CN114539109B - Beta-ketone sulfosulfone synthesis method - Google Patents
Beta-ketone sulfosulfone synthesis method Download PDFInfo
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- CN114539109B CN114539109B CN202210261087.2A CN202210261087A CN114539109B CN 114539109 B CN114539109 B CN 114539109B CN 202210261087 A CN202210261087 A CN 202210261087A CN 114539109 B CN114539109 B CN 114539109B
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- dimethyl sulfur
- sulfur bromide
- benzoylmethylene
- chloroform
- nmr
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- 238000001308 synthesis method Methods 0.000 title description 2
- RWCMHQZUYWBVAE-UHFFFAOYSA-N OS(=O)(=O)S(=O)(=O)S(O)(=O)=O Chemical compound OS(=O)(=O)S(=O)(=O)S(O)(=O)=O RWCMHQZUYWBVAE-UHFFFAOYSA-N 0.000 title 1
- -1 sulfone compounds Chemical class 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 9
- UNGVHYYDHXGTTP-UHFFFAOYSA-N C[S](C)Br Chemical compound C[S](C)Br UNGVHYYDHXGTTP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- GWIKYPMLNBTJHR-UHFFFAOYSA-M thiosulfonate group Chemical group S(=S)(=O)[O-] GWIKYPMLNBTJHR-UHFFFAOYSA-M 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 4
- ATKJLMWDXASAJA-UHFFFAOYSA-N benzenesulfonylsulfanylbenzene Chemical group C=1C=CC=CC=1S(=O)(=O)SC1=CC=CC=C1 ATKJLMWDXASAJA-UHFFFAOYSA-N 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- MTJBOYQKJGSLQP-UHFFFAOYSA-N 1-(benzenesulfonylsulfanyl)-4-chlorobenzene Chemical compound C1=CC(Cl)=CC=C1SS(=O)(=O)C1=CC=CC=C1 MTJBOYQKJGSLQP-UHFFFAOYSA-N 0.000 claims description 2
- ZZFQKSMSHVYLKA-UHFFFAOYSA-N 1-(benzenesulfonylsulfanyl)-4-methoxybenzene Chemical compound C1=CC(OC)=CC=C1SS(=O)(=O)C1=CC=CC=C1 ZZFQKSMSHVYLKA-UHFFFAOYSA-N 0.000 claims description 2
- GELXBJUSJVWYSU-UHFFFAOYSA-N 1-(benzenesulfonylsulfanyl)-4-methylbenzene Chemical compound C1=CC(C)=CC=C1SS(=O)(=O)C1=CC=CC=C1 GELXBJUSJVWYSU-UHFFFAOYSA-N 0.000 claims description 2
- PAIRPKMSBFJAQB-UHFFFAOYSA-N 1-methyl-4-phenylsulfanylsulfonylbenzene Chemical compound C1=CC(C)=CC=C1S(=O)(=O)SC1=CC=CC=C1 PAIRPKMSBFJAQB-UHFFFAOYSA-N 0.000 claims description 2
- WETCFJNRXCWODC-UHFFFAOYSA-N 2-(benzenesulfonylsulfanyl)pyridine Chemical compound O=S(=O)(Sc1ccccn1)c1ccccc1 WETCFJNRXCWODC-UHFFFAOYSA-N 0.000 claims description 2
- CJVYYNOHQJUBDG-UHFFFAOYSA-N C1(=CC=CC=C1)S(=O)(SC1=C(C=CC=C1)F)=O Chemical compound C1(=CC=CC=C1)S(=O)(SC1=C(C=CC=C1)F)=O CJVYYNOHQJUBDG-UHFFFAOYSA-N 0.000 claims description 2
- KVQGMWRWELTCME-UHFFFAOYSA-N C[S](C)(Br)=C Chemical compound C[S](C)(Br)=C KVQGMWRWELTCME-UHFFFAOYSA-N 0.000 claims description 2
- DMZGCUIECTUYAM-UHFFFAOYSA-N butylsulfanylsulfonylbenzene Chemical compound CCCCSS(=O)(=O)C1=CC=CC=C1 DMZGCUIECTUYAM-UHFFFAOYSA-N 0.000 claims description 2
- BZDBCNNPIPQCBV-UHFFFAOYSA-N dodecylsulfanylsulfonylbenzene Chemical compound CCCCCCCCCCCCSS(=O)(=O)C1=CC=CC=C1 BZDBCNNPIPQCBV-UHFFFAOYSA-N 0.000 claims description 2
- ZPEHNXXWDYBSRN-UHFFFAOYSA-N propylsulfanylsulfonylbenzene Chemical compound CCCSS(=O)(=O)C1=CC=CC=C1 ZPEHNXXWDYBSRN-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- XTYIPOLJGLYUPC-UHFFFAOYSA-N COC1=CC=CC(C(C=[S](C)(C)Br)=O)=C1 Chemical compound COC1=CC=CC(C(C=[S](C)(C)Br)=O)=C1 XTYIPOLJGLYUPC-UHFFFAOYSA-N 0.000 claims 1
- VITKQGRRNZRNFJ-UHFFFAOYSA-N C[S](C)(Br)=CC(C(C=C1)=CC=C1Br)=O Chemical compound C[S](C)(Br)=CC(C(C=C1)=CC=C1Br)=O VITKQGRRNZRNFJ-UHFFFAOYSA-N 0.000 claims 1
- HAOKLYMDGMSSRN-UHFFFAOYSA-N C[S](C)(Br)=CC(C(C=C1)=CC=C1C#N)=O Chemical compound C[S](C)(Br)=CC(C(C=C1)=CC=C1C#N)=O HAOKLYMDGMSSRN-UHFFFAOYSA-N 0.000 claims 1
- IRBXPYHSPAUCOW-UHFFFAOYSA-N C[S](C)(Br)=CC(C(C=C1)=CC=C1Cl)=O Chemical compound C[S](C)(Br)=CC(C(C=C1)=CC=C1Cl)=O IRBXPYHSPAUCOW-UHFFFAOYSA-N 0.000 claims 1
- QOQCOBWFKRTANW-UHFFFAOYSA-N C[S](C)(Br)=CC(C(C=C1)=CC=C1F)=O Chemical compound C[S](C)(Br)=CC(C(C=C1)=CC=C1F)=O QOQCOBWFKRTANW-UHFFFAOYSA-N 0.000 claims 1
- AKMNDCOYXIZXAJ-UHFFFAOYSA-N C[S](C)(Br)=CC(C(C=C1)=CC=C1OC(F)(F)F)=O Chemical compound C[S](C)(Br)=CC(C(C=C1)=CC=C1OC(F)(F)F)=O AKMNDCOYXIZXAJ-UHFFFAOYSA-N 0.000 claims 1
- QXGKNPDIHQWVSW-UHFFFAOYSA-N C[S](C)(Br)=CC(C(C=C1)=CC=C1[N+]([O-])=O)=O Chemical compound C[S](C)(Br)=CC(C(C=C1)=CC=C1[N+]([O-])=O)=O QXGKNPDIHQWVSW-UHFFFAOYSA-N 0.000 claims 1
- PGCABVLFANBMLN-UHFFFAOYSA-N C[S](C)(Br)=CC(C1=CC(Br)=CC=C1)=O Chemical compound C[S](C)(Br)=CC(C1=CC(Br)=CC=C1)=O PGCABVLFANBMLN-UHFFFAOYSA-N 0.000 claims 1
- XFYATMCGUKMJTN-UHFFFAOYSA-N C[S](C)(Br)=CC(C1=CC(Cl)=CC=C1)=O Chemical compound C[S](C)(Br)=CC(C1=CC(Cl)=CC=C1)=O XFYATMCGUKMJTN-UHFFFAOYSA-N 0.000 claims 1
- AHMQSPZRVXTSRD-UHFFFAOYSA-N C[S](C)(Br)=CC(C1=CC=C(C(F)(F)F)C=C1)=O Chemical compound C[S](C)(Br)=CC(C1=CC=C(C(F)(F)F)C=C1)=O AHMQSPZRVXTSRD-UHFFFAOYSA-N 0.000 claims 1
- RAGAFKCILNOUPG-UHFFFAOYSA-N C[S](C)(Br)=CC(C1CC1)=O Chemical compound C[S](C)(Br)=CC(C1CC1)=O RAGAFKCILNOUPG-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 6
- 150000003457 sulfones Chemical class 0.000 abstract description 5
- 229940079593 drug Drugs 0.000 abstract description 4
- 239000008204 material by function Substances 0.000 abstract description 3
- 239000000575 pesticide Substances 0.000 abstract description 3
- 208000024827 Alzheimer disease Diseases 0.000 abstract description 2
- 206010006187 Breast cancer Diseases 0.000 abstract description 2
- 208000026310 Breast neoplasm Diseases 0.000 abstract description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 2
- 229960002472 eletriptan Drugs 0.000 abstract description 2
- 239000003540 gamma secretase inhibitor Substances 0.000 abstract description 2
- 230000002363 herbicidal effect Effects 0.000 abstract description 2
- 239000004009 herbicide Substances 0.000 abstract description 2
- 239000002917 insecticide Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 201000008482 osteoarthritis Diseases 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract description 2
- YHKBGVDUSSWOAB-UHFFFAOYSA-N 2-chloro-3-{2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl]-4-fluorophenyl}propanoic acid Chemical compound O=C1N(C(F)F)C(C)=NN1C1=CC(CC(Cl)C(O)=O)=C(Cl)C=C1F YHKBGVDUSSWOAB-UHFFFAOYSA-N 0.000 abstract 1
- 230000002460 anti-migrenic effect Effects 0.000 abstract 1
- PWVXXGRKLHYWKM-LJQANCHMSA-N eletriptan Chemical compound CN1CCC[C@@H]1CC(C1=C2)=CNC1=CC=C2CCS(=O)(=O)C1=CC=CC=C1 PWVXXGRKLHYWKM-LJQANCHMSA-N 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 62
- 239000011734 sodium Substances 0.000 description 31
- 239000007787 solid Substances 0.000 description 20
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 11
- 239000003921 oil Substances 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- MRLUWCIEBHJONW-UHFFFAOYSA-N 1-phenyl-2-phenylsulfanylethanone Chemical compound C=1C=CC=CC=1C(=O)CSC1=CC=CC=C1 MRLUWCIEBHJONW-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000012230 colorless oil Substances 0.000 description 3
- DREVPGKOIZVPQV-UHFFFAOYSA-N 2-(benzenesulfonyl)-1-phenylethanone Chemical compound C=1C=CC=CC=1C(=O)CS(=O)(=O)C1=CC=CC=C1 DREVPGKOIZVPQV-UHFFFAOYSA-N 0.000 description 2
- WZOFQWMKQRSDCS-UHFFFAOYSA-N C1(=CC=CC=C1)C(C(SCCC)S(=O)(=O)C1=CC=CC=C1)=O Chemical compound C1(=CC=CC=C1)C(C(SCCC)S(=O)(=O)C1=CC=CC=C1)=O WZOFQWMKQRSDCS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- DJPMFFUIZSGZPG-UHFFFAOYSA-N 1-bromo-4-phenylsulfanylsulfonylbenzene Chemical compound Brc1ccc(cc1)S(=O)(=O)Sc1ccccc1 DJPMFFUIZSGZPG-UHFFFAOYSA-N 0.000 description 1
- OZBQHMNNLSUKDP-UHFFFAOYSA-N 1-chloro-4-phenylsulfanylsulfonylbenzene Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)SC1=CC=CC=C1 OZBQHMNNLSUKDP-UHFFFAOYSA-N 0.000 description 1
- OZPCZSITCIWWJA-UHFFFAOYSA-N 1-fluoro-4-phenylsulfanylsulfonylbenzene Chemical compound Fc1ccc(cc1)S(=O)(=O)Sc1ccccc1 OZPCZSITCIWWJA-UHFFFAOYSA-N 0.000 description 1
- GUZLFPYGIFRQQG-UHFFFAOYSA-N 2-(benzenesulfonyl)-1-phenyl-2-phenylsulfanylethanone Chemical compound O=C(C(Sc1ccccc1)S(=O)(=O)c1ccccc1)c1ccccc1 GUZLFPYGIFRQQG-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- IDGOWCMMGLQYJY-UHFFFAOYSA-N COC(C=C1)=CC=C1SC(C(C1=CC=CC=C1)=O)S(C1=CC=CC=C1)(=O)=O Chemical compound COC(C=C1)=CC=C1SC(C(C1=CC=CC=C1)=O)S(C1=CC=CC=C1)(=O)=O IDGOWCMMGLQYJY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GODGVECPKUATJL-UHFFFAOYSA-N O=C(C(SC1=CC=CC=C1)S(C1=CC=CC=C1)(=O)=O)C(C=C1)=CC=C1F Chemical compound O=C(C(SC1=CC=CC=C1)S(C1=CC=CC=C1)(=O)=O)C(C=C1)=CC=C1F GODGVECPKUATJL-UHFFFAOYSA-N 0.000 description 1
- MMANPHRHTHGEEW-UHFFFAOYSA-N O=C(C(SC1=CC=CC=C1)S(C1=CC=CC=C1)(=O)=O)C1CC1 Chemical compound O=C(C(SC1=CC=CC=C1)S(C1=CC=CC=C1)(=O)=O)C1CC1 MMANPHRHTHGEEW-UHFFFAOYSA-N 0.000 description 1
- KOQSDYJSCCHNAP-UHFFFAOYSA-N O=C(C(SC1=NC=CC=C1)S(C(C=C1)=CC=C1Br)(=O)=O)C1=CC=CC=C1 Chemical compound O=C(C(SC1=NC=CC=C1)S(C(C=C1)=CC=C1Br)(=O)=O)C1=CC=CC=C1 KOQSDYJSCCHNAP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000006981 Stevens rearrangement reaction Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940124433 antimigraine drug Drugs 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- OTLDLQZJRFYOJR-LJQANCHMSA-N eletriptan Chemical compound CN1CCC[C@@H]1CC1=CN=C2[C]1C=C(CCS(=O)(=O)C=1C=CC=CC=1)C=C2 OTLDLQZJRFYOJR-LJQANCHMSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
砜作为一种重要的有机中间体，广泛存在与药物中，如治疗抗偏头痛药物依来曲普坦、治疗乳腺癌的阿多醌、治疗骨关节炎的依他昔布，以及用于用于预防阿尔茨海默氏病的药物γ‑分泌酶抑制剂都含有砜的结构单元。因砜类化合物具有很好的抗菌活性，因此在有机农药方面也有所应用，例如除草剂唑草胺和杀虫剂氧化萎锈灵。此外在新型功能材料方面，多元二芳砜分子具有特殊的光物理性质，在发光二极管材料中也具有广阔的用途。本专利开发了一种简便高效的芳甲酰亚甲基二甲基溴化硫和硫代磺酸酯双官能团化反应一步合成β‑酮硫代砜类化合物的方法，此方法以中等至良好的产率获得产物，且底物范围宽、官能团耐受性高，具有很好的适用性。As an important organic intermediate, sulfone is widely used in drugs, such as eletriptan for the treatment of anti-migraine, adoquinone for the treatment of breast cancer, etacoxib for the treatment of osteoarthritis, and Drugs for the prevention of Alzheimer's disease γ-secretase inhibitors all contain sulfone structural units. Because sulfone compounds have good antibacterial activity, they are also used in organic pesticides, such as the herbicide carfentrazone and the insecticide oxycarboxyl. In addition, in terms of new functional materials, polyvalent diaryl sulfone molecules have special photophysical properties and have broad applications in light-emitting diode materials. This patent has developed a simple and efficient method for the one-step synthesis of β-ketonethiosulfone compounds through the bifunctional reaction of araformylmethylene dimethyl sulfur bromide and thiosulfonate. This method has a moderate to good The product is obtained in high yield, and has a wide substrate range and high functional group tolerance, which has good applicability.
Description
技术领域technical field
该专利涉及有机合成、药物合成、有机化工的研究领域，具体的方法是从芳甲酰亚甲基二甲基溴化硫和硫代磺酸酯的在碳酸钠的作用下进行双官能团化反应一步合成β-酮硫代砜类化合物。The patent involves the research fields of organic synthesis, drug synthesis, and organic chemical industry. The specific method is to carry out the bifunctional reaction of aromethylene dimethyl sulfur bromide and thiosulfonate under the action of sodium carbonate. One-step synthesis of β-ketothiosulfones.
背景技术Background technique
砜类化合物是一种常见的有机中间体，在医药、农药以及新型功能材料等领域中都扮演着极其重要的角色。在医药方面，例如用于治疗抗偏头痛药物依来曲普坦、治疗乳腺癌的阿多醌、治疗骨关节炎的依他昔布(Ye.S,Yang.M,Wu.J,Chem.Commun.2020,56,4145-4155.)，以及用于用于预防阿尔茨海默氏病的药物γ-分泌酶抑制剂(I.Churcher,D.Beher,J.D.Best,J.L.Castro,E.E.Clarke,A.Gentry,T.Harrison,L.Hitzel,E.Kay,S.Kerrad,H.D.Lewis,P.M.Gutierrez,R.M.Smith,P.J.Oakley,M.Reilly,D.E.Shaw,M.S.Shearman,M.R.Teall,S.Williams and J.D.J.Wrigley,Bioorg.Med.Chem.Lett.,2006,16,280.)均含有砜的单元结构。在有机农药方面，砜类化合物具有很好的抗菌活性，例如除草剂唑草胺(G.Mitchell,D.W.Bartlett,T.E.M.Fraser,T.R.Hawkes,D.C.Holt,J.K.Townson,R.A.Wichert,Pest Manag.Sci.2001,57,120-128.)、异唑草酮(S.Taylor-Lovell,G.K.Sims,L.M.Wax,J.Agr.Food.Chem.2002,50,5626-5633.)、杀虫剂氧化萎锈灵(K.Hustert,P.N.Moza,A.Kettrup,Chemosphere.1999,38,3423-3429.)。在新型功能材料方面，多元二芳砜分子具有特殊的光物理性质，在发光二极管材料中具有广阔的用途(G.Barbarella,L.Favaretto,A.Zanelli,G.Gigli,G.M.Mazzeo,M.Anni,A.Bongini,Adv.Funct.Mater.2005,15,664-670.)。砜也常被用作有机合成的重要中间体(N.S.Simpkins,Sulfones in Organic Synthesis；Pergamon Press:Oxford,1993.)。基于此重要性，拓展新的砜类化合物的合成方法具有极大的价值。Sulfone compounds are common organic intermediates that play an extremely important role in the fields of medicine, pesticides and new functional materials. In medicine, such as eletriptan for the treatment of anti-migraine drugs, adoquinone for the treatment of breast cancer, etacoxib for the treatment of osteoarthritis (Ye.S, Yang.M, Wu.J, Chem. Commun.2020,56,4145-4155.), and drug gamma-secretase inhibitors for the prevention of Alzheimer's disease (I.Churcher, D.Beher, J.D.Best, J.L.Castro, E.E.Clarke, A. Gentry, T. Harrison, L. Hitzel, E. Kay, S. Kerrad, H.D. Lewis, P.M. Gutierrez, R.M. Smith, P.J. Oakley, M. Reilly, D.E. Shaw, M.S. Shearman, M.R. Teall, S. Williams and J.D.J. Wrigley, Bioorg. Med. Chem. Lett., 2006, 16, 280.) all contain a sulfone unit structure. In terms of organic pesticides, sulfone compounds have good antibacterial activity, such as the herbicide mefentrazone (G.Mitchell, D.W.Bartlett, T.E.M.Fraser, T.R.Hawkes, D.C.Holt, J.K.Townson, R.A.Wichert, Pest Manag.Sci.2001 , 57, 120-128.), isoxaflumele (S.Taylor-Lovell, G.K.Sims, L.M.Wax, J.Agr.Food.Chem.2002, 50, 5626-5633.), the insecticide oxidized carboxyl ( K. Hustert, P.N. Moza, A. Kettrup, Chemosphere. 1999, 38, 3423-3429.). In terms of new functional materials, polyvalent diaryl sulfone molecules have special photophysical properties and have broad applications in light-emitting diode materials (G.Barbarella, L.Favaretto, A.Zanelli, G.Gigli, G.M.Mazzeo, M.Anni , A. Bongini, Adv. Funct. Mater. 2005, 15, 664-670.). Sulfones are also often used as important intermediates in organic synthesis (N.S. Simpkins, Sulfones in Organic Synthesis; Pergamon Press: Oxford, 1993.). Based on this importance, it is of great value to expand the synthetic methods of new sulfone compounds.
合成β-酮硫代砜主要有以下几种方法：(1)通过铜/二联吡啶配合物催化重氮乙酸芳基酯和硫叶立德的stevens重排反应(H.Yuan,T.Nuligonda,H.Gao,C.H.Tung,Z.Xu,Org.Chem.Front.2018,5,1371-1374.)。(2)铜催化烯烃的氧化三官能化反应(S.Huang,N.Thirupathi,C.H.Tung,Z.Xu,J.Org.Chem.2018,83,9449-9455.)。(3)硫代磺酸盐和氧硫叶立德的串联自由基反应(F.Wang,B.X.Liu,W.Rao,S.Y.Wang,Org.Lett.2020,22,6600-6604.)。上述各种合成β-酮硫代砜的方法存在需要金属催化，原料不易制备、操作繁琐等缺点，因此开发高效、便捷的合成砜类化合物的新方法具有极大的意义。Synthesis of β-ketothiosulfone mainly has the following methods: (1) catalyzing the stevens rearrangement of aryl diazoacetate and sulfur ylide by copper/bipyridine complex (H.Yuan, T.Nuligonda, H . Gao, C.H. Tung, Z. Xu, Org. Chem. Front. 2018, 5, 1371-1374.). (2) Copper-catalyzed oxidative trifunctionalization of alkenes (S. Huang, N. Thirupathi, C.H. Tung, Z. Xu, J. Org. Chem. 2018, 83, 9449-9455.). (3) Tandem radical reaction of thiosulfonate and oxysulfide ylides (F.Wang, B.X.Liu, W.Rao, S.Y.Wang, Org. Lett. 2020, 22, 6600-6604.). The above-mentioned methods for the synthesis of β-ketothiosulfones have the disadvantages of requiring metal catalysis, difficult preparation of raw materials, and cumbersome operations. Therefore, it is of great significance to develop new methods for the synthesis of sulfone compounds that are efficient and convenient.
我们在此报告了一种芳甲酰亚甲基二甲基溴化硫和硫代磺酸酯的双官能团化反应，开发了一种新的β-酮硫代砜类化合物的合成方法。We report here a bifunctionalization reaction of arylformylmethylene dimethylsulfur bromide and thiosulfonate and develop a new synthetic method for β-ketothiosulfones.
尽我们所知，未见与本申请相同的文献报道。As far as we know, there is no similar bibliographical report with the present application.
发明内容Contents of the invention
本发明提供β-酮硫代砜类化合物的合成方法。The invention provides a method for synthesizing β-ketothiosulfone compounds.
本发明公开的β-酮硫代砜类化合物合成方法均一步完成，即在乙腈的溶液条件下，以碳酸钠为碱，芳甲酰亚甲基二甲基溴化硫与硫代磺酸酯发生双官能团化反应一步合成β-酮硫代砜类化合物，反应方程式如下所示。The synthesis method of β-ketothiosulfone compounds disclosed by the present invention is all completed in one step, that is, under the solution condition of acetonitrile, using sodium carbonate as base, aromethylene dimethyl sulfur bromide and thiosulfonate A bifunctional reaction occurs to synthesize β-ketothiosulfone compounds in one step, and the reaction equation is shown below.
结合下面的实施例,更详细地阐述本发明，但并不认为它们是对本发明范围的限制。In conjunction with the following examples, the present invention is described in more detail, but they are not considered to limit the scope of the present invention.
具体实施方式Detailed ways
实施例一Embodiment one
向装有搅拌子的25mL玻璃试管中加入苯甲酰亚甲基二甲基溴化硫(0.6mmol)，S-苯基硫代苯磺酸酯(0.5mmol,碳酸钠(4当量)，5mL乙腈，最后用橡皮塞密封磨口试管。在氮气氛围下用预热的80℃油浴锅将试管搅拌4h，之后将反应混合物冷却至室温。然后向反应混合物中加入饱和氯化钠溶液(10mL)淬灭，用乙酸乙酯(15mL)萃取3次，并将合并的有机层用无水MgSO4干燥，然后在旋转蒸发仪上用碱性氧化铝吸附干燥。残余物通过硅胶快速柱色谱纯化(石油醚：乙酸乙酯＝10∶1-5：1用作洗脱剂)，纯化后，得到1-苯基-2-(苯磺酰基)-2-(苯硫基)乙烷-1-酮为白色固体，产率为82％。Add benzoyl dimethylsulfur bromide (0.6mmol), S-phenylthiobenzenesulfonate (0.5mmol, sodium carbonate (4 equivalents), 5mL Acetonitrile, and finally seal the ground test tube with a rubber stopper. The test tube was stirred for 4h with a preheated 80°C oil bath under a nitrogen atmosphere, and then the reaction mixture was cooled to room temperature. Then a saturated sodium chloride solution (10 mL ), extracted 3 times with ethyl acetate (15 mL), and the combined organic layers were dried over anhydrous MgSO , and then dried by adsorption on a rotary evaporator with basic alumina. The residue was purified by flash column chromatography on silica gel (Petroleum ether: ethyl acetate = 10:1-5:1 used as eluent), after purification, 1-phenyl-2-(benzenesulfonyl)-2-(phenylthio)ethane-1 - The ketone was a white solid in 82% yield.
产物1-苯基-2-(苯磺酰基)-2-(苯硫基)乙烷-1-酮的结构表征数据如下：The structural characterization data of the product 1-phenyl-2-(benzenesulfonyl)-2-(phenylthio)ethan-1-one are as follows:
1H NMR(400MHz,Chloroform-d)δ8.05–7.97(m,2H),7.91–7.83(m,2H),7.70–7.64(m,1H),7.63–7.57(m,1H),7.57–7.41(m,6H),7.37–7.22(m,3H),5.82(s,1H). 1 H NMR (400MHz, Chloroform-d) δ8.05–7.97(m,2H),7.91–7.83(m,2H),7.70–7.64(m,1H),7.63–7.57(m,1H),7.57– 7.41(m,6H),7.37–7.22(m,3H),5.82(s,1H).
13C NMR(101MHz,Chloroform-d)δ189.3,136.3,135.1,134.5,134.4,133.6,132.1,130.7,129.5,129.4,129.2,128.9,128.7,75.6. 13 C NMR (101MHz, Chloroform-d) δ189.3, 136.3, 135.1, 134.5, 134.4, 133.6, 132.1, 130.7, 129.5, 129.4, 129.2, 128.9, 128.7, 75.6.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C20H16NaO3S2 +:391.0433；found:391.0443.实施例二HRMS (ESI-TOF): m/z[M+Na] + calcd for C 20 H 16 NaO 3 S 2 + : 391.0433; found: 391.0443. Example two
4-(氟)苯甲酰亚甲基二甲基溴化硫代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到白色固体1-(4-氟苯基)-2-(苯磺酰基)-2-(苯硫基)乙烷-1-酮为88％。4-(Fluoro)benzoyl dimethyl sulfur bromide replaces the benzoyl dimethyl sulfur bromide in Example 1 to obtain a white solid 1-(4-fluorophenyl)-2 -(Benzenesulfonyl)-2-(phenylthio)ethan-1-one was 88%.
1H NMR(400MHz,Chloroform-d)δ7.91(d,J＝7.4Hz,2H),7.88–7.81(m,2H),7.59(t,J＝7.5Hz,1H),7.46(t,J＝7.8Hz,2H),7.42–7.36(m,2H),7.22(tq,J＝12.7,6.7,5.9Hz,3H),7.04(t,J＝8.5Hz,2H),5.66(s,1H). 1 H NMR (400MHz, Chloroform-d) δ7.91(d, J=7.4Hz, 2H), 7.88–7.81(m, 2H), 7.59(t, J=7.5Hz, 1H), 7.46(t, J =7.8Hz,2H),7.42–7.36(m,2H),7.22(tq,J=12.7,6.7,5.9Hz,3H),7.04(t,J=8.5Hz,2H),5.66(s,1H) .
13C NMR(101MHz,Chloroform-d)δ187.8,166.5(d,J＝257.8Hz),136.2,134.6,133.6,132.2(d,J＝9.7Hz),132.0,131.5(d,J＝2.9Hz),130.7,129.5(d,J＝5.5Hz),128.8,116.2(d,J＝22.2Hz),75.9. 13 C NMR (101MHz, Chloroform-d) δ187.8, 166.5 (d, J = 257.8Hz), 136.2, 134.6, 133.6, 132.2 (d, J = 9.7Hz), 132.0, 131.5 (d, J = 2.9Hz), 130.7, 129.5 (d, J=5.5Hz), 128.8, 116.2 (d, J=22.2Hz), 75.9.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C20H15FNaO3S2 +:409.0339；found:409.0370.实施例三HRMS (ESI-TOF): m/z[M+Na] + calcd for C 20 H 15 FNaO 3 S 2 + : 409.0339; found: 409.0370. Example three
4-(氯)苯甲酰亚甲基二甲基溴化硫代替代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到黄色油1-(4-氯苯基)-2-(苯磺酰基)-2-(苯硫基)乙烷-1-酮产率为75％。4-(Chloro) benzoyl dimethyl sulfur bromide replaces the benzoyl dimethyl sulfur bromide in Example 1 to obtain yellow oil 1-(4-chlorophenyl)- The yield of 2-(phenylsulfonyl)-2-(phenylthio)ethan-1-one was 75%.
1H NMR(400MHz,Chloroform-d)δ8.03–7.97(m,2H),7.86–7.81(m,2H),7.72–7.66(m,1H),7.55(t,J＝7.8Hz,2H),7.45(ddd,J＝16.5,7.3,1.5Hz,4H),7.37–7.27(m,3H),5.72(s,1H). 1 H NMR (400MHz, Chloroform-d) δ8.03–7.97(m,2H),7.86–7.81(m,2H),7.72–7.66(m,1H),7.55(t,J=7.8Hz,2H) ,7.45(ddd,J＝16.5,7.3,1.5Hz,4H),7.37–7.27(m,3H),5.72(s,1H).
13C NMR(101MHz,Chloroform-d)δ188.2,141.1,136.2,134.6,133.6,133.4,131.9,130.7,129.6,129.5,129.3,128.8,128.6,75.9. 13 C NMR (101MHz, Chloroform-d) δ188.2, 141.1, 136.2, 134.6, 133.6, 133.4, 131.9, 130.7, 129.6, 129.5, 129.3, 128.8, 128.6, 75.9.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C20H15ClNaO3S2 +:425.0043；found:425.0060.实施例四HRMS (ESI-TOF): m/z[M+Na] + calcd for C 20 H 15 ClNaO 3 S 2 + : 425.0043; found: 425.0060. Example 4
4-(溴)苯甲酰亚甲基二甲基溴化硫代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到白色固体1-(4-溴苯基)-2-(苯磺酰基)-2-(苯硫基)乙烷-1-酮产率为75％。4-(bromo)benzoyl dimethyl sulfur bromide replaces the benzoyl dimethyl sulfur bromide in Example 1 to obtain white solid 1-(4-bromophenyl)-2 The yield of -(phenylsulfonyl)-2-(phenylthio)ethan-1-one was 75%.
1H NMR(400MHz,Chloroform-d)δ7.96–7.87(m,2H),7.69–7.63(m,2H),7.62–7.56(m,1H),7.54–7.43(m,4H),7.41–7.35(m,2H),7.22(ddd,J＝12.7,7.9,6.1Hz,3H),5.64(s,1H). 1 H NMR (400MHz, Chloroform-d) δ7.96–7.87(m,2H),7.69–7.63(m,2H),7.62–7.56(m,1H),7.54–7.43(m,4H),7.41– 7.35(m,2H),7.22(ddd,J=12.7,7.9,6.1Hz,3H),5.64(s,1H).
13C NMR(101MHz,Chloroform-d)δ188.4,136.2,134.6,133.8,133.6,132.3,131.8,130.7,130.7,130.0,129.6,129.6,128.8,75.8. 13 C NMR (101MHz, Chloroform-d) δ188.4, 136.2, 134.6, 133.8, 133.6, 132.3, 131.8, 130.7, 130.7, 130.0, 129.6, 129.6, 128.8, 75.8.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C20H15BrNaO3S2 +:468.9538；found:468.9535实施例五HRMS (ESI-TOF): m/z[M+Na] + calcd for C 20 H 15 BrNaO 3 S 2 + : 468.9538; found: 468.9535 Example five
4-(氰基)苯甲酰亚甲基二甲基溴化硫代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到4-(2-(苯磺酰基)-2-(苯硫基)乙酰基)苄腈产率为62％。4-(cyano) benzoyl dimethyl sulfur bromide replaces benzoyl dimethyl sulfur bromide in Example 1 to obtain 4-(2-(benzenesulfonyl)-2 The yield of -(phenylthio)acetyl)benzonitrile was 62%.
1H NMR(400MHz,Chloroform-d)δ8.03–7.97(m,4H),7.80–7.68(m,3H),7.58(t,J＝7.7Hz,2H),7.47–7.41(m,2H),7.39–7.25(m,3H),5.72(s,1H). 1 H NMR (400MHz, Chloroform-d) δ8.03–7.97(m,4H),7.80–7.68(m,3H),7.58(t,J=7.7Hz,2H),7.47–7.41(m,2H) ,7.39–7.25(m,3H),5.72(s,1H).
13C NMR(101MHz,Chloroform-d)δ187.2,136.9,135.0,133.8,132.6,131.6,130.5,130.4,129.6,128.7,128.6,127.9,116.6,116.4,74.9. 13 C NMR (101MHz, Chloroform-d) δ187.2, 136.9, 135.0, 133.8, 132.6, 131.6, 130.5, 130.4, 129.6, 128.7, 128.6, 127.9, 116.6, 116.4, 74.9.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C21H15NNaO3S2 +:416.0386；found:416.0378.实施例六HRMS (ESI-TOF): m/z[M+Na] + calcd for C 21 H 15 NNaO 3 S 2 + : 416.0386; found: 416.0378. Embodiment six
4-(硝基)苯甲酰亚甲基二甲基溴化硫代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到红色固体1-(4-硝基苯基)-2-(苯磺酰基)-2-(苯硫基)乙烷-1-酮产率为63％。4-(nitro)benzoyl dimethyl sulfur bromide replaces the benzoyl dimethyl sulfur bromide in Example 1 to obtain a red solid 1-(4-nitrophenyl) The yield of -2-(benzenesulfonyl)-2-(phenylthio)ethan-1-one was 63%.
1H NMR(400MHz,Chloroform-d)δ7.95–7.88(m,2H),7.87–7.81(m,2H),7.59(td,J＝7.3,1.3Hz,1H),7.46(t,J＝7.9Hz,2H),7.41–7.36(m,2H),7.28–7.16(m,3H),7.09–6.99(m,2H),5.67(s,1H). 1 H NMR (400MHz, Chloroform-d) δ7.95–7.88(m,2H),7.87–7.81(m,2H),7.59(td,J=7.3,1.3Hz,1H),7.46(t,J= 7.9Hz,2H),7.41–7.36(m,2H),7.28–7.16(m,3H),7.09–6.99(m,2H),5.67(s,1H).
13C NMR(101MHz,Chloroform-d)δ187.8,167.8,165.2,136.2,134.6,133.6,132.2(d,J＝9.8Hz),132.0,131.5(d,J＝3.0Hz),130.7,129.5(d,J＝5.4Hz),128.8,116.2(d,J＝22.1Hz),75.9. 13 C NMR (101MHz, Chloroform-d) δ187.8, 167.8, 165.2, 136.2, 134.6, 133.6, 132.2(d, J=9.8Hz), 132.0, 131.5(d, J=3.0Hz), 130.7, 129.5(d, J=5.4Hz), 128.8, 116.2(d, J=22.1Hz), 75.9.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C20H15NNaO5S2 +:436.0284；found:436.0278.实施例七HRMS (ESI-TOF): m/z[M+Na] + calcd for C 20 H 15 NNaO 5 S 2 + : 436.0284; found: 436.0278. Example 7
4-(三氟甲基)苯甲酰亚甲基二甲基溴化硫代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到黄色固体2-(苯磺酰基)-2-(苯硫基)-1-(4-(三氟甲基)苯基)乙烷-1-酮产率为61％。4-(trifluoromethyl)benzoyl dimethyl sulfur bromide replaces the benzoyl dimethyl sulfur bromide in Example 1 to obtain a yellow solid 2-(benzenesulfonyl)- The yield of 2-(phenylthio)-1-(4-(trifluoromethyl)phenyl)ethan-1-one was 61%.
1H NMR(400MHz,Chloroform-d)δ8.05–7.98(m,4H),7.76–7.67(m,3H),7.57(dd,J＝8.4,7.2Hz,2H),7.50–7.43(m,2H),7.39–7.27(m,3H),5.76(s,1H). 1 H NMR (400MHz, Chloroform-d) δ8.05–7.98(m,4H),7.76–7.67(m,3H),7.57(dd,J＝8.4,7.2Hz,2H),7.50–7.43(m, 2H),7.39–7.27(m,3H),5.76(s,1H).
13C NMR(101MHz,Chloroform-d)δ188.5,137.7,136.2,135.5,135.2,134.7,133.6,131.6,130.7,129.7,129.6,128.9,125.98,125.95,125.9,125.9,75.9. 13 C NMR (101MHz, Chloroform-d) δ188.5, 137.7, 136.2, 135.5, 135.2, 134.7, 133.6, 131.6, 130.7, 129.7, 129.6, 128.9, 125.98, 125.95, 125.9, 125.9, 75.9.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C21H15F3NaO3S2 +:459.0307；found:459.0328.实施例八HRMS (ESI-TOF): m/z[M+Na] + calcd for C 21 H 15 F 3 NaO 3 S 2 + : 459.0307; found: 459.0328. Example 8
4-(三氟甲氧基)苯甲酰亚甲基二甲基溴化硫代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到白色固体2-(苯磺酰基)-2-(苯硫基)-1-(4-(三氟甲氧基)苯基)乙烷-1-酮产率为75％。4-(trifluoromethoxy) benzoyl dimethyl sulfur bromide replaces the benzoyl dimethyl sulfur bromide in Example 1 to obtain a white solid 2-(benzenesulfonyl) The yield of -2-(phenylthio)-1-(4-(trifluoromethoxy)phenyl)ethan-1-one was 75%.
1H NMR(400MHz,Chloroform-d)δ8.07–7.96(m,4H),7.71(t,J＝7.5Hz,1H),7.58(t,J＝7.8Hz,2H),7.53–7.47(m,2H),7.41–7.27(m,5H),5.78(s,1H). 1 H NMR (400MHz, Chloroform-d) δ8.07–7.96(m, 4H), 7.71(t, J=7.5Hz, 1H), 7.58(t, J=7.8Hz, 2H), 7.53–7.47(m ,2H),7.41–7.27(m,5H),5.78(s,1H).
13C NMR(101MHz,Chloroform-d)δ187.9,153.5(d,J＝1.7Hz),136.2,134.6,133.6,133.1,131.9,131.5,130.7,129.6(d,J＝2.8Hz),128.8,121.5,120.4,119.0,75.9. 13 C NMR (101MHz, Chloroform-d) δ187.9, 153.5 (d, J=1.7Hz), 136.2, 134.6, 133.6, 133.1, 131.9, 131.5, 130.7, 129.6 (d, J=2.8Hz), 128.8, 121.5, 120.4, 119.0, 75.9.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C21H15F3NaO4S2 +:475.0256；found:475.0249.实施例九HRMS (ESI-TOF): m/z[M+Na] + calcd for C 21 H 15 F 3 NaO 4 S 2 + : 475.0256; found: 475.0249. Example 9
4-(甲氧基)苯甲酰亚甲基二甲基溴化硫代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到黄色油1-(4-甲氧基苯基)-2-(苯磺酰基)-2-(苯硫基)乙烷-1-酮产率为64％。4-(Methoxy) benzoyl dimethyl sulfur bromide replaces benzoyl dimethyl sulfur bromide in Example 1 to obtain yellow oil 1-(4-methoxybenzene The yield of -2-(phenylsulfonyl)-2-(phenylthio)ethan-1-one was 64%.
1H NMR(400MHz,Chloroform-d)δ8.01–7.96(m,2H),7.91–7.85(m,2H),7.65(d,J＝7.5Hz,1H),7.58–7.44(m,4H),7.35–7.25(m,3H),6.97–6.87(m,2H),5.78(s,1H),3.86(s,3H). 1 H NMR (400MHz, Chloroform-d) δ8.01–7.96(m,2H),7.91–7.85(m,2H),7.65(d,J=7.5Hz,1H),7.58–7.44(m,4H) ,7.35–7.25(m,3H),6.97–6.87(m,2H),5.78(s,1H),3.86(s,3H).
13C NMR(101MHz,Chloroform-d)δ187.6,164.7,136.4,134.4,133.5,132.4,131.9,130.7,129.5,129.3,128.7,128.0,114.2,75.7,55.7. 13 C NMR (101MHz, Chloroform-d) δ187.6, 164.7, 136.4, 134.4, 133.5, 132.4, 131.9, 130.7, 129.5, 129.3, 128.7, 128.0, 114.2, 75.7, 55.7.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C21H18NaO4S2 +:421.0539；found:421.0560.实施例十HRMS (ESI-TOF): m/z[M+Na] + calcd for C 21 H 18 NaO 4 S 2 + : 421.0539; found: 421.0560. Example 10
4-(苯基)苯甲酰亚甲基二甲基溴化硫代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到白色固体1-([1,1'-联苯]-4-基)-2-(苯磺酰基)-2-(苯硫基)乙烷-1-酮产率为91％。4-(Phenyl) benzoyl dimethyl sulfur bromide replaces the benzoyl dimethyl sulfur bromide in Example 1 to obtain a white solid 1-([1,1'-linked The yield of phenyl]-4-yl)-2-(benzenesulfonyl)-2-(phenylthio)ethan-1-one was 91%.
1H NMR(400MHz,Chloroform-d)δ8.09–8.04(m,2H),8.03–7.97(m,2H),7.74–7.69(m,3H),7.65(dt,J＝8.3,1.9Hz,2H),7.62–7.54(m,4H),7.54–7.48(m,2H),7.47–7.42(m,1H),7.41–7.32(m,3H),5.87(s,1H). 1 H NMR (400MHz, Chloroform-d) δ8.09–8.04 (m, 2H), 8.03–7.97 (m, 2H), 7.74–7.69 (m, 3H), 7.65 (dt, J＝8.3, 1.9Hz, 2H),7.62–7.54(m,4H),7.54–7.48(m,2H),7.47–7.42(m,1H),7.41–7.32(m,3H),5.87(s,1H).
13C NMR(101MHz,Chloroform-d)δ188.8,147.1,139.4,136.3,134.5,133.7,133.6,132.3,130.8,129.9,129.5,129.4,129.1,128.7,128.7,127.5,127.4,75.8. 13 C NMR (101MHz, Chloroform-d) δ188.8, 147.1, 139.4, 136.3, 134.5, 133.7, 133.6, 132.3, 130.8, 129.9, 129.5, 129.4, 129.1, 128.7, 128.7, 127.5, 127.4, 75.8.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C26H20NaO3S2 +:467.0746；found:467.0747.实施例十一HRMS (ESI-TOF): m/z[M+Na] + calcd for C 26 H 20 NaO 3 S 2 + : 467.0746; found: 467.0747. Embodiment 11
3-(溴)苯甲酰亚甲基二甲基溴化硫代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到白色固体1-(3-溴苯基)-2-(苯磺酰基)-2-(苯硫基)乙烷-1-酮产率为85％。3-(Bromo) benzoyl dimethyl sulfur bromide replaces benzoyl dimethyl sulfur bromide in Example 1 to obtain white solid 1-(3-bromophenyl)-2 The yield of -(phenylsulfonyl)-2-(phenylthio)ethan-1-one was 85%.
1H NMR(400MHz,Chloroform-d)δ8.01(d,J＝7.5Hz,2H),7.96(t,J＝1.6Hz,1H),7.80(d,J＝7.9Hz,1H),7.75–7.66(m,2H),7.57(t,J＝7.8Hz,2H),7.51–7.47(m,2H),7.40–7.29(m,4H),5.70(s,1H). 1 H NMR (400MHz, Chloroform-d) δ8.01 (d, J = 7.5Hz, 2H), 7.96 (t, J = 1.6Hz, 1H), 7.80 (d, J = 7.9Hz, 1H), 7.75– 7.66(m,2H),7.57(t,J=7.8Hz,2H),7.51–7.47(m,2H),7.40–7.29(m,4H),5.70(s,1H).
13C NMR(101MHz,Chloroform-d)δ188.1,137.2,136.8,136.2,134.7,133.7,132.0,131.7,130.7,130.4,129.7,129.6,128.8,127.8,123.2,75.7. 13 C NMR (101MHz, Chloroform-d) δ188.1, 137.2, 136.8, 136.2, 134.7, 133.7, 132.0, 131.7, 130.7, 130.4, 129.7, 129.6, 128.8, 127.8, 123.2, 75.7.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C20H15BrNaO3S2 +:468.9538；found:468.9544.实施例十二HRMS (ESI-TOF): m/z[M+Na] + calcd for C 20 H 15 BrNaO 3 S 2 + : 468.9538; found: 468.9544. Example 12
3-(氯)苯甲酰亚甲基二甲基溴化硫代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到无色油1-(3-氯苯基)-2-(苯磺酰基)-2-(苯硫基)乙烷-1-酮产率为84％。3-(Chloro) benzoyl dimethyl sulfur bromide replaces benzoyl dimethyl sulfur bromide in Example 1 to obtain colorless oil 1-(3-chlorophenyl)- The yield of 2-(phenylsulfonyl)-2-(phenylthio)ethan-1-one was 84%.
1H NMR(400MHz,Chloroform-d)δ8.01(dd,J＝8.4,1.1Hz,2H),7.81(t,J＝1.8Hz,1H),7.76(dt,J＝7.8,1.3Hz,1H),7.69(tt,J＝7.1,1.2Hz,1H),7.56(td,J＝7.1,6.2,1.6Hz,3H),7.51–7.45(m,2H),7.41(d,J＝7.9Hz,1H),7.39–7.32(m,2H),7.32–7.27(m,1H),5.70(s,1H). 1 H NMR (400MHz, Chloroform-d) δ8.01(dd, J＝8.4, 1.1Hz, 2H), 7.81(t, J＝1.8Hz, 1H), 7.76(dt, J＝7.8, 1.3Hz, 1H ),7.69(tt,J=7.1,1.2Hz,1H),7.56(td,J=7.1,6.2,1.6Hz,3H),7.51–7.45(m,2H),7.41(d,J=7.9Hz, 1H),7.39–7.32(m,2H),7.32–7.27(m,1H),5.70(s,1H).
13C NMR(101MHz,Chloroform-d)δ188.2,136.6,136.2,135.3,134.7,134.3,133.7,131.8,130.7,130.2,129.6,129.6,129.1,128.8,127.3,75.7. 13 C NMR (101MHz, Chloroform-d) δ188.2, 136.6, 136.2, 135.3, 134.7, 134.3, 133.7, 131.8, 130.7, 130.2, 129.6, 129.6, 129.1, 128.8, 127.3, 75.7.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C20H15ClNaO3S2 +:425.0043；found:425.0025.实施例十三HRMS (ESI-TOF): m/z[M+Na] + calcd for C 20 H 15 ClNaO 3 S 2 + : 425.0043; found: 425.0025. Example 13
3-(甲氧基)苯甲酰亚甲基二甲基溴化硫代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到黄色油1-(3-甲氧基苯基)-2-(苯磺酰基)-2-(苯硫基)乙烷-1-酮产率产率为63％。3-(Methoxy) benzoyl dimethyl sulfur bromide replaces benzoyl dimethyl sulfur bromide in Example 1 to obtain yellow oil 1-(3-methoxybenzene The yield of -2-(phenylsulfonyl)-2-(phenylthio)ethan-1-one was 63%.
1H NMR(400MHz,Chloroform-d)δ8.09–8.01(m,2H),7.69(d,J＝7.4Hz,1H),7.61–7.50(m,4H),7.45(d,J＝7.7Hz,1H),7.42–7.29(m,5H),7.21–7.15(m,1H),5.81(s,1H),3.82(s,3H). 1 H NMR (400MHz, Chloroform-d) δ8.09–8.01(m,2H),7.69(d,J=7.4Hz,1H),7.61–7.50(m,4H),7.45(d,J=7.7Hz ,1H),7.42–7.29(m,5H),7.21–7.15(m,1H),5.81(s,1H),3.82(s,3H).
13C NMR(101MHz,Chloroform-d)δ189.1,160.0,136.4(d,J＝0.9Hz),134.5,133.6,132.2,130.8,129.9,129.5,129.4,128.7,121.8,121.3,113.1,75.6,55.5. 13 C NMR (101MHz, Chloroform-d) δ189.1, 160.0, 136.4 (d, J=0.9Hz), 134.5, 133.6, 132.2, 130.8, 129.9, 129.5, 129.4, 128.7, 121.8, 121.3, 113.1, 75.6, 55.5.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C21H18NaO4S2 +:421.0539；found:421.0532.实施例十四HRMS (ESI-TOF): m/z[M+Na] + calcd for C 21 H 18 NaO 4 S 2 + : 421.0539; found: 421.0532. Example 14
2-(甲氧基)苯甲酰亚甲基二甲基溴化硫代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到白色固体1-(2-甲氧基苯基)-2-(苯磺酰基)-2-(苯硫基)乙烷-1-酮产率为45％。2-(Methoxy) benzoyl dimethyl sulfur bromide replaces benzoyl dimethyl sulfur bromide in Example 1 to obtain white solid 1-(2-methoxybenzene The yield of -2-(phenylsulfonyl)-2-(phenylthio)ethan-1-one was 45%.
1H NMR(400MHz,Chloroform-d)δ8.07–8.00(m,2H),7.71–7.63(m,2H),7.60–7.46(m,5H),7.33(dd,J＝4.9,1.7Hz,3H),7.02(t,J＝7.5Hz,1H),6.87(d,J＝8.4Hz,1H),6.50(s,1H),3.54(s,3H). 1 H NMR (400MHz, Chloroform-d) δ8.07–8.00 (m, 2H), 7.71–7.63 (m, 2H), 7.60–7.46 (m, 5H), 7.33 (dd, J＝4.9, 1.7Hz, 3H), 7.02(t, J=7.5Hz, 1H), 6.87(d, J=8.4Hz, 1H), 6.50(s, 1H), 3.54(s, 3H).
13C NMR(101MHz,Chloroform-d)δ190.2,158.5,137.1,135.3,134.2,133.5,132.6,131.8,130.6,129.2,128.7,128.5,125.8,121.3,111.7,78.2,55.4. 13 C NMR (101MHz, Chloroform-d) δ190.2, 158.5, 137.1, 135.3, 134.2, 133.5, 132.6, 131.8, 130.6, 129.2, 128.7, 128.5, 125.8, 121.3, 111.7, 78.2, 55.4.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C21H18NaO4S2 +:421.0539；found:421.0538.实施例十五HRMS (ESI-TOF): m/z[M+Na] + calcd for C 21 H 18 NaO 4 S 2 + : 421.0539; found: 421.0538. Example 15
2，5-(二甲氧基)苯甲酰亚甲基二甲基溴化硫代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到黄色油1-(2,5-二甲氧基苯基)-2-(苯磺酰基)-2-(苯硫基)乙烷-1-酮产率为58％。2,5-(Dimethoxy) benzoyl dimethyl sulfur bromide replaces benzoyl dimethyl sulfur bromide in Example 1 to obtain yellow oil 1-(2,5 The yield of -dimethoxyphenyl)-2-(phenylsulfonyl)-2-(phenylthio)ethan-1-one was 58%.
1H NMR(400MHz,Chloroform-d)δ8.05–7.98(m,2H),7.65(tt,J＝6.9,1.2Hz,1H),7.58–7.50(m,4H),7.34–7.29(m,3H),7.21–7.14(m,1H),7.05(dd,J＝9.1,3.3Hz,1H),6.80(d,J＝9.1Hz,1H),6.57(s,1H),3.76(s,3H),3.48(s,3H). 1 H NMR (400MHz, Chloroform-d) δ8.05–7.98(m,2H),7.65(tt,J＝6.9,1.2Hz,1H),7.58–7.50(m,4H),7.34–7.29(m, 3H),7.21–7.14(m,1H),7.05(dd,J＝9.1,3.3Hz,1H),6.80(d,J＝9.1Hz,1H),6.57(s,1H),3.76(s,3H ),3.48(s,3H).
13C NMR(101MHz,Chloroform-d)δ189.7,153.7,153.2,137.1,134.2,133.4,132.6,130.7,129.2,128.7,128.5,125.7,122.5,114.5,113.3,78.0(d,J＝3.5Hz),55.8(d,J＝5.6Hz). 13 C NMR (101MHz, Chloroform-d) δ189.7, 153.7, 153.2, 137.1, 134.2, 133.4, 132.6, 130.7, 129.2, 128.7, 128.5, 125.7, 122.5, 114.5, 113.3, 78.0 (d, J=3.5Hz), 55.8(d,J=5.6Hz).
HRMS(ESI-TOF):m/z[M+Na]+calcd for C22H20NaO5S2 +:451.0644；found:451.0638.实施例十六HRMS (ESI-TOF): m/z[M+Na] + calcd for C 22 H 20 NaO 5 S 2 + : 451.0644; found: 451.0638. Embodiment 16
1-(萘基)苯甲酰亚甲基二甲基溴化硫代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到白色固体1-(萘基)-2-(苯磺酰基)-2-(苯硫基)乙烷-1-酮产率为64％。1-(naphthyl) benzoyl dimethyl sulfur bromide replaces the benzoyl dimethyl sulfur bromide in Example 1 to obtain white solid 1-(naphthyl)-2-( The yield of phenylsulfonyl)-2-(phenylthio)ethan-1-one was 64%.
1H NMR(400MHz,Chloroform-d)δ8.34(s,1H),8.09–8.02(m,2H),7.95–7.91(m,1H),7.89–7.82(m,3H),7.63(dt,J＝15.9,7.4Hz,2H),7.54(t,J＝7.7Hz,5H),7.38–7.27(m,3H),5.96(s,1H). 1 H NMR (400MHz, Chloroform-d) δ8.34(s,1H),8.09–8.02(m,2H),7.95–7.91(m,1H),7.89–7.82(m,3H),7.63(dt, J＝15.9, 7.4Hz, 2H), 7.54(t, J＝7.7Hz, 5H), 7.38–7.27(m, 3H), 5.96(s, 1H).
13C NMR(101MHz,Chloroform-d)δ189.2,136.4,136.0,134.5,133.8,132.4,132.3,131.7,130.8,130.0,129.6,129.5,129.5,128.9,128.8,127.8,127.2,124.1,75.8. 13 C NMR (101MHz, Chloroform-d) δ189.2, 136.4, 136.0, 134.5, 133.8, 132.4, 132.3, 131.7, 130.8, 130.0, 129.6, 129.5, 129.5, 128.9, 128.8, 127.8, 127.1, 75.8.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C24H18NaO3S2 +:441.0590；found:441.0582.实施例十七HRMS (ESI-TOF): m/z[M+Na] + calcd for C 24 H 18 NaO 3 S 2 + : 441.0590; found: 441.0582. Example 17
环丙基甲酰亚甲基二甲基溴化硫代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到无色油1-环丙基-2-(苯磺酰基)-2-(苯硫基)乙烷-1-酮产率为68％。Cyclopropylformyl methylene dimethyl sulfur bromide replaces benzoyl methylene dimethyl sulfur bromide in Example 1 to obtain colorless oil 1-cyclopropyl-2-(benzenesulfonyl) -2-(Phenylthio)ethan-1-one yield was 68%.
1H NMR(400MHz,Chloroform-d)δ8.00–7.94(m,2H),7.68(t,J＝7.5Hz,1H),7.55(t,J＝7.8Hz,2H),7.42–7.37(m,2H),7.33–7.23(m,3H),4.93(s,1H),2.44–2.33(m,1H),1.19–1.07(m,4H). 1 H NMR (400MHz, Chloroform-d) δ8.00–7.94(m, 2H), 7.68(t, J=7.5Hz, 1H), 7.55(t, J=7.8Hz, 2H), 7.42–7.37(m ,2H),7.33–7.23(m,3H),4.93(s,1H),2.44–2.33(m,1H),1.19–1.07(m,4H).
13C NMR(101MHz,Chloroform-d)δ198.8,136.9,134.6,133.2,131.8,129.8,129.5,129.2,129.0,80.6,20.8,14.1,13.7. 13 C NMR (101MHz, Chloroform-d) δ198.8, 136.9, 134.6, 133.2, 131.8, 129.8, 129.5, 129.2, 129.0, 80.6, 20.8, 14.1, 13.7.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C17H16NaO3S2 +:355.0433；found:355.0430.实施例十八HRMS (ESI-TOF): m/z[M+Na] + calcd for C 17 H 16 NaO 3 S 2 + : 355.0433; found: 355.0430. Embodiment 18
噻吩甲酰亚甲基二甲基溴化硫代替实施例一中的苯甲酰亚甲基二甲基溴化硫，得到无色油2-(苯磺酰基)-2-(苯硫基)-1-(噻吩-2-基)乙烷-1-酮产率为65％。Thiophenoyl methylene dimethyl sulfur bromide replaces benzoyl methylene dimethyl sulfur bromide in Example 1 to obtain colorless oil 2-(benzenesulfonyl)-2-(phenylthio) The yield of -1-(thiophen-2-yl)ethan-1-one was 65%.
1H NMR(400MHz,Chloroform-d)δ8.02–7.96(m,2H),7.74(dd,J＝7.9,4.4Hz,2H),7.67(t,J＝7.5Hz,1H),7.57–7.48(m,4H),7.37–7.27(m,3H),7.16–7.10(m,1H),5.57(s,1H). 1 H NMR (400MHz, Chloroform-d) δ8.02–7.96 (m, 2H), 7.74 (dd, J=7.9, 4.4Hz, 2H), 7.67 (t, J=7.5Hz, 1H), 7.57–7.48 (m,4H),7.37–7.27(m,3H),7.16–7.10(m,1H),5.57(s,1H).
13C NMR(101MHz,Chloroform-d)δ181.7,142.1,136.7,136.1,134.8,134.6,133.6,132.4,130.7,129.5,129.4,128.8,128.7,77.4. 13 C NMR (101MHz, Chloroform-d) δ181.7, 142.1, 136.7, 136.1, 134.8, 134.6, 133.6, 132.4, 130.7, 129.5, 129.4, 128.8, 128.7, 77.4.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C18H14NaO3S3 +:396.9997；found:396.9978实施例十九HRMS (ESI-TOF): m/z[M+Na] + calcd for C 18 H 14 NaO 3 S 3 + : 396.9997; found: 396.9978 Example 19
S-(4-氯苯基)-硫代苯磺酸酯代替实施例一中的S-苯基硫代苯磺酸酯，得到白色固体2-((4-氯苯基)硫代)-1-苯基-2-(苯磺酰基)乙烷-1-酮产率为77％。S-(4-chlorophenyl)-thiobenzenesulfonate replaces the S-phenylthiobenzenesulfonate in Example 1 to obtain a white solid 2-((4-chlorophenyl)thio)- The yield of 1-phenyl-2-(phenylsulfonyl)ethan-1-one was 77%.
1H NMR(400MHz,Chloroform-d)δ7.98–7.93(m,2H),7.88(dd,J＝8.4,1.1Hz,2H),7.64–7.58(m,1H),7.55–7.49(m,4H),7.49–7.42(m,2H),7.38–7.28(m,3H),5.85(s,1H). 1 H NMR (400MHz, Chloroform-d) δ7.98–7.93 (m, 2H), 7.88 (dd, J=8.4, 1.1Hz, 2H), 7.64–7.58 (m, 1H), 7.55–7.49 (m, 4H),7.49–7.42(m,2H),7.38–7.28(m,3H),5.85(s,1H).
13C NMR(101MHz,Chloroform-d)δ189.3,141.5,135.0 134.6,134.6,133.6,132.4,131.9,129.8,129.6,129.3,129.1,129.0,75.3,75.3. 13 C NMR (101MHz, Chloroform-d) δ189.3, 141.5, 135.0 134.6, 134.6, 133.6, 132.4, 131.9, 129.8, 129.6, 129.3, 129.1, 129.0, 75.3, 75.3.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C20H15ClNaO3S2 +:425.0043；found:425.0046.实施例二十HRMS (ESI-TOF): m/z[M+Na] + calcd for C 20 H 15 ClNaO 3 S 2 + : 425.0043; found: 425.0046. Example 20
S-(4-甲基苯基)-硫代苯磺酸酯代替实施例一中的S-苯基硫代苯磺酸酯，得到白色固体2-((4-甲基苯基)硫代)-1-苯基-2-(苯磺酰基)乙烷-1-酮产率为61％。S-(4-methylphenyl)-thiobenzenesulfonate replaces the S-phenylthiobenzenesulfonate in Example 1 to obtain white solid 2-((4-methylphenyl)thiobenzenesulfonate )-1-phenyl-2-(phenylsulfonyl)ethan-1-one yield was 61%.
1H NMR(400MHz,Chloroform-d)δ8.04–7.98(m,2H),7.90–7.84(m,2H),7.67(tt,J＝7.0,1.2Hz,1H),7.64–7.52(m,3H),7.45(td,J＝7.5,1.6Hz,2H),7.40–7.35(m,2H),7.10(d,J＝7.9Hz,2H),5.74(s,1H),2.33(s,3H). 1 H NMR (400MHz, Chloroform-d) δ8.04–7.98(m,2H),7.90–7.84(m,2H),7.67(tt,J＝7.0,1.2Hz,1H),7.64–7.52(m, 3H), 7.45(td, J=7.5, 1.6Hz, 2H), 7.40–7.35(m, 2H), 7.10(d, J=7.9Hz, 2H), 5.74(s, 1H), 2.33(s, 3H ).
13C NMR(101MHz,Chloroform-d)δ189.3,140.0,136.5,135.1,134.5,134.4,134.2,130.8,130.3,129.2,128.9,128.7,128.4,75.8(d,J＝5.3Hz),21.32(d,J＝6.0Hz). 13 C NMR (101MHz, Chloroform-d) δ189.3, 140.0, 136.5, 135.1, 134.5, 134.4, 134.2, 130.8, 130.3, 129.2, 128.9, 128.7, 128.4, 75.8 (d, J=5.3Hz), 21.32 (d, J=6.0Hz).
HRMS(ESI-TOF):m/z[M+Na]+calcd for C21H18NaO3S2 +:405.0590；found:405.0596.实施例二十一HRMS (ESI-TOF): m/z[M+Na] + calcd for C 21 H 18 NaO 3 S 2 + : 405.0590; found: 405.0596. Example 21
S-(4-甲氧基苯基)-硫代苯磺酸酯代替实施例一中的S-苯基硫代苯磺酸酯，得到白色固体2-((4-甲氧基苯基)硫代)-1-苯基-2-(苯磺酰基)乙烷-1-酮产率为69％。S-(4-methoxyphenyl)-thiobenzenesulfonate replaces the S-phenylthiobenzenesulfonate in Example 1 to obtain white solid 2-((4-methoxyphenyl) Thio)-1-phenyl-2-(benzenesulfonyl)ethan-1-one yield was 69%.
1H NMR(400MHz,Chloroform-d)δ8.06–8.00(m,2H),7.88–7.83(m,2H),7.67(t,J＝7.5Hz,1H),7.57(dt,J＝21.1,7.5Hz,3H),7.48–7.37(m,4H),6.80(d,J＝8.8Hz,2H),5.68(s,1H),3.78(s,3H). 1 H NMR (400MHz, Chloroform-d) δ8.06–8.00 (m, 2H), 7.88–7.83 (m, 2H), 7.67 (t, J=7.5Hz, 1H), 7.57 (dt, J=21.1, 7.5Hz, 3H), 7.48–7.37(m, 4H), 6.80(d, J=8.8Hz, 2H), 5.68(s, 1H), 3.78(s, 3H).
13C NMR(101MHz,Chloroform-d)δ184.5 156.3,131.9,130.4,129.7,129.6,125.9,124.4,124.2,124.0,117.2,110.2,71.2,50.7. 13 C NMR (101MHz, Chloroform-d) δ184.5 156.3, 131.9, 130.4, 129.7, 129.6, 125.9, 124.4, 124.2, 124.0, 117.2, 110.2, 71.2, 50.7.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C21H18NaO4S2 +:421.0539；found:421.0541.实施例二十二HRMS (ESI-TOF): m/z[M+Na] + calcd for C 21 H 18 NaO 4 S 2 + : 421.0539; found: 421.0541. Example 22
S-(2-氟苯基)-硫代苯磺酸酯代替实施例一中的S-苯基硫代苯磺酸酯，得到白色固体2-((2-氟苯基)硫代)-1-苯基-2-(苯磺酰基)乙烷-1-酮产率为60％。S-(2-fluorophenyl)-thiobenzenesulfonate replaces the S-phenylthiobenzenesulfonate in Example 1 to obtain a white solid 2-((2-fluorophenyl)thio)- The yield of 1-phenyl-2-(phenylsulfonyl)ethan-1-one was 60%.
1H NMR(400MHz,Chloroform-d)δ7.95(ddd,J＝19.3,8.4,1.1Hz,4H),7.69–7.60(m,2H),7.60–7.48(m,5H),7.40–7.32(m,1H),7.17–7.03(m,2H),6.02(d,J＝0.7Hz,1H). 1 H NMR (400MHz, Chloroform-d) δ7.95 (ddd, J=19.3, 8.4, 1.1Hz, 4H), 7.69–7.60 (m, 2H), 7.60–7.48 (m, 5H), 7.40–7.32 ( m,1H),7.17–7.03(m,2H),6.02(d,J＝0.7Hz,1H).
13C NMR(101MHz,Chloroform-d)δ188.4,162.5,160.0,134.9,134.7,134.2,133.5(d,J＝4.2Hz),130.8(d,J＝8.2Hz),129.5,128.3,127.9,127.7,124.0(d,J＝3.8Hz),117.8(d,J＝17.3Hz),115.2(d,J＝22.6Hz),72.6(d,J＝2.7Hz). 13 C NMR (101MHz, Chloroform-d) δ188.4, 162.5, 160.0, 134.9, 134.7, 134.2, 133.5 (d, J = 4.2Hz), 130.8 (d, J = 8.2Hz), 129.5, 128.3, 127.9, 127.7, 124.0(d, J=3.8Hz), 117.8(d, J=17.3Hz), 115.2(d, J=22.6Hz), 72.6(d, J=2.7Hz).
HRMS(ESI-TOF):m/z[M+Na]+calcd for C20H15FNaO3S2 +:409.0339；found:409.0349.实施例二十三HRMS (ESI-TOF): m/z[M+Na] + calcd for C 20 H 15 FNaO 3 S 2 + : 409.0339; found: 409.0349. Example 23
S-丙基硫代苯磺酸酯代替实施例一中的S-苯基硫代苯磺酸酯，得到黄色固体1-苯基-2-(苯磺酰基)-2-(丙硫基)乙烷-1-酮产率为65％。S-propyl thiobenzenesulfonate replaces the S-phenyl thiobenzenesulfonate in Example 1 to obtain yellow solid 1-phenyl-2-(benzenesulfonyl)-2-(propylthio) Ethan-1-one yield was 65%.
1H NMR(400MHz,Chloroform-d)δ8.03–7.90(m,4H),7.72–7.58(m,2H),7.55(t,J＝7.8Hz,2H),7.48(t,J＝7.8Hz,2H),5.59(s,1H),2.87(ddd,J＝12.1,8.1,6.5Hz,1H),2.72(ddd,J＝12.1,7.9,7.0Hz,1H),1.57(dt,J＝15.2,7.8Hz,2H),0.92(t,J＝7.3Hz,3H). 1 H NMR (400MHz, Chloroform-d) δ8.03–7.90(m,4H),7.72–7.58(m,2H),7.55(t,J=7.8Hz,2H),7.48(t,J=7.8Hz ,2H),5.59(s,1H),2.87(ddd,J=12.1,8.1,6.5Hz,1H),2.72(ddd,J=12.1,7.9,7.0Hz,1H),1.57(dt,J=15.2 ,7.8Hz,2H),0.92(t,J=7.3Hz,3H).
13C NMR(101MHz,Chloroform-d)δ189.1,136.3,135.0,134.4,134.4,130.6,129.0,129.0,128.7,70.6(d,J＝6.8Hz),34.7,22.4,13.3. 13 C NMR (101MHz, Chloroform-d) δ189.1, 136.3, 135.0, 134.4, 134.4, 130.6, 129.0, 129.0, 128.7, 70.6 (d, J=6.8Hz), 34.7, 22.4, 13.3.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C17H18NaO3S2 +:357.0590；found:357.0590.实施例二十四HRMS (ESI-TOF): m/z[M+Na] + calcd for C 17 H 18 NaO 3 S 2 + : 357.0590; found: 357.0590. Example 24
S-丁基硫代苯磺酸酯代替实施例一中的S-苯基硫代苯磺酸酯，得到白色固体1-苯基-2-(苯磺酰基)-2-(丙硫基)乙烷-1-酮产率为66％。S-butyl thiobenzenesulfonate replaces the S-phenyl thiobenzenesulfonate in Example 1 to obtain white solid 1-phenyl-2-(benzenesulfonyl)-2-(propylthio) Ethan-1-one yield was 66%.
1H NMR(400MHz,Chloroform-d)δ8.04–7.92(m,4H),7.63(dt,J＝21.2,7.4Hz,2H),7.54(t,J＝7.8Hz,2H),7.47(t,J＝7.8Hz,2H),5.61(s,1H),2.88(ddd,J＝12.0,8.2,6.5Hz,1H),2.73(ddd,J＝12.0,8.1,7.0Hz,1H),1.60–1.44(m,2H),1.32(h,J＝7.2Hz,2H),0.85(t,J＝7.3Hz,3H). 1 H NMR (400MHz, Chloroform-d) δ8.04–7.92(m, 4H), 7.63(dt, J=21.2,7.4Hz, 2H), 7.54(t, J=7.8Hz, 2H), 7.47(t ,J=7.8Hz,2H),5.61(s,1H),2.88(ddd,J=12.0,8.2,6.5Hz,1H),2.73(ddd,J=12.0,8.1,7.0Hz,1H),1.60– 1.44(m,2H),1.32(h,J=7.2Hz,2H),0.85(t,J=7.3Hz,3H).
13C NMR(101MHz,Chloroform-d)δ189.1,136.4,135.0,134.4,134.3,130.6,129.0,128.9,128.7,70.7,32.4,30.9,21.8,13.6. 13 C NMR (101MHz, Chloroform-d) δ189.1, 136.4, 135.0, 134.4, 134.3, 130.6, 129.0, 128.9, 128.7, 70.7, 32.4, 30.9, 21.8, 13.6.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C18H20NaO3S2 +:371.0746；found:371.0749.实施例二十五HRMS (ESI-TOF): m/z[M+Na] + calcd for C 18 H 20 NaO 3 S 2 + : 371.0746; found: 371.0749. Example 25
S-十二烷基硫代苯磺酸酯代替实施例一中的S-苯基硫代苯磺酸酯，得到白色固体2-(十二硫基)-1-苯基-2-(苯磺酰基)乙烷-1-酮产率为65％。S-dodecylthiobenzenesulfonate replaces the S-phenylthiobenzenesulfonate in Example 1 to obtain white solid 2-(dodecylthio)-1-phenyl-2-(benzene The yield of sulfonyl)ethan-1-one was 65%.
1H NMR(400MHz,Chloroform-d)δ8.00(d,J＝7.4Hz,2H),7.96(d,J＝7.4Hz,2H),7.64(dt,J＝21.3,7.4Hz,2H),7.54(t,J＝7.8Hz,2H),7.47(t,J＝7.8Hz,2H),5.60(s,1H),2.87(ddd,J＝12.1,8.1,6.6Hz,1H),2.78–2.68(m,1H),1.58–1.44(m,2H),1.24(t,J＝14.6Hz,18H),0.88(t,J＝6.8Hz,3H). 1 H NMR (400MHz, Chloroform-d) δ8.00 (d, J = 7.4Hz, 2H), 7.96 (d, J = 7.4Hz, 2H), 7.64 (dt, J = 21.3, 7.4Hz, 2H), 7.54(t, J=7.8Hz, 2H), 7.47(t, J=7.8Hz, 2H), 5.60(s, 1H), 2.87(ddd, J=12.1, 8.1, 6.6Hz, 1H), 2.78–2.68 (m,1H),1.58–1.44(m,2H),1.24(t,J=14.6Hz,18H),0.88(t,J=6.8Hz,3H).
13C NMR(101MHz,Chloroform-d)δ189.1,136.4,135.1,134.3,134.3,130.6,129.0,128.9,128.6,70.7,32.8,31.9,29.6,29.5,29.4,29.35,29.1,28.8,28.6,22.7,14.2. 13 C NMR (101MHz, Chloroform-d) δ189.1, 136.4, 135.1, 134.3, 134.3, 130.6, 129.0, 128.9, 128.6, 70.7, 32.8, 31.9, 29.6, 29.5, 29.4, 29.35, 29.1, 28.8, 27.6, 2 14.2.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C26H36NaO3S2 +:483.1998；found:483.2004.实施例二十六HRMS (ESI-TOF): m/z[M+Na] + calcd for C 26 H 36 NaO 3 S 2 + : 483.1998; found: 483.2004. Example 26
S-吡啶基硫代苯磺酸酯代替实施例一中的S-苯基硫代苯磺酸酯，得到红色油2-((4-溴苯基)磺酰基)-1-苯基-2-(吡啶-2-基硫基)乙烷-1-酮产率为50％。S-pyridylthiobenzenesulfonate replaces the S-phenylthiobenzenesulfonate in Example 1 to obtain red oil 2-((4-bromophenyl)sulfonyl)-1-phenyl-2 -(Pyridin-2-ylthio)ethan-1-one yield 50%.
1H NMR(400MHz,Chloroform-d)δ8.37(ddd,J＝4.9,1.7,0.9Hz,1H),8.14–8.07(m,2H),7.96(dt,J＝8.6,1.7Hz,2H),7.71(s,1H),7.63–7.57(m,1H),7.57–7.50(m,1H),7.50–7.40(m,5H),7.16–7.11(m,1H),7.04(ddd,J＝7.3,4.9,0.9Hz,1H). 1 H NMR (400MHz, Chloroform-d) δ8.37 (ddd, J＝4.9, 1.7, 0.9Hz, 1H), 8.14–8.07 (m, 2H), 7.96 (dt, J＝8.6, 1.7Hz, 2H) ,7.71(s,1H),7.63–7.57(m,1H),7.57–7.50(m,1H),7.50–7.40(m,5H),7.16–7.11(m,1H),7.04(ddd,J= 7.3,4.9,0.9Hz,1H).
13C NMR(101MHz,Chloroform-d)δ189.7,152.9,149.3,137.1,137.0,135.4,134.3,134.2,130.3,129.4,128.8,128.9,122.2,121.2,67.5. 13 C NMR (101MHz, Chloroform-d) δ189.7, 152.9, 149.3, 137.1, 137.0, 135.4, 134.3, 134.2, 130.3, 129.4, 128.8, 128.9, 122.2, 121.2, 67.5.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C19H15NNaO3S2 +:392.0386；found:392.0381.实施例二十七HRMS (ESI-TOF): m/z[M+Na] + calcd for C 19 H 15 NNaO 3 S 2 + : 392.0386; found: 392.0381. Example 27
Se-苯基硒代苯磺酸酯代替实施例一中的S-苯基硫代苯磺酸酯，得到白色固体1-苯基-2-(苯基硒基)-2-(苯基磺酰基)乙烷-1-酮产率为35％。Se-phenylselenobenzenesulfonate replaces the S-phenylthiobenzenesulfonate in Example 1 to obtain white solid 1-phenyl-2-(phenylselenyl)-2-(phenylsulfonate The yield of acyl)ethan-1-one was 35%.
1H NMR(400MHz,Chloroform-d)δ8.09–8.03(m,2H),7.80(d,J＝7.4Hz,2H),7.67(t,J＝7.4Hz,1H),7.58(dq,J＝15.6,7.5Hz,5H),7.41(dt,J＝15.5,7.6Hz,3H),7.29(t,J＝7.5Hz,2H),5.82(s,1H). 1 H NMR (400MHz, Chloroform-d) δ8.09–8.03 (m, 2H), 7.80 (d, J = 7.4Hz, 2H), 7.67 (t, J = 7.4Hz, 1H), 7.58 (dq, J =15.6,7.5Hz,5H),7.41(dt,J=15.5,7.6Hz,3H),7.29(t,J=7.5Hz,2H),5.82(s,1H).
13C NMR(101MHz,Chloroform-d)δ189.4,137.1,135.8,135.0,134.3,134.2,130.6,129.7,129.5,128.9,128.8,128.7,127.7,68.1. 13 C NMR (101MHz, Chloroform-d) δ189.4, 137.1, 135.8, 135.0, 134.3, 134.2, 130.6, 129.7, 129.5, 128.9, 128.8, 128.7, 127.7, 68.1.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C20H16NaO3SSe+:438.9578；found:438.9561.实施例二十八HRMS (ESI-TOF): m/z[M+Na] + calcd for C 20 H 16 NaO 3 SSe + : 438.9578; found: 438.9561. Example 28
S-苯基-4-甲基硫代苯磺酸酯代替实施例一中的S-苯基硫代苯磺酸酯，得到白色油1-苯基-2-(苯硫基)-2-甲苯磺酸-1-酮产率为80％。S-phenyl-4-methylthiobenzenesulfonate replaces the S-phenylthiobenzenesulfonate in Example 1 to obtain white oil 1-phenyl-2-(phenylthio)-2- The yield of tosylate-1-one was 80%.
1H NMR(400MHz,Chloroform-d)δ7.88(dd,J＝7.8,4.4Hz,4H),7.59(d,J＝7.4Hz,1H),7.53–7.48(m,2H),7.44(t,J＝7.8Hz,2H),7.35–7.28(m,5H),5.82(s,1H),2.43(s,3H). 1 H NMR (400MHz, Chloroform-d) δ7.88(dd, J=7.8,4.4Hz,4H),7.59(d,J=7.4Hz,1H),7.53–7.48(m,2H),7.44(t ,J＝7.8Hz,2H),7.35–7.28(m,5H),5.82(s,1H),2.43(s,3H).
13C NMR(101MHz,Chloroform-d)δ189.5,145.7,135.2,134.4,133.5,133.3,132.3,130.8,129.5,129.4,129.3,129.3,128.9,75.5,21.8. 13 C NMR (101MHz, Chloroform-d) δ189.5, 145.7, 135.2, 134.4, 133.5, 133.3, 132.3, 130.8, 129.5, 129.4, 129.3, 129.3, 128.9, 75.5, 21.8.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C21H18ClNaO3S2 +:405.0590；found:405.0600.实施例二十九HRMS (ESI-TOF): m/z[M+Na] + calcd for C 21 H 18 ClNaO 3 S 2 + : 405.0590; found: 405.0600. Example 29
S-苯基-4-氟硫代苯磺酸酯代替实施例一中的S-苯基硫代苯磺酸酯，得到白色固体2-((4-氟苯基)磺酰基)-1-苯基-2-(苯硫基)乙烷-1-酮产率为70％。S-phenyl-4-fluorothiobenzenesulfonate replaces the S-phenylthiobenzenesulfonate in Example 1 to obtain a white solid 2-((4-fluorophenyl)sulfonyl)-1- The yield of phenyl-2-(phenylthio)ethan-1-one was 70%.
1H NMR(400MHz,Chloroform-d)δ8.03(ddd,J＝10.0,5.1,2.5Hz,2H),7.90–7.84(m,2H),7.64–7.58(m,1H),7.53(dt,J＝6.6,1.5Hz,2H),7.49–7.42(m,2H),7.36–7.28(m,3H),7.26–7.17(m,2H),5.85(s,1H). 1 H NMR (400MHz, Chloroform-d) δ8.03 (ddd, J = 10.0, 5.1, 2.5Hz, 2H), 7.90–7.84 (m, 2H), 7.64–7.58 (m, 1H), 7.53 (dt, J＝6.6,1.5Hz,2H),7.49–7.42(m,2H),7.36–7.28(m,3H),7.26–7.17(m,2H),5.85(s,1H).
13C NMR(101MHz,Chloroform-d)δ189.4,167.7,165.2,135.0,134.6,133.9,133.8,133.5,132.1(d,J＝3.1Hz),131.9,129.6(d,J＝4.4Hz),129.2,129.0,116.2,115.9,75.3. 13 C NMR (101MHz, Chloroform-d) δ189.4, 167.7, 165.2, 135.0, 134.6, 133.9, 133.8, 133.5, 132.1 (d, J=3.1Hz), 131.9, 129.6 (d, J=4.4Hz), 129.2, 129.0, 116.2, 115.9, 75.3.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C20H15FNaO3S2 +:409.0339；found:409.0339.实施例三十HRMS (ESI-TOF): m/z[M+Na] + calcd for C 20 H 15 FNaO 3 S 2 + : 409.0339; found: 409.0339. Example Thirty
S-苯基-4-氯硫代苯磺酸酯代替实施例一中的S-苯基硫代苯磺酸酯，得到黄色油2-((4-氯苯基)磺酰基)-1-苯基-2-(苯硫基)乙烷-1-酮产率为67％。S-phenyl-4-chlorothiobenzenesulfonate replaces the S-phenylthiobenzenesulfonate in Example 1 to obtain yellow oil 2-((4-chlorophenyl)sulfonyl)-1- The yield of phenyl-2-(phenylthio)ethan-1-one was 67%.
1H NMR(400MHz,Chloroform-d)δ7.95(d,J＝8.5Hz,2H),7.88(d,J＝7.6Hz,2H),7.62(t,J＝7.4Hz,1H),7.57–7.49(m,4H),7.46(t,J＝7.7Hz,2H),7.33(dt,J＝14.1,6.8Hz,3H),5.84(s,1H). 1 H NMR (400MHz, Chloroform-d) δ7.95 (d, J = 8.5Hz, 2H), 7.88 (d, J = 7.6Hz, 2H), 7.62 (t, J = 7.4Hz, 1H), 7.57– 7.49(m,4H),7.46(t,J=7.7Hz,2H),7.33(dt,J=14.1,6.8Hz,3H),5.84(s,1H).
13C NMR(101MHz,Chloroform-d)δ189.3,141.5,135.0,134.6,134.6,133.6,132.3,131.9,129.6,129.6,129.2,129.0,75.3. 13 C NMR (101MHz, Chloroform-d) δ189.3, 141.5, 135.0, 134.6, 134.6, 133.6, 132.3, 131.9, 129.6, 129.6, 129.2, 129.0, 75.3.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C20H15ClNaO3S2 +:425.0043；found:425.0063.实施例三十一HRMS (ESI-TOF): m/z[M+Na] + calcd for C 20 H 15 ClNaO 3 S 2 + : 425.0043; found: 425.0063. Example 31
S-苯基-4-溴硫代苯磺酸酯代替实施例一中的S-苯基硫代苯磺酸酯，得到白色固体2-((4-溴苯基)磺酰基)-1-苯基-2-(苯硫基)乙烷-1-酮产率为66％。S-phenyl-4-bromothiobenzenesulfonate replaces the S-phenylthiobenzenesulfonate in Example 1 to obtain a white solid 2-((4-bromophenyl)sulfonyl)-1- The yield of phenyl-2-(phenylthio)ethan-1-one was 66%.
1H NMR(400MHz,Chloroform-d)δ7.92–7.83(m,4H),7.72–7.67(m,2H),7.63(t,J＝7.4Hz,1H),7.55–7.51(m,2H),7.47(t,J＝7.8Hz,2H),7.38–7.29(m,3H),5.82(s,1H). 1 H NMR (400MHz, Chloroform-d) δ7.92–7.83(m,4H),7.72–7.67(m,2H),7.63(t,J=7.4Hz,1H),7.55–7.51(m,2H) ,7.47(t,J＝7.8Hz,2H),7.38–7.29(m,3H),5.82(s,1H).
13C NMR(101MHz,Chloroform-d)δ189.2,135.1,135.0,134.6,133.6,132.4,132.0,131.9,130.2,129.59,129.55,129.2,129.0,75.4. 13 C NMR (101MHz, Chloroform-d) δ189.2, 135.1, 135.0, 134.6, 133.6, 132.4, 132.0, 131.9, 130.2, 129.59, 129.55, 129.2, 129.0, 75.4.
HRMS(ESI-TOF):m/z[M+Na]+calcd for C20H15BrNaO3S2 +:468.9538；found:468.9549.HRMS(ESI-TOF):m/z[M+Na] + calcd for C 20 H 15 BrNaO 3 S 2 + : 468.9538; found: 468.9549.
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| Metal-Free Chemoselective Reaction of Sulfoxonium Ylides and Thiosulfonates: Diverse Synthesis of 1,4-Diketones, Aryl Sulfursulfoxonium Ylides, and β-Keto Thiosulfones Derivatives;Wang, Fei ET AL;《Organic Letters》;20201231;6600-6604 * |
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