CN114702417B - Synthesis method for preparing difluoroethylene sulfide by nucleophilic substitution of beta-site of geminal difluoroallene compound - Google Patents
Synthesis method for preparing difluoroethylene sulfide by nucleophilic substitution of beta-site of geminal difluoroallene compound Download PDFInfo
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- CN114702417B CN114702417B CN202210103194.2A CN202210103194A CN114702417B CN 114702417 B CN114702417 B CN 114702417B CN 202210103194 A CN202210103194 A CN 202210103194A CN 114702417 B CN114702417 B CN 114702417B
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- difluoroallene
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 33
- WHEHARLKIQJDDA-UHFFFAOYSA-N 2,3-difluorothiirane Chemical compound FC1C(S1)F WHEHARLKIQJDDA-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000010534 nucleophilic substitution reaction Methods 0.000 title claims abstract description 16
- 238000001308 synthesis method Methods 0.000 title claims abstract description 11
- IXHBTMCLRNMKHZ-LBPRGKRZSA-N levobunolol Chemical class O=C1CCCC2=C1C=CC=C2OC[C@@H](O)CNC(C)(C)C IXHBTMCLRNMKHZ-LBPRGKRZSA-N 0.000 title claims abstract description 10
- -1 mercaptan compound Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 12
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 125000001624 naphthyl group Chemical group 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 229940125904 compound 1 Drugs 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 125000002541 furyl group Chemical group 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 229930192474 thiophene Chemical group 0.000 claims description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000001041 indolyl group Chemical group 0.000 claims description 6
- 229940125782 compound 2 Drugs 0.000 claims description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
- 229940126214 compound 3 Drugs 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Chemical group C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052736 halogen Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Chemical group CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Chemical group C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- 229940095102 methyl benzoate Drugs 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 241000282326 Felis catus Species 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000010948 rhodium Substances 0.000 abstract description 7
- 229910052703 rhodium Inorganic materials 0.000 abstract description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000005935 nucleophilic addition reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 238000002955 isolation Methods 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WLWNRAWQDZRXMB-YLFCFFPRSA-N (2r,3r,4r,5s)-n,3,4,5-tetrahydroxy-1-(4-phenoxyphenyl)sulfonylpiperidine-2-carboxamide Chemical compound ONC(=O)[C@H]1[C@@H](O)[C@H](O)[C@@H](O)CN1S(=O)(=O)C(C=C1)=CC=C1OC1=CC=CC=C1 WLWNRAWQDZRXMB-YLFCFFPRSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000006711 (C2-C12) alkynyl group Chemical group 0.000 description 1
- BLRHMMGNCXNXJL-UHFFFAOYSA-N 1-methylindole Chemical group C1=CC=C2N(C)C=CC2=C1 BLRHMMGNCXNXJL-UHFFFAOYSA-N 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- SAMCXPGNUAXAOO-UHFFFAOYSA-N diphenylphosphane;pentane Chemical compound CCCCC.C=1C=CC=CC=1PC1=CC=CC=C1 SAMCXPGNUAXAOO-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution 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
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 125000005069 octynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/16—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of hydrogen sulfide or its salts to unsaturated 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a synthesis method for preparing difluoroethylene sulfide by nucleophilic substitution of beta-site of geminal difluoroallene compounds. The method adopts a gem-difluoro allene compound as a raw material, and in a high-universality catalytic system formed by a rhodium catalyst and a bidentate ligand, a mercaptan compound carries out high-selectivity nucleophilic addition on beta-position of the gem-difluoro allene compound to prepare various difluoro ethylene sulfides. The whole synthesis method has simple steps, mild reaction conditions, high selectivity and ideal yield, is suitable for quickly constructing a large amount of difluoroethylene sulfides, and can further promote the development and application of the compounds.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a synthesis method for preparing difluoroethylene sulfide by nucleophilic substitution of beta-site of geminal difluoroallene compounds.
Background
Fluorine-containing compounds are important chemical intermediates and are widely applied to the fields of medicines, pesticides, materials and the like. In recent years, gem-difluoroallenes containing two fluorine atomsThe compound is concerned by various fields because of the great application potential in the fields of new medicine development, organic synthesis, material science and the like. However, gem-difluoroallenes have more reaction sites than non-fluorinated analogues and react not only in the alpha, beta, gamma positions of the diene, CF at the end 2 Nucleophilic substitution of the group that can also result in cleavage of the C-F bond, resulting in regioselective nucleophilic substitution of such compounds is very challenging.
In addition, the dominant reaction sites of the gem-difluoroallene compound are alpha and gamma, in the prior art, nucleophilic reagents such as mercaptan and the like carry out selective nucleophilic substitution on the gem-difluoroallene compound, only a small amount of reports are shown on the alpha and gamma, and for the beta site with lower reaction activity, the high-selectivity nucleophilic substitution on the site is not realized, so as to prepare the difluoroethylene sulfide.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a synthesis method for preparing difluoroethylene sulfide by nucleophilic substitution of beta-site of a geminal difluoroallene compound. The method adopts a rhodium catalyst and a bidentate ligand to form a high-universality catalytic system, promotes mercaptan to carry out high-selectivity nucleophilic addition on beta-site of the geminal difluoroallene compound, and prepares various difluoroethylene sulfides. The method has simple steps, mild reaction conditions and high selectivity, and is suitable for quickly constructing the compounds in large quantities.
In order to achieve the technical purpose, the invention provides a synthesis method for preparing difluoroethylene sulfide by nucleophilic substitution of beta-site of geminal difluoroallene compound, which is characterized by comprising the following synthesis route:
wherein the method comprises the steps of
R1 is C1-C12 alkyl or C2-C12 diluent or C2-C12 alkynyl;
r2 is phenyl or naphthyl or furyl or benzyl or C1-C4 alkyl;
r1 can be substituted by one or more R3, which are identical or different;
r3 is phenyl or naphthyl or thiophene or indolyl or furyl or tert-butyldimethylsiloxy or C3-C12 cycloalkyl or C4-C12 multi-dilute, and one of phenyl or naphthyl or thiophene or indole substituted by benzyloxy or C1-C4 alkyl or C1-C4 alkoxycarbonyl;
r2 can be substituted by one or more R4, which are identical or different;
r4 is one of C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, halogen, C1-C4 alkoxycarbonyl or phenyl.
Further, the R1 is preferably ethyl or undecyl or octynyl; r3 is phenyl or naphthyl or thiophene or furyl or indolyl or tert-butyldimethylsilyloxy or cyclohexyl or p-benzyloxy phenyl or methyl benzoate or N-methylindole or 2-methylfuryl; r2 is one of phenyl, naphthyl, furyl, benzyl, ethyl or n-hexyl; and R4 is one of methyl, methoxy, tertiary butyl, trifluoromethyl, fluorine, chlorine, bromine or methyl formate.
Further, the preparation method comprises the following steps:
(1) Under the protection of inert gas, dissolving a catalyst and a ligand in a solvent I, then adding a compound 1 and a compound 2, and uniformly mixing;
(2) Controlling the temperature of the system to be between minus 20 and 150 ℃, reacting for 0.5 to 96 hours, concentrating the reaction mixture, desolventizing, and purifying the obtained residue to obtain the compound 3.
Further, in the step (1), the catalyst is a rhodium catalyst.
Further, the rhodium catalyst is (R, R) -2, 3-bis (2, 5-dimethyl-thiocyclophosphorus-1-yl) benzo [ B ]]Thiophene cyclooctadiene rhodium tetrafluoroborate (I) ([ Rh (cod))]BF 4 )。
Further, in the step (1), the ligand is a bidentate ligand.
Further, the bidentate ligand is one or more of 1, 10-phenanthroline or 5, 5-bis (diphenylphosphine) -4, 4-di-1, 3-piperonyl or (2S, 4S) - (-) -2, 4-bis (diphenylphosphine) pentane.
Further, in the step (1), the solvent I is one or more of dichloromethane or dichloroethane, methanol or ethanol, toluene or xylene or acetonitrile; when more than two mixed solvents are adopted, the solvents are mixed according to any ratio; the ratio of solvent one to compound 1 is 5-40mL/g.
Further, in the step (1), trifluoroacetic acid is adopted to promote the reaction; the molar ratio of compound 1 to trifluoroacetic acid is 1: (0.1-1).
Further, in the step (1), the molar ratio of the compound 1 to the catalyst, the ligand and the compound 2 is 1 (0.003-0.1): (0.003-0.1): (1-4).
Advantageous effects
The invention provides a synthesis method for preparing difluoroethylene sulfide by nucleophilic substitution of beta-site of geminal difluoroallene compounds. In the method, a gem-difluoroallene compound is used as a raw material, and in a high-universality catalytic system formed by a rhodium catalyst and a bidentate ligand, mercaptan carries out high-selectivity nucleophilic addition on beta-position of the gem-difluoroallene compound to prepare various difluoroethylene sulfur compounds. The method has simple steps, mild reaction conditions, high selectivity and ideal yield, and provides a new way for developing and applying the gem-difluoroallene compounds.
It should be understood that all combinations of the foregoing concepts, as well as additional concepts described in more detail below, may be considered a part of the inventive subject matter of the present disclosure as long as such concepts are not mutually inconsistent.
The foregoing and other aspects, embodiments, and features of the present teachings will be more fully understood from the following description, taken together with the accompanying drawings. Other additional aspects of the invention, such as features and/or advantages of the exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of the embodiments according to the teachings of the invention.
Drawings
The drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures may be represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. Embodiments of various aspects of the invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of compound 3aa in example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of compound 3ab in example 1 of the present invention.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of compound 3ak in example 1 of the present invention.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of compound 3ap in example 1 of the present invention.
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of compound 3ia in example 1 of the present invention.
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of compound 3ja in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention fall within the protection scope of the present invention. Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
A synthesis method of a difluoroethylene compound comprises the following steps:
in the first step, under the protection of inert gas, a catalyst and a ligand are dissolved in a solvent I, and then a compound 1 and a compound 2 are added and mixed uniformly.
Secondly, controlling the temperature of the system to be between 20 ℃ below zero and 150 ℃ to react for 0.5 to 96 hours, concentrating the reaction mixture, desolventizing, and purifying the obtained residue to obtain the compound 3.
In the step (1), trifluoroacetic acid is adopted to promote the reaction;
compound 1 can be synthesized using the following general scheme I:
the synthesis process includes dissolving diisopropylamine in tetrahydrofuran solution at 0 deg.c for 5-60 min, adding n-butyllithium, maintaining the temperature and stirring for 5-60 min. Controlling the temperature to be between 100 ℃ below zero and 50 ℃ for 5 to 60 minutes, and adding CF 3 CH 2 The solution of I dissolved in THF is dripped into the solution, and the solution is stirred for 5 to 60 minutes under heat preservation. Adding a solution of the compound A dissolved in THF, and stirring the mixture at a constant temperature for 5-60 min, and then raising the temperature of the reaction mixture to-30-50 ℃ within 30-120 min. Acetic anhydride was added and the reaction mixture was then raised to-5 to 50 ℃ over 2 h. The reaction solution was washed with an aqueous ammonium chloride solution, extracted with ethyl acetate, and the organic phases were combined, washed with saturated brine, dried, desolventized, and purified by column chromatography to give compound B.
Under the protection of argon, zinc powder is placed in N, N-dimethylformamide at room temperature, the obtained mixed solution is added into a solution of a compound B dissolved in the N, N-dimethylformamide, and the mixture is stirred for 1 to 6 hours under the heat preservation. Filtering, diluting filtrate with ethyl acetate and brine, extracting with ethyl acetate, mixing organic phases, washing with saturated brine, drying, desolventizing, and purifying by column chromatography to obtain the compound 1.
The present invention will be described in detail with reference to the following specific examples, but is not limited thereto.
Example 1
Compound 1a was prepared according to general procedure I:
to diisopropylamine (20.0 mmol) in tetrahydrofuran at 0deg.C for 10minTo a solution of the pyran (10 mL), n-BuLi (20.0 mmol) was added, and the mixture was stirred for 15 minutes while keeping the temperature at-93 ℃. Within 10min, CF is added 3 CH 2 A solution of I (10.0 mmol) in THF (5 mL) was added dropwise thereto, and the mixture was stirred at a constant temperature for 20min. A solution of Compound A (10.0 mmol) in THF (5 mL) was added over 5 min. After stirring the mixture for a further 30min at a temperature, the reaction mixture was brought to-30℃over 90 min. Acetic anhydride (12.0 mmol) was added and the reaction mixture was raised to 0 ℃ over 2 h. Then washing the reaction solution with an ammonium chloride aqueous solution, extracting with ethyl acetate, combining organic phases, washing with saturated saline solution, drying, desolventizing and purifying by column chromatography to obtain the compound Ba.
Zinc powder (17.0 mmol) was placed in N, N-dimethylformamide (26 mL) under argon at room temperature to prepare a mixture, and the obtained mixture was added to a solution of Compound B (8.5 mmol) in N, N-dimethylformamide (17 mL) and stirred at constant temperature for 3h. Filtration, dilution of the filtrate with ethyl acetate and brine, extraction with ethyl acetate, combining the organic phases, washing with saturated brine, drying, desolventizing, and purification by column chromatography gave 2.01g of compound 1a in 71% yield.
1 H NMR(500MHz,CDCl3)δ7.47(d,J＝7.3Hz,2H),7.43(dd,J＝10.1,4.8Hz,2H),7.39–7.34(m,1H),7.14(d,J＝8.6Hz,2H),6.96(d,J＝8.6Hz,2H),6.54–6.43(m,1H),5.08(s,2H),2.79(t,J＝7.7Hz,2H),2.65–2.50(m,2H).
13 C NMR(126MHz,CDCl3)δ170.1(t,J＝36.1Hz),157.2,152.7(t,J＝261.1Hz),137.1,133.0,129.3,128.5,127.9,127.4,121.5(t,J＝5.5Hz),114.8,70.0,34.0(t,J＝1.6Hz),32.9(t,J＝1.3Hz).
19 F NMR(471MHz,CDCl 3 )δ-101.7.
ATR-FTIR(cm -1 ):2357,1275,750.
HRMS(ESI + )Calcd for C 18 H 16 F 2 ONa[M+Na] + :309.1061,found:309.1057
Synthesis of (Z) - (5- (4- (benzyloxy) phenyl) -1, 1-difluoropent-2-en-2-yl) (4-methoxyphenyl) sulfa-ne (3 aa) as shown in FIG. 1:
after purging 25mL Schlenk tube with argon 3 times, [ Rh (cod) ] was added]BF 4 (3.2 mg,0.04 eq), 1, 10-phenanthroline (1.7 mg,0.048 eq) and 1mL acetonitrile/toluene (v/v=1:1). Then compound 1a (57.2 mg,0.2mmol,1.0 eq) and compound 2a (64.0 mg,0.4mmol,2.0 eq) were added. The reaction mixture was stirred at 60℃for 12 hours, the ratio of Z-3aa to E-3aa was 85:15 as determined by GC, and the reaction mixture was concentrated in vacuo and purified by silica gel column chromatography to give 68.0mg of Z/E-3aa in 80% yield.
Further isolation gave white solid Z-3aa, which was characterized as follows:
mp:57-59oC.
1 H NMR(500MHz,CDCl 3 )δ7.45(d,J＝7.4Hz,2H),7.40(t,J＝7.4Hz,2H),7.34(t,J＝7.2Hz,1H),7.23–7.13(m,2H),7.10(d,J＝8.5Hz,2H),6.93(t,J＝5.6Hz,2H),6.84–6.74(m,2H),6.54(t,J＝6.9Hz,1H),5.92(t,J＝56.3Hz,1H),5.06(s,2H),3.77(s,3H),2.82–2.61(m,4H). 13 C NMR(126MHz,CDCl 3 )δ159.1,157.3,141.9(t,J＝7.1Hz),137.1,133.0,132.5,129.4,129.1(t,J＝21.3Hz),128.5,127.9,127.4,123.9,114.8,114.7,113.9(t,J＝241.7Hz),70.0,55.3,33.7(t,J＝1.5Hz),31.2.
19 F NMR(471MHz,CDCl 3 )δ-112.4(d,J＝2.3Hz).
ATR-FTIR(cm -1 ):2361,2338,1275,750,671.
HRMS(ESI + )Calcd for C 25 H 25 F 2 O 2 S[M+H] + :427.1538,found:427.1536.
example 2
Synthesis of (Z) - (5- (4- (benzyloxy) phenyl) -1, 1-difluoropent-2-en-2-yl) (phenyl) sulfonamide (3 ab) as shown in FIG. 2
The preparation is carried out in accordance with example one.
The ratio of Z-3ab to E-3ab detected by GC-MS was 83:17, and the reaction solution was concentrated in vacuo and purified by silica gel column chromatography to give 56.0mg of Z/E-3ab in 71% yield.
Further separation gave a white solid Z-3ab, characterized as follows: 1 H NMR(500MHz,CDCl 3 )δ7.47(d,J＝7.3Hz,2H),7.43(dd,J＝10.1,4.7Hz,2H),7.39–7.34(m,1H),7.30–7.24(m,2H),7.24–7.17(m,3H),7.10(d,J＝8.6Hz,2H),6.93(d,J＝8.6Hz,2H),6.73(t,J＝6.8Hz,1H),6.01(t,J＝56.2Hz,1H),5.08(s,2H),2.81–2.68(m,4H).
13 C NMR(126MHz,CDCl 3 )δ157.3,144.7(t,J＝7.4Hz),137.1,134.2,132.9,129.4,129.0,128.7,128.6,127.9,127.8(t,J＝21.2Hz),127.4,126.5,114.8,114.0(t,J＝242.2Hz),70.0,33.6(t,J＝1.5Hz),31.3.
19 F NMR(471MHz,CDCl 3 )δ-112.1.
ATR-FTIR(cm -1 ):2361,2339,1275,750.
HRMS(ESI + )Calcd for C 24 H 23 F 2 OS[M+H] + :397.1432,found:397.1434.
example 3
Synthesis of (Z) - (5- (4- (benzyloxy) phenyl) -1, 1-difluoropent-2-en-2-yl) (naphthalen-2-yl) sulfonamide (3 ak) as shown in FIG. 3
The preparation is carried out in accordance with example one.
GC-MS detected a ratio of Z-3ak to E-3ak of 65:35, and the reaction mixture was concentrated in vacuo and purified by silica gel column chromatography to give 46.0mg of Z/E-3ak in 52% yield.
Further isolation gave a white solid Z-3ak, characterized as follows: 1 H NMR(400MHz,CDCl 3 )δ7.80–7.74(m,1H),7.74–7.67(m,2H),7.65(d,J＝1.5Hz,1H),7.51–7.29(m,7H),7.27–7.20(m,1H),7.04(d,J＝8.6Hz,2H),6.87(d,J＝8.6Hz,2H),6.78–6.68(m,1H),6.01(t,J＝56.2Hz,1H),5.01(s,2H),2.84–2.61(m,4H).
13 C NMR(101MHz,CDCl 3 )δ157.3,144.9(t,J＝6.9Hz),137.1,133.7,132.8,132.0,131.6,129.4,128.7,128.6,127.9,127.7,127.6,127.4,127.2,127.2,126.7,126.6,126.0,114.9,114.0(t,J＝241.8Hz),70.0,33.6(t,J＝1.7Hz),31.3.
19 F NMR(377MHz,CDCl 3 )δ-112.0.
ATR-FTIR(cm -1 ):2361,2338,1275,1261,750,670,435.
HRMS(ESI + )Calcd for C 28 H 24 F 2 NaOS[M+Na] + 469.1408, found:469.1404, example 4
Synthesis of (Z) -methyl 3- ((5- (4- (benzyloxy) phenyl) -1, 1-difluoropent-2-en-2-yl) thio) propanoate (3 ap) as shown in FIG. 4
The preparation is carried out in accordance with example one.
The ratio of Z-3ap to E-3ap was 89:11 as measured by GC-MS, and the reaction mixture was concentrated in vacuo and purified by silica gel column chromatography to give 55.9mg of Z/E-3ap in 71% yield.
Further isolation gave a white solid Z-3ap, which was characterized as follows: 1 H NMR(400MHz,CDCl 3 )δ7.52–7.29(m,5H),7.16–7.06(m,2H),6.96–6.86(m,2H),6.44(t,J＝4.5Hz,1H),6.06(t,J＝56.3Hz,1H),5.05(s,2H),3.67(s,3H),2.92(t,J＝7.3Hz,2H),2.69(s,4H),2.54(t,J＝7.3Hz,2H).
13 C NMR(101MHz,CDCl 3 )δ172.1,157.4,144.2(t,J＝8.0Hz),137.2,133.0,129.4,128.6,128.0,127.5,116.1(t,J＝239.9Hz),114.9,70.1,51.9,34.6,33.7(t,J＝1.8Hz),31.2,29.8,28.8. 19 F NMR(377MHz,CDCl 3 )δ-110.0.
ATR-FTIR(cm -1 ):2362,2339,1275,1261,750,671,490,420.
HRMS(ESI + )Calcd for C 22 H 24 F 2 NaO 3 S[M+Na] + 429.1306, found:429.1305, example 5
Synthesis of methyl (Z) -2- (5, 5-difluoro-4- ((4-methoxyphenyl) thio) pent-3-en-1-yl) benzoate (3 ia) as shown in FIG. 5
The preparation is carried out in accordance with example one.
The ratio of Z-3ia to E-3ia was 90:10 as measured by GC-MS, and the reaction mixture was concentrated in vacuo and purified by silica gel column chromatography to give 63.5mg of Z/E-3ia in a yield of 84%.
Further isolation gave a bright yellow oil, Z-3ia, which was characterized as follows: 1 H NMR(400MHz,CDCl 3 )δ7.91(dd,J＝7.8,1.3Hz,1H),7.44(td,J＝7.5,1.4Hz,1H),7.32–7.24(m,1H),7.25–7.15(m,3H),6.82–6.73(m,2H),6.59(tt,J＝7.3,1.8Hz,1H),5.91(t,J＝56.3Hz,1H),3.89(s,3H),3.78(s,3H),3.12(t,J＝7.6Hz,2H),2.90–2.64(m,2H).
13 C NMR(101MHz,CDCl 3 )δ167.8,159.1,142.6,141.9(t,J＝7.1Hz),132.5,132.1,131.1,130.9,129.4,129.0(t,J＝21.3Hz),126.3,124.0,114.7,114.0(t,J＝241.7Hz),55.3,52.0,33.0,(t,J＝1.5Hz)31.0.
19 F NMR(377MHz,CDCl 3 )δ-112.4.
ATR-FTIR(cm -1 ):2361,2339,1275,1261,750,671,490,420.
HRMS(ESI + )Calcd for C 20 H 20 F 2 NaO 3 S[M+Na] + 401.0993, found:401.0986, example 6
Synthesis of (Z) -tert-butyl ((8, 8-difluoro-7- ((4-methoxyphenyl) thio) oct-6-en-1-yl) oxy) dimethylsilane (3 ja) as shown in FIG. 6
The preparation is carried out in accordance with example one.
GC-MS detected that the ratio of Z-3ja to E-3ja was 86:14, and the reaction mixture was concentrated in vacuo and purified by silica gel column chromatography to give 61.1mg of Z/E-3ja in 74% yield.
Further isolation gave a bright yellow oil, Z-3ja, which was characterized as follows: 1 H NMR(400MHz,CDCl 3 )δ7.25(d,J＝8.9Hz,2H),6.84–6.66(m,2H),6.55–6.41(m,1H),5.90(t,J＝56.3Hz,1H),3.74(s,3H),3.55(t,J＝6.5Hz,2H),2.48–2.31(m,2H),1.47(dd,J＝14.2,6.8Hz,2H),1.39(dd,J＝14.6,7.5Hz,2H),1.36–1.26(m,2H),0.85(s,9H),0.00(s,6H).
13 C NMR(101MHz,CDCl 3 )δ159.1,143.2(t,J＝7.1Hz),132.4,128.4(t,J＝21.5Hz),124.2,114.7,114.2(t,J＝241.5Hz),63.0,55.3,32.6,29.2,28.3(t,J＝1.5Hz),26.0,25.5,18.4,-5.3.
19 F NMR(377MHz,CDCl 3 )δ-112.1.
ATR-FTIR(cm -1 ):2361,2339,1275,1261,750,671,490,420.
HRMS(ESI + )Calcd for C 21 H 34 F 2 NaO 2 SSi[M+Na] + :439.1909,found:439.1905.
while the invention has been described with reference to preferred embodiments, it is not intended to be limiting. Those skilled in the art will appreciate that various modifications and adaptations can be made without departing from the spirit and scope of the present invention. Accordingly, the scope of the invention is defined by the appended claims.
Claims (5)
1. A synthesis method for preparing difluoroethylene sulfide by nucleophilic substitution of beta-site of geminal difluoroallene compound is characterized by comprising the following synthesis route:
wherein the method comprises the steps of
R1 is C1-C12 alkyl;
r2 is phenyl or naphthyl or furyl or benzyl or C1-C4 alkyl;
r1 can be substituted by one or more R3, which are identical or different;
r3 is phenyl or naphthyl or thiophene or indolyl or furyl or tert-butyldimethylsilyloxy or C3-C12 cycloalkyl, and one of phenyl or naphthyl or thiophene or indole substituted by benzyloxy or C1-C4 alkyl or C1-C4 alkoxycarbonyl;
r2 can be substituted by one or more R4, which are identical or different;
r4 is C1-C4 alkyl or C1-C4 alkoxy or C1-C4 haloalkyl or halogen or C1-C4 alkoxycarbonyl or phenyl;
catalyst cat [ Rh ]]Is [ Rh (cod)]BF 4 The method comprises the steps of carrying out a first treatment on the surface of the The ligand L is 1, 10-phenanthroline.
2. The method for preparing difluoroethylene sulfide by nucleophilic substitution of beta-position of geminal difluoroallene compound as in claim 1, wherein R1 is ethyl or undecyl; r3 is one of phenyl, naphthyl, thiophene, furyl, indolyl, tert-butyldimethylsilyloxy, cyclohexyl, p-benzyloxyphenyl or methyl benzoate; r2 is one of phenyl, naphthyl, furyl, benzyl or ethyl; and R4 is one of methyl, methoxy, tertiary butyl, trifluoromethyl, fluorine, chlorine, bromine or methyl formate.
3. The synthesis method for preparing difluoroethylene sulfide by nucleophilic substitution of beta-position of geminal difluoroallene compound as claimed in claim 1, wherein the preparation method comprises the following steps:
(1) Under the protection of inert gas, dissolving a catalyst and a ligand in a solvent I, then adding a compound 1 and a compound 2, and uniformly mixing;
(2) Controlling the temperature of the system to be between minus 20 and 150 ℃, reacting for 0.5 to 96 hours, concentrating the reaction mixture, desolventizing, and purifying the obtained residue to obtain the compound 3.
4. The method for preparing difluoroethylene sulfide by nucleophilic substitution at β -position of geminal difluoroallene compound as claimed in claim 3, wherein in said step (1), solvent one is one or more of dichloromethane or dichloroethane, methanol or ethanol, toluene or xylene or acetonitrile; when more than two mixed solvents are adopted, the solvents are mixed according to any ratio; the ratio of solvent one to compound 1 is 5-40mL/g.
5. The method for preparing difluoroethylene sulfide by nucleophilic substitution of beta-position of geminal difluoroallene compound as claimed in claim 3, wherein in said step (1), the molar ratio of compound 1 to catalyst, ligand and compound 2 is 1 (0.003-0.1): (0.003-0.1): (1-4).
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0710840A (en) * | 1993-06-23 | 1995-01-13 | Mitsubishi Chem Corp | Sulfide derivative, bactericidal agent using the same as effective component and intermediate therefor |
| JPH0717944A (en) * | 1993-07-06 | 1995-01-20 | Mitsubishi Chem Corp | Trifluorobutenone derivative and fungicide containing the same as active ingredient |
| CN111517954A (en) * | 2020-06-08 | 2020-08-11 | 浙江师范大学 | (Z) -5-fluoro-2-difluoromethylene olefin derivative and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0710840A (en) * | 1993-06-23 | 1995-01-13 | Mitsubishi Chem Corp | Sulfide derivative, bactericidal agent using the same as effective component and intermediate therefor |
| JPH0717944A (en) * | 1993-07-06 | 1995-01-20 | Mitsubishi Chem Corp | Trifluorobutenone derivative and fungicide containing the same as active ingredient |
| CN111517954A (en) * | 2020-06-08 | 2020-08-11 | 浙江师范大学 | (Z) -5-fluoro-2-difluoromethylene olefin derivative and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| A. Roedig et al..Thiol- und Aminaddukte von 3,3-Dichlorallencarboxamiden.《Chem. Ber.》.1983,第116卷第1595-1602页. * |
| Asymmetric Rhodium-Catalyzed Addition of Thiols to Allenes: Synthesis of Branched Allylic Thioethers and Sulfones;Adrian B. Pritzius et al.;《Angew. Chem. Int. Ed.》;第54卷;第3121-3125页 * |
| Highly Regioselective Addition of Benzenethiol to Allenes Catalyzed by Palladium Acetate;Akiya Ogawa et al.;《J. Org. Chem.》;第61卷;第4161-4163页 * |
| Palladium(II) acetate;Helena Grennberg et al.;《e-EROS Encyclopedia of Reagents for Organic Synthesis》;第1-35页 * |
| Rhodium-catalyzed asymmetric hydroalkoxylation and hydrosulfenylation of diphenylphosphinylallenes;Takahiro Kawamoto et al.;《Chem. Commun.》;第3528-3530页 * |
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