CN110627693A - Allyl sulfone compound and preparation method and application thereof - Google Patents
Allyl sulfone compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN110627693A CN110627693A CN201910983148.4A CN201910983148A CN110627693A CN 110627693 A CN110627693 A CN 110627693A CN 201910983148 A CN201910983148 A CN 201910983148A CN 110627693 A CN110627693 A CN 110627693A
- Authority
- CN
- China
- Prior art keywords
- sulfinic acid
- allyl
- solvent
- allyl alcohol
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Allyl sulfone compound Chemical class 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 46
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 14
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 claims abstract description 14
- WFABOCFDABTAPE-UHFFFAOYSA-N calcium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Ca+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F WFABOCFDABTAPE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical compound O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 12
- MHHJQVRGRPHIMR-UHFFFAOYSA-N 1-phenylprop-2-en-1-ol Chemical compound C=CC(O)C1=CC=CC=C1 MHHJQVRGRPHIMR-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000004809 thin layer chromatography Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007818 Grignard reagent Substances 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 6
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- AYQPVPFZWIQERS-VOTSOKGWSA-N (E)-oct-2-en-1-ol Chemical compound CCCCC\C=C\CO AYQPVPFZWIQERS-VOTSOKGWSA-N 0.000 claims description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- ZGYBYYJGIKPBFD-UHFFFAOYSA-N 2-methyl-1-phenylprop-2-en-1-ol Chemical compound CC(=C)C(O)C1=CC=CC=C1 ZGYBYYJGIKPBFD-UHFFFAOYSA-N 0.000 claims description 2
- LRYWJUOPPCVNFT-UHFFFAOYSA-N 2-phenylbut-3-en-2-ol Chemical compound C=CC(O)(C)C1=CC=CC=C1 LRYWJUOPPCVNFT-UHFFFAOYSA-N 0.000 claims description 2
- DRXICXADZKJOTI-UHFFFAOYSA-N 3-(4-methylphenyl)prop-2-en-1-ol Chemical compound CC1=CC=C(C=CCO)C=C1 DRXICXADZKJOTI-UHFFFAOYSA-N 0.000 claims description 2
- IMMPLAUVBYOSBD-UHFFFAOYSA-N 3-methylbenzenesulfinic acid Chemical compound CC1=CC=CC(S(O)=O)=C1 IMMPLAUVBYOSBD-UHFFFAOYSA-N 0.000 claims description 2
- 241000723346 Cinnamomum camphora Species 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- NVSONFIVLCXXDH-UHFFFAOYSA-N benzylsulfinic acid Chemical compound O[S@@](=O)CC1=CC=CC=C1 NVSONFIVLCXXDH-UHFFFAOYSA-N 0.000 claims description 2
- 229960000846 camphor Drugs 0.000 claims description 2
- 229930008380 camphor Natural products 0.000 claims description 2
- AYQPVPFZWIQERS-UHFFFAOYSA-N cis-2-octen-1-ol Natural products CCCCCC=CCO AYQPVPFZWIQERS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- RVAUVEOTZNLMQL-UHFFFAOYSA-N cyclohexanesulfinic acid Chemical compound OS(=O)C1CCCCC1 RVAUVEOTZNLMQL-UHFFFAOYSA-N 0.000 claims description 2
- XNEFVTBPCXGIRX-UHFFFAOYSA-N methanesulfinic acid Chemical compound CS(O)=O XNEFVTBPCXGIRX-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 230000004071 biological effect Effects 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- GNODXHAEOSCFQM-UHFFFAOYSA-N C1=CC=C(C=C1)C=CC(=O)S(=O)(=O)C2=CC=CC=C2 Chemical compound C1=CC=C(C=C1)C=CC(=O)S(=O)(=O)C2=CC=CC=C2 GNODXHAEOSCFQM-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- AWOQCRQDXFVJPL-JXMROGBWSA-N [(e)-3-(benzenesulfonyl)prop-1-enyl]benzene Chemical compound C=1C=CC=CC=1S(=O)(=O)C\C=C\C1=CC=CC=C1 AWOQCRQDXFVJPL-JXMROGBWSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- NZEDMAWEJPYWCD-UHFFFAOYSA-N 3-prop-2-enylsulfonylprop-1-ene Chemical group C=CCS(=O)(=O)CC=C NZEDMAWEJPYWCD-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000002246 antineoplastic agent Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002852 cysteine proteinase inhibitor Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- HBOMLICNUCNMMY-XLPZGREQSA-N zidovudine Chemical compound O=C1NC(=O)C(C)=CN1[C@@H]1O[C@H](CO)[C@@H](N=[N+]=[N-])C1 HBOMLICNUCNMMY-XLPZGREQSA-N 0.000 description 2
- 229960002555 zidovudine Drugs 0.000 description 2
- OTFZDCHWYNNDRP-UHFFFAOYSA-N 1-(4-trimethylsilylphenyl)prop-2-en-1-ol Chemical compound C[Si](C)(C)C1=CC=C(C=C1)C(C=C)O OTFZDCHWYNNDRP-UHFFFAOYSA-N 0.000 description 1
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical compound COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 description 1
- 101000749287 Clitocybe nebularis Clitocypin Proteins 0.000 description 1
- 101000767029 Clitocybe nebularis Clitocypin-1 Proteins 0.000 description 1
- 229940094664 Cysteine protease inhibitor Drugs 0.000 description 1
- 102100030412 Matrix metalloproteinase-9 Human genes 0.000 description 1
- 108010015302 Matrix metalloproteinase-9 Proteins 0.000 description 1
- 208000019695 Migraine disease Diseases 0.000 description 1
- 206010060862 Prostate cancer Diseases 0.000 description 1
- 208000000236 Prostatic Neoplasms Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UWZMKHTYDFOZPT-BQYQJAHWSA-N [4-[(E)-3-(benzenesulfonyl)prop-1-enyl]phenyl]-trimethylsilane Chemical compound C[Si](C)(C)C1=CC=C(C=C1)/C=C/CS(=O)(=O)C2=CC=CC=C2 UWZMKHTYDFOZPT-BQYQJAHWSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical group 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005828 desilylation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 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
- 229960002472 eletriptan Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 206010027599 migraine Diseases 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
- 229930014626 natural product Natural products 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/02—Sulfinic acids; Derivatives thereof
- C07C313/04—Sulfinic acids; Esters thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- 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
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- 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
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H19/00—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof
- C07H19/02—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof sharing nitrogen
- C07H19/04—Heterocyclic radicals containing only nitrogen atoms as ring hetero atom
- C07H19/06—Pyrimidine radicals
- C07H19/073—Pyrimidine radicals with 2-deoxyribosyl as the saccharide radical
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an allyl sulfone compound and a preparation method and application thereof. Sequentially adding allyl alcohol, sulfinic acid, palladium tetrakis (triphenylphosphine) and calcium bis (trifluoromethylsulfonyl) imide into a reaction solvent in an inert gas atmosphere, and stirring and reacting for 12-48 h at the temperature of 30 ℃; wherein the equivalent ratio of allyl alcohol, sulfinic acid, tetrakis (triphenylphosphine) palladium and calcium bis (trifluoromethylsulfonyl) imide is 1: (1.5-2): (1-3%): (5-10%); and removing the reaction solvent in the reaction liquid, and then purifying to obtain the allyl sulfone compound. The preparation method has high economy and wide applicable substrate range; in addition, the obtained allyl sulfone compound has potential pharmaceutical activity and biological activity and is an important skeleton widely existing in biological and pharmaceutical active molecules.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to an allyl sulfone compound and a preparation method and application thereof.
Background
Sulfones play an important role in organic synthesis and are also widely found in many biologically active natural products and in some well-established drugs (e.g., eletriptan ([2H ] -SB-3CT) for the treatment of migraine, MMP-9 inhibitors for the treatment of prostate cancer).
Furthermore, the widespread distribution of the allylsulfone backbone in biologically and pharmaceutically active molecules (e.g. anticancer agents, cysteine protease inhibitors, antibacterial agents, herbicides) has also attracted considerable attention. Therefore, the development of synthetic methods for allyl sulfone has attracted considerable attention in the synthetic community. Existing synthetic methods include the use of transition metal catalyzed (oxidation) -cross-coupling reactions and hydrosulfiding by the use of highly reactive allylic substrates and sulfinyl nucleophiles. However, from an environmental and economic point of view, it is very attractive to develop an energy-saving and efficient green synthesis method using nontoxic, inexpensive, readily available and relatively harmless raw materials, and particularly to a method using allyl alcohol as a raw material and water as a byproduct.
Disclosure of Invention
The invention aims to provide an allyl sulfone compound.
The invention further aims to provide a preparation method of the allyl sulfone compound.
The invention further aims to provide application of the allyl sulfone compound.
The invention is realized by the following steps that the chemical structural formula of the compound is shown as the following formula (I):
in the above formula (I), R1Is aryl or alkyl; r2~R5Any of hydrogen radicals, aryl radicals and alkyl radicals.
The invention further discloses a preparation method of the allyl sulfone compound, which comprises the following steps:
(1) sequentially adding allyl alcohol, sulfinic acid, tetrakis (triphenylphosphine) palladium and calcium bis (trifluoromethylsulfonyl) imide into a reaction solvent in an inert gas atmosphere, and stirring and reacting for 12-48 h at the temperature of 30 ℃; wherein the equivalent ratio of allyl alcohol, sulfinic acid, tetrakis (triphenylphosphine) palladium and calcium bis (trifluoromethylsulfonyl) imide is 1: (1.5-2): (1-3%): (5-10%);
(2) and removing the reaction solvent in the reaction liquid, and then purifying to obtain the allyl sulfone compound.
Preferably, in step (1), the inert gas is argon;
the allyl alcohol comprises primary cinnamyl alcohol allyl alcohol, secondary allyl alcohol and tertiary allyl alcohol;
the sulfinic acid is any one of phenyl sulfinic acid, 3-methyl phenyl sulfinic acid, methyl sulfinic acid, cyclohexane sulfinic acid, camphor sulfinic acid and benzyl sulfinic acid;
the reaction solvent is any one of 1, 2-dichloroethane, tetrahydrofuran and N, N-dimethylacetamide.
Preferably, the allyl alcohol is any one of cinnamyl alcohol, p-methyl cinnamyl alcohol, p-fluoro cinnamyl alcohol, trans-2-octen-1-ol, 1-phenylprop-2-en-1-ol, 2-methyl-1-phenyl-2-propen-1-ol and 2-phenylbut-3-en-2-ol.
Preferably, the allyl alcohol is 1-phenylprop-2-en-1-ol.
Preferably, the synthesis method of the 1-phenylprop-2-en-1-ol comprises the following steps:
A. adding benzaldehyde into a tetrahydrofuran solvent at room temperature to obtain a solution 1; adding a vinyl Grignard reagent into the solution 1 at 0 ℃, and stirring for 2 hours to obtain a reaction mixture; wherein the ratio of the quantities of the benzaldehyde, the vinyl Grignard reagent and the tetrahydrofuran solvent is 10 mmol: (15-20) mmol: (10-20) mL;
B. the reaction mixture was quenched by addition to saturated ammonium chloride, extracted 3 times with ethyl acetate, the organic phases combined, dried over anhydrous magnesium sulfate, the solvent removed with a rotary evaporator, and the residue purified by column silica gel chromatography with petroleum ether and ethyl acetate (PE/EA ═ 50:1 to 10:1) to give 1-phenylpropan-2-en-1-ol as a pale yellow liquid.
Preferably, the sulfinic acid is phenyl sulfinic acid; the reaction solvent is N, N-dimethylacetamide.
Preferably, the method for synthesizing the phenylsulfinic acid comprises the following steps:
A. dissolving sodium benzene sulfinate in water, adding tert-butyl methyl ether, slowly adding hydrochloric acid with the mass fraction of 36-38% within 2 minutes, and stirring the mixture for 10 minutes; wherein the ratio of the quantities of the sodium benzene sulfinate, the hydrochloric acid, the water and the tert-butyl methyl ether is 17.5 mmol: (1-2) mL: (10-15) mL: (5-10) mL;
B. the mixture was transferred to a separatory funnel, the aqueous layer was removed, the organic layer was concentrated on a rotary evaporator until the solvent disappeared, and the obtained white solid was dried in vacuo to give benzenesulfinic acid.
Preferably, in step (2), the reaction solvent is removed by extraction with EA (50mL x 3 times) followed by vacuum rotary evaporation; the purification adopts a thin layer chromatography method, namely, a system mixture is uniformly coated on a silica gel plate, the silica gel plate is dried by a blower, the silica gel plate is placed in a spreading cylinder containing a developing agent PE/EA (2: 1-3: 1), when a solvent reaches the front edge of the solvent, silica gel powder at the position of a product is scraped off under the detection of an ultraviolet lamp, EA (60mL for 3 times) is washed off in a sand core funnel instrument to obtain the product, and the developing agent system is petroleum ether/ethyl acetate (PE/EA: 2: 1-3: 1).
The invention further discloses application of the allyl sulfone compound in serving as a skeleton of bioactive molecules and pharmaceutical active molecules.
The invention discloses a preparation method and application of an allyl sulfone compound. The allyl alcohol raw material, sulfinic acid, tetrakis (triphenylphosphine) palladium and calcium bis (trifluoromethylsulfonyl) imide are sequentially added into a reaction solvent, stirred under the condition of argon and 30 ℃ for catalytic reaction, and the obtained reaction liquid is purified after the reaction solvent is removed to obtain the allyl sulfone compound. The synthesis method has high economy and wide applicable substrate range, and the obtained allyl sulfone compound has potential pharmaceutical activity and biological activity and is an important skeleton widely existing in biological and pharmaceutical active molecules.
Compared with the defects and shortcomings of the prior art, the invention has the following beneficial effects:
(1) part of the raw materials used by the method is low-cost commercial cinnamyl alcohol raw materials, and the obtained by-product is only water, so that the method is high in atom economy, green and environment-friendly;
(2) the method of the invention needs not very harsh conditions, the substrate has wide application range, for example, allyl alcohol can be various substituted phenyl, heterocycle and alkyl;
(3) the process of the invention is applicable to different types of allyl alcohol;
(4) the allyl sulfone compound has wide application prospect in biologically and pharmaceutically active molecules (such as anticancer agents, cysteine protease inhibitors, antibacterial agents and herbicides).
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of (cinnamoylsulfonyl) benzene;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of (cinnamoylsulfonyl) benzene.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
(1) Adding 10mmol of benzaldehyde into 10mL of tetrahydrofuran solvent at room temperature to obtain a solution 1; slowly adding 15mmol of vinyl Grignard reagent into the solution 1 at the temperature of 0 ℃, and stirring for 2 hours to obtain a reaction mixture; the reaction equation is:
(2) the reaction mixture was quenched by addition to saturated ammonium chloride solution, extracted 3 times with ethyl acetate, the organic phases combined, dried over anhydrous magnesium sulfate, the solvent removed with a rotary evaporator, and the residue purified by column silica gel chromatography with petroleum ether and ethyl acetate (PE/EA ═ 50:1 to 10:1) to give 1-phenylpropan-2-en-1-ol as a pale yellow liquid.
Example 2
This example is substantially the same as example 1 above except that, in step (1), 10mmol of benzaldehyde was added to 20mL of tetrahydrofuran solvent to give a solution 1; at 0 deg.C, 20mmol of vinyl Grignard reagent was slowly added to solution 1.
Example 3
(1) Dissolving 17.5mmol of sodium benzene sulfinate in 10mL of water, adding 5mL of tert-butyl methyl ether, slowly adding 1.6mL of concentrated hydrochloric acid with the mass fraction of 36-38% within 2 minutes, and stirring the mixture for 30 minutes to obtain a reaction mixture; the reaction equation is:
(2) transferring the mixed solution to a separating funnel, and removing a water layer; the organic layer was concentrated on a rotary evaporator until the solvent disappeared and the white solid obtained was dried in vacuo to give the benzenesulfinic acid.
Example 4
This example is substantially the same as example 3 above, except that in step (1), 17.5mmol of sodium benzenesulfinate was dissolved in 15mL of water, 10mL of t-butyl methyl ether was added, 2mL of concentrated hydrochloric acid with a mass fraction of 36-38% was slowly added over 2 minutes, and the mixture was stirred for another 30 minutes to obtain a reaction mixture.
Example 5
(1) In a 10mL Schlenk tube, under argon atmosphere, 1-phenylprop-2-en-1-ol (0.3mmol), benzenesulfinic acid (0.45mmol), tetrakis (triphenylphosphine) palladium (1 mol%), calcium bis (trifluoromethylsulfonyl) imide (5 mol%) was added with N, N-dimethylacetamide (2mL) and stirred at 30 ℃ for reaction, the equation is:
(2) after completion of the reaction monitored by TLC, the reaction solution was extracted with EA extraction (50mL × 3 times), and the solvent was removed by vacuum rotary evaporator;
uniformly coating the system mixture on a silica gel plate, drying by using a blower, and putting the silica gel plate into a solution containing a developing agent PE/EA (2-3): 1, scraping silica gel powder at the product position under the detection of an ultraviolet lamp when the solvent reaches the front edge of the solvent, and washing the silica gel powder in a sand core funnel instrument by using EA (60mL for 3 times) to obtain a product, wherein a developing agent system is petroleum ether/ethyl acetate (PE/EA is 2: 1-3: 1), the product is white solid (cinnamyl sulfonyl) benzene, and the yield is 68%.
Example 6
(1) In a 10ml Schlenk tube, under argon atmosphere, cinnamyl alcohol (0.3mmol), benzene sulfinic acid (0.45mmol), tetrakis (triphenylphosphine) palladium (1 mol%), calcium bis (trifluoromethylsulfonyl) imide (5 mol%), N-dimethylacetamide (2ml) was added, and the reaction was stirred at 30 ℃ according to the equation:
(2) after TLC monitoring reaction, the reaction solution was extracted, the solvent was removed by vacuum rotary evaporator, and the product was isolated by thin layer chromatography with a white solid (cinnamyl sulfonyl) benzene as the developing agent in the petroleum ether/ethyl acetate system in 93% yield.
The product (cinnamoylsulfonyl) benzene obtained in this example was subjected to a nuclear magnetic resonance test, and as shown in fig. 1 to 2, fig. 1 is a nuclear magnetic resonance hydrogen spectrum of (cinnamoylsulfonyl) benzene, and fig. 2 is a nuclear magnetic resonance carbon spectrum of (cinnamoylsulfonyl) benzene.
Example 7
(1) The embodiment is different from embodiments 5 to 6 in that: the allyl alcohol starting material used was 1- (4- (trimethylsilyl) phenyl) prop-2-en-1-ol, the reaction equation is:
(2) after TLC monitoring reaction was complete, the reaction was extracted, solvent was removed by vacuum rotary evaporator and the product was isolated by thin layer chromatography using petroleum ether/ethyl acetate system as developing agent in 80% yield as white solid (E) -trimethyl (4- (3- (phenylsulfonyl) prop-1-en-1-yl) phenyl) silane.
In the technical scheme provided by the applicant, the (cinnamyl sulfonyl) benzene prepared by the method has potential pharmaceutical activity and biological activity.
Application example 1
This example is the same as example 6 above, except that cinnamyl alcohol (6mmol), 4-ethynylanisole (7.5mmol), tetrakis (triphenylphosphine) palladium (1 mol%), calcium bis (trifluoromethylsulfonyl) imide (5 mol%) were added to a 50mL reaction tube followed by addition of N, N-dimethylacetamide (10mL) to give (cinnamyl sulfonyl) benzene 1.3g, 85% yield.
Application example 2
The allyl sulfone compound prepared in the above example 7 of the present invention has potential pharmaceutical activity and biological activity, and is modified with the pharmaceutical raw material zidovudine having pharmaceutical activity to synthesize a macromolecular skeleton containing both sulfur and nitrogen heteroatoms.
(1) The product obtained in example 7 was subjected to desilylation reaction with TBAF reagent, and to a solution (1.5mL) of the terminal alkyne (0.2mmol) and zidovudine (0.22mmol) in t-butanol, copper sulfate pentahydrate (0.1mmol) and an aqueous solution (1.5mL) of sodium ascorbate (0.1mmol) were added, and the mixture was stirred at room temperature for 2 hours. The equation is:
(2) the reaction mixture was diluted with ethyl acetate, washed with water, and the organic phase was dried over anhydrous sodium sulfate. Filtration afforded a white solid in 85% yield.
Application example 3
The allyl sulfone compound prepared by the invention is an important skeleton widely existing in biological and pharmaceutical active molecules, such as a cysteine protease inhibitor, and has the following structural formula:
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. An allyl sulfone compound, which is characterized in that the chemical structural formula of the compound is shown as the following formula (I):
in the above formula (I), R1Is aryl or alkyl; r2~R5Any of hydrogen radicals, aryl radicals and alkyl radicals.
2. A process for the preparation of the allylic sulfone compound of claim 1, comprising the steps of:
(1) sequentially adding allyl alcohol, sulfinic acid, tetrakis (triphenylphosphine) palladium and calcium bis (trifluoromethylsulfonyl) imide into a reaction solvent in an inert gas atmosphere, and stirring and reacting for 12-48 h at the temperature of 30 ℃; wherein the equivalent ratio of allyl alcohol, sulfinic acid, tetrakis (triphenylphosphine) palladium and calcium bis (trifluoromethylsulfonyl) imide is 1: (1.5-2): (1-3%): (5-10%);
(2) and removing the reaction solvent in the reaction liquid, and then purifying to obtain the allyl sulfone compound.
3. The method for preparing an allylsulfone compound according to claim 2, wherein in the step (1), the inert gas is argon;
the allyl alcohol comprises primary cinnamyl alcohol allyl alcohol, secondary allyl alcohol and tertiary allyl alcohol;
the sulfinic acid is any one of phenyl sulfinic acid, 3-methyl phenyl sulfinic acid, methyl sulfinic acid, cyclohexane sulfinic acid, camphor sulfinic acid and benzyl sulfinic acid;
the reaction solvent is any one of 1, 2-dichloroethane, tetrahydrofuran and N, N-dimethylacetamide.
4. The method for producing an allylsulfone compound according to claim 3, wherein the allyl alcohol is any one of cinnamyl alcohol, p-methylcinnamyl alcohol, p-fluorocinnamyl alcohol, trans-2-octen-1-ol, 1-phenylpropan-2-en-1-ol, 2-methyl-1-phenyl-2-propen-1-ol, and 2-phenylbut-3-en-2-ol.
5. The method for preparing an allylsulfone compound according to claim 4, wherein the allyl alcohol is 1-phenylprop-2-en-1-ol.
6. The method for preparing the allyl sulfone compound as claimed in claim 5, wherein the method for synthesizing the 1-phenylprop-2-en-1-ol comprises the following steps:
A. adding benzaldehyde into a tetrahydrofuran solvent at room temperature to obtain a solution 1; adding a vinyl Grignard reagent into the solution 1 at 0 ℃, and stirring for 2 hours to obtain a reaction mixture; wherein the ratio of the quantities of the benzaldehyde, the vinyl Grignard reagent and the tetrahydrofuran solvent is 10 mmol: (15-20) mmol: (10-20) mL;
B. the reaction mixture was quenched by addition to saturated ammonium chloride, extracted 3 times with ethyl acetate, the organic phases combined, dried over anhydrous magnesium sulfate, the solvent removed with a rotary evaporator, and the residue purified by column silica gel chromatography with petroleum ether and ethyl acetate to give 1-phenylprop-2-en-1-ol as a pale yellow liquid.
7. The method for preparing an allylsulfone compound according to claim 3, wherein the sulfinic acid is a sulfinic acid such as phenylsulfinic acid;
the reaction solvent is N, N-dimethylacetamide.
8. The method for preparing an allylsulfone compound of claim 7, wherein the method for synthesizing the phenylsulfinic acid comprises the following steps:
A. dissolving sodium benzene sulfinate in water, adding tert-butyl methyl ether, slowly adding hydrochloric acid with the mass fraction of 36-38% within 2 minutes, and stirring the mixture for 10 minutes; wherein the ratio of the quantities of the sodium benzene sulfinate, the hydrochloric acid, the water and the tert-butyl methyl ether is 17.5 mmol: (1-2) mL: (10-15) mL: (5-10) mL;
B. the mixture was transferred to a separatory funnel, the aqueous layer was removed, the organic layer was concentrated on a rotary evaporator until the solvent disappeared, and the obtained white solid was dried in vacuo to give benzenesulfinic acid.
9. The method for preparing an allylsulfone compound according to claim 2, wherein in the step (2), the reaction solvent is removed by extraction with EA and vacuum rotary evaporation; the purification adopts thin layer chromatography, and the developing agent system is petroleum ether/ethyl acetate.
10. Use of the allylic sulfone of claim 1 as a scaffold for biologically and pharmaceutically active molecules.
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