be applied to the method, various phosphorus reagents can also be reacted, and various compounds containing the P-O bond or the P-S bond can be synthesized in one step by the method.
The technical scheme for realizing the invention is as follows:
a process for preparing the compound containing P-O bond or P-S bond features that the compound containing hydroxy or mercapto (alcohol, phenol, thiol or thiophenol) and phosphorus reagent are used as raw materials and the trifluoromethane sulfonic anhydride (Tf) is added in the atmosphere of inertial gas2O) and dimethyl sulfoxide (DMSO) according to a molar ratio, wherein the hydroxyl-containing or sulfhydryl-containing compound comprises: phosphorus reagent: trifluoromethanesulfonic anhydride, namely dimethyl sulfoxide (1-5): 1-2.5): 2-3): 2, in an organic solvent, reacting at a reaction temperature t for 12 hours to prepare a compound with a structural general formula (I), wherein the structural general formula (I) is as follows;
specifically, the specific reaction mode is carried out according to the following three types of reaction formulas according to the specific types of compounds containing hydroxyl or sulfhydryl groups:
reaction mode 1 is shown in reaction formula (II):
the specific operation steps are as follows:
using mercaptan or thiophenol substrate and phosphorus reagent as starting raw materials, under the protection of inert gas, reacting for 12 hours in organic solvent acetonitrile at room temperature under the action of trifluoromethane sulfonic anhydride and dimethyl sulfoxide, removing the solvent by rotary evaporation after the reaction is finished, and performing reaction by using a solvent in a volume ratio of 3:1, taking a mixed solution of petroleum ether and ethyl acetate as an eluent, and carrying out column chromatography to obtain a product;
the thiol or thiophenol substrate is selected from any one of n-butylthiol, cyclohexylthiol, benzylthiol, 2-naphthylthiol, 4-methylthiophenol, 4-tert-butylthiophenol, 4-methoxythiophenol, 4-fluorothiophenol, 4-chlorothiophenol, 4-bromophenylthiophenol, 2-methylthiophenol and 3-chlorothiophenol.
The phosphorus reagent is any one of diphenyl phosphorus oxide, di (4-methylphenyl) phosphorus oxide, di (4-methoxyphenyl) phosphorus oxide, di (4-tert-butylphenyl) phosphorus oxide, di (3, 5-dimethylphenyl) phosphorus oxide, dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, dibutyl phosphite, diphenyl phosphite, DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), ethyl phenylphosphate and phenyl n-butyl phosphorus oxide.
In the reaction mode, the feeding molar ratio of the mercaptan or thiophenol substrate, the phosphorus reagent, the trifluoromethanesulfonic anhydride and the dimethyl sulfoxide is 1 (1.5-2.5) to 2:2, preferably 1: 2:2:2.
Reaction mode 2 is shown in reaction formula (III):
the specific operation steps are as follows:
taking an alcohol substrate and a phosphorus reagent as initial raw materials, reacting for 12 hours at room temperature in an organic solvent DMF under the protection of inert gas and the action of trifluoromethanesulfonic anhydride and dimethyl sulfoxide, adding water for quenching after the reaction is finished, extracting for 3 times by using ethyl acetate, concentrating an organic phase, and reacting at a volume ratio of 3:1, taking a mixed solution of petroleum ether and ethyl acetate as an eluent, and carrying out column chromatography to obtain a product;
the alcohol substrate is selected from any one of methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, n-pentanol, n-hexanol, n-octanol, ethylene glycol, 4-chlorobutanol, phenylpropanol, trifluoroethanol, allyl alcohol, propiolic alcohol, cyclohexanol, cyclopropylmethanol, 3-phenylallyl alcohol, 9-fluorenylmethanol, benzyl alcohol, p-fluorobenzyl alcohol, p-chlorobenzyl alcohol, 1-naphthylmethanol and ferrocenylmethanol.
The phosphorus reagent is any one of diphenyl phosphorus oxygen, di (4-methylphenyl) phosphorus oxygen, di (4-methoxyphenyl) phosphorus oxygen, di (4-tert-butylphenyl) phosphorus oxygen and di (3, 5-dimethylphenyl) phosphorus oxygen.
In the reaction mode, the feeding molar ratio of alcohol to phosphorus reagent to trifluoromethanesulfonic anhydride to dimethyl sulfoxide is 1 (2-3) to 2:2, preferably 1: 2.5:2:2.
Reaction mode 3 is shown in reaction formula (IV):
the specific operation steps are as follows:
taking a phenol substrate and a phosphorus reagent as initial raw materials, reacting for 12 hours in an organic solvent acetonitrile at the reaction temperature of 90 ℃ under the protection of inert gas and the action of trifluoromethanesulfonic anhydride and dimethyl sulfoxide, removing the solvent through rotary evaporation after the reaction is finished, and performing reaction in a volume ratio of 3:1, taking a mixed solution of petroleum ether and ethyl acetate as an eluent, and carrying out column chromatography to obtain a product;
the phenolic substrate is any one of phenol, p-methyl phenol, p-methoxy phenol, p-fluorophenol, p-chlorophenol, p-bromophenol, 4-cyanophenol, 4-nitrophenol, 2-phenylphenol, 3-cyanophenol, 2-methyl-4-bromophenol and 2-naphthol.
The phosphorus reagent is any one of diphenyl phosphorus oxygen, di (4-methylphenyl) phosphorus oxygen, di (4-methoxyphenyl) phosphorus oxygen, di (4-tert-butylphenyl) phosphorus oxygen and di (3, 5-dimethylphenyl) phosphorus oxygen.
In the reaction mode, the feeding molar ratio of the phenol substrate, the phosphorus reagent, the trifluoromethanesulfonic anhydride and the dimethyl sulfoxide is (4-6) to (1: 3):2, preferably 5: 1:3:2.
The outstanding substantive characteristics of the invention are that the phosphorus reagent and the trifluoromethanesulfonic anhydride (Tf)2O) reacting to generate an electrophilic phosphorus positive ion intermediate, carrying out nucleophilic substitution reaction on the intermediate by a compound containing hydroxyl or sulfhydryl to obtain a trivalent phosphorus intermediate product, and further carrying out in-situ oxidation to obtain a pentavalent phosphorus target product. The key point is that dimethyl sulfoxide (DMSO) reagent is used as a mild alkaline reagent to enhance the nucleophilicity of a compound containing hydroxyl or sulfhydryl, and promote the conversion of a trivalent phosphorus intermediate product into a pentavalent phosphorus target product, and correspondingly, the selection of DMSO avoids the use of a strong oxidant and the damage of the strong oxidant to a substrate structure, and the invention can be compatible with the reaction of alcohol, phenol, mercaptan, thiophenol containing various functional groups and phosphorus reagents such as aryl phosphorus reagent and phosphite ester, and further can synthesize various compounds containing P-O bonds or P-S bonds by a one-pot method.
Compared with the prior art, the invention has the following advantages:
1, the reagent used in the invention is low in toxicity, green and environment-friendly, and noble metal catalysts (Pd, Pt, Rh, Ag and the like) with high price and high toxicity are avoided; reagent trifluoromethane sulfonic anhydride (Tf) used in the present invention2O) and dimethyl sulfoxide (DMSO) are not only low in toxicity, but also very inexpensive in cost (DMSO: 99%, 10L,380 yuan; tf299.5 percent of O, 1kg of O, 850 yuan), which ensures that the invention is environment-friendly, has high economical efficiency and is suitable for large-scale production.
2, the reaction substrate used in the invention is simple and easy to obtain, has wide selection range, and is suitable for hydroxyl-containing or sulfhydryl-containing compounds, such as alcohol, thiol, phenol and thiophenol, which contain various functional groups; as the phosphorus reagent, various aryl phosphorus reagents, phosphate ester reagents and alkyl phosphorus reagents can be reacted. In addition, the two types of reaction substrates related by the invention do not need to be modified by functional groups, so that the waste of atoms and the generation of a large number of byproducts are avoided, and the method has higher atom economy and step economy;
3, the reaction conditions of the invention are mild, most reactions are carried out at room temperature, no additional heating device is needed to provide a heat source, and dangerous and harsh reaction conditions such as high temperature, high pressure and the like are avoided, so that the safety is high when the invention is used for production, and the used production equipment is simple and easy to operate.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
The first embodiment is as follows:
taking p-methoxy thiophenol and diphenyl phosphorus oxide as raw materials, the reaction formula and the experimental steps are as follows:
p-methoxythiophenol (28.0mg, 0.2mmol), diphenylphosphine oxide (80.8mg, 0.4mmol) were introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double calandria, trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation to obtain a product S- (4-methoxyphenyl) thiodiphenyl phosphorus oxide with the yield of 91 percent by taking a mixed solution of petroleum ether and ethyl acetate as an eluent.
1H NMR(500MHz,CDCl3):7.86-7.82(m,4H),7.52-7.49(m,2H),7.45-7.42(m,4H),7.34-7.32(m,2H),6.73(d,J＝8.75Hz,2H),3.72(s,3H).31PNMR(203MHz,CDCl3) 41.27. comparative example one:
[ Li, Y.J.; in the method of et al chem.comm.,2019,55,4981, p-methoxythiophenol and diphenyl phosphorus oxide are used as raw materials, and the same product is prepared by the following reaction formula and experimental steps:
adding diphenyl phosphine oxide (60.6mg,0.3mmol), p-methoxythiophenol (149.4mg,0.9mmol) and water in a dry three-necked flask (10 ml) with a stirring rod,nBu4BF4(296.1mg,0.9mmol) and acetonitrile (5.0mL), 15mm × 10mm × 0.1mm Pt plates were inserted into a three-necked flask as positive and negative electrodes, respectively, and the system was electrolyzed at room temperature in a constant current mode at a current density of 3.3mA/cm2The electrolysis time was 4 hours. After the reaction was completed, the solvent was removed by a rotary evaporator. Purification and separation by silica gel column chromatography (petroleum: diethyl ether ═ 5:1-3:1) gave the product, S- (4-methoxyphenyl) thiodiphenyl phosphorus oxide, in a yield of 70%.
The preparation method of the present invention is discussed by taking example one and comparative example one as examples. Compared with the first example, the reaction operation of the first example uses a specially-made Pt plate electrolysis device, the reaction device is complex, the equipment requirement of the specific operation is high, the large-scale production is difficult, the yield of the obtained product is 21 percent lower than that of the first example, the method is only suitable for aryl phosphorus reagents, and phosphite esters and other phosphorus reagents cannot obtain target products through the method. Comparison of comparative example one, by phosphorus reagent with trifluoromethanesulfonic anhydride (Tf)2O) reaction to generate electrophilic phosphorus positive ion intermediate, then nucleophilic substitution reaction is carried out to obtain trivalent phosphorus intermediate product, in-situ oxidation is carried out to obtain pentavalent phosphorus target product, and DMSO selection not only avoids the use of strong oxidant and the damage of strong oxidant to substrate structure, but also is compatible with the reaction of alcohol, phenol, mercaptan, thiophenol and aryl phosphorus reagent containing various functional groups, phosphite ester and other phosphorus reagents.
To further discuss the preparation method of the present invention, the preparation method of the present invention and the literature [ Li, y.j.; the difference of the methods in et al, chem.comm.,2019,55,4981 proves that the preparation method of the invention can simultaneously and compatibly react alcohols, phenols, thiols, thiophenols containing various functional groups with aryl phosphorus reagents, phosphorous acid esters and other phosphorus reagents, and the yield is far higher than that of the document [ Li, Y.J.; method of et al chem.Comm.,2019,55,4981 ]. Meanwhile, the four to sixty subsequent examples are listed to prove the universality of the preparation method.
Example two:
the method takes p-tert-butyl thiophenol and diphenyl phosphorus oxide as raw materials, and comprises the following reaction formula and experimental steps:
p-tert-butylphenol (33.2mg, 0.2mmol), diphenylphosphine oxide (80.8mg, 0.4mmol) and the mixture were introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double row tube, and trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto and the reaction was allowed to proceed at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation to obtain a product S- (4-tert-butylphenyl) thiodiphenyl phosphorus oxide with the yield of 96 percent by using a mixed solution of petroleum ether and ethyl acetate as an eluent.
1H NMR(500MHz,CDCl3):7.86-7.82(m,4H),7.50-7.48(m,2H),7.44-7.40(m,4H),7.35(d,J＝7.05Hz,2H),7.21(d,J＝8.35Hz,2H),1.23(s,9H).31PNMR(203MHz,CDCl3) 41.54, comparative example two:
[ Li, Y.J.; in the method of et al, chem.comm.,2019,55,4981, p-tert-butyl thiophenol and diphenyl phosphorus oxide are used as raw materials, and the same product is prepared by the following reaction formula and experimental steps:
adding diphenyl phosphine oxide (60.6mg,0.3mmol), p-tert-butyl thiophenol (149.4mg,0.9mmol), and sodium chloride in a dry three-necked bottle (10 ml) with a stirring rod,nBu4BF4(296.1mg,0.9mmol) and acetonitrile (5.0 mL). Respectively inserted into three-mouth bottlesThe Pt plates with the thickness of 15mm × 10mm, the thickness of 10mm × 0.1.1 mm are used as the positive and negative electrodes, the system carries out electrolysis in a constant current mode at room temperature, and the current density is 3.3mA/cm2The electrolysis time was 4 hours. After the reaction was completed, the solvent was removed by a rotary evaporator. Purification and separation by silica gel column chromatography (petroleum: diethyl ether ═ 5:1-3:1) gave the product, S- (4-tert-butylphenyl) thiodiphenyl phosphorus oxide, in a yield of 75%.
Example three:
p-methyl thiophenol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
p-methylthiophenol (24.8mg, 0.2mmol), diphenylphosphine oxide (80.8mg, 0.4mmol) were charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria for three times, and trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were then added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation to obtain a product S- (4-methylphenyl) thiodiphenyl phosphorus oxide with the yield of 97 percent.
1H NMR(500MHz,CDCl3):7.87-7.83(m,4H),7.50-7.47(m,2H),7.44-7.40(m,4H),7.32(d,J＝6.90Hz,2H),7.00(d,J＝8.0Hz,2H),2.23(s,3H).31PNMR(203MHz,CDCl3) 41.25, comparative example three:
[ Li, Y.J.; in the method of et al chem.comm.,2019,55,4981, p-methylthiophenol and diphenyl phosphorus oxide are used as raw materials, and the same product is prepared by the following reaction formula and experimental steps:
adding diphenyl phosphine oxide (60.6mg,0.3mmol), p-methylthiophenol (111.6mg,0.9mmol) and sodium chloride in a dry three-necked flask (10 ml) with a stirring rod,nBu4BF4(296.1mg,0.9mmol) and acetonitrile (5.0mL), 15mm × 10mm × 0.1mm Pt plates were inserted into a three-necked flask as positive and negative electrodes, respectively, and the system was electrolyzed at room temperature in a constant current mode at a current density of 3.3mA/cm2The electrolysis time was 4 hours. After the reaction was completed, the solvent was removed by a rotary evaporator. Purification and separation by silica gel column chromatography (petroleum: diethyl ether ═ 5:1-3:1) gave the product, S- (4-methylphenyl) thiodiphenyl phosphorus oxide, in a yield of 84%.
Example four:
p-fluorobenzothiophenol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
p-fluorophenylthiophenol (25.6mg, 0.2mmol), diphenylphosphine oxide (80.8mg, 0.4mmol) were put into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria three times, trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product S- (4-fluorophenyl) thiodiphenyl phosphorus oxide, wherein the yield is 90%.
1H NMR(500MHz,CDCl3):7.86-7.81(m,4H),7.53-7.50(m,2H),7.46-7.39(m,6H),6.91-6.88(m,2H).31PNMR(203MHz,CDCl3):41.52(d,JF-P＝4.34Hz).19F NMR(470MHz,CDCl3):-111.69(d,JP-F＝3.62Hz).
Example five:
p-chlorothiophenol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
p-chlorothiophenol (28.8mg, 0.2mmol), diphenylphosphine oxide (80.8mg, 0.4mmol) were introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double calandria, trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation to obtain a product S- (4-chlorphenyl) thiodiphenyl phosphorus oxide with the yield of 90 percent by taking a mixed solution of petroleum ether and ethyl acetate as an eluent.
1H NMR(500MHz,CDCl3):7.86-7.82(m,4H),7.53-7.50(m,2H),7.46-7.43(m,4H),7.39-7.37(m,2H),7.18-7.16(m,2H).31PNMR(203MHz,CDCl3):41.49.
Example six:
p-bromothiophenol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
p-bromothiophenol (37.8mg, 0.2mmol), diphenylphosphinophosphorus oxide (80.8mg, 0.4mmol) were taken out and introduced into a 10mL reaction tube, and the air in the reaction tube was replaced with nitrogen gas using a double calandria for three times, to which trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were then added, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation to obtain a product S- (4-bromophenyl) thiodiphenyl phosphorus oxide with the yield of 80 percent.
1H NMR(500MHz,CDCl3):7.86-7.82(m,4H),7.53-7.51(m,2H),7.46-7.43(m,4H),7.33-7.31(m,4H).31PNMR(203MHz,CDCl3):41.35.
Example seven:
2-methyl thiophenol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
2-Methylthiophenol (24.8mg, 0.2mmol), diphenylphosphine oxide (80.8mg, 0.4mmol) and the mixture were introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double row tube, trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto, and the reaction was allowed to proceed at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation to obtain a product S- (2-methylphenyl) thiodiphenyl phosphorus oxide with the yield of 96 percent by using a mixed solution of petroleum ether and ethyl acetate as an eluent.
1H NMR(500MHz,CDCl3):7.84-7.80(m,4H),7.51-7.40(m,7H),7.17-7.11(m,2H),7.01-6.68(m,1H),2.34(s,3H).31PNMR(203MHz,CDCl3):40.96.
Example eight:
3-chlorobenzenethiol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
3-Chlorobenzothiophenol (28.8mg, 0.2mmol) and diphenylphosphoric oxide (80.8mg, 0.4mmol) were introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double row tube, and trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation to obtain a product S- (3-chlorphenyl) thiodiphenyl phosphorus oxide with the yield of 94 percent.
1H NMR(500MHz,CDCl3):7.86-7.82(m,4H),7.54-7.51(m,2H),7.47-7.43(m,4H),7.39-7.38(m,2H),7.22-7.20(m,1H),7.14-7.11(m,1H).31PNMR(203MHz,CDCl3):41.58.
Example nine:
2-naphthylthiophenol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
2-Naphthylthiol (32.0mg, 0.2mmol), diphenylphosphine oxide (80.8mg, 0.4mmol) and the mixture were introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double row tube, trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto, and the reaction was allowed to proceed at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation to obtain a product S- (2-naphthyl) thiodiphenyl phosphorus oxide with the yield of 93 percent.
1H NMR(500MHz,CDCl3):7.99(s,1H),7.89-7.85(m,4H),7.72-7.67(m,2H),7.63(d,J＝8.55Hz,1H),7.49-7.38(m,9H).31PNMR(203MHz,CDCl3):41.44.
Example ten:
1-butyl mercaptan and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
phosphorus dipheny oxide (80.8mg, 0.4mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, then 1-butanethiol (18.0mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL acetonitrile were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation to obtain a product S-n-butyl thiodiphenyl phosphorus oxide with the yield of 83 percent.
1H NMR(500MHz,CDCl3):7.90-7.86(m,4H),7.55-7.51(m,2H),7.49-7.45(m,4H),2.82-2.77(m,2H),1.63-1.58(m,2H),1.39-1.32(m,2H),0.83(t,J＝7.35Hz,3H).31P NMR(203MHz,CDCl3):43.11.
Example eleven:
1-pentanethiol and diphenyl phosphorus oxide are used as raw materials, and the reaction formula and the experimental steps are as follows:
phosphorus dipheny oxide (80.8mg, 0.4mmol) was taken and charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria three times, then 1-pentanethiol (20.8mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethylsulfoxide (15.6mg, 0.4mmol) and 2.0mL acetonitrile were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation to obtain a product S-n-pentylthiodiphenyl phosphorus oxide with the yield of 77 percent.
1H NMR(500MHz,CDCl3):7.90-7.86(m,4H),7.55-7.51(m,2H),7.49-7.45(m,4H),2.82-2.77(m,2H),1.56-1.59(m,2H),1.33-1.19(m,4H),0.83(t,J＝7.20Hz,3H).31P NMR(203MHz,CDCl3):43.16.
Example twelve:
the method takes cyclohexanethiol and diphenyl phosphorus oxide as raw materials, and comprises the following reaction formula and experimental steps:
phosphorus dipheny oxide (80.8mg, 0.4mmol) was taken and charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, and then cyclohexanethiol (23.2mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL acetonitrile were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation to obtain a product S-cyclohexyl thiodiphenyl phosphorus oxide with the yield of 72 percent.
1H NMR(500MHz,CDCl3):7.90-7.85(m,4H),7.54-7.44(m,6H),3.33-3.26(m,1H),1.95-1.92(m,2H),1.69-1.65(m,2H),1.56-1.47(m,3H),1.32-1.22(m,3H).31P NMR(203MHz,CDCl3):41.95.
Example thirteen:
the method takes benzyl mercaptan and diphenyl phosphorus oxide as raw materials, and comprises the following reaction formula and experimental steps:
phosphorus dipheny oxide (80.8mg, 0.4mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, and then benzyl mercaptan (24.8mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL acetonitrile were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation to obtain a product S-benzylthiodiphenyl phosphorus oxide with the yield of 50 percent.
1H NMR(500MHz,CDCl3):7.89-7.84(m,4H),7.54-7.43(m,6H),7.26-7.17(m,5H),4.02(d,J＝9.2Hz,2H).31PNMR(203MHz,CDCl3):42.79.
Example fourteen:
p-methyl thiophenol and di (4-methylphenyl) phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
p-methylthiophenol (24.8mg, 0.2mmol), bis (4-methylphenyl) phosphorus oxide (92.0mg, 0.4mmol) and p-methylthiophenol were charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double row tube three times, and trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were then added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product S- (4-methylphenyl) thiobis (4-methylphenyl) phosphorus oxide, wherein the yield is 80%.
1H NMR(500MHz,CDCl3):7.74-7.70(m,4H),7.33(d,J＝7.30Hz,2H),7.24-7.21(m,4H),7.00(d,J＝7.90Hz,2H),2.36(s,6H),2.24(s,3H).31PNMR(203MHz,CDCl3):41.84.
Example fifteen:
p-methylthiophenol and di (4-methoxyphenyl) phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
p-methylthiophenol (24.8mg, 0.2mmol), bis (4-methoxyphenyl) phosphorus oxide (104.8mg, 0.4mmol) were charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria three times, trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL acetonitrile were then added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product S- (4-methylphenyl) thiobis (4-methoxyphenyl) phosphorus oxide, wherein the yield is 91%.
1H NMR(500MHz,CDCl3):7.77-7.73(m,4H),7.32(d,J＝7.15Hz,2H),7.00(d,J＝7.90Hz,2H),6.93-6.91(m,4H),3.80(s,6H),2.24(s,3H).31PNMR(203MHz,CDCl3):41.58.
Example sixteen:
p-methyl thiophenol and di (4-tert-butylphenyl) phosphorus oxide are used as raw materials, and the reaction formula and the experimental steps are as follows:
p-methylthiophenol (24.8mg, 0.2mmol), bis (4-t-butylphenyl) phosphine oxide (125.6mg, 0.4mmol) were charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double row tube, and trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL acetonitrile were then added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation to obtain a product S- (4-methylphenyl) thiobis (4-tert-butylphenyl) phosphine oxide with the yield of 98 percent.
1H NMR(500MHz,CDCl3):7.78-7.74(m,4H),7.45-7.43(m,4H),7.31(d,J＝7.10Hz,2H),6.99(d,J＝7.90Hz,2H),2.25(s,3H),1.30(s,18H).31PNMR(203MHz,CDCl3):41.42.
Example seventeen:
p-methyl thiophenol and di (3, 5-dimethylphenyl) phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
p-methylthiophenol (24.8mg, 0.2mmol), bis (3, 5-dimethylphenyl) phosphorus oxide (103.2mg, 0.4mmol) and p-methylthiophenol were charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double-row tube three times, and then trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethylsulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product S- (4-methylphenyl) thiobis (3, 5-dimethylphenyl) phosphorus oxide, wherein the yield is 88%.
1H NMR(500MHz,CDCl3):7.44(d,J＝13.2Hz,4H),7.32(d,J＝7.35Hz,2H),7.11(s,2H),7.01(d,J＝7.90Hz,2H),2.31(s,12H),2.26(s,3H).31PNMR(203MHz,CDCl3):42.49.
Example eighteen:
p-methyl thiophenol and dimethyl phosphite are taken as raw materials, and the reaction formula and the experimental steps are as follows:
p-methylthiophenol (24.8mg, 0.2mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, dimethyl phosphite (44.0mg, 0.4mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL acetonitrile were then added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product S- (4-methylphenyl) thiophosphite dimethyl ester, wherein the yield is 40%.
1H NMR(500MHz,CDCl3):7.45-7.43(m,2H),7.16(d,J＝7.95Hz,2H),3.81(d,J＝12.6Hz,6H),2.35(d,J＝1.75Hz,3H).31PNMR(203MHz,CDCl3):26.66.
Example nineteenth:
p-methylthiophenol and diethyl phosphite are taken as raw materials, and the reaction formula and the experimental steps are as follows:
p-methylthiophenol (24.8mg, 0.2mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, and then diethyl phosphite (55.2mg, 0.4mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL acetonitrile were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product S- (4-methylphenyl) thiophosphorous acid diethyl ester, wherein the yield is 76%.
1H NMR(500MHz,CDCl3):7.45-7.43(m,2H),7.15(d,J＝7.90Hz,2H),4.25-4.12(m,2H),2.34(s,3H),1.31(t,J＝7.05Hz,6H).31PNMR(203MHz,CDCl3):23.32.
Example twenty:
p-methyl thiophenol and diisopropyl phosphite are taken as raw materials, and the reaction formula and the experimental steps are as follows:
p-methylthiophenol (24.8mg, 0.2mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, and then diisopropyl phosphite (55.2mg, 0.4mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL acetonitrile were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product S- (4-methylphenyl) diisopropyl thiophosphite, wherein the yield is 42%.
1H NMR(500MHz,CDCl3):7.48-7.46(m,2H),7.14(d,J＝8.00Hz,2H),4.79-4.73(m,2H),2.34(d,J＝1.45Hz,3H),1.33(d,J＝6.15Hz,6H),1.26(d,J＝6.20Hz,6H).31P NMR(203MHz,CDCl3):20.87.
Example twenty one:
p-methyl thiophenol and dibutyl phosphite are taken as raw materials, and the reaction formula and the experimental steps are as follows:
p-methylthiophenol (24.8mg, 0.2mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, and then dibutyl phosphite (77.6mg, 0.4mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL acetonitrile were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation to obtain a product S- (4-methylphenyl) dibutyl thiophosphate by taking a mixed solution of petroleum ether and ethyl acetate as an eluent, wherein the yield is 75%.
1H NMR(500MHz,CDCl3):7.45-7.43(m,2H),7.14(d,J＝8.00Hz,2H),4.16-4.05(m,4H),2.34(d,J＝1.40Hz,3H),1.65-1.60(m,4H),1.39-1.32(m,4H),0.90(t,J＝7.40Hz,6H).31P NMR(203MHz,CDCl3):23.39.
Example twenty two:
p-methyl thiophenol and diphenyl phosphite are taken as raw materials, and the reaction formula and the experimental steps are as follows:
p-methylthiophenol (24.8mg, 0.2mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, diphenyl phosphite (93.6mg, 0.4mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL acetonitrile were then added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product S- (4-methylphenyl) diphenyl thiophosphite, wherein the yield is 85%.
1H NMR(500MHz,CDCl3):7.38-7.31(m,6H),7.24-7.18(m,6H),7.13(d,J＝8.05Hz,2H),2.34(d,J＝2.25Hz,3H).31PNMR(203MHz,CDCl3):15.30.
Example twenty three:
p-methylthiophenol and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) are used as raw materials, and the reaction formula and the experimental steps are as follows:
p-methylthiophenol (24.8mg, 0.2mmol), DOPO (86.4mg, 0.4mmol) and the like were charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas by using a double calandria for three times, and trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were then added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product S- (4-methylphenyl) thio-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, wherein the yield is 93%.
1H NMR(500MHz,CDCl3):7.93-7.88(m,1H),7.80(t,J＝7.40Hz,1H),7.71-7.63(m,2H),7.49-7.45(m,1H),7.32(t,J＝7.60Hz,1H),7.18-7.13(m,2H),7.09-7.07(m,2H),6.85(d,J＝7.90Hz,2H),2.20(s,3H).31PNMR(203MHz,CDCl3):34.40.
Example twenty-four:
p-methyl thiophenol and phenyl ethyoxyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
p-methylthiophenol (24.8mg, 0.2mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, and then phenylethoxyphosphorus oxide (68.0mg, 0.4mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethylsulfoxide (15.6mg, 0.4mmol) and 2.0mL acetonitrile were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation to obtain a product S- (4-methylphenyl) thiophenylethoxyphosphorus oxide with the yield of 80 percent, wherein the mixed solution of petroleum ether and ethyl acetate is used as an eluent.
1H NMR(500MHz,CDCl3):7.68-7.64(m,2H),7.51-7.47(m,1H),7.39-7.35(m,2H),7.17-7.15(m,2H),7.01(d,J＝7.90Hz,2H),4.40-4.27(m,2H),2.29(s,3H),1.39(t,J＝7.05Hz,3H).31PNMR(203MHz,CDCl3):41.77.
Example twenty-five:
p-methyl thiophenol and phenyl n-butyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
p-methylthiophenol (24.8mg, 0.2mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, then phenyl n-butylphosphine oxide (72.8mg, 0.4mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethylsulfoxide (15.6mg, 0.4mmol) and 2.0mL acetonitrile were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction was completed, the reaction solution was concentrated to obtain a reaction mixture having a volume ratio of 3:1, and performing column chromatography separation to obtain a product S- (4-methylphenyl) thiophenyl n-butyl phosphorus oxide with the yield of 85 percent.
1H NMR(500MHz,CDCl3):7.77-7.73(m,2H),7.51-7.48(m,1H),7.45-7.41(m,2H),7.31(d,J＝7.30Hz,2H),7.04(d,J＝7.85Hz,2H),2.28(s,3H),2.25-2.07(m,2H),1.67-1.59(m,1H),1.58-1.48(m,1H),1.38-1.31(m,2H),0.85(t,J＝7.30Hz,3H).31P NMR(203MHz,CDCl3):50.39.
Example twenty-six:
methanol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
phosphorus diphenylpxide (101.0mg, 0.5mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double calandria tube, and then methanol (6.4mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product methyl diphenylphosphate with the yield of 86%.
1H NMR(500MHz,CDCl3):7.84-7.79(m,4H),7.54-7.51(m,2H),7.48-7.44(m,4H),3.77(d,J＝11.1Hz,3H).31PNMR(203MHz,CDCl3):33.28.
Example twenty-seven:
ethanol and diphenyl phosphorus oxide are used as raw materials, and the reaction formula and the experimental steps are as follows:
phosphorus dipheny oxide (101.0mg, 0.5mmol) was taken and added to a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, and then ethanol (9.2mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, and performing column chromatography by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product ethyl diphenylphosphate with the yield of 78%.
1H NMR(500MHz,CDCl3):7.84-7.80(m,4H),7.53-7.50(m,2H),7.46-7.43(m,4H),4.14-4.08(m,2H),1.37(t,J＝7.05Hz,3H).31PNMR(203MHz,CDCl3):31.41.
Example twenty-eight:
the method takes n-propanol and diphenyl phosphorus oxide as raw materials, and comprises the following reaction formula and experimental steps:
phosphorus diphenylpxide (101.0mg, 0.5mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double calandria tube, and then N-propanol (12.0mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product, namely n-propyl diphenylphosphate with the yield of 70%.
1H NMR(500MHz,CDCl3):7.84-7.80(m,4H),7.52-7.42(m,6H),4.01-3.97(m,2H),1.78-1.71(m,2H),0.98(t,J＝7.40Hz,3H).31PNMR(203MHz,CDCl3):31.14.
Example twenty-nine:
isopropanol and diphenyl phosphorus oxide are used as raw materials, and the reaction formula and the experimental steps are as follows:
phosphorus diphenylpxide (101.0mg, 0.5mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double calandria tube, and then isopropyl alcohol (12.0mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product of isopropyl diphenylphosphate with the yield of 71%.
1HNMR(500MHz,CDCl3):7.84-7.80(m,4H),7.52-7.48(m,2H),7.45-7.42(m,4H),4.71-4.64(m,1H),1.35(d,J＝6.15Hz,6H).31PNMR(203MHz,CDCl3):29.82.
Example thirty:
the reaction formula and the experimental steps are as follows by taking n-butanol and diphenyl phosphorus oxide as raw materials:
phosphorus dipheny oxide (101.0mg, 0.5mmol) was taken and added to a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, then N-butanol (14.8mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product of n-butyl diphenylphosphate with the yield of 76%.
1H NMR(500MHz,CDCl3):7.84-7.80(m,4H),7.52-7.42(m,6H),4.05-4.01(m,2H),1.74-1.68(m,2H),1.47-1.40(m,2H),0.91(t,J＝7.40Hz,3H).31P NMR(203MHz,CDCl3):31.18.
Example thirty one:
taking n-pentanol and diphenyl phosphorus oxide as raw materials, the reaction formula and the experimental steps are as follows:
phosphorus dipheny oxide (101.0mg, 0.5mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, then N-pentanol (17.6mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, and performing column chromatography to obtain a product, namely n-amyl diphenylphosphate by taking a mixed solution of petroleum ether and ethyl acetate as an eluent, wherein the yield is 86%.
1H NMR(500MHz,CDCl3):7.83-7.80(m,4H),7.53-7.50(m,2H),7.46-7.43(m,4H),4.04-4.00(m,2H),1.76-1.70(m,2H),1.41-1.28(m,4H),0.88(t,J＝7.20Hz,3H).31P NMR(203MHz,CDCl3):31.10.
Example thirty-two:
the reaction formula and the experimental steps are as follows by taking n-hexanol and diphenyl phosphorus oxide as raw materials:
phosphorus dipheny oxide (101.0mg, 0.5mmol) was taken and added to a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, and then N-hexanol (20.4mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, and performing column chromatography to obtain a product of n-hexyl diphenylphosphate by taking a mixed solution of petroleum ether and ethyl acetate as an eluent, wherein the yield is 80%.
1H NMR(500MHz,CDCl3):7.84-7.79(m,4H),7.53-7.49(m,2H),7.46-7.42(m,4H),4.04-4.00(m,2H),1.75-1.69(m,2H),1.42-1.36(m,2H),1.32-1.25(m,4H),0.87(t,J＝6.85Hz,3H).31PNMR(203MHz,CDCl3):31.13.
Example thirty-three:
the method takes n-octanol and diphenyl phosphorus oxide as raw materials, and comprises the following reaction formula and experimental steps:
phosphorus diphenylpoxide (101.0mg, 0.5mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double row tube three times, and then N-octanol (26.0mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product of the n-octyl diphenylphosphate with the yield of 80%.
1H NMR(500MHz,CDCl3):7.83-7.79(m,4H),7.53-7.50(m,2H),7.47-7.43(m,4H),4.04-4.00(m,2H),1.74-1.69(m,2H),1.40-1.37(m,2H),1.30-1.26(m,8H),0.87(t,J＝6.85Hz,3H).31PNMR(203MHz,CDCl3):31.14.
Example thirty-four:
the method takes ethylene glycol and diphenyl phosphorus oxide as raw materials, and comprises the following reaction formula and experimental steps:
phosphorus diphenylpoxide (101.0mg, 0.5mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double calandria tube, and then ethylene glycol (12.4mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product 2-hydroxyethyl diphenyl phosphate with the yield of 41%.
1H NMR(500MHz,CDCl3):7.85-7.81(m,4H),7.55-7.52(m,2H),7.47-7.44(m,4H),4.16-4.12(m,2H),3.84-3.83(m,2H).31PNMR(203MHz,CDCl3):34.80.
Example thirty-five:
4-chlorobutanol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
phosphorus dipheny oxide (101.0mg, 0.5mmol) was taken and added to a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, and then 4-chlorobutanol (21.6mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, and performing column chromatography by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product, namely 4-chlorobutyl diphenyl phosphate, wherein the yield is 50%.
1H NMR(500MHz,CDCl3):7.83-7.80(m,4H),7.54-7.51(m,2H),7.48-7.44(m,4H),4.08-4.05(m,2H),3.56(t,J＝6.00Hz,2H),1.94-1.87(m,4H).31P NMR(203MHz,CDCl3):31.62.
Example thirty-six:
the method takes phenylpropanol and diphenyl phosphorus oxide as raw materials, and comprises the following reaction formula and experimental steps:
phosphorus diphenylpoxide (101.0mg, 0.5mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double row tube, and then phenylpropanol (27.2mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethylsulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was carried out at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, and performing column chromatography by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product, namely 3-phenylpropyl diphenyl phosphate, wherein the yield is 72%.
1H NMR(500MHz,CDCl3):7.84-7.79(m,4H),7.53-7.50(m,2H),7.46-7.43(m,4H),7.28-7.25(m,2H),7.19-7.15(m,3H),4.08-4.04(m,2H),2.75(t,J＝7.40Hz,2H),2.08-2.02(m,2H).31PNMR(203MHz,CDCl3):31.40.
Example thirty-seven:
the method takes trifluoroethanol and diphenyl phosphorus oxide as raw materials, and comprises the following reaction formula and experimental steps:
phosphorus dipheny oxide (101.0mg, 0.5mmol) was taken and added to a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, trifluoroethanol (20.0mg, 0.2mmol), trifluoromethane sulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were then added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product, namely trifluoroethyl diphenyl phosphate, wherein the yield is 60%.
1H NMR(500MHz,CDCl3):7.84-7.80(m,4H),7.59-7.56(m,2H),7.51-7.47(m,4H),4.37-4.31(m,2H).31P NMR(203MHz,CDCl3):35.15.19F NMR(470MHz,CDCl3):-74.72.
Example thirty-eight:
taking allyl alcohol and diphenyl phosphorus oxide as raw materials, the reaction formula and the experimental steps are as follows:
phosphorus dipheny oxide (101.0mg, 0.5mmol) was taken and charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, then allyl alcohol (11.6mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product, namely allyl diphenyl phosphate, wherein the yield is 70%.
1H NMR(500MHz,CDCl3):7.85-7.81(m,4H),7.54-7.51(m,2H),7.47-7.44(m,4H),6.00-5.93(m,1H),5.36(dd,J1＝1.35Hz,J2＝17.1Hz,1H),5.23(dd,J1＝0.80Hz,J2＝10.4Hz,1H),4.56-4.53(m,2H).31PNMR(203MHz,CDCl3):32.21.
Example thirty-nine:
propargyl alcohol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
diphenylphosphine oxide (101.0mg, 0.5mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double calandria tube, and then propargyl alcohol (11.2mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, and performing column chromatography by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product of propargyl diphenyl phosphate, wherein the yield is 35%.
1H NMR(500MHz,CDCl3):7.86-7.82(m,4H),7.56-7.53(m,2H),7.48-7.45(m,4H),4.70(dd,J1＝2.45Hz,J2＝8.40Hz,2H),2.48(t,J＝2.45Hz,1H).31P NMR(203MHz,CDCl3):34.11.
Example forty:
taking cyclohexanol and diphenyl phosphorus oxide as raw materials, the reaction formula and the experimental steps are as follows:
diphenylphosphine oxide (101.0mg, 0.5mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double row tube three times, and then cyclohexanol (20.0mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product, namely cyclohexyl diphenyl phosphate, wherein the yield is 65%.
1H NMR(500MHz,CDCl3):7.84-7.79(m,4H),7.51-7.48(m,2H),7.45-7.41(m,4H),4.45-4.39(m,1H),1.91-1.88(m,2H),1.77-1.71(m,2H),1.64-1.57(m,2H),1.48-1.45(m,1H),1.33-1.25(m,3H).31P NMR(203MHz,CDCl3):29.72.
Example forty one:
the method takes the cyclopropane methanol and the diphenyl phosphorus oxide as raw materials, and has the following reaction formula and experimental steps:
phosphorus diphenylpxide (101.0mg, 0.5mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double calandria tube, and then cyclopropylmethanol (14.4mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product, namely the cyclopropylmethyl diphenyl phosphate, wherein the yield is 62%.
1H NMR(500MHz,CDCl3):7.85-7.81(m,4H),7.53-7.50(m,2H),7.46-7.43(m,4H),3.89(t,J＝7.40Hz,2H),1.22-1.15(m,1H),0.56-0.53(m,2H),0.28-0.25(m,2H).31PNMR(203MHz,CDCl3):31.03.
Example forty two:
3-phenyl allyl alcohol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
phosphorus dipheny oxide (101.0mg, 0.5mmol) was taken and charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, and then 3-phenylallyl alcohol (26.8mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, and performing column chromatography by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product, namely 3-phenylallyl diphenyl phosphate, wherein the yield is 30%.
1H NMR(500MHz,CDCl3):7.87-7.83(m,4H),7.54-7.51(m,2H),7.48-7.44(m,4H),7.36-7.30(m,4H),7.27-7.25(m,1H),6.62(d,J＝15.85Hz,1H),6.34-6.28(m,1H),4.71(t,J＝6.55Hz,2H).31PNMR(203MHz,CDCl3):32.28.
Example forty-three:
the 9-fluorenylmethanol and diphenyl phosphorus oxide are used as raw materials, and the reaction formula and the experimental steps are as follows:
9-Fluorenylmethanol (39.2mg, 0.2mmol), diphenylphosphine oxide (101.0mg, 0.5mmol) and the mixture were introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double row tube, and trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto and the reaction was allowed to proceed at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product 9-fluorenylmethyl diphenyl phosphate with the yield of 90%.
1H NMR(500MHz,CDCl3):7.75-7.72(m,6H),7.58(d,J＝7.50Hz,2H),7.50-7.47(m,2H),7.42-7.37(m,6H),7.29-7.26(m,2H),4.35-4.31(m,3H).31PNMR(203MHz,CDCl3):32.12.
Example forty-four:
taking benzyl alcohol and diphenyl phosphorus oxide as raw materials, the reaction formula and the experimental steps are as follows:
diphenylphosphine oxide (101.0mg, 0.5mmol) was charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double row tube, and then benzyl alcohol (21.6mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, and performing column chromatography by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product of benzyl diphenyl phosphate, wherein the yield is 56%.
1H NMR(500MHz,CDCl3):7.85-7.81(m,4H),7.53-7.50(m,2H),7.46-7.42(m,4H),7.37-7.29(m,5H),5.06(d,J＝6.75Hz,2H).31PNMR(203MHz,CDCl3):32.33.
Example forty-five:
4-fluorobenzyl alcohol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
phosphorus dipheny oxide (101.0mg, 0.5mmol) was taken and added to a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria tube three times, and then 4-fluorobenzyl alcohol (25.2mg, 0.2mmol), trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, and performing column chromatography by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product 4-fluorobenzyl diphenyl phosphate with the yield of 53 percent.
1H NMR(500MHz,CDCl3):7.84-7.79(m,4H),7.54-7.50(m,2H),7.46-7.42(m,4H),7.35-7.32(m,2H),7.03-7.00(m,2H),5.03(d,J＝7.25Hz,2H).31P NMR(203MHz,CDCl3):32.47.19F NMR(470MHz,CDCl3):-113.55.
Example forty-six:
4-chlorobenzyl alcohol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
4-chlorobenzyl alcohol (28.4mg, 0.2mmol), diphenylphosphoric oxide (101.0mg, 0.5mmol) and the like were charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas by using a double row tube three times, and trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were then added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product, namely 4-chlorobenzyl diphenyl phosphate with the yield of 65%.
1H NMR(500MHz,CDCl3):7.84-7.80(m,4H),7.54-7.51(m,2H),7.46-7.43(m,4H),7.32-7.28(m,4H),5.02(d,J＝7.25Hz,2H).31PNMR(203MHz,CDCl3):32.68.
Example forty-seven:
2-naphthyl methanol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
2-Naphthalenemethanol (31.6mg, 0.2mmol), diphenylphosphine oxide (101.0mg, 0.5mmol) and the mixture were introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double row tube, trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to proceed at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, and performing column chromatography by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product 2-naphthylmethyl diphenyl phosphate with the yield of 42%.
1H NMR(500MHz,CDCl3):8.10(d,J＝8.05Hz,1H),7.87-7.86(m,1H),7.83-7.79(m,5H),7.55-7.48(m,4H),7.46(d,J＝6.80Hz,1H),7.42-7.38(m,5H),5.53(d,J＝6.55Hz,2H).31P NMR(203MHz,CDCl3):32.44.
Example forty-eight:
taking ferrocene methanol and diphenyl phosphorus oxide as raw materials, the reaction formula and the experimental steps are as follows:
ferrocene methanol (43.2mg, 0.2mmol), diphenylphosphine oxide (101.0mg, 0.5mmol) were charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double row tube three times, and then trifluoromethanesulfonic anhydride (56.4mg, 0.4mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of N, N-dimethylformamide were added thereto, and the reaction was allowed to react at room temperature for 12 hours. After the reaction is finished, water is added for quenching, extraction is carried out for 3 times by using ethyl acetate, and an organic phase is concentrated and is added into a reaction solution in a volume ratio of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product of ferrocene methyl diphenyl phosphate with the yield of 41%.
1H NMR(500MHz,CDCl3):7.69-7.65(m,4H),7.50-7.43(m,6H),4.08(s,5H),4.01(s,4H),3.42(d,J＝12.65Hz,2H).31P NMR(203MHz,CDCl3):28.33.
Example forty-nine:
phenol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
phenol (94.0mg, 1.0mmol), diphenylphosphine oxide (40.4mg, 0.2mmol) were charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria for three times, and trifluoromethanesulfonic anhydride (169mg, 0.6mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto, and the reaction was allowed to react at 90 ℃ for 12 hours. After the reaction was completed, the organic phase was concentrated to obtain a solution of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product, namely phenyl diphenyl phosphate, wherein the yield is 75%.
1H NMR(500MHz,CDCl3):7.91-7.87(m,4H),7.54-7.51(m,2H),7.47-7.43(m,4H),7.26-7.19(m,4H),7.08-7.05(m,1H).31PNMR(203MHz,CDCl3):30.42.
Example fifty:
4-methylphenol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
4-methylphenol (108mg, 1.0mmol), diphenylphosphine oxide (40.4mg, 0.2mmol) and the mixture were introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double row tube three times, and trifluoromethanesulfonic anhydride (169mg, 0.6mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto, and the reaction was allowed to react at 90 ℃ for 12 hours. After the reaction was completed, the organic phase was concentrated to obtain a solution of 3:1, and performing column chromatography by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product, namely 4-methylphenyl diphenyl phosphate, wherein the yield is 66%.
1H NMR(500MHz,CDCl3):7.90-7.86(m,4H),7.53-7.50(m,2H),7.46-7.42(m,4H),7.07(d,J＝8.10Hz,2H),7.01(d,J＝8.55Hz,2H),2.23(s,3H).31PNMR(203MHz,CDCl3):30.24.
Example fifty one:
4-methoxyphenol and diphenyl phosphorus oxide are used as raw materials, and the reaction formula and the experimental steps are as follows:
4-methoxyphenol (124mg, 1.0mmol) and diphenylphosphorus oxide (40.4mg, 0.2mmol) were introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double row tube three times, and trifluoromethanesulfonic anhydride (169mg, 0.6mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto, and the reaction was allowed to react at 90 ℃ for 12 hours. After the reaction was completed, the organic phase was concentrated to obtain a solution of 3:1, and performing column chromatography by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product 4-methoxyphenyl diphenyl phosphate with the yield of 45 percent.
1H NMR(500MHz,CDCl3):7.90-7.86(m,4H),7.54-7.51(m,2H),7.47-7.44(m,4H),7.10(d,J＝8.95Hz,2H),6.74(d,J＝9.05Hz,2H),3.72(s,3H).31PNMR(203MHz,CDCl3):30.50.
Example fifty two:
the method takes 4-fluorophenol and diphenyl phosphorus oxide as raw materials, and comprises the following reaction formula and experimental steps:
4-fluorophenol (112mg, 1.0mmol) and diphenylphosphoric oxide (40.4mg, 0.2mmol) were introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double row tube three times, and trifluoromethanesulfonic anhydride (169mg, 0.6mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto, and the reaction was allowed to react at 90 ℃ for 12 hours. After the reaction was completed, the organic phase was concentrated to obtain a solution of 3:1, and performing column chromatography by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product, namely 4-fluorophenyl diphenyl phosphate with the yield of 93%.
1H NMR(500MHz,CDCl3):7.90-7.85(m,4H),7.55-7.52(m,2H),7.48-7.44(m,4H),7.16-7.13(m,2H),6.92-6.89(m,2H).31P NMR(203MHz,CDCl3):31.24.19F NMR(470MHz,CDCl3):-118.31.
Example fifty three:
4-chlorophenol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
4-chlorophenol (128mg, 1.0mmol), diphenylphosphine oxide (40.4mg, 0.2mmol) were charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria for three times, and trifluoromethanesulfonic anhydride (169mg, 0.6mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto, and the reaction was allowed to react at 90 ℃ for 12 hours. After the reaction was completed, the organic phase was concentrated to obtain a solution of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product, namely 4-chlorophenyl diphenyl phosphate with the yield of 96%.
1H NMR(500MHz,CDCl3):7.89-7.85(m,4H),7.56-7.53(m,2H),7.49-7.45(m,4H),7.19(d,J＝8.85Hz,2H),7.14(d,J＝8.65Hz,2H).31PNMR(203MHz,CDCl3):31.24.
Example fifty-four:
the method takes 4-bromophenol and diphenyl phosphorus oxide as raw materials, and comprises the following reaction formula and experimental steps:
4-bromophenol (173mg, 1.0mmol), diphenylphosphine oxide (40.4mg, 0.2mmol) were charged into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double row tube three times, and trifluoromethanesulfonic anhydride (169mg, 0.6mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were then added thereto, and the reaction was allowed to react at 90 ℃ for 12 hours. After the reaction was completed, the organic phase was concentrated to obtain a solution of 3:1, and performing column chromatography by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product, namely 4-bromophenyl diphenyl phosphate, wherein the yield is 96%.
1H NMR(500MHz,CDCl3):7.89-7.85(m,4H),7.55-7.52(m,2H),7.48-7.44(m,4H),7.34-7.32(m,2H),7.10-7.08(m,2H).31PNMR(203MHz,CDCl3):31.41.
Example fifty-five:
4-nitrophenol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
4-nitrophenol (139mg, 1.0mmol) and diphenylphosphoric oxide (40.4mg, 0.2mmol) were introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double row tube three times, and trifluoromethanesulfonic anhydride (169mg, 0.6mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL acetonitrile were added thereto, and the reaction was allowed to react at 90 ℃ for 12 hours. After the reaction was completed, the organic phase was concentrated to obtain a solution of 3:1, and performing column chromatography to obtain a product 4-nitrophenyl diphenyl phosphate with the yield of 92 percent by taking a mixed solution of petroleum ether and ethyl acetate as an eluent.
1H NMR(500MHz,CDCl3):8.15(d,J＝9.10Hz,2H),7.91-7.87(m,4H),7.61-7.57(m,2H),7.52-7.48(m,4H),7.38(d,J＝8.40Hz,2H).31PNMR(203MHz,CDCl3):32.77.
Example fifty-six:
the method takes 4-cyanophenol and diphenyl phosphorus oxide as raw materials, and comprises the following reaction formula and experimental steps:
4-cyanophenol (119mg, 1.0mmol) and diphenylphosphoric oxide (40.4mg, 0.2mmol) were introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double row tube three times, and trifluoromethanesulfonic anhydride (169mg, 0.6mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto, and the reaction was allowed to react at 90 ℃ for 12 hours. After the reaction was completed, the organic phase was concentrated to obtain a solution of 3:1, and performing column chromatography by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product, namely 4-cyanophenyl diphenyl phosphate, wherein the yield is 89%.
1H NMR(500MHz,CDCl3):7.90-7.86(m,4H),7.59-7.54(m,4H),7.51-7.47(m,4H),7.34(d,J＝8.00Hz,2H).31PNMR(203MHz,CDCl3):32.45.
Example fifty-seven:
2-phenylphenol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
2-phenylphenol (170mg, 1.0mmol) and diphenylphosphorus oxide (40.4mg, 0.2mmol) were introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double row tube three times, and trifluoromethanesulfonic anhydride (169mg, 0.6mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto, and the reaction was allowed to react at 90 ℃ for 12 hours. After the reaction was completed, the organic phase was concentrated to obtain a solution of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product 2-phenyl diphenyl phosphate with the yield of 55%.
1H NMR(500MHz,CDCl3):7.63(d,J＝8.20Hz,1H),7.57-7.52(m,4H),7.44-7.38(m,7H),7.31-7.27(m,5H),7.24-7.20(m,1H),7.14-7.11(m,1H).31PNMR(203MHz,CDCl3):30.74.
Example fifty-eight:
3-cyanophenol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
4-cyanophenol (119mg, 1.0mmol) and diphenylphosphoric oxide (40.4mg, 0.2mmol) were introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double row tube three times, and trifluoromethanesulfonic anhydride (169mg, 0.6mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto, and the reaction was allowed to react at 90 ℃ for 12 hours. After the reaction was completed, the organic phase was concentrated to obtain a solution of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product, namely 3-cyanophenyl diphenyl phosphate, wherein the yield is 70%.
1H NMR(500MHz,CDCl3):7.90-7.86(m,4H),7.60-7.57(m,2H),7.52-7.48(m,6H),7.40-7.34(m,2H).31PNMR(203MHz,CDCl3):32.55.
Example fifty-nine:
the method takes 2-methyl-4 bromophenol and diphenyl phosphorus oxide as raw materials, and comprises the following reaction formula and experimental steps:
2-methyl-4-bromophenol (187mg, 1.0mmol), diphenylphosphine oxide (40.4mg, 0.2mmol) and the mixture were introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas three times using a double row tube, and trifluoromethanesulfonic anhydride (169mg, 0.6mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto, and the reaction was allowed to react at 90 ℃ for 12 hours. After the reaction was completed, the organic phase was concentrated to obtain a solution of 3:1, using a mixed solution of petroleum ether and ethyl acetate as an eluent, and performing column chromatography to obtain a product 2-methyl-4-bromophenyl diphenyl phosphate with the yield of 71%.
1H NMR(500MHz,CDCl3):7.89-7.85(m,4H),7.56-7.53(m,2H),7.48-7.45(m,4H),7.27(s,1H),7.16-7.11(m,2H),2.26(s,3H).31PNMR(203MHz,CDCl3):30.77.
Example sixty:
2-naphthol and diphenyl phosphorus oxide are taken as raw materials, and the reaction formula and the experimental steps are as follows:
2-Naphthol (187mg, 1.0mmol), diphenylphosphine oxide (40.4mg, 0.2mmol) and the like were taken out and introduced into a 10mL reaction tube, the air in the reaction tube was replaced with nitrogen gas using a double calandria and replaced three times, and then trifluoromethanesulfonic anhydride (169mg, 0.6mmol), dimethyl sulfoxide (15.6mg, 0.4mmol) and 2.0mL of acetonitrile were added thereto and the reaction was allowed to react at 90 ℃ for 12 hours. After the reaction was completed, the organic phase was concentrated to obtain a solution of 3:1, and performing column chromatography by using a mixed solution of petroleum ether and ethyl acetate as an eluent to obtain a product 2-naphthyl diphenyl phosphate with the yield of 51 percent.
1H NMR(500MHz,CDCl3):7.95-7.91(m,4H),7.76-7.70(m,4H),7.54-7.51(m,2H),7.48-7.35(m,7H).31PNMR(203MHz,CDCl3):30.68.
Although the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the details of the embodiments, and various equivalent modifications can be made within the technical spirit of the present invention, and the scope of the present invention is also within the scope of the present invention.
Claims (8)
1. A method for preparing a compound containing a P-O bond or a P-S bond is characterized in that the method takes a compound containing hydroxyl or sulfhydryl and a phosphorus reagent as starting materials,
wherein the hydroxyl-containing or thiol-containing compound is:
R1-X-H
x is O or S, and R1Adopts one of the following schemes:
when X ═ O, R1Any one selected from the group consisting of C1-C8 alkyl, 2-hydroxyethyl, 4-chlorobutyl, 3-phenylpropyl, trifluoroethyl, allyl, propynyl, cyclohexyl, cyclopropylmethyl, 3-phenylallyl, 9-fluorenyl, benzyl, p-fluorobenzyl, p-chlorobenzyl, 1-naphthylmethyl, ferrocenylmethyl, phenyl, p-methylphenyl, p-methoxyphenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, 4-cyanophenyl, 4-nitrophenyl, 2-phenylphenyl, 3-cyanophenyl, 2-methyl-4-bromophenyl, and 2-naphthyl,
when X ═ S, R1Is selected from R3Is any one of C4-C8 alkyl, cyclohexyl, benzyl, 2-naphthyl, 4-methylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 2-methylphenyl and 3-chlorophenyl;
the phosphorus reagent is:
R2any one selected from phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-tert-butylphenyl, 3, 5-dimethylphenyl, methoxy, ethoxy, isopropoxy, n-butoxy, phenoxy, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxy,
R3selected from phenyl, 4-methylphenyl,Any one of 4-methoxyphenyl, 4-tert-butylphenyl, 3, 5-dimethylphenyl, n-butyl, methoxy, ethoxy, isopropoxy, n-butoxy and phenoxy;
then, the starting material was reacted under an inert gas atmosphere in trifluoromethane sulfonic anhydride (Tf)2O) and dimethyl sulfoxide (DMSO) according to a molar ratio, wherein the hydroxyl-containing or sulfhydryl-containing compound comprises: phosphorus reagent: reacting trifluoromethane sulfonic anhydride and dimethyl sulfoxide in a ratio of 1-5: 1-2.5: 2-3: 2 in an organic solvent at a reaction temperature of 25-100 ℃ for 6-20 hours to obtain a compound with a structural general formula (I),
and X, R in the compound of the general formula (I)1、R2、R3The designation of (b) is consistent with the foregoing.
2. The method according to claim 1, wherein the organic solvent is selected from the group consisting of N, N-Dimethylformamide (DMF), ethanol, and acetonitrile.
3. The method according to claim 1, wherein the inert gas is N2、Ar。
4. The method according to claim 1, wherein the hydroxyl-or thiol-group-containing compound is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, n-pentanol, n-hexanol, n-octanol, ethylene glycol, 4-chlorobutanol, phenylpropanol, trifluoroethanol, allyl alcohol, propynyl alcohol, cyclohexanol, cyclopropylmethanol, 3-phenylallylalcohol, 9-fluorenylmethanol, benzyl alcohol, p-fluorobenzyl alcohol, p-chlorobenzyl alcohol, 1-naphthalenylmethanol, ferrocenylmethanol, phenol, p-methylphenol, p-methoxyphenol, p-fluorophenol, p-chlorophenol, p-bromophenol, 4-cyanophenol, 4-nitrophenol, 2-phenylphenol, 3-cyanophenol, 2-methyl-4-bromophenol, 2-naphthol, n-butylmercaptan, cyclohexylmercaptan, benzylmercaptan, 2-methyloxyphenol, 2-naphthol, n-butylmercaptan, cyclohexylmercaptan, benzylmercaptan, 2-naphthalene thiol, 4-methyl thiophenol, 4-tert-butyl thiophenol, 4-methoxy thiophenol, 4-fluorobenzothiophenol, 4-chlorobenzothiophenol, 4-bromobenzothiophenol, 2-methyl thiophenol, 3-chlorobenzothiophenol.
5. The method according to claim 1, wherein the phosphorus reagent is selected from the group consisting of diphenylphosphoroxy, bis (4-methylphenyl) phosphoroxy, bis (4-methoxyphenyl) phosphoroxy, bis (4-tert-butylphenyl) phosphoroxy, bis (3, 5-dimethylphenyl) phosphoroxy, dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, dibutyl phosphite, diphenyl phosphite, DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), ethylphenylphosphate, and phenyl n-butylphosphoroxy.
6. The process according to claim 1, wherein when X ═ O, R in the formula (I)1When the compound is an aliphatic substituent, the molar ratio of the hydroxyl-containing or sulfhydryl-containing compound to the phosphorus reagent, the trifluoromethanesulfonic anhydride and the dimethyl sulfoxide is 1 (2-3) to 2: 2.
7. The process according to claim 1, wherein when X ═ O, R in the formula (I)1When the compound is an aromatic substituent, the molar ratio of the compound containing hydroxyl or sulfhydryl, the phosphorus reagent, the trifluoromethanesulfonic anhydride and the dimethyl sulfoxide is (3-5) 1:3: 2.
8. The preparation method according to claim 1, wherein when X ═ S in the general formula (I), the molar ratio of the hydroxyl group-or thiol group-containing compound to the phosphorus reagent, trifluoromethanesulfonic anhydride, and dimethyl sulfoxide is 1 (2-3): 2: 2.
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| CN114751936A (en) * | 2022-03-28 | 2022-07-15 | 河南大学 | Method for phosphorylation of amine, amide, alcohol and mercaptan |
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| CN112391644A (en) * | 2020-10-23 | 2021-02-23 | 云南民族大学 | Preparation method of disulfoxide compound |
| CN114751936A (en) * | 2022-03-28 | 2022-07-15 | 河南大学 | Method for phosphorylation of amine, amide, alcohol and mercaptan |
| CN114751936B (en) * | 2022-03-28 | 2024-03-29 | 河南大学 | Method for phosphorylating amine, amide, alcohol and mercaptan |
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