CN108912042A - A method of aromatic ketone is directly prepared from aromatic acid - Google Patents
A method of aromatic ketone is directly prepared from aromatic acid Download PDFInfo
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- CN108912042A CN108912042A CN201810756654.5A CN201810756654A CN108912042A CN 108912042 A CN108912042 A CN 108912042A CN 201810756654 A CN201810756654 A CN 201810756654A CN 108912042 A CN108912042 A CN 108912042A
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- 238000000034 method Methods 0.000 title abstract description 101
- 150000008365 aromatic ketones Chemical class 0.000 title description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 384
- 229910001868 water Inorganic materials 0.000 claims abstract description 203
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 193
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000003054 catalyst Substances 0.000 claims abstract description 100
- 238000006243 chemical reaction Methods 0.000 claims abstract description 100
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 96
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims abstract description 96
- -1 aryl ketones Chemical class 0.000 claims abstract description 41
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001336 alkenes Chemical class 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 18
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000002790 naphthalenes Chemical class 0.000 claims description 2
- 125000005493 quinolyl group Chemical group 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 2
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 189
- 239000012074 organic phase Substances 0.000 description 185
- 238000005160 1H NMR spectroscopy Methods 0.000 description 96
- 239000000047 product Substances 0.000 description 96
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 94
- 239000007832 Na2SO4 Substances 0.000 description 93
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 93
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 93
- 239000007789 gas Substances 0.000 description 93
- 239000003208 petroleum Substances 0.000 description 93
- 239000012071 phase Substances 0.000 description 93
- 239000000741 silica gel Substances 0.000 description 93
- 229910002027 silica gel Inorganic materials 0.000 description 93
- 229910052938 sodium sulfate Inorganic materials 0.000 description 93
- 239000002904 solvent Substances 0.000 description 92
- SRCZQMGIVIYBBJ-UHFFFAOYSA-N ethoxyethane;ethyl acetate Chemical compound CCOCC.CCOC(C)=O SRCZQMGIVIYBBJ-UHFFFAOYSA-N 0.000 description 91
- 238000004440 column chromatography Methods 0.000 description 82
- 239000000284 extract Substances 0.000 description 55
- 238000001035 drying Methods 0.000 description 17
- LPNBBFKOUUSUDB-UHFFFAOYSA-N Cc(cc1)ccc1C(O)=O Chemical compound Cc(cc1)ccc1C(O)=O LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 6
- 0 *c1cnc(C=C)cc1 Chemical compound *c1cnc(C=C)cc1 0.000 description 4
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BLIOKBFRPGZNKW-UHFFFAOYSA-N C=CCOc1cccc(C(CCc2ncccc2)=O)c1 Chemical compound C=CCOc1cccc(C(CCc2ncccc2)=O)c1 BLIOKBFRPGZNKW-UHFFFAOYSA-N 0.000 description 1
- BMUGETBICLRMFY-UHFFFAOYSA-N C=Cc(cc1)ccc1C(NCCC1c2ccccc2NC1)=O Chemical compound C=Cc(cc1)ccc1C(NCCC1c2ccccc2NC1)=O BMUGETBICLRMFY-UHFFFAOYSA-N 0.000 description 1
- WHTROILZSHNABU-UHFFFAOYSA-N C=[Br]c(cc1)ccc1C(O)=O Chemical compound C=[Br]c(cc1)ccc1C(O)=O WHTROILZSHNABU-UHFFFAOYSA-N 0.000 description 1
- GQKBRMARDIUGGV-UHFFFAOYSA-N CC(CC(c(cccc1)c1OCCCCCCCCCCO1)=O)C1=O Chemical compound CC(CC(c(cccc1)c1OCCCCCCCCCCO1)=O)C1=O GQKBRMARDIUGGV-UHFFFAOYSA-N 0.000 description 1
- LOYIKIOKPRTKGL-UHFFFAOYSA-N CCOC(C(C(C)C(c1ccc(C)cc1)=O)C(OCC)=O)=O Chemical compound CCOC(C(C(C)C(c1ccc(C)cc1)=O)C(OCC)=O)=O LOYIKIOKPRTKGL-UHFFFAOYSA-N 0.000 description 1
- PPOSEWLHQCCBIF-UHFFFAOYSA-N CCOC(c1cnc(CCC(c2ccc(C)cc2)=O)cc1)=O Chemical compound CCOC(c1cnc(CCC(c2ccc(C)cc2)=O)cc1)=O PPOSEWLHQCCBIF-UHFFFAOYSA-N 0.000 description 1
- RUZAEEOUQCYUKM-UHFFFAOYSA-N COC(c(cc1)ccc1C(c1ccccc1)=C)=O Chemical compound COC(c(cc1)ccc1C(c1ccccc1)=C)=O RUZAEEOUQCYUKM-UHFFFAOYSA-N 0.000 description 1
- NUMHUJZXKZKUBN-UHFFFAOYSA-N COC(c1ccc(C=C)cc1)=O Chemical compound COC(c1ccc(C=C)cc1)=O NUMHUJZXKZKUBN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- HVOQRJDUNDPOOX-UHFFFAOYSA-N Cc(cc1)ccc1C(CC(c1cc(cccc2)c2cc1)c1ccccn1)=O Chemical compound Cc(cc1)ccc1C(CC(c1cc(cccc2)c2cc1)c1ccccn1)=O HVOQRJDUNDPOOX-UHFFFAOYSA-N 0.000 description 1
- PECKXFPYBFPLOM-UHFFFAOYSA-N Cc(cc1)ccc1C(CCc(cccc1)c1C(OCc1ccccc1)=O)=O Chemical compound Cc(cc1)ccc1C(CCc(cccc1)c1C(OCc1ccccc1)=O)=O PECKXFPYBFPLOM-UHFFFAOYSA-N 0.000 description 1
- OJQMTWXYXDCESE-UHFFFAOYSA-N Cc1cccc(C(CCc2ncccc2)=O)c1 Chemical compound Cc1cccc(C(CCc2ncccc2)=O)c1 OJQMTWXYXDCESE-UHFFFAOYSA-N 0.000 description 1
- KHSDEFIYURFTFO-UHFFFAOYSA-N Cc1ccccc1C(CCc1ncccc1)=O Chemical compound Cc1ccccc1C(CCc1ncccc1)=O KHSDEFIYURFTFO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- IGYGFNOYLNULSP-UHFFFAOYSA-N O=C(CCc1ccccn1)c(cc1)ccc1Cl Chemical compound O=C(CCc1ccccn1)c(cc1)ccc1Cl IGYGFNOYLNULSP-UHFFFAOYSA-N 0.000 description 1
- MOFYNGCVZYGMJE-UHFFFAOYSA-N O=C(CCc1ncccc1)c1ccc2OCOc2c1 Chemical compound O=C(CCc1ncccc1)c1ccc2OCOc2c1 MOFYNGCVZYGMJE-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000010916 retrosynthetic analysis Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/46—Oxygen atoms
- C07D213/50—Ketonic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
- C07C49/784—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with all keto groups bound to a non-condensed ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
- C07C49/813—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/738—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/53—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/55—Acids; Esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
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Abstract
A method of aryl ketones being prepared, it is using aromatic carboxylic acids (ArCOOH) and alkene as raw material, and triphenylphosphine is as deoxidier, under blue light light irradiation, in the solution of methylene chloride and water, under argon atmosphere, in the presence of a small amount of dipotassium hydrogen phosphate, with [Ir (dF (CF3)ppy)2(dtbbpy)]PF6For photochemical catalyst, aromatic ketone compound is obtained.This method raw material is easy to get, and reaction condition is mild, and adaptability is extensive.
Description
Technical field
The present invention relates to a kind of methods that aromatic ketone is directly prepared from aromatic carboxylic acids.
Background technique
Aromatic ketone is a kind of very important organic compound, in natural products and the relevant retrosynthetic analysis of pharmacy,
Committed step (the Nat. that ketone molecular skeleton is often used as during organic synthesis is constructed by the coupling reaction of C-C key
Chem.2012,4,228).The coupling reaction of nucleophilic organometallic reagent and electrophilic carboxylic acid derivates (such as amide, acyl chlorides, ester)
It is a kind of effective way (the Tetrahedron Lett.1981,22,3815 for synthesizing ketone；Chem.Soc.Rev.1995,24,
89).However, excessive acylting agent, cumbersome operating procedure, harsh reaction condition and poor chemo-selective etc. because
Element constrains their synthesis application to a certain extent.Aromatic carboxylic acids and olefin(e) compound are two kinds cheap and easy to get, deposit ten
Divide abundant chemical raw material, it is very ideal that ketone compounds are synthesized by them.It is urged using a kind of light of mild condition
Change approach is raw material from the aromatic carboxylic acids being easy to get and alkene is stablized, can efficiently realize the preparation of all kinds of aromatic ketone compounds,
Fine chemistry industry, material science and pharmaceutical field have ideal application prospect.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation of the aryl ketones of mild condition and its applications.
Synthetic route of the invention is as follows：
A method of aryl ketones being prepared, it is with aromatic carboxylic acids (ArCOOH) (1) and alkene (2) for raw material, triphenyl
Phosphine is as deoxidier, under blue light light irradiation, in the solution of methylene chloride and water, under argon atmosphere, in a small amount of phosphoric acid hydrogen two
In the presence of potassium, with [Ir (dF (CF3)ppy)2(dtbbpy)]PF6For photochemical catalyst, aromatic ketone compound is obtained；The light is urged
Agent [Ir (dF (CF3)ppy)2(dtbbpy)]PF6Such as flowering structure：
Above-mentioned preparation method, the carbocyclic rings virtue that the Ar group in the aromatic carboxylic acids can be various substitutions or not replace
Base or heterocyclic aryl, R group can be substitution or not substituted pyridinyl, quinolyl, isoquinolyl, pyrimidine radicals, phenyl, ester group,
Phosphonate group or sulfuryl etc..
Above-mentioned preparation method, the phenyl ring that the Ar group in the aromatic carboxylic acids can be various substitutions or not replace
Base, naphthalene nucleus base, thienyl, isoquinolyl or indyl.
Above-mentioned preparation method, described is in methylene chloride (dichloromethane) and water (water) in the solution
Middle magnetic agitation, 1200 turns/min of revolving speed.
The ratio between the amount of substance of above-mentioned preparation method, the aromatic carboxylic acids 1 and alkene 2 is 1:1 to 1:5；Most ratio of greater inequality
Example is 1:1.5.
Above-mentioned preparation method, the photochemical catalyst [Ir (dF (CF3)ppy)2(dtbbpy)]PF6Dosage is fragrant carboxylic
The mole of the 0.1-10% of sour 1 molal quantity；Optimal mole is 1%.
Above-mentioned preparation method, the dipotassium hydrogen phosphate are the moles of the 10-100% of 1 molal quantity of aromatic carboxylic acids；Most
It is 20% under the conditions of good.
Typical reaction is as follows：
Method reaction condition of the invention is mild, does not need hot conditions, from various aryl carboxylic acids cheap and easy to get and alkene
Hydrocarbon directly obtains aromatic ketone compound.
Specific embodiment
It will be helpful to understand the present invention using following embodiments, but be not intended to limit the contents of the present invention.
Embodiment 1
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then slowly added into(31.5mg, 0.3mmol) is subsequently placed in blue led s lamp (brand:Ai Delang, led light bar, similarly hereinafter) irradiation
Under, 36-60h is reacted at room temperature.Reaction terminates, and 20mL water is added, and extract (3x 10mL) water phase with DCM, with organic phase
Merge.Organic phase is through anhydrous Na2SO4Solvent, dry method loading is evaporated off in dry back spin, and column chromatographs (300-400 mesh chromatographic silica gel)
(eluant, eluent：Petroleum ether-ethyl acetate) product 32.4mg is obtained,Yield 72%.1H NMR
(400MHz, Chloroform-d) δ 8.51 (d, J=4.8 Hz, 1H), 7.89 (d, J=8.2Hz, 2H), 7.59 (td, J=
7.7,1.8Hz, 1H), 7.30-7.20 (m, 3H), 7.15-6.76 (m, 1H), 3.48 (t, J=7.3Hz, 2H), 3.23 (t, J=
7.3Hz,2H),2.40(s,3H).13C NMR(100 MHz,Chloroform-d)δ198.9,160.8,149.2,143.7,
136.4,134.4,129.2,128.2,123.4,121.2, 37.8,32.2,21.6.HRMS(ESI)Calculated for
C15H16NO+([M+H]+):226.1226,found: 226.1228.
Embodiment 2
It weighs(39.6mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)PF6
(2.3mg, 0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction tube is added in P (62.9mg, 0.24mmol), leads to
It crosses vacuum pipeline and substitutes gas three times, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Reaction knot
Beam adds 20mL water, and extracts (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4After drying
Revolving removes solvent, dry method loading, and column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product
32.7mg,Yield 57%.1H NMR (400MHz, Chloroform-d) δ 8.52 (d, J=
5.6Hz, 1H), 8.07 (d, J=10.4Hz, 2H), 7.74-7.52 (m, 6H), 7.46 (t, J=7.4Hz, 2H), 7.39 (t, J
=6.7Hz, 1H), 7.27 (d, J=9.5Hz, 1H), 7.16-7.05 (m, 1H), 3.54 (t, J=7.3Hz, 2H), 3.26 (t, J
=7.3Hz, 2H)13C NMR(100MHz,Chloroform-d)δ198.9, 160.7,149.2,145.7,139.9,136.4,
135.6,128.9,128.7,128.2,127.3,127.2,123.4,121.3,37.9, 32.1.HRMS(ESI)
Calculated for C20H18NO+([M+H]+):288.1383,found:288.1382.
Embodiment 3
First weigh(45.6mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 30.4mg,Yield 48%.1H NMR (400MHz, Chloroform-d) δ 8.51 (d, J=4.9Hz,
1H), 7.97 (d, J=6.9Hz, 2H), 7.70-7.52 (m, 1H), 7.48-7.30 (m, 5H), 7.25 (d, J=7.8Hz, 1H),
7.10 (dd, J=8.5,4.9Hz, 1H), 6.99 (d, J=8.9Hz, 2H), 5.11 (s, 2H), 3.45 (t, J=7.3Hz, 2H),
3.22 (t, J=7.3Hz, 2H)13C NMR(100MHz,Chloroform-d)δ197.9, 162.6,160.9,149.2,
136.4,136.2,130.4,130.2,128.7,128.2,127.5,123.4,121.2,114.5,70.1, 37.6,
32.2.HRMS(ESI)Calculated for C21H20NO2 +([M+H]+):318.1489,found:318.1488.
Embodiment 4
First weigh(24.4mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)PF6
(2.3mg,1 0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction tube is added in P (62.9mg, 0.24mmol),
Gas is substituted three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 32.9mg,Yield 78%.1H NMR (400MHz, Chloroform-d) δ 8.51 (d, J=5.6Hz, 1H),
7.98 (d, J=1.4Hz, 2H), 7.61-7.52 (m, 2H), 7.45 (t, J=7.6Hz, 2H), 7.26 (d, J=7.6Hz, 1H),
7.14-7.06 (m, 1H), 3.51 (t, J=7.3Hz, 2H), 3.24 (t, J=7.3Hz, 2H)13C NMR(100MHz,
Chloroform-d)δ199.3,160.7,149.2,136.9,136.4,133.0,128.6, 128.1,123.4,121.3,
37.8,32.1.HRMS(ESI)Calculated for C14H14NO+([M+H]+):212.1070, found:212.1073.
Embodiment 5
First weigh(28.0mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)PF6
(2.3mg, 0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction tube is added in P (62.9mg, 0.24mmol), leads to
It crosses vacuum pipeline and substitutes gas three times, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 34.4mg,Yield 75%.1H NMR (400MHz, Chloroform-d) δ 8.51 (d, J=4.8Hz,
1H), 8.12-7.87 (m, 2H), 7.60 (t, J=7.7Hz, 1H), 7.26 (d, J=9.9Hz, 1H), 7.17-7.05 (m, 3H),
3.49 (t, J=7.2Hz, 2H), 3.23 (t, J=7.2Hz, 2H)13C NMR(100 MHz,Chloroform-d)δ197.8,
165.7 (d, J=254.5Hz), 160.5,149.2,136.4,133.3 (d, J=3.1 Hz), 130.7 (d, J=9.2Hz),
(123.4,121.3,115.6 d, J=21.8Hz), 37.7,32.0.HRMS (ESI) Calculated for C14H13FNO+([M
+H]+):230.0976,found:230.0976.
Embodiment 6
First weigh(31.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 34.3mg,Yield 70%.1H NMR (400MHz, Chloroform-d) δ 8.51 (d, J=4.8Hz,
1H), 7.94 (d, J=9.1Hz, 2H), 7.68-7.51 (m, 1H), 7.42 (d, J=13.4Hz, 2H), 7.31-7.20 (m,
1H), 7.15-7.06 (m, 1H), 3.48 (t, J=7.2Hz, 2H), 3.23 (t, J=7.2Hz, 2H)13C NMR(100MHz,
Chloroform-d)δ198.1,160.4,149.2,139.4,136.4,135.2,129.5, 128.9,123.4,121.3,
37.7,31.9.HRMS(ESI)Calculated for C14H13ClNO+([M+H]+): 246.0680,found:246.0681.
Embodiment 7
First weigh(40.0mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 36.0mg,Yield 62%.1H NMR (400MHz, Chloroform-d) δ 8.50 (d, J=5.6Hz,
1H), 7.86 (d, J=8.6Hz, 2H), 7.66-7.52 (m, 3H), 7.25 (d, J=7.8Hz, 1H), 7.16-7.06 (m, 1H),
3.47 (t, J=7.2Hz, 2H), 3.23 (t, J=7.2Hz, 2H)13C NMR(100 MHz,Chloroform-d)δ198.3,
160.4,149.2,136.4,135.6,131.9,129.6,128.2,123.4,121.3, 37.7,31.9.HRMS(ESI)
Calculated for C14H13BrNO+([M+H]+):290.0175,found:290.0176.
Embodiment 8
First weigh(49.6mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)PF6
(2.3mg, 0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction tube is added in P (62.9mg, 0.24mmol), leads to
It crosses vacuum pipeline and substitutes gas three times, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 35.1mg,Yield 52%.1H NMR (400MHz, Chloroform-d) δ 8.50 (d, J=5.5Hz,
1H), 7.81 (d, J=10.6Hz, 2H), 7.70 (d, J=8.6Hz, 2H), 7.59 (d, J=15.3 Hz, 1H), 7.33-7.21
(m, 1H), 7.16-7.07 (m, 1H), 3.46 (t, J=7.2Hz, 2H), 3.23 (t, J=7.2Hz, 2H)13C NMR
(100MHz,Chloroform-d)δ198.6,160.4,149.2,137.9,136.4,136.2,129.5, 123.4,121.3,
101.0,37.6,31.9.HRMS(ESI)Calculated for C14H13INO+([M+H]+):338.0036, found:
338.0037.
Embodiment 9
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)PF6
(2.3mg, 0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction tube is added in P (62.9mg, 0.24mmol), leads to
It crosses vacuum pipeline and substitutes gas three times, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 35.1mg,Yield 78%.1H NMR (400MHz, Chloroform-d) δ 8.52 (d, J=4.3Hz, 1H),
7.79 (d, J=7.9Hz, 2H), 7.58 (d, J=5.9Hz, 1H), 7.37-7.31 (m, 2H), 7.26 (d, J=8.4Hz, 1H),
7.16-7.05 (m, 1H), 3.50 (t, J=7.3Hz, 2H), 3.23 (t, J=7.3Hz, 2H), 2.39 (s, 3H)13C NMR
(100MHz,Chloroform-d)δ199.5,160.8,149.2,138.3,136.9, 136.4,133.8,128.6,128.4,
125.3,123.4,121.2,37.9,32.1,21.4.HRMS(ESI)Calculated for C15H16NO+([M+H]+):
226.1226,found:226.1228.
Embodiment 10
First weigh(47.4mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)PF6
(2.3mg, 0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction tube is added in P (62.9mg, 0.24mmol), leads to
It crosses vacuum pipeline and substitutes gas three times, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 48.4mg,Yield 74%.1H NMR (400MHz, Chloroform-d) δ 8.50 (d, J=4.8Hz, 1H),
7.91 (s, 1H), 7.72-7.56 (m, 3H), 7.35 (t, J=7.9Hz, 1H), 7.25 (d, J=7.8Hz, 1H), 7.12-7.08
(m, 1H), 6.97 (br s, 1H), 3.48 (t, J=7.3Hz, 2H), 3.22 (t, J=7.3Hz, 2H), 1.51 (s, 9H)13C
NMR(100MHz,Chloroform-d)δ199.0,160.6,152.8,149.1,139.0, 137.5,136.5,129.2,
123.4,123.0,122.6,121.3,117.9,80.8,38.0,32.0,28.3.HRMS(ESI) Calculated for
C19H23N2O3 +([M+H]+):327.1703,found:327.1704.
Embodiment 11
First weigh(30.0mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)PF6
(2.3mg, 0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction tube is added in P (62.9mg, 0.24mmol), leads to
It crosses vacuum pipeline and substitutes gas three times, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 29.2mg,Yield 61%.1H NMR(400MHz,Chloroform-d)δ 10.08(s,1H),8.57-8.40
(m, 2H), 8.26 (d, J=9.3Hz, 1H), 8.08 (d, J=7.6Hz, 1H), 7.69- 7.54 (m, 2H), 7.32-7.22 (m,
1H), 7.12 (dd, J=7.2,5.1Hz, 1H), 3.57 (t, J=7.2Hz, 2H), 3.28 (t, J=7.2Hz, 2H)13C NMR
(100MHz,Chloroform-d)δ198.3,191.5,160.2,149.2, 137.7,136.6,136.4,133.6,133.3,
129.6,129.5,123.4,121.4,37.8,31.8.HRMS(ESI) Calculated for C15H14NO2 +([M+H]+):
240.1019,found:240.1018.
Embodiment 12
First weigh(36.0mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)PF6
(2.3mg, 0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction tube is added in P (62.9mg, 0.24mmol), leads to
It crosses vacuum pipeline and substitutes gas three times, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 26.9mg,Yield 50%.1H NMR (400MHz, Chloroform-d) δ 8.64 (s, 1H), 8.51 (d, J=
5.7Hz, 1H), 8.23-8.17 (m, 2H), 7.66-7.49 (m, 2H), 7.27 (d, J=8.6Hz, 1H), 7.11 (dd, J=
7.5,4.9Hz, 1H), 3.95 (s, 3H), 3.56 (t, J=7.2Hz, 2H), 3.26 (t, J=7.2Hz, 2H)13C NMR
(100MHz,Chloroform-d)δ198.5,166.3,160.4,149.2,137.1,136.4,133.8, 132.2,130.7,
129.2,128.8,123.4,121.3,52.4,37.8,31.9.HRMS(ESI)Calculated for C16H16NO3 +([M+H
]+):270.1125,found:270.1126.
Embodiment 13
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)PF6
(2.3mg, 0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction tube is added in P (62.9mg, 0.24mmol), leads to
It crosses vacuum pipeline and substitutes gas three times, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 31.5mg,Yield 70%.1H NMR(400MHz,Chloroform-d)δ8.50 (d,1H,4.1Hz),7.69
(d, J=7.7Hz, 1H), 7.59 (td, J=7.7,1.8Hz, 1H), 7.34 (d, J=8.7Hz, 1H), 7.23 (t, J=
7.4Hz, 3H), 7.10 (t, J=7.6Hz, 1H), 3.41 (t, J=7.1Hz, 2H), 3.22 (t, J=7.2Hz, 2H), 2.46
(s,3H).13C NMR(100MHz,Chloroform-d)δ203.5,160.6,149.2,138.0 (2C),136.4,131.9,
131.2,128.5,125.6,123.3,121.2,40.6,32.3,21.2.HRMS(ESI) Calculated for C15H16NO+
([M+H]+):226.1226,found:226.1227.
Embodiment 14
First weigh(36.0mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)PF6
(2.3mg, 0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction tube is added in P (62.9mg, 0.24mmol), leads to
It crosses vacuum pipeline and substitutes gas three times, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 34.4mg,Yield 64%.1H NMR (400MHz, Chloroform-d) δ 8.50 (d, J=5.5Hz, 1H),
7.84 (dd, J=7.8,1.6Hz, 1H), 7.65-7.45 (m, 2H), 7.35-7.28 (m, 1H), 7.22 (d, J=7.8Hz,
1H), 7.12-7.08 (m, 1H), 3.41 (t, J=7.3Hz, 2H), 3.19 (t, J=7.3Hz, 2H), 2.32 (s, 3H)13C
NMR(100MHz,Chloroform-d)δ199.3,169.6,160.4,149.2,148.9, 136.4,133.1,130.9,
129.9,126.0,123.8,123.3,121.3,40.5,32.0,21.2.HRMS(ESI) Calculated for C16H16NO3 +([M+H]+):270.1125,found:270.1127.
Embodiment 15
First weigh(58.4mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)PF6
(2.3mg, 0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction tube is added in P (62.9mg, 0.24mmol), leads to
It crosses vacuum pipeline and substitutes gas three times, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 39.6mg,Yield 52%.1H NMR (400MHz, Chloroform-d) δ 8.48 (d, J=4.2Hz, 1H),
7.68 (d, J=8.3Hz, 2H), 7.63-7.53 (m, 2H), 7.41 (td, J=7.8,1.8Hz, 1H), 7.30 (dd, J=
15.8,8.2Hz, 3H), 7.20 (d, J=7.8Hz, 1H), 7.15-7.04 (m, 2H), 3.32 (t, J=7.3Hz, 2H), 3.13
(t, J=7.3Hz, 2H), 2.43 (s, 3H)13C NMR(100MHz,Chloroform-d)δ 199.8,160.4,149.1,
146.6,145.8,136.3,134.0,132.4,132.0,130.0,129.9,128.6,127.2, 123.4,123.2,
121.2,41.6,32.1,21.8.HRMS(ESI)Calculated for C21H20NO4S+([M+H]+): 382.1108,
found:382.1109.
Embodiment 16
First weigh(30.4mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 32.8mg,Yield 68%.1H NMR (400MHz, Chloroform-d) δ 8.48 (d, J=4.9Hz,
1H), 7.90 (d, J=8.3Hz, 2H), 7.61 (td, J=7.7,1.8Hz, 1H), 7.41 (d, J=8.4Hz, 2H), 7.26 (d,
J=8.3Hz, 1H), 7.17-7.07 (m, 1H), 4.76 (s, 2H), 3.41 (t, J=7.4Hz, 2H), 3.20 (t, J=7.3Hz,
2H).13C NMR(100MHz,Chloroform-d)δ198.8,160.7,149.0, 146.6,136.6,135.8,128.3,
126.5,123.5,121.4,64.3,38.0,32.0.HRMS(ESI)Calculated for C15H16NO2 +([M+H]+):
242.1176,found:242.1176.
Embodiment 17
First weigh(35.6mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2
(dtbbpy)PF6 (2.3mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3P (62.9mg, 0.24mmol) adds
Enter reaction tube, gas is substituted three times by vacuum pipeline, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), then small
The heart is added(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.
20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin
Solvent, dry method loading is evaporated off, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 34.7mg,Yield 65%.1H NMR (400MHz, Chloroform-d) δ 8.51 (d, J=
4.8Hz, 1H), 7.65-7.56 (m, 2H), 7.54-7.51 (m, 1H), 7.35 (t, J=7.9Hz, 1H), 7.26 (d, J=
9.0Hz, 1H), 7.11 (dd, J=9.5,3.2Hz, 2H), 6.14-5.96 (m, 1H), 5.42 (dd, J=17.3,1.5Hz,
1H), 5.30 (dd, J=10.5,1.3Hz, 1H), 4.58 (dt, J=5.3,1.4Hz, 2H), 3.49 (t, J=7.2Hz, 2H),
3.23 (t, J=7.2Hz, 2H)13C NMR(100MHz,Chloroform-d)δ199.1, 160.7,158.8,149.2,
138.2,136.4,132.9,129.6,123.4,121.3,120.9,120.2,118.0,113.2,68.9, 38.0,
32.1.HRMS(ESI)Calculated for C17H18NO2 +([M+H]+):268.1332,found:268.1334.
Embodiment 18
First weigh(35.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2
(dtbbpy)PF6 (2.3mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3P (62.9mg, 0.24mmol) adds
Enter reaction tube, gas is substituted three times by vacuum pipeline, under argon atmosphere, addition DCM/H2O (2.0mL, 4:1v/v), then small
The heart is added(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.
20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin
Solvent, dry method loading is evaporated off, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 37.6mg,Yield 71%.1H NMR (400MHz, Chloroform-d) δ 8.51 (d, J=
5.7Hz, 1H), 7.70-7.53 (m, 3H), 7.38 (t, J=7.9Hz, 1H), 7.26 (d, J=9.0Hz, 1H), 7.17 (dd, J
=9.1,2.7Hz, 1H), 7.11 (dd, J=7.9,5.4Hz, 1H), 4.73 (d, J=2.4Hz, 2H), 3.50 (t, J=
7.2Hz, 2H), 3.23 (t, J=7.2Hz, 2H), 2.54 (t, J=2.4Hz, 1H)13C NMR(100MHz,Chloroform-d)
δ198.9,160.6,157.7,149.2,138.3,136.4,129.7,123.4, 121.6,121.3,120.3,113.5,
78.1,75.9,56.0,37.9,32.0.HRMS(ESI)Calculated for C17H16NO2 +([M+H]+):266.1176,
found:266.1177.
Embodiment 19
First weigh(34.4mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 28.7mg,Yield 55%.1H NMR (400MHz, Chloroform-d) δ 8.54 (d, J=6.4Hz,
2H), 8.06 (dd, J=8.6,1.7Hz, 1H), 7.95 (d, J=8.0Hz, 1H), 7.90- 7.82 (m, 2H), 7.66-7.49
(m, 3H), 7.29 (d, J=7.8Hz, 1H), 7.12 (dd, J=7.8,5.4Hz, 1H), 3.65 (t, J=7.3Hz, 2H), 3.31
(t, J=7.3Hz, 2H)13C NMR(100MHz,Chloroform-d)δ199.3, 160.8,149.3,136.5,135.6,
134.2,132.5,129.8,129.6,128.4,128.4,127.8,126.7,123.9, 123.5,121.3,37.9,
32.2.HRMS(ESI)Calculated for C18H16NO+([M+H]+):262.1226,found: 262.1228.
Embodiment 20
First weigh(33.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 31.6mg,Yield 62%.1H NMR (400MHz, Chloroform-d) δ 8.51 (d, J=4.8Hz,
1H), 7.74-7.50 (m, 2H), 7.46 (d, J=1.7Hz, 1H), 7.26 (t, J=7.8Hz, 1H), 7.11 (d, J=5.1Hz,
1H), 6.83 (d, J=8.2Hz, 1H), 6.02 (s, 2H), 3.42 (t, J=7.3Hz, 2H), 3.21 (t, J=7.3Hz, 2H)
.13C NMR(100MHz,Chloroform-d)δ197.4,160.8,151.7,149.2, 148.1,136.5,131.8,
124.3,123.4,121.2,107.9,107.8,101.8,37.6,32.4.HRMS(ESI) Calculated for
C15H14NO3 +([M+H]+):256.0968,found:256.0969.
Embodiment 21
First weigh(22.4mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)PF6
(2.3mg, 0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction tube is added in P (62.9mg, 0.24mmol), leads to
It crosses vacuum pipeline and substitutes gas three times, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 25.7mg,Yield 64%.1H NMR (400MHz, Chloroform-d) δ 8.51 (d, J=3.4Hz, 1H),
7.66-7.51 (m, 2H), 7.34-7.17 (m, 2H), 7.15-7.04 (m, 1H), 6.52 (d, J=3.2Hz, 1H), 3.35 (t, J
=7.3Hz, 2H), 3.22 (t, J=7.3Hz, 2H)13C NMR(100MHz, Chloroform-d)δ188.5,160.4,
152.6,149.2,146.3,136.4,123.3,121.3,117.1,112.1,37.6, 31.8.HRMS(ESI)
Calculated for C12H12NO2 +([M+H]+):202.0863,found:202.0864.
Embodiment 22
First weigh(25.6mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)PF6
(2.3mg, 0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction tube is added in P (62.9mg, 0.24mmol), leads to
It crosses vacuum pipeline and substitutes gas three times, under argon atmosphere, DCM/H is added2O (2.0mL, 4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 29.5mg,Yield 68%.1H NMR (400MHz, Chloroform-d) δ 8.52 (d, J=5.6Hz, 1H),
7.76 (dd, J=3.8,1.1Hz, 1H), 7.65-7.50 (m, 2H), 7.30-7.21 (m, 1H), 7.17-7.03 (m, 2H),
3.45 (t, J=7.3Hz, 2H), 3.23 (t, J=7.3Hz, 2H)13C NMR(100MHz, Chloroform-d)δ192.3,
160.4,149.2,144.2,136.4,133.5,132.0,128.1,123.4,121.3,38.5, 32.2.HRMS(ESI)
Calculated for C12H12NOS+([M+H]+):218.0634,found:218.0635.
Embodiment 23
First weigh(34.6mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 19.9mg,Yield 38%.1H NMR (400MHz, Chloroform-d) δ 9.01 (dd, J=4.2,
1.7Hz, 1H), 8.63-8.42 (m, 2H), 8.37-8.24 (m, 2H), 8.16 (d, J=8.9Hz, 1H), 7.61 (t, J=
7.7Hz, 1H), 7.48 (dd, J=8.3,4.2Hz, 1H), 7.30 (d, J=7.8Hz, 1H), 7.21-7.06 (m, 1H), 3.67
(t, J=7.2Hz, 2H), 3.31 (t, J=7.2Hz, 2H)13C NMR(100MHz, Chloroform-d)δ198.7,160.5,
152.6,150.1,149.2,137.6,136.5,134.7,130.0,129.6,127.7, 127.5,123.5,121.9,
121.4,37.9,32.1.HRMS(ESI)Calculated for C17H15N2O+([M+H]+): 263.1179,found:
263.1181.
Embodiment 24
First weigh(35.0mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)PF6
(2.3mg, 0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction tube is added in P (62.9mg, 0.24mmol), leads to
It crosses vacuum pipeline and substitutes gas three times, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 31.2mg,Yield 59%.1H NMR (400MHz, Chloroform-d) δ 8.53 (d, J=4.9Hz,
1H), 7.66 (d, J=8.0Hz, 1H), 7.58 (td, J=7.7,1.8Hz, 1H), 7.35 (d, J=5.2Hz, 3H), 7.24 (d,
J=7.8Hz, 1H), 7.18-6.96 (m, 2H), 4.05 (s, 3H), 3.50 (t, J=7.4Hz, 2H), 3.24 (t, J=7.4Hz,
2H).13C NMR(100MHz,Chloroform-d)δ193.3,160.7,149.3, 140.0,136.4,134.7,125.8,
123.3,122.9,121.3,120.7,111.4,110.3,39.0,32.6,32.2.HRMS (ESI)Calculated for
C17H17N2O+([M+H]+):265.1335,found:265.1338.
Embodiment 25
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(35.7mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again
20mL water is added, and extracts (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4It is rotated after drying
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 30.6mg,Yield 64%.1H NMR(400MHz, Chloroform-d)δ8.34(s,1H),
7.89 (d, J=8.1Hz, 2H), 7.40 (d, J=6.3Hz, 1H), 7.24 (d, J=8.0Hz, 2H), 7.14 (d, J=7.9Hz,
1H), 3.45 (t, J=7.3Hz, 2H), 3.18 (t, J=7.3Hz, 2H), 2.40 (s, 3H), 2.28 (s, 3H)13C NMR
(100MHz,Chloroform-d)δ199.1,157.8,149.5,143.7,137.0, 134.4,130.5,129.2,128.2,
122.8,38.0,31.7,21.6,18.0.HRMS(ESI)Calculated for C16H18NO+([M+H]+):240.1383,
found:240.1384.
Embodiment 26
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(41.7mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again
20mL water is added, and extracts (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4It is rotated after drying
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 38.9mg,Yield 75%.1H NMR(400MHz, Chloroform-d)δ8.45(s,1H),7.88
(d, J=8.1Hz, 2H), 7.56 (dd, J=8.3,2.3Hz, 1H), 7.23 (t, J=8.4Hz, 3H), 3.46 (t, J=
7.1Hz, 2H), 3.20 (t, J=7.1Hz, 2H), 2.40 (s, 3H)13C NMR (100MHz,Chloroform-d)δ198.7,
159.0,148.0,143.9,136.0,134.3,129.5,129.3,128.2, 124.2,37.4,31.4,21.6.HRMS
(ESI)Calculated for C15H15ClNO+([M+H]+):260.0837,found: 260.0838.
Embodiment 27
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(39.9mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again
20mL water is added, and extracts (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4It is rotated after drying
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 43.5mg,Yield 86%.1H NMR(400 MHz,Chloroform-d)δ10.06(s,1H),
8.95 (s, 1H), 8.08 (dd, J=8.0,2.2Hz, 1H), 7.89 (d, J=8.2Hz, 2H), 7.46 (d, J=8.0Hz, 1H),
7.26 (d, J=8.7Hz, 2H), 3.55 (t, J=7.0Hz, 2H), 3.33 (t, J=7.0Hz, 2H), 2.41 (s, 3H)13C
NMR(100MHz,Chloroform-d)δ198.4,190.5,151.9, 144.0,136.0,134.2,129.60,129.3,
128.2,124.0,37.0,32.4,21.7.HRMS(ESI)Calculated for C16H16NO2 +([M+H]+):254.1176,
found:254.1177.
Embodiment 28
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(44.1mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.
20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin
Solvent, dry method loading is evaporated off, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product
43.9mg,Yield 82%.1H NMR(400 MHz,Chloroform-d)δ9.06
(d, J=1.9Hz, 1H), 8.15 (dd, J=8.1,2.3Hz, 1H), 7.89 (d, J=8.2Hz, 2H), 7.39 (d, J=8.1Hz,
1H), 7.25 (d, J=8.0Hz, 2H), 3.53 (t, J=7.0Hz, 2H), 3.31 (t, J=7.0Hz, 2H), 2.60 (s, 3H),
2.40(s,3H).13C NMR(100MHz,Chloroform-d)δ198.5, 196.6,165.7,149.6,144.0,135.9,
134.3,130.3,129.3,128.2,123.5,37.1,32.1,26.7,21.7. HRMS(ESI)Calculated for
C17H18NO2 +([M+H]+):268.1332,found:268.1334.
Embodiment 29
First weigh(0.67g, 5mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)PF6
(56.1mg, 0.002mmol),K2HPO4(174mg, 0.994mmol), and Ph3Reaction tube is added in P (1.57g, 6mmol), passes through
Vacuum pipeline substitutes gas three times, and under argon atmosphere, DCM/H is added2O(50mL,4:1v/v), it is then carefully added into(1.33mg, 7.5mmol) is subsequently placed under 5W blue led s light irradiation, reacts 60 h at room temperature.Again
20mL water is added, and extracts (3x 40mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4It is rotated after drying
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 1.14g,Yield 77%.1H NMR(400MHz, Chloroform-d)δ9.11(s,
1H), 8.19 (d, J=10.3Hz, 1H), 7.89 (d, J=8.2Hz, 2H), 7.35 (d, J=8.1Hz, 1H), 7.29-7.19 (m,
2H), 4.39 (q, J=7.1Hz, 2H), 3.51 (t, J=7.1Hz, 2H), 3.29 (t, J=7.1Hz, 2H), 2.40 (s, 3H),
1.39 (t, J=7.1Hz, 3H)13C NMR(100MHz,Chloroform-d)δ 198.6,165.5,165.4,150.5,
143.9,137.3,134.3,129.3,128.2,124.0,123.1,61.2,37.2,32.2, 21.7,14.3.HRMS(ESI)
Calculated for C16H18NO+([M+H]+):298.1438,found:298.1439.
Embodiment 30
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(51.9mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 49.2mg,Yield 84%.1H NMR (400MHz, Chloroform-d) δ 8.63 (d, J=4.6Hz,
1H), 8.15-7.81 (m, 3H), 7.27-7.21 (m, 3H), 3.52 (t, J=8.3Hz, 2H), 3.44 (t, J=8.3Hz, 2H),
2.41(s,3H).13C NMR(100MHz,Chloroform-d)δ198.5,159.1, 151.7,143.7,134.5,133.9
(q, J=5.3Hz), 129.2,128.2,124.7 (q, J=31.6Hz), 124.0 (q, J=272.3Hz), 120.7,36.5,
29.1,21.6.HRMS(ESI)Calculated for C16H15F3NO+([M+H]+): 294.1100,found:294.1102.
Embodiment 31
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(54.9mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 44.2mg,Yield 73%.1H NMR (400MHz, Chloroform-d) δ 8.31 (d, J=5.3Hz,
1H), 7.89 (d, J=8.2Hz, 2H), 7.46 (s, 1H), 7.26 (dd, J=13.6,7.6Hz, 3H), 3.47 (t, J=
7.2Hz, 2H), 3.20 (t, J=7.2Hz, 2H), 2.40 (s, 3H)13C NMR(100MHz, Chloroform-d)δ198.5,
162.5,149.9,143.9,134.3,133.0,129.3,128.2,126.7,124.6,37.3, 31.8,21.7.HRMS
(ESI)Calculated for C15H15BrNO+([M+H]+):304.0332,found:304.0334.
Embodiment 32
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(40.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.
20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin
Solvent, dry method loading is evaporated off, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 22.5mg,Yield 50%.1H NMR (400MHz, Chloroform-d) δ 7.91 (d, J=
8.2Hz, 2H), 7.46 (t, J=7.7Hz, 1H), 7.25 (d, J=8.4Hz, 2H), 6.79 (d, J=7.2Hz, 1H), 6.53
(d, J=8.2Hz, 1H), 3.82 (s, 3H), 3.44 (t, J=7.2Hz, 2H), 3.16 (t, J=7.2Hz, 2H), 2.41 (s,
3H).13C NMR(100MHz,Chloroform-d)δ199.3,163.6,158.4, 143.7,138.8,134.6,129.2,
128.2,115.5,107.6,53.2,37.2,31.8,21.7.HRMS(ESI) Calculated for C16H18NO2 +([M+H
]+):256.1332,found:256.1335.
Embodiment 33
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(54.9mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again
20mL water is added, and extracts (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4It is rotated after drying
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 25.5mg,Yield 42%.1H NMR (400MHz, Chloroform-d) δ 7.88 (d, J=
8.1Hz, 2H), 7.44 (t, J=7.7Hz, 1H), 7.34-7.19 (m, 4H), 3.46 (t, J=7.1Hz, 2H), 3.20 (t, J=
7.1Hz,2H),2.40(s,3H).13C NMR(100MHz,Chloroform-d) δ198.6,162.6,143.9,141.6,
138.7,134.3,129.3,128.2,125.6,122.3,37.6,31.8,21.7. HRMS(ESI)Calculated for
C15H15BrNO+([M+H]+):304.0332,found:304.0333.
Embodiment 34
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(31.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 30.6mg,Yield 68%.1H NMR (400MHz, Chloroform-d) δ 8.52 (d, J=5.9Hz,
2H), 7.85 (d, J=8.2Hz, 2H), 7.27 (d, J=8.2Hz, 2H), 7.20 (d, J=5.9 Hz, 2H), 3.30 (t, J=
7.4Hz, 2H), 3.08 (t, J=7.4Hz, 2H), 2.41 (s, 3H)13C NMR(100MHz, Chloroform-d)δ197.9,
150.7,149.6,144.2,134.1,129.4,128.1,124.0,38.7,29.3,21.7. HRMS(ESI)Calculated
for C15H16NO+([M+H]+):226.1226,found:226.1228.
Embodiment 35
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(46.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again
20mL water is added, and extracts (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4It is rotated after drying
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 28.6mg,Yield 52%.1H NMR (400 MHz, Chloroform-d) δ 8.06 (d, J=
8.4Hz, 1H), 7.98 (d, J=8.5Hz, 1H), 7.93 (d, J=8.2Hz, 2H), 7.77 (d, J=8.1Hz, 1H), 7.69-
7.62 (m, 1H), 7.47 (t, J=7.5Hz, 1H), 7.39 (d, J=8.4 Hz, 1H), 7.25 (d, J=7.5Hz, 2H), 3.60
(t, J=7.2Hz, 2H), 3.43 (t, J=7.1Hz, 2H), 2.40 (s, 3H)13C NMR(100MHz,Chloroform-d)δ
161.3,147.9,143.7,136.2,134.6,129.3,129.2, 128.8,128.3,127.5,126.8,125.8,
122.0,37.5,32.8,21.7.HRMS(ESI)Calculated for C19H18NO+([M+H]+):276.1383,found:
276.1385.
Embodiment 36
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(46.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again plus
Enter 20mL water, and extract (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 27.0mg,Yield 49%.1H NMR (400 MHz, Chloroform-d) δ 8.40 (d, J=
5.7Hz, 1H), 8.26 (d, J=8.3Hz, 1H), 7.96 (d, J=9.6Hz, 2H), 7.81 (d, J=8.1Hz, 1H), 7.64
(dt, J=24.8,7.3Hz, 2H), 7.51 (d, J=4.9Hz, 1H), 7.26 (d, J=6.9Hz, 2H), 3.76 (t, J=
6.8Hz, 2H), 3.65 (t, J=6.8Hz, 2H), 2.41 (s, 3H)13C NMR (100MHz,Chloroform-d)δ199.3,
160.2,143.7,141.7,136.1,134.6,129.9,129.2,128.3, 127.4,127.2,127.1,125.1,
119.4,36.6,28.6,21.7.HRMS(ESI)Calculated for C19H18NO+ ([M+H]+):276.1383,found:
276.1384.
Embodiment 37
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(49.8mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again
20mL water is added, and extracts (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4It is rotated after drying
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 49.7mg,Yield 87%.1H NMR (400MHz, Chloroform-d) δ 7.93 (d, J=
8.2Hz, 2H), 7.26 (d, J=7.7Hz, 2H), 5.83 (s, 1H), 3.82 (s, 6H), 3.47 (t, J=6.9Hz, 2H), 3.26
(t, J=6.9Hz, 2H), 2.41 (s, 3H)13C NMR(100 MHz,Chloroform-d)δ199.0,171.3,169.1,
143.6,134.7,129.2,128.2,86.9,53.8,35.3,32.9, 21.6.13C NMR(100MHz,Chloroform-d)
δ199.0,171.3,169.1,143.6,134.7,129.2,128.2, 86.9,53.8,35.3,32.9,21.6.HRMS
(ESI)Calculated for C16H19N2O3 +([M+H]+):287.1390, found:287.1391.
Embodiment 38
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(72.3mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again
20mL water is added, and extracts (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4It is rotated after drying
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 31.0mg,Yield 43%.1H NMR (400 MHz, Chloroform-d) δ 8.49 (d, J=
2.5Hz, 1H), 7.89 (d, J=8.1Hz, 2H), 7.54 (t, J=7.7Hz, 1H), 7.22 (t, J=8.6Hz, 3H), 7.09-
7.00 (m, 1H), 6.90 (d, J=12.4Hz, 2H), 6.77 (d, J=8.1 Hz, 1H), 4.84 (t, J=7.0Hz, 1H), 4.25
(dd, J=18.4,7.5Hz, 1H), 3.84-3.80 (m, 6H), 3.54- 3.49 (m, 1H), 2.37 (s, 3H)13C NMR
(100MHz,Chloroform-d)δ198.4,162.6,148.9,148.8, 147.7,143.7,136.5,136.3,134.7,
129.2,128.3,123.8,121.4,120.0,111.4,111.2,55.9,55.8, 47.7,43.9,21.6.HRMS(ESI)
Calculated for C23H24NO3 +([M+H]+):362.1751,found: 362.1752.
Embodiment 39
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(35.7mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 33.5mg,Yield 70%.1H NMR (400MHz, Chloroform-d) δ 8.50 (d, J=4.7Hz,
1H), 7.87 (d, J=6.7Hz, 2H), 7.68-7.53 (m, 1H), 7.29-7.16 (m, 3H), 7.13-7.01 (m, 1H),
3.66-3.60 (m, 2H), 3.26-3.08 (m, 1H), 2.38 (s, 3H), 1.37 (d, J=6.6Hz, 2H)13C NMR
(100MHz,Chloroform-d)δ198.9,165.1,149.1,143.7,136.4,134.7,129.2, 128.3,122.5,
121.3,44.8,37.3,21.6,21.1.HRMS(ESI)Calculated for C16H18NO+([M+H]+): 240.1383,
found:240.1385.
Embodiment 40
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(54.3mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 48.2mg,Yield 80%.1H NMR (400MHz, Chloroform-d) δ 8.48 (d, J=5.6Hz,
1H), 7.89 (d, J=8.2Hz, 2H), 7.52 (td, J=7.7,1.8Hz, 1H), 7.36 (d, J=7.4Hz, 2H), 7.31-
7.14 (m, 6H), 7.04 (dd, J=6.9,5.4Hz, 1H), 4.89 (dd, J=8.7,5.5Hz, 1H), 4.31 (dd, J=
17.5,8.7Hz, 1H), 3.50 (dd, J=17.5,5.4Hz, 1H), 2.37 (s, 3H)13C NMR (100MHz,
Chloroform-d)δ198.3,162.4,148.9,143.8,143.7,136.4,134.7,129.2,128.6, 128.3,
128.1,126.6,123.9,121.4,48.1,43.8,21.6.HRMS(ESI)Calculated for C21H20NO+ ([M+H
]+):302.1539,found:302.1541.
Embodiment 41
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(95.1mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again
20mL water is added, and extracts (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4It is rotated after drying
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 77.8mg,Yield 89%.1H NMR (400MHz, Chloroform-d) δ 8.54 (d, J=
4.6Hz, 1H), 7.95-7.82 (m, 4H), 7.71 (s, 1H), 7.59 (t, J=7.7Hz, 1H), 7.25 (dd, J=17.4,
7.9Hz, 3H), 7.16-7.07 (m, 1H), 5.00 (dd, J=8.0,5.9 Hz, 1H), 4.30 (dd, J=17.7,8.2Hz,
1H), 3.57 (dd, J=17.7,5.8Hz, 1H), 2.39 (s, 3H)13C NMR(100MHz,Chloroform-d)δ197.2,
160.6,149.5,146.1,144.1,136.8,134.2,131.7 (q, J=33.1Hz), 129.3,128.5,128.5,
(128.3,123.8,123.3 q, J=273.1Hz), 122.1,121.1-120.5 (m), 47.7,43.9,21.6.HRMS
(ESI)Calculated for C23H18F6NO+([M+H]+):438.1287,found: 438.1288.
Embodiment 42
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(96.0mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again
20mL water is added, and extracts (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4It is rotated after drying
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 49.3mg,Yield 56%.1H NMR (400MHz, Chloroform-d) δ 8.49 (d, J=
5.7Hz, 1H), 8.05 (s, 1H), 7.90 (d, J=8.2Hz, 2H), 7.59-7.44 (m, 3H), 7.33 (d, J=8.6Hz,
1H), 7.24-7.12 (m, 3H), 7.07-6.96 (m, 1H), 6.49 (d, J=3.6 Hz, 1H), 5.00 (dd, J=8.4,
5.7Hz, 1H), 4.35 (dd, J=17.5,8.5Hz, 1H), 3.57 (dd, J=17.5,5.7Hz, 1H), 2.36 (s, 3H),
1.63(s,9H).13C NMR(100MHz,Chloroform-d)δ198.4,162.9, 149.8,148.8,143.6,138.2,
136.4,134.8,134.0,130.9,129.2,128.3,126.2,124.5,123.9, 121.3,120.3,115.3,
107.4,83.6,47.9,44.1,28.2,21.6.HRMS(ESI)Calculated for C28H29N2O3 +([M+H]+):
441.2173,found:441.2175.
Embodiment 43
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(66.3mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again
20mL water is added, and extracts (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4It is rotated after drying
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 46.5mg,Yield 68%.1H NMR (400MHz, Chloroform-d) δ 8.49 (d, J=
4.8Hz, 1H), 7.89 (d, J=8.2Hz, 2H), 7.59 (s, 1H), 7.56-7.47 (m, 2H), 7.39 (d, J=8.5Hz,
1H), 7.30 (dd, J=8.5,1.8Hz, 1H), 7.22 (dd, J=14.8,7.9Hz, 3H), 7.03 (dd, J=8.4,4.9Hz,
1H), 6.67 (dd, J=2.1,0.7Hz, 1H), 5.00 (dd, J=8.5,5.6Hz, 1H), 4.34 (dd, J=17.5,8.5Hz,
1H), 3.56 (dd, J=17.5,5.6Hz, 1H), 2.36 (s, 3H)13C NMR (100MHz,Chloroform-d)δ198.3,
162.8,153.9,148.9,145.3,143.7,138.4,136.4,134.7, 129.2,128.3,127.7,124.6,
123.9,121.4,120.5,111.4,106.7,47.9,44.3,21.6.HRMS(ESI) Calculated for C23H20NO2 +([M+H]+):342.1489,found:342.1490.
Embodiment 44
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(69.3mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again
20mL water is added, and extracts (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4It is rotated after drying
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 43.5mg,Yield 62%.1H NMR (400MHz, Chloroform-d) δ 8.51 (d, J=
4.8Hz, 1H), 7.90 (d, J=8.2Hz, 2H), 7.82-7.72 (m, 4H), 7.57-7.36 (m, 4H), 7.28-7.19 (m,
3H), 7.10-6.98 (m, 1H), 5.07 (dd, J=8.5,5.6Hz, 1H), 4.40 (dd, J=17.5,8.5Hz, 1H), 3.60
(dd, J=17.5,5.5Hz, 1H), 2.37 (s, 3H)13C NMR (100MHz,Chloroform-d)δ198.2,162.3,
148.9,143.7,141.2,136.4,134.7,133.6,132.3, 129.2,128.3,127.8,127.6,126.5,
126.0,125.6,124.0,121.4,48.2,43.7,21.7.HRMS(ESI) Calculated for C25H22NO+([M+H
]+):352.1696,found:352.1698.
Embodiment 45
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(43.5mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 32.3mg,Yield 61%, d.r.=3.8/1.Principal product (cis-isomer)：1H NMR(400MHz,
Chloroform-d) δ 8.28 (d, J=4.7Hz, 1H), 7.63 (d, J=8.1Hz, 2H), 7.39 (t, J=8.4Hz, 1H),
7.09 (d, J=8.0Hz, 2H), 7.04 (d, J=7.9Hz, 1H), 6.89 (dd, J=7.3,5.0 Hz, 1H), 4.33 (q, J=
8.0Hz, 1H), 3.71 (q, J=8.5Hz, 1H), 2.33 (s, 3H), 2.28-2.17 (m, 3H), 2.14-2.02 (m, 2H),
1.91-1.75(m,1H).13C NMR(100MHz,Chloroform-d)δ202.2,162.0, 148.5,142.9,135.8,
135.3,128.8,128.3,122.1,121.0,52.0,50.4,31.3,29.3,24.8, 21.5.HRMS(ESI)
Calculated for C18H20NO+([M+H]+):266.1539,found:266.1538. by-product (transisomer)：1H
NMR (400MHz, Chloroform-d) δ 8.53 (d, J=4.8Hz, 1H), 7.79 (d, J=8.2Hz, 2H), 7.50 (td, J=
7.7,1.9Hz, 1H), 7.20-7.16m, 3H), 7.06 (dd, J=8.6,4.9Hz, 1H), 4.26-4.14 (m, 1H), 3.86-
3.70(m,1H),2.36(s,3H),2.33-2.16(m,2H),2.11-1.95(m,2H), 1.94-1.71(m,2H).HRMS
(ESI)Calculated for C18H20NO+([M+H]+):266.1539,found: 266.1540.
Embodiment 46
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(47.7mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 32.5mg,Yield 58%, d.r.=4.3/1.Principal product (cis-isomer)：1H NMR(400MHz,
Chloroform-d) δ 8.38 (d, J=4.2Hz, 1H), 7.68 (d, J=8.2Hz, 2H), 7.52 (td, J=7.8,1.8Hz,
1H), 7.29 (d, J=7.9Hz, 1H), 7.14 (d, J=8.1Hz, 2H), 6.98 (dd, J=7.2,5.0Hz, 1H), 4.45-
4.26 (m, 1H), 3.16 (dt, J=12.1,4.2Hz, 1H), 2.77-2.56 (m, 1H), 2.34 (s, 3H), 2.10-2.03 (m,
1H),2.02-1.85(m,3H),1.60-1.40(m,3H).13C NMR(100MHz, Chloroform-d)δ202.9,163.7,
148.4,142.9,136.1,135.1,129.0,128.2,121.6,121.0,46.9, 44.9,29.1,26.1,25.9,
21.6,21.5.HRMS(ESI)Calculated for C16H18NO+([M+H]+): 280.1696,found:280.1699. secondary
Product (transisomer)：1H NMR (400MHz, Chloroform-d) δ 8.37 (d, J=5.5Hz, 1H), 7.79 (d, J=
8.2Hz, 2H), 7.47 (td, J=7.7,1.8Hz, 1H), 7.19-7.15 (m, 3H), 6.95 (dd, J=8.0,4.4Hz, 1H),
4.03-4.00(m,1H),3.39-3.18(m,1H),2.36(s,3H), 2.05-2.00(m,2H),1.94-1.84(m,2H),
1.76-1.73(m,1H),1.53-1.44(m,3H).HRMS (ESI)Calculated for C16H18NO+([M+H]+):
280.1696,found:280.1697.
Embodiment 47
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(73.0mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again
20mL water is added, and extracts (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4It is rotated after drying
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 34.8mg,Yield 48%.1H NMR (400MHz, Chloroform-d) δ 8.47 (d, J=3.9Hz,
1H), 7.64 (d, J=7.6Hz, 2H), 7.41 (t, J=7.7Hz, 1H), 7.16 (d, J=7.9Hz, 2H), 7.05-6.96 (m,
1H), 6.84 (d, J=7.8Hz, 1H), 4.04-3.71 (m, 1H), 3.46-3.16 (m, 1H), 2.37 (s, 3H), 2.29-2.17
(m,1H),1.94-1.87(m,1H),1.80-1.73(m,1H), 1.66–1.29(m,17H).13C NMR(100MHz,
Chloroform-d)δ202.4,162.3,148.9,143.1,135.7, 135.4,129.1,128.2,122.6,121.3,
47.4,46.3,24.6,24.5,24.2,23.8,23.7,22.1,22.1,21.6. HRMS(ESI)Calculated for
C25H34NO+([M+H]+):364.2635,found:364.2636.
Embodiment 48
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(51.6mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again
20mL water is added, and extracts (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4It is rotated after drying
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 37.4mg,Yield 64%.1H NMR (400 MHz, Chloroform-d) δ 7.85 (d, J=
8.2Hz, 2H), 7.54 (d, J=8.0Hz, 1H), 7.37 (d, J=8.0Hz, 1H), 7.25 (d, J=8.2Hz, 2H), 3.30
(t, J=7.6Hz, 2H), 3.12 (t, J=7.6Hz, 2H), 2.41 (s, 3H)13C NMR(100MHz,Chloroform-d)δ
(198.2,145.6,144.1,134.2,129.4,128.8,128.1,125.4 q, J=3.8Hz), 124.3 (q, J=
272.2Hz),39.7,29.9,21.7.HRMS(ESI)Calculated for C17H16F3O+([M+H]+):293.1148,
found:293.1149.
Embodiment 49
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O (2.0mL, 4:1v/v), it is then carefully added into(48.6mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.
20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin
Solvent, dry method loading is evaporated off, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product
37.8mg,Yield 67%.1H NMR (400MHz,Chloroform-d)δ
7.97 (d, J=8.2Hz, 2H), 7.85 (d, J=8.2Hz, 2H), 7.32 (d, J=8.2 Hz, 2H), 7.25 (d, J=8.2Hz,
2H), 3.90 (s, 3H), 3.29 (t, J=7.6Hz, 2H), 3.12 (t, J=7.6Hz, 2H), 2.41 (s, 3H)13C NMR
(100MHz,Chloroform-d)δ198.4,167.1,146.9,144.0,134.2, 129.9,129.3,128.5,128.2,
126.6,52.0,39.7,30.1,21.7.HRMS(ESI)Calculated for C18H19O3 +([M+H]+):283.1329,
found:283.1332.
Embodiment 50
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(33.9mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again plus
Enter 20mL water, and extract (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 37.8mg,Yield 67%.1H NMR (400MHz, Chloroform-d) δ 7.84 (d, J=
8.2Hz, 2H), 7.58 (d, J=8.2Hz, 2H), 7.36 (d, J=8.4 Hz, 2H), 7.26 (d, J=8.4Hz, 2H), 3.30
(t, J=7.4Hz, 2H), 3.13 (t, J=7.4Hz, 2H), 2.41 (s, 3H)13C NMR(100MHz,Chloroform-d)δ
197.9,147.1,144.2,134.1,132.3,129.4,129.3, 128.1,119.0,110.0,39.3,30.1,
21.7.HRMS(ESI)Calculated for C17H16NO+([M+H]+): 250.1226,found:250.1228.
Embodiment 51
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(71.4mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again plus
Enter 20mL water, and extract (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 45.8mg,Yield 64%.1H NMR (400 MHz, Chloroform-d) δ 7.95 (d, J=
9.0Hz, 1H), 7.81 (d, J=8.2Hz, 2H), 7.41 (d, J=7.5Hz, 3H), 7.35-7.14 (m, 7H), 5.33 (s,
2H),3.38–3.33(m,2H),3.28–3.21(m,2H),2.39(s,3H). 13C NMR(100MHz,Chloroform-d)δ
198.9,167.2,143.6,143.5,135.9,134.4,132.3,131.5, 131.0,129.5,129.2,128.6,
128.4,128.3,128.2,126.3,66.8,40.5,29.4,21.7.HRMS(ESI) Calculated for C24H23O3 +
([M+H]+):359.1642,found:359.1644.
Embodiment 52
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4Reaction is added in (7.0mg, 0.04mmol), and Ph3P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O (2.0mL, 4:1v/v), it is then carefully added into(46.2mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again
20mL water is added, and extracts (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4It is rotated after drying
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 22.5mg,Yield 41%.1H NMR (400MHz, Chloroform-d) δ 7.88 (d, J=
8.2Hz, 2H), 7.80 (t, J=8.0Hz, 3H), 7.69 (s, 1H), 7.50-7.35 (m, 3H), 7.25 (d, J=7.9Hz,
2H),3.40–3.32(m,2H),3.28–3.18(m,2H),2.40(s,3H).13C NMR(100MHz,Chloroform-d)δ
198.9,143.9,138.9,134.4,133.6,132.0,129.3,128.2, 128.1,127.6,127.5,127.2,
126.5,126.0,125.3,40.3,30.4,21.7.HRMS(ESI)Calculated for C20H19O+([M+H]+):
275.1430,found:275.1432.
Embodiment 53
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(58.2mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again plus
Enter 20mL water, and extract (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 32.7mg,Yield 52%.1H NMR (400MHz, Chloroform-d) δ 7.84 (d, J=
8.2Hz, 2H), 7.26 (d, J=8.2Hz, 2H), 3.27 (t, J=7.4Hz, 2H), 3.13 (t, J=7.4Hz, 2H), 2.41
(s,3H).13C NMR(100MHz,Chloroform-d)δ197.3,146.8– 146.1(m),144.3,144.2–143.7
(m),139.1–138.4(m),136.3–135.8(m),133.8,129.4, 128.1,37.3,21.7,17.2.HRMS(ESI)
Calculated for C16H12F5O+([M+H]+):315.0803,found: 315.0805.
Embodiment 54
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(64.2mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.
20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin
Solvent, dry method loading is evaporated off, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 52.8mg,Yield 79%.1H NMR (400MHz, Chloroform-d) δ 7.92 (d, J=
8.4Hz, 2H), 7.82 (d, J=8.4Hz, 2H), 7.50 (d, J=8.2 Hz, 2H), 7.25 (d, J=8.2Hz, 2H), 4.33-
4.29 (m, 1H), 3.72 (dd, J=17.8,9.7Hz, 1H), 3.60 (dd, J=17.8,3.8Hz, 1H), 2.57 (s, 3H),
2.40(s,3H).13C NMR(100MHz,Chloroform-d)δ 197.5,194.5,144.7,139.8,136.9,133.6,
(129.5,129.4,128.7,128.2,126.6 q, J=279.6Hz), 44.9 (q, J=27.6Hz), 37.9,26.6,
21.7.HRMS(ESI)Calculated for C19H18F3O2 +([M+H]+): 335.1253,found:335.1255.
Embodiment 55
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O (2.0mL, 4:1v/v), it is then carefully added into(54.0mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 43.2mg,Yield 72%.1H NMR (400MHz, Chloroform-d) δ 7.84 (d, J=8.2Hz,
2H), 7.28-7.20 (m, 10H), 7.19-7.14 (m, 2H), 4.82 (t, J=7.3Hz, 1H), 3.71 (d, J=7.3Hz,
2H),2.39(s,3H).13C NMR(100MHz,Chloroform-d)δ197.6,144.2, 143.9,134.6,129.3,
128.6,128.2,127.9,126.4,46.0,44.6,21.7.HRMS(ESI)Calculated for C22H21O+([M+H
]+):301.1587,found:301.1588.
Embodiment 56
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(76.8mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.
20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin
Solvent, dry method loading is evaporated off, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 39.1mg,Yield 52%.1H NMR (400MHz, Chloroform-d) δ 7.86 (d, J=
8.2Hz, 2H), 7.57-7.51 (m, 2H), 7.49 (d, J=8.3Hz, 2H), 7.39 (t, J=7.6Hz, 2H), 7.35-7.15
(m, 10H), 4.87 (t, J=7.3Hz, 1H), 3.80-3.68 (m, 2H), 2.39 (s, 3H)13C NMR(100MHz,
Chloroform-d)δ197.6,144.2,144.0,143.4,140.9, 139.2,134.6,129.3,128.7,128.6,
128.3,128.2,127.9,127.3,127.1,127.0,126.5,45.7,44.6, 21.7.HRMS(ESI)Calculated
for C28H25O+([M+H]+):377.1900,found:377.1901.
Embodiment 57
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(67.8mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 40.1mg,Yield 58%.1H NMR (400MHz, Chloroform-d) δ 7.83 (d, J=8.2Hz,
2H), 7.33-7.08 (m, 11H), 4.78 (t, J=7.3Hz, 1H), 3.70 (dd, J=17.6,7.8Hz, 1H), 3.65 (dd, J
=17.6,7.8Hz, 1H), 2.42 (s, 3H), 2.39 (s, 3H)13C NMR(100MHz,Chloroform-d)δ197.5,
144.2,144.0,141.3,136.1,134.5,129.3,128a.6, 128.4,128.2,127.8,127.0,126.4,
45.5,44.5,21.7,16.0.HRMS(ESI)Calculated for C23H23OS+([M+H]+):347.1464,found:
347.1465.
Embodiment 58
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(66.6mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.
20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin
Solvent, dry method loading is evaporated off, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 45.8mg,Yield 67%.1H NMR (400MHz,Chloroform-d)δ7.92–7.78
(m, 4H), 7.36 (d, J=8.3Hz, 2H), 7.31-7.16 (m, 7H), 4.88 (t, J=7.3Hz, 1H), 3.77 (dd, J=
17.2,7.3Hz, 1H), 3.69 (dd, J=17.2,7.3Hz, 1H), 2.53 (s, 3H), 2.39 (s, 3H)13C NMR
(100MHz,Chloroform-d)δ197.7,197.4,149.8,144.2, 143.4,135.4,134.4,129.4,128.8,
128.7,128.2,128.1,127.8,126.7,45.9,44.2,26.6,21.7. HRMS(ESI)Calculated for
C24H23O2 +([M+H]+):343.1693,found:343.1696.
Embodiment 59
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(71.4mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 50.1mg,Yield 70%.1H NMR (400MHz, Chloroform-d) δ 7.93 (d, J=8.4Hz,
2H), 7.83 (d, J=8.2Hz, 2H), 7.33 (d, J=8.3Hz, 2H), 7.30-7.15 (m, 7H), 4.88 (t, J=7.3Hz,
1H),3.86(s,3H),3.78–3.66(m,2H),2.39(s,3H). 13C NMR(100MHz,Chloroform-d)δ197.2,
166.9,149.5,144.1,143.5,134.4,129.9,129.4, 128.7,128.3,128.2,127.9(2C),126.7,
52.0,46.0,44.2,21.7.HRMS(ESI)Calculated for C24H23O3 +([M+H]+):359.1642,found:
359.1643.
Embodiment 60
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(76.2mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again plus
Enter 20mL water, and extract (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 32.2mg,Yield 43%.1H NMR (400 MHz, Chloroform-d) δ 7.83 (d, J=
8.2Hz, 2H), 7.29-7.16 (m, 4H), 7.13 (d, J=8.6Hz, 2H), 6.94 (t, J=8.7Hz, 2H), 6.82 (d, J=
8.7Hz, 2H), 6.28-5.82 (m, 1H), 5.38 (d, J=18.8Hz, 1H), 5.26 (d, J=10.5Hz, 1H), 4.75 (t, J
=7.3Hz, 1H), 4.50-4.46 (m, 2H), 3.64 (d, J=7.4 Hz, 2H), 2.40 (s, 3H)13C NMR(100MHz,
Chloroform-d) δ 197.6,162.5,160.1,157.2,144.0,140.3 (d, J=3.2Hz), 135.5 (d, J=
188.8Hz), 133.3,129.3,129.2 (2C), 128.4 (d, J=47.6Hz), 117.6,115.3 (d, J=21.2Hz),
114.8,68.8,44.9,44.5,21.7.HRMS(ESI)Calculated for C25H24FO2 +([M+H]+):375.1755,
found:375.1756.
Embodiment 61
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O (2.0mL, 4:1v/v), it is then carefully added into(75.6mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again plus
Enter 20mL water, and extract (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 35.0mg,Yield 47%.1H NMR (400 MHz, Chloroform-d) δ 7.83 (d, J=
8.2Hz 2H), 7.30-7.10 (m, 6H), 7.05-6.79 (m, 4H), 4.76 (t, J=7.4Hz, 1H), 4.64 (d, J=
2.4Hz, 2H), 3.64 (d, J=7.4Hz, 2H), 2.50 (t, J=2.4Hz, 1H), 2.40 (s, 3H)13C NMR(100MHz,
Chloroform-d) δ 197.5,161.4 (d, J=244.6Hz), 156.1,144.0,140.1,137.2,134.5,129.3,
129.2 (d, J=7.9Hz), 128.7,128.2,115.3 (d, J=21.2Hz), 115.0,78.6,75.5,55.8,44.8,
44.4,21.7.HRMS(ESI)Calculated for C25H22FO2 +([M+H]+): 373.1598,found:373.1599.
Embodiment 62
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(66.0mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again
20mL water is added, and extracts (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4It is rotated after drying
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 27.2mg,Yield 40%.1H NMR (400 MHz, Chloroform-d) δ 7.85 (d, J=8.2Hz,
2H), 7.56 (d, J=2.2Hz, 1H), 7.48 (d, J=1.8Hz, 1H), 7.39 (d, J=8.5Hz, 1H), 7.32-7.14 (m,
8H), 6.68 (d, J=3.1Hz, 1H), 4.93 (t, J=7.3 Hz, 1H), 3.76 (d, J=7.3Hz, 2H), 2.40 (s, 3H)
.13C NMR(100MHz,Chloroform-d)δ197.7, 153.7,145.2,144.7,143.9,138.9,134.6,
129.3,128.6,128.2,127.8,127.6,126.3,124.5, 120.0,111.3,106.6,45.8,45.0,
21.7.HRMS(ESI)Calculated for C24H21O2 +([M+H]+): 341.1536,found:341.1536.
Embodiment 63
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(16.8mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 18.0mg,Yield 51%.1H NMR(400MHz, Chloroform-d)δ9.91(s,1H),7.89(d,J
=8.2Hz, 2H), 7.27 (d, J=8.2Hz, 2H), 3.31 (t, J=6.4Hz, 2H), 2.93 (t, J=6.4Hz, 2H), 2.42
(s,3H).13C NMR(100MHz,Chloroform-d)δ 200.8,197.4,144.2,134.0,129.3,128.2,37.7,
30.9,21.7.HRMS(ESI)Calculated for C11H13O2 +([M+H]+):177.0910,found:177.0912.
Embodiment 64
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(25.2mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again plus
Enter 20mL water, and extract (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 33.5mg,Yield 82%.1H NMR (400MHz, Chloroform-d) δ 7.88 (d, J=8.2Hz,
2H), 7.26 (d, J=8.2Hz, 2H), 3.27 (t, J=6.3Hz, 2H), 2.85 (t, J=6.3Hz, 2H), 2.57 (q, J=
7.3Hz, 2H), 2.41 (s, 3H), 1.10 (t, J=7.3Hz, 3H)13C NMR(100MHz,Chloroform-d)δ210.3,
198.4,143.9,134.2,129.3,128.2,36.1,35.8,32.3, 21.7,7.9.HRMS(ESI)Calculated
for C13H17O2 +([M+H]+):205.1223,found:205.1224.
Embodiment 65
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(25.2mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again plus
Enter 20mL water, and extract (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 33.5mg,Yield 82%.1H NMR (400MHz, Chloroform-d) δ 7.88 (d, J=8.2Hz,
2H), 7.26 (d, J=8.2Hz, 2H), 3.27 (t, J=6.3Hz, 2H), 2.85 (t, J=6.3Hz, 2H), 2.57 (q, J=
7.3Hz, 2H), 2.41 (s, 3H), 1.10 (t, J=7.3Hz, 3H)13C NMR(100MHz,Chloroform-d)δ210.3,
198.4,143.9,134.2,129.3,128.2,36.1,35.8,32.3, 21.7,7.9.HRMS(ESI)Calculated
for C13H17O2 +([M+H]+):205.1223,found:205.1224.
Embodiment 66
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(48.6mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again plus
Enter 20mL water, and extract (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 44.6mg,Yield 79%.1H NMR (400MHz, Chloroform-d) δ 7.88 (d, J=8.2Hz,
2H), 7.43-7.17 (m, 7H), 5.15 (s, 2H), 3.31 (t, J=6.7 Hz, 2H), 2.81 (t, J=6.7Hz, 2H), 2.41
(s,3H).13C NMR(100MHz,Chloroform-d)δ197.6, 172.9,144.0,135.9,134.1,129.3,
128.6,128.2,128.2,66.5,33.2,28.3,21.7.HRMS(ESI) Calculated for C18H19O3 +([M+H
]+):283.1329,found:283.1330.
Embodiment 67
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(50.4mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again plus
Enter 20mL water, and extract (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 44.9mg,Yield 78%.1H NMR(400MHz, Chloroform-d)δ7.99–7.92(m,2H),
7.82 (d, J=8.2Hz, 2H), 7.67 (d, J=6.2Hz, 1H), 7.58 (t, J=7.6Hz, 2H), 7.30-7.23 (m, 2H),
3.58–3.54(m,2H),3.55–3.42(m,2H),2.42(s, 3H).13C NMR(100MHz,Chloroform-d)δ
195.0,144.8,139.1,133.9,133.4,129.5,129.4, 128.2,128.0,51.1,31.2,21.7.HRMS
(ESI)Calcd for C16H17O3S[M+H]+:289.0893,found: 289.0895.
Embodiment 68
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(49.2mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 39.2mg,Yield 69%.1H NMR (400MHz, Chloroform-d) δ 7.88 (d, J=8.1Hz,
2H), 7.27 (d, J=8.1Hz, 2H), 4.18-4.08 (m, 4H), 3.35-3.12 (m, 2H), 2.42 (s, 3H), 2.29-2.04
(m, 2H), 1.33 (t, J=7.1Hz, 6H)13C NMR (100 MHz, Chloroform-d) δ 197.1 (d, J=15.7Hz),
(144.0,133.8,129.4,128.2,61.8 d, J=6.4Hz), 31.6 (d, J=3.0Hz), 21.7,19.8 (d, J=
144.5Hz), 16.5 (d, J=6.1Hz) .HRMS (ESI) Calcd for C14H22O4P[M+H]+:285.1250,found:
285.1251.
Embodiment 69
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, under argon atmosphere, addition DCM/H2O (2.0mL, 4:1v/v), it is then carefully added into(24.6mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 30.3mg,Yield 75%.1H NMR (400MHz, Chloroform-d) δ 7.90 (d, J=8.2Hz,
2H), 7.30 (d, J=8.0Hz, 2H), 4.15-4.07 (m, 1H), 2.71 (dd, J=18.4,7.9Hz, 1H), 2.48-2.45
(m,1H),2.44(s,3H),2.42–2.25(m,3H),2.22–2.11 (m,1H).13C NMR(100MHz,Chloroform-
d)δ217.1,199.8,144.5,133.1,129.6,128.6,42.9, 41.1,37.4,27.1,21.7.HRMS(ESI)
Calculated for C13H15O2 +([M+H]+):203.1067,found: 203.1069.
Embodiment 70
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(28.8mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 29.8mg,Yield 69%.1H NMR (400MHz, Chloroform-d) δ 7.78 (d, J=8.2Hz,
2H), 7.20 (d, J=8.2Hz, 2H), 3.80-3.62 (m, 1H), 2.65 (dd, J=14.9,11.3Hz, 1H), 2.46-2.23
(m,6H),2.06–2.02(m,2H),1.87–1.52(m,2H).13C NMR(100 MHz,Chloroform-d)δ209.4,
199.0,143.4,131.8,128.5,127.5,44.1,42.2,40.0,27.5,23.9, 20.7.HRMS(ESI)
Calculated for C14H17O2 +([M+H]+):217.1223,found:217.1224.
Embodiment 71
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(25.2mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 29.8mg,Yield 73%.1H NMR (400MHz, Chloroform-d) δ 7.83 (d, J=8.3Hz,
2H), 7.32 (d, J=8.0Hz, 2H), 4.62 (t, J=8.8Hz, 1H), 4.47 (dd, J=9.1,6.9Hz, 1H), 4.41-
4.31 (m, 1H), 3.03 (dd, J=17.8,7.6Hz, 1H), 2.79 (dd, J=17.8,9.4Hz, 1H), 2.44 (s, 3H)13C
NMR/(100MHz,Chloroform-d)δ195.8,175.4, 145.4,132.5,129.8,128.6,69.1,42.1,
30.9,21.8.HRMS(ESI)Calculated for C12H13O3 + ([M+H]+):205.0859,found:205.0861.
Embodiment 72
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(34.2mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 33.7mg,Yield 72%.1H NMR (400MHz, Chloroform-d) δ 7.90 (d, J=8.2Hz,
2H), 7.27 (d, J=8.2Hz, 2H), 4.10 (q, J=7.1Hz, 2H), 3.97-3.88 (m, 1H), 2.99-2.88 (dd, J=
16.2,8.1Hz,1H),2.53–2.33(m,4H),1.25–1.19 (m,6H).13C NMR(100MHz,Chloroform-d)δ
202.4,172.4,143.9,133.4,129.4,128.6,60.6, 37.6,37.1,21.7,18.0,14.2.HRMS(ESI)
Calculated for C14H19O3 +([M+H]+):235.1329, found:235.1330.
Embodiment 73
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(30.0mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60h at room temperature.Again plus
Enter 20mL water, and extract (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 35.2mg,Yield 80%.1H NMR (400MHz, Chloroform-d) δ 7.87 (d, J=8.2Hz,
2H), 7.26 (d, J=8.0Hz, 2H), 3.70 (s, 3H), 3.46 (dd, J=17.5,7.8Hz, 1H), 3.17-3.08m, 1H),
3.01 (dd, J=17.5,5.5Hz, 1H), 2.41 (s, 3H), 1.27 (d, J=7.1Hz, 3H)13C NMR(100MHz,
Chloroform-d)δ197.6,176.5,144.0,134.2,129.3,128.2, 51.9,41.9,34.9,21.6,
17.3.HRMS(ESI)Calculated for C13H17O3 +([M+H]+):221.1172, found:221.1173.
Embodiment 74 first weighs(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2
(dtbbpy)PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3P (62.9mg, 0.24mmol) adds
Enter reaction tube, gas is substituted three times by vacuum pipeline, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), then small
The heart is added(43.2mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, at room temperature instead
Answer 36-60h.20mL water is added, and extracts (3x10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous Na2SO4
Solvent, dry method loading is evaporated off in dry back spin, and column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) is produced
Object 45.4mg,Yield 86%.1H NMR (400MHz,Chloroform-d)δ7.94(d,J
=8.2Hz, 2H), 7.29 (d, J=8.2Hz, 2H), 4.87 (t, J=7.2 Hz, 1H), 3.68 (s, 3H), 3.68 (s, 3H),
3.23–3.01(m,2H),2.42(s,3H).13C NMR(100MHz, Chloroform-d)δ193.6,171.8,169.3,
144.8,133.2,129.5,129.1,52.8,52.1,49.2,33.1,21.7. HRMS(ESI)Calculated for
C14H17O5 +([M+H]+):265.1071,found:265.1074.
Embodiment 75
First weigh(27.2mg, 0.2mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (62.9mg, 0.24mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(55.8mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 36-60 h at room temperature.It adds
20mL water, and (3x10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off molten
Agent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 51.4mg,Yield 84%.1H NMR (400MHz, Chloroform-d) δ 7.91 (d, J=8.2Hz,
2H), 7.28 (d, J=8.2Hz, 2H), 4.32-4.05 (m, 5H), 3.98 (d, J=10.8Hz, 1H), 2.42 (s, 3H), 1.32
(t, J=7.1Hz, 3H), 1.21-1.11 (m, 6H)13C NMR(100MHz, Chloroform-d)δ201.2,168.9,
168.4,144.1,133.0,129.4,128.7,61.6,54.9,40.4,21.7,16.0, 14.2,13.9.HRMS(ESI)
Calcd for C17H23O5[M+H]+:307.1540, found:307.1542.
Embodiment 76
First weigh(51.4mg, 0.1mmol), photochemical catalyst Ir [dF
(CF3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(3.5mg, 0.02mmol), and Ph3P (31.5mg,
Reaction tube 0.12mmol) is added, gas is substituted three times by vacuum pipeline, under argon atmosphere, DCM/H is added2O(2.0mL,4:
1v/v), it is then carefully added into(27.0mg, 0.15mmol) is subsequently placed under 5W blue led s light irradiation,
48h is reacted at room temperature.20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through nothing
Water Na2SO4Solvent, dry method loading is evaporated off in dry back spin, and column chromatographs (300-400 mesh chromatographic silica gel) (petroleum ether-acetic acid second
Ester) product 39.4mg is obtained,Yield 58%.1H NMR(400MHz,
Chloroform-d) δ 7.83-7.79 (m, 1H), 7.48-7.39 (m, 3H), 7.34-7.24 (m, 5H), 7.20 (d, J=
7.6Hz, 1H), 7.12-6.92 (m, 14H), 5.38 (s, 2H), 4.44 (t, J=7.6Hz, 1H), 3.70 (s, 3H), 3.18 (d,
J=7.6Hz, 2H), 2.93-2.86 (m, 2H), 2.78 (s, 3H), 1.96-1.72 (m, 2H), 1.02 (t, J=7.4Hz, 3H)
.13C NMR (100MHz,Chloroform-d)δ204.3,156.4,154.7,143.4,143.2,142.9,140.3(2C),
139.4, 136.7,135.2,135.1,130.7,130.4,129.5(2C),128.4,127.9,127.7,127.5,126.4,
124.0,123.9, 122.5,122.3,119.6,109.6,108.8,48.6,47.0,46.5,31.8,29.8,21.9,
17.0,14.1.HRMS(ESI) Calculated for C47H43N4O+([M+H]+):679.3431,found:679.3432.
Embodiment 77
First weigh(29.8mg, 0.1mmol), photochemical catalyst Ir [dF (CF3)ppy]2
(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(3.5mg, 0.02mmol), and Ph3P (31.5mg, 0.12mmol) adds
Enter reaction tube, gas is substituted three times by vacuum pipeline, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), then
It is carefully added into(27.0mg, 0.15mmol) is subsequently placed under 5W blue led s light irradiation, reacts at room temperature
48h.20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous Na2SO4It is dry
Solvent, dry method loading is evaporated off in back spin, and column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product
24.5mg,Yield 53%.1H NMR(400MHz,Chloroform-d)δ7.72
(d, J=8.2Hz, 1H), 7.67 (s, 1H), 7.36 (d, J=8.2Hz, 1H), 7.26 (d, J=4.2Hz, 8H), 7.20-7.12
(m, 2H), 4.83 (t, J=7.3Hz, 1H), 3.70 (d, J=7.3Hz, 2H), 2.99-2.83 (m, 2H), 2.62-2.39 (m,
2H),2.38–2.25(m,1H),2.17–1.98(m,4H),1.65–1.42(m,6H),0.91(s,3H).13C NMR(100MHz,
Chloroform-d)δ220.6,197.8,145.5,144.3,137.0,134.7,128.8,128.6, 127.9,126.4,
125.6,125.5,50.5,47.9,45.9,44.7(2C),37.8,35.8,31.6,29.3,26.3,25.6,21.6,
13.8.HRMS(ESI)Calculated for C33H35O2 +([M+H]+):463.2632,found:463.2634.
Embodiment 78
First weigh(41.2mg, 0.1mmol), photochemical catalyst Ir [dF (CF3)
ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(3.5mg, 0.02mmol), and Ph3P (31.5mg,
Reaction tube 0.12mmol) is added, gas is substituted three times by vacuum pipeline, under argon atmosphere, DCM/H is added2O(2.0mL,4:
1v/v), it is then carefully added into(15.8mg, 0.15mmol) is subsequently placed under 5W blue led s light irradiation, room temperature
Lower reaction 48h.20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous
Na2SO4Solvent, dry method loading is evaporated off in dry back spin, and column chromatographs (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate)
Product 24.0mg is obtained,Yield 48%.1H NMR(400MHz,
Chloroform-d) δ 8.56 (d, J=4.3Hz, 1H), 8.53 (s, 1H), 8.06 (d, J=10.1Hz, 1H), 7.99 (d, J=
10.5Hz, 2H), 7.91 (d, J=8.6Hz, 1H), 7.80 (d, J=6.9Hz, 1H), 7.68-7.49 (m, 3H), 7.33 (d, J
=7.8Hz, 1H), 7.19-7.11 (m, 1H), 7.00 (d, J=8.5Hz, 1H), 3.90 (s, 3H), 3.67 (t, J=7.3Hz,
2H), 3.33 (t, J=7.3Hz, 2H), 2.18 (s, 6H), 2.10 (s, 3H), 1.80 (s, 6H)13C NMR(100MHz,
Chloroform-d)δ199.1,160.7,159.0,148.9,141.6,139.0,136.8,136.0,133.7,132.5,
131.3, 130.0,129.7,128.5,126.5,126.0,125.7,124.7,124.2,123.7,121.4,112.1,
55.2,40.6,37.9, 37.2,37.1,32.1,29.1.HRMS(ESI)Calculated for C35H36NO2 +([M+H]+):
502.2741,found: 502.2742.
Embodiment 79
First weigh(13.6mg, 0.1mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(3.5mg, 0.02mmol), and Ph3Reaction is added in P (31.5mg, 0.12mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(79.8mg, 0.15mmol) is subsequently placed under 5W blue led s light irradiation,
48h is reacted at room temperature.20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous
Na2SO4Solvent, dry method loading is evaporated off in dry back spin, and column chromatographs (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate)
Product 45.6mg is obtained,Yield 70%.1H NMR
(400MHz, Chloroform-d) δ 7.86 (d, J=8.2Hz, 2H), 7.26 (d, J=8.2Hz, 2H), 4.47-4.35 (m,
2H), 3.45 (dd, J=17.4,8.0Hz, 1H), 3.16-2.99 (m, 2H), 2.57-2.43 (m, 2H), 2.40 (s, 3H),
1.28 (d, J=7.1Hz, 3H)13C NMR(100MHz,Chloroform-d)δ197.4,175.6,144.1,134.1,
129.3,128.1,122.00-107.44 (m, 8C), 56.4 (t, J=4.3Hz), 41.7,34.9,30.4 (t, J=
21.7Hz),21.5,17.0. HRMS(ESI)Calculated for C22H18F17O3 +([M+H]+):653.0979,found:
653.0980.
Embodiment 80
First weigh(13.6mg, 0.1mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(3.5mg, 0.02mmol), and Ph3Reaction is added in P (31.5mg, 0.12mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(33.3mg, 0.15mmol) is subsequently placed under 5W blue led s light irradiation, reacts 48h at room temperature.Again plus
Enter 20mL water, and extract (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 25.3mg,Yield 74%.1H NMR (400MHz, Chloroform-d) δ 7.86 (d, J=
8.2Hz, 2H), 7.32-6.98 (m, 2H), 4.82-4.29 (m, 1H), 3.46 (dd, J=7.4,4.5Hz, 0.45H), 3.41
(dd, J=7.4,4.5Hz, 0.55H), 3.15-3.05 (m, 1H), 3.02-2.90 (m, 1H), 2.40 (s, 3H), 1.89-1.77
(m,1H),1.75–1.64(m,2H),1.59–1.49(m, 1H),1.29–1.25(m,3H),1.19–1.03(m,3H),0.80-
0.78(m,3H),0.69-0.65(m,6H).13C NMR(100MHz,Chloroform-d)δ197.7,197.6,175.3,
175.2,143.9,134.3(2C),129.2, 128.1(2C),81.2,81.1,48.7,48.6,46.9(2C),45.0,
41.8,41.7,38.8,38.7,35.3(2C),33.8,27.1, 27.0,21.7,20.1,20.0,19.9,17.4,17.3,
11.5,11.4.
Embodiment 81
First weigh(20.4mg, 0.15mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (31.5mg, 0.12mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(36.2mg, 0.1mmol) is subsequently placed under 5W blue led s light irradiation, reacts 48h at room temperature.Again plus
Enter 20mL water, and extract (3x 10mL) water phase with DCM, merges with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading are removed, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 34.2mg,Yield 71%.1H NMR (400MHz, Chloroform-d) δ 7.91 (d, J=
8.4Hz, 2H), 7.82 (d, J=8.2Hz, 2H), 7.28 (d, J=8.3 Hz, 2H), 7.23 (d, J=8.0Hz, 2H), 7.12
(s, 1H), 7.01 (s, 1H), 4.99 (t, J=8.1Hz, 1H), 3.86 (s, 3H), 3.73-3.56 (m, 2H), 2.39 (s, 3H),
2.22(s,3H),1.63(s,4H),1.23(s,6H),1.19(s,3H), 1.14(s,3H).13C NMR(100MHz,
Chloroform-d)δ197.8,167.0,149.6,144.0,142.9,142.4, 138.0,134.6,133.1,129.7,
129.3,128.7,128.2(2C),128.0,124.6,52.0,44.6,42.4,35.4,34.0, 33.8,32.0,31.8
(3C),21.7,19.5.HRMS(ESI)Calculated for C33H39O3 +([M+H]+):483.2894, found:
483.2895.
Embodiment 82
First weigh(20.4mg, 0.15mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (31.5mg, 0.12mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(44.6mg, 0.1mmol) is subsequently placed under 5W blue led s light irradiation,
48h is reacted at room temperature.20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous
Na2SO4Solvent, dry method loading is evaporated off in dry back spin, and column chromatographs (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate)
Product 43.0mg is obtained,Yield 76%.1H NMR
(400MHz, Chloroform-d) δ 7.97 (d, J=8.2Hz, 2H), 7.85 (d, J=8.2Hz, 2H), 7.31 (d, J=
8.3Hz 2H), 7.25 (d, J=8.3Hz, 2H), 5.41 (d, J=3.9Hz, 1H), 4.98-4.73 (m, 1H), 3.29 (t, J=
7.5Hz, 2H), 3.11 (t, J=7.5Hz, 2H), 2.54 (t, J=8.9Hz, 1H), 2.46 (d, J=7.7Hz, 2H), 2.40
(s, 3H), 2.19 (d, J=9.5Hz, 1H), 2.13 (s, 3H), 2.09-1.87 (m, 4H), 1.77-1.59 (m, 5H), 1.54-
1.41 (m,4H),1.32–1.14(m,3H),1.07(s,3H),0.64(s,3H).13C NMR(100MHz,Chloroform-d)
δ209.6,198.3,165.9,146.8,144.0,139.7,134.2,129.8,129.3,128.7,128.4,128.1,
122.4, 74.3,63.7,56.8,49.9,44.0,39.8,38.8,38.2,37.1,36.7,31.8(2C),31.6,30.1,
27.9,24.5,22.8, 21.7,21.1,19.4,13.3.HRMS(ESI)Calculated for C38H47O4 +([M+H]+):
567.3469,found: 567.3471.
Embodiment 83
First weigh(20.4mg, 0.15mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (31.5mg, 0.12mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(40.0mg, 0.1mmol) is subsequently placed under 5W blue led s light irradiation, room
Temperature is lower to react 48h.20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous
Na2SO4Solvent, dry method loading is evaporated off in dry back spin, and column chromatographs (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) and obtains
To product 27.6mg,Yield 53%.1H NMR
(400MHz, Chloroform-d) δ 8.11 (d, J=8.3Hz, 2H), 7.86 (d, J=8.5Hz, 2H), 7.38 (d, J=
8.3Hz, 2H), 7.32 (d, J=8.5Hz, 1H), 7.26 (d, J=3.7Hz, 2H), 6.97 (d, J=8.4Hz, 1H), 6.93
(s, 1H), 3.32 (t, J=7.4Hz, 2H), 3.15 (t, J=7.4Hz, 2H), 2.96-2.87 (m, 2H), 2.51 (dd, J=
18.8,8.6Hz, 1H), 2.41 (s, 3H), 2.31 (t, J=10.4Hz, 1H), 2.20-2.12 (m, 1H), 2.11-1.94 (m,
4H),1.68– 1.58(m,2H),1.56–1.40(m,4H),0.92(s,3H).13C NMR(100MHz,Chloroform-d)δ
220.9, 198.3,165.4,148.9,147.7,144.1,138.1,137.4,134.2,130.4,129.4,128.7,
128.2,127.6, 126.5,121.8,118.9,50.5,48.0,44.2,39.7,38.0,35.9,31.6,30.2,29.5,
26.4,25.8,21.7,21.6, 13.9.HRMS(ESI)Calculated for C35H37O4 +([M+H]+):521.2686,
found:521.2687.
Embodiment 84
First weigh(20.4mg, 0.15mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (31.5mg, 0.12mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(39.0mg, 0.1mmol) is subsequently placed under 5W blue led s light irradiation, reacts at room temperature
48h.20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous Na2SO4It is dry
Solvent, dry method loading is evaporated off in back spin, and column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product
32.1mg,Yield 63%.1H NMR(400MHz,Chloroform-d)δ
7.95 (d, J=8.2Hz, 2H), 7.85 (d, J=8.2Hz, 2H), 7.34 (d, J=8.2Hz, 2H), 7.25 (d, J=8.0Hz,
2H), 5.95 (d, J=3.7Hz, 1H), 5.49 (d, J=2.5Hz, 1H), 4.62 (d, J=3.7Hz, 1H), 4.44-4.27 (m,
1H), 4.13-4.07 (m, 1H), 3.30 (t, J=7.3Hz, 2H), 3.13 (t, J=7.4Hz, 2H), 2.40 (s, 3H), 1.56
(s,3H),1.42(s,3H),1.32(s,3H), 1.27(s,3H).13C NMR(100MHz,Chloroform-d)δ198.2,
165.1,147.7,144.1,134.2,130.0, 129.3,128.7,128.1,127.4,112.3,109.4,105.1,
83.4,80.0,76.5,72.6,67.2,39.6,30.1,26.8 (2C),26.2,25.2,21.7.HRMS(ESI)
Calculated for C29H35O8 +([M+H]+):511.2326,found: 511.2327.
Embodiment 85
First weigh(20.4mg, 0.15mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (31.5mg, 0.12mmol)
Pipe, substitutes gas three times by vacuum pipeline, under argon atmosphere, addition DCM/H2O (2.0mL, 4:1v/v), it is then carefully added into(28.0mg, 0.1mmol) is subsequently placed under 5W blue led s light irradiation, reacts at room temperature
48h.20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous Na2SO4It is dry
Solvent, dry method loading is evaporated off in back spin, and column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product
16.0mg,Yield 40%.1H NMR(400MHz,Chloroform-d)δ
7.86 (d, J=8.2Hz, 2H), 7.30-7.18 (m, 3H), 7.05 (d, J=8.0Hz, 1H), 7.00 (s, 1H), 3.27 (t, J
=8.5Hz, 2H), 3.00 (t, J=8.5Hz, 2H), 2.93-2.86 (m, 2H), 2.51 (dd, J=18.8,8.5Hz, 1H),
2.41(s,3H),2.31–2.28(m,1H),2.21–2.12 (m,1H),2.10–1.91(m,3H),1.71–1.38(m,7H),
0.91(s,3H).13C NMR(100MHz, Chloroform-d)δ221.0,199.0,143.8,138.9,137.6,136.6,
134.4,129.3,129.1,128.2,125.9, 125.5,50.5,48.0,44.3,40.4,38.2,35.9,31.6,29.7,
29.4,26.6,25.8,21.7,21.6,13.9.HRMS (ESI)Calculated for C28H33O2 +([M+H]+):
401.2475,found:401.2477.
Embodiment 86
First weigh(20.4mg, 0.15mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (31.5mg, 0.12mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(42.0mg, 0.1mmol) is subsequently placed under 5W blue led s light irradiation, room
Temperature is lower to react 48h.20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous
Na2SO4Solvent, dry method loading is evaporated off in dry back spin, and column chromatographs (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) and obtains
To product 38.3mg,Yield 71%.1H NMR
(400MHz, Chloroform-d) δ 7.96 (d, J=8.2Hz, 2H), 7.85 (d, J=8.2Hz, 2H), 7.31 (d, J=
8.3Hz, 2H), 7.25 (d, J=8.3Hz, 2H), 5.00-4.79 (m, 1H), 3.28 (t, J=7.5Hz, 2H), 3.11 (t, J=
7.5Hz,2H), 2.50–2.42(m,1H),2.40(s,3H),2.13–2.01(m,1H),1.98–1.90(m,2H),1.84–
1.72(m, 4H),1.69–1.46(m,5H),1.38–1.21(m,6H),1.14–0.99(m,2H),0.90(s,3H),0.87
(s,3H), 0.79–0.73(m,1H).13C NMR(100MHz,Chloroform-d)δ221.3,198.3,166.0,146.7,
144.0, 134.2,129.8,129.3,128.8,128.4,128.1,74.0,54.3,51.4,47.8,44.7,39.8,
36.8,35.9,35.7, 35.1,34.1,31.5,30.8,30.1,28.3,27.5,21.8,21.7,20.5,13.8,
12.3.HRMS(ESI)Calculated for C36H45O4 +([M+H]+):541.3312,found:541.3313.
Embodiment 87
First weigh(20.4mg, 0.15mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (31.5mg, 0.12mmol)
Pipe, substitutes gas three times by vacuum pipeline, under argon atmosphere, addition DCM/H2O (2.0mL, 4:1v/v), it is then carefully added into(31.2mg, 0.1mmol) is subsequently placed under 5W blue led s light irradiation, reacts at room temperature
48h.20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous Na2SO4It is dry
Solvent, dry method loading is evaporated off in back spin, and column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product
30.2mg,Yield 70%, d.r.=4.5:1.Principal product (transisomer)1H
NMR (400MHz, Chloroform-d) δ 7.86 (d, J=8.2Hz, 2H), 7.26 (d, J=8.2Hz, 2H), 5.71 (s, 1H),
4.47-4.18 (m, 1H), 3.37 (d, J=8.6Hz, 1H), 2.41 (s, 3H), 2.40-2.29 (m, 2H), 2.26-2.21 (m,
1H), 2.17 (s, 3H), 2.13-2.00 (m, 2H), 1.86 (q, J=12.5Hz, 1H), 1.77-1.60 (m, 6H), 1.58-
1.42(m,2H),1.37–1.32(m,1H),1.19(s,3H), 1.08–0.94(m,2H),0.80(s,3H).13C NMR
(100MHz,Chloroform-d)δ208.0,201.2,199.3, 170.4,143.9,133.6,129.3,128.9,124.1,
64.7,54.6,53.3,44.5,44.4,38.5,35.7,35.3,33.9, 32.6,31.6,31.0,21.7,21.0,17.4,
14.3.HRMS(ESI)Calculated for C29H37O3 +([M+H]+): 433.2737,found:433.2739. by-product
(cis-isomer)1H NMR (400MHz, Chloroform-d) δ 7.64 (d, J=8.2Hz, 2H), 7.20 (d, J=8.2Hz,
2H), 5.72 (s, 1H), 3.90-3.76 (m, 1H), 3.42 (d, J=8.0Hz, 1H), 2.85-2.58 (m, 1H), 2.49-2.40
(m,1H),2.38(s,3H),2.36–2.23(m,3H),2.03 –1.89(m,2H),1.79(s,3H),1.74–1.62(m,
4H),1.56–1.40(m,4H),1.18(s,3H),1.13(s, 3H),0.95–0.85(m,2H).HRMS(ESI)
Calculated for C29H37O3 +([M+H]+):433.2737,found: 433.2738.
Embodiment 88
First weigh(20.4mg, 0.15mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.3 mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3Reaction is added in P (31.5mg, 0.12mmol)
Pipe, substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it is then carefully added into(29.0mg, 0.1mmol) is subsequently placed under 5W blue led s light irradiation, reacts 48h at room temperature.
20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin
Solvent, dry method loading is evaporated off, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtains product 19.7mg,Yield 48%.1H NMR(400 MHz,Chloroform-d)δ8.15(br s,1H),
7.84 (d, J=8.2Hz, 2H), 7.65 (d, J=7.9Hz, 1H), 7.59 (d, J=8.2Hz, 2H), 7.37 (d, J=7.9Hz,
1H), 7.28-7.19 (m, 5H), 7.13 (t, J=7.5Hz, 1H), 7.06 (s, 1H), 6.20 (br s, 1H), 3.79 (q, J=
6.5Hz, 2H), 3.26 (t, J=7.5Hz, 2H), 3.12-3.05 (m, 4H), 2.40 (s, 3H)13C NMR(100MHz,
Chloroform-d)δ198.5,167.3,145.1,144.0,136.5, 134.2,132.6,129.3,128.6,128.1,
127.3,127.1,122.3,122.1,119.6,118.8,113.1,111.3,40.2, 39.8,29.9,25.3,
21.7.HRMS(ESI)Calculated for C27H27N2O2 +([M+H]+):411.2067,found: 411.2067.
Embodiment 89
First weigh(77.1mg, 0.15mmol), photochemical catalyst Ir [dF
(CF3)ppy]2(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3P (31.5mg,
Reaction tube 0.12mmol) is added, gas is substituted three times by vacuum pipeline, under argon atmosphere, DCM/H is added2O(2.0mL,4:
1v/v), it is then carefully added into(39.0mg, 0.1mmol) is subsequently placed in 5W blue led s lamp
Under irradiation, 48h is reacted at room temperature.20mL water is added, and extracts (3x 10mL) water phase with DCM, is merged with organic phase.It is organic
Mutually through anhydrous Na2SO4Solvent, dry method loading is evaporated off in dry back spin, and column chromatographs (300-400 mesh chromatographic silica gel) (petroleum ether-second
Acetoacetic ester) product 45.3mg is obtained,Yield
51%.1H NMR (400MHz, Chloroform-d) δ 7.83 (d, J=8.2Hz, 2H), 7.80-7.75 (m, 1H), 7.52 (s,
1H), 7.49-7.46 (m, 1H), 7.42 (s, 1H), 7.40-7.33 (m, 3H), 7.32-7.27 (m, 3H), 7.23 (d, J=
8.2Hz, 2H), 7.09 (d, J=8.1Hz, 2H), 7.02 (d, J=8.2Hz, 2H), 5.93 (d, J=3.7Hz, 1H), 5.55-
5.41 (m, 3H), 4.60 (d, J=3.7Hz, 1H), 4.33 (t, J=3.9Hz, 2H), 4.08 (d, J=4.6Hz, 2H), 3.81
(s, 3H), 2.90 (t, J=7.2Hz, 2H), 2.79-2.75 (m, 5H), 2.63 (t, J=7.2Hz, 2H), 1.91-1.84 (m,
2H), 1.55 (s, 3H), 1.41 (s, 3H), 1.31 (s, 3H), 1.25 (s, 3H), 1.02 (t, J=7.4Hz, 3H)13C NMR
(100MHz, Chloroform-d)δ205.4,165.0,156.4,154.6,146.9,143.2,142.9,140.4,140.3,
139.3,136.7, 135.6,135.1,130.8,130.4,129.8,129.5,129.4,128.5,127.7(2C),127.4,
126.5,124.0,123.8, 122.6,122.4,119.6,112.4,109.5,109.4,108.8,105.1,83.4,79.9,
76.5,72.6,67.2,46.9,43.7, 31.9,30.4,29.9,26.9,26.8,26.2,25.3,21.8,16.9.HRMS
(ESI)Calculated for C54H57N4O8 + ([M+H]+):889.4171,found:889.4172.
Embodiment 90
First weigh(34.1mg, 0.25mmol), photochemical catalyst Ir [dF (CF3)ppy]2(dtbbpy)
PF6(2.8 mg,0.0024mmol),K2HPO4(8.7mg, 0.0497mmol), and Ph3P (78.5mg, 0.24mmol) is added anti-
Ying Guan substitutes gas three times by vacuum pipeline, and under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), then careful to add
Enter(37.1mg, 0.3mmol) is subsequently placed under 5W blue led s light irradiation, reacts 48h at room temperature.It adds
20mL water, and (3x 10mL) water phase is extracted with DCM, merge with organic phase.Organic phase is through anhydrous Na2SO4Dry back spin is evaporated off
Solvent, dry method loading, column chromatography (300-400 mesh chromatographic silica gel) (petroleum ether-ethyl acetate) obtain product 44.9mg,Yield 82%.1H NMR (400MHz, Chloroform-d) δ 7.92 (d, J=8.2Hz,
2H), 7.26 (d, J=8.2Hz, 2H), 3.33 (t, J=6.7Hz, 2H), 3.09 (s, 3H), 2.96 (s, 3H), 2.77 (t, J=
6.7Hz,2H),2.40(s,3H).13C NMR(100MHz, Chloroform-d)δ199.0,171.8,143.8,134.4,
129.2,128.2,37.2,35.6,33.6,27.3,21.7.HRMS (ESI)Calculated for C13H18NO2 +([M+H
]+):220.1332,found:220.1334.
Embodiment 91
First weigh(36.2mg, 0.1mmol), photochemical catalyst Ir [dF (CF3)ppy]2
(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3P (31.5mg, 0.12mmol) adds
Enter reaction tube, gas is substituted three times by vacuum pipeline, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it seals
It is subsequently placed in 5W blue led s light irradiation, reacts 48h at room temperature, adds 20mL water, and extract (3x 10mL) water phase with DCM,
Merge with organic phase.Organic phase is through anhydrous Na2SO4Solvent, dry method loading is evaporated off in dry back spin, and column chromatographs (300-400 mesh layer
Analysis silica gel) (petroleum ether-ethyl acetate) obtain product14.9mg, yield 43%.1H NMR(400MHz,
Chloroform-d) δ 7.95 (d, J=8.8Hz, 2H), 6.97 (d, J=8.8Hz, 2H), 4.35-4.25 (m, 2H), 3.86
(t, J=6.2Hz, 2H), 3.52 (dd, J=15.9,10.6Hz, 1H), 3.24-3.16 (m, 1H), 2.66 (dd, J=15.9,
3.6Hz, 1H), 1.80-1.61 (m, 2H), 1.45-1.36 (m, 2H), 1.33 (d, J=7.2Hz, 3H), 1.30-1.25 (m,
2H),1.23–1.15(m, 2H),1.09–1.02(m,2H),0.98–0.92(m,2H),0.88–0.80(m,2H),0.78–
0.72(m,2H).13C NMR(100MHz,Chloroform-d)δ197.1,175.0,162.4,130.5,129.7,115.4,
67.2,64.8,41.2, 36.5,29.7,28.6,27.6,27.5,26.8,26.5,26.2,22.9,17.6.HRMS(ESI)
Calculated for C21H31O4 +([M+H]+):347.2217,found:347.2218.
Embodiment 92
First weigh(36.2mg, 0.1mmol), photochemical catalyst Ir [dF (CF3)ppy]2
(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3P (31.5mg, 0.12mmol) adds
Enter reaction tube, gas is substituted three times by vacuum pipeline, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it seals
It is subsequently placed in 5W blue led s light irradiation, reacts 48h at room temperature, adds 20mL water, and extract (3x 10mL) water phase with DCM,
Merge with organic phase.Organic phase is through anhydrous Na2SO4Solvent, dry method loading is evaporated off in dry back spin, and column chromatographs (300-400 mesh layer
Analysis silica gel) (petroleum ether-ethyl acetate) obtain product16.6mg, yield 48%.1H NMR
(400MHz, Chloroform-d) δ 7.77-7.49 (m, 2H), 7.37 (t, J=8.1Hz, 1H), 7.11 (dd, J=7.7,
3.0Hz, 1H), 4.26-4.07 (m, 3H), 4.01-3.96 (m, 1H), 3.51 (dd, J=17.2,9.0Hz, 1H), 3.25-
3.08 (m, 1H), 2.91 (dd, J=17.2,4.7Hz, 1H), 1.84-1.66 (m, 2H), 1.52-1.46 (m, 3H), 1.41-
1.35 (m, 2H), 1.31 (d, J=7.2 Hz, 3H), 1.29-1.18 (m, 9H)13C NMR(100MHz,Chloroform-d)δ
197.7,175.5,158.8, 137.8,129.7,120.9,120.5,113.5,67.7,64.4,42.2,35.6,28.9,
28.7,28.3,27.6,27.3,26.7, 25.8,23.5,17.2.HRMS(ESI)Calculated for C21H31O4 +([M+
H]+):347.2217,found: 347.2219。
Embodiment 93
First weigh(36.2mg, 0.1mmol), photochemical catalyst Ir [dF (CF3)ppy]2
(dtbbpy)PF6(2.3mg,0.002mmol),K2HPO4(7.0mg, 0.04mmol), and Ph3P (31.5mg, 0.12mmol) adds
Enter reaction tube, gas is substituted three times by vacuum pipeline, under argon atmosphere, DCM/H is added2O(2.0mL,4:1v/v), it seals
It is subsequently placed in 5W blue led s light irradiation, reacts 48h at room temperature, adds 20mL water, and extract (3x 10mL) water phase with DCM,
Merge with organic phase.Organic phase is through anhydrous Na2SO4Solvent, dry method loading is evaporated off in dry back spin, and column chromatographs (300-400 mesh layer
Analysis silica gel) (petroleum ether-ethyl acetate) obtain product13.8mg, yield 40%.1H NMR
(400MHz, Chloroform-d) δ 7.74 (dd, J=7.7,1.8Hz, 1H), 7.53-7.37 (m, 1H), 7.13-6.81 (m,
2H), 4.35-4.26 (m, 1H), 4.16-3.99 (m, 3H), 3.43 (dd, J=17.5,4.1Hz, 1H), 3.31-3.07 (m,
2H),1.86–1.80(m,2H), 1.71–1.65(m,2H),1.55–1.50(m,2H),1.45–1.30(m,10H),1.18(d,
J=6.7Hz, 3H)13C NMR(100MHz,Chloroform-d)δ199.7,176.3,158.4,133.7,130.5,128.0,
120.4,112.3,68.5, 63.8,47.4,35.5,29.1,27.9,27.1(2C),26.4,25.9,24.6,16.6.HRMS
(ESI)Calculated for C21H31O4 +([M+H]+):347.2217,found:347.2218。
Claims (10)
1. a kind of preparation method of aryl ketones, it is characterized in that：It is with aromatic carboxylic acids (1) and the alkene (2) of R substitution for raw material,
Triphenylphosphine is as deoxidier, under blue light light irradiation, in the solution of methylene chloride and water, under argon atmosphere, in a small amount of phosphorus
In the presence of sour hydrogen dipotassium, with [Ir (dF (CF3)ppy)2(dtbbpy)]PF6It for photochemical catalyst, is vigorously stirred, reaction obtains aryl
Ketone compound；Photochemical catalyst [Ir (dF (the CF3)ppy)2(dtbbpy)]PF6Such as flowering structure：
。
2. preparation method according to claim 1, it is characterized in that：Ar group in the aromatic carboxylic acids (1) is various
The isocyclic aryl or heterocyclic aryl for replacing or not replacing, the R group in alkene (2) that R replaces are various substitutions or do not replace pyrrole
Piperidinyl, quinolyl, isoquinolyl, pyrimidine radicals, phenyl, ester group, phosphonate group or sulfuryl.
3. preparation method according to claim 1, it is characterized in that：Ar group in the aromatic carboxylic acids (1) is various
The isocyclic aryl or heterocyclic aryl for replacing or not replacing are phenyl ring base, naphthalene nucleus base, thienyl, isoquinolyl or indyl.
4. preparation method according to claim 1, it is characterized in that：Described is the magnetic in methylene chloride and water in the solution
Power stirring, 1200 turns/min of revolving speed.
5. preparation method according to claim 1, it is characterized in that：The substance of the aromatic carboxylic acids (1) and alkene (2)
The ratio between amount is 1:1 to 1:5.
6. preparation method according to claim 1, it is characterized in that：The substance of the aromatic carboxylic acids (1) and alkene (2)
The ratio between amount is 1:1.5.
7. preparation method according to claim 1, it is characterized in that：Photochemical catalyst [Ir (dF (the CF3)ppy)2
(dtbbpy)]PF6Dosage is the mole of the 0.1-10% of aromatic carboxylic acids (1) molal quantity.
8. preparation method according to claim 1, it is characterized in that：Photochemical catalyst [Ir (dF (the CF3)ppy)2
(dtbbpy)]PF6Dosage is the 1% of aromatic carboxylic acids (1) molal quantity.
9. preparation method according to claim 1, it is characterized in that：The dipotassium hydrogen phosphate is aromatic carboxylic acids (1) mole
The mole of several 10-100%.
10. preparation method according to claim 1, it is characterized in that：The dipotassium hydrogen phosphate is aromatic carboxylic acids (1) mole
Several 20%.
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| CN109824530A (en) * | 2019-04-04 | 2019-05-31 | 南京大学 | A method of adjacent amino aromatic ketone is synthesized by aromatic carboxylic acids |
| CN111072478A (en) * | 2019-12-31 | 2020-04-28 | 南京大学 | Synthetic method of fenofibrate drug molecule |
| CN111943826A (en) * | 2020-08-19 | 2020-11-17 | 河南师范大学 | Preparation method of novel deuterated aromatic aldehyde compound |
| CN112778238A (en) * | 2020-12-31 | 2021-05-11 | 大连理工大学 | Method for preparing amide from carboxylic acid by using iridium and cobalt complex as catalyst under blue light irradiation |
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| CN102964232A (en) * | 2011-08-30 | 2013-03-13 | 北京大学深圳研究生院 | Preparation method of ketone compound and its derivatives |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109824530A (en) * | 2019-04-04 | 2019-05-31 | 南京大学 | A method of adjacent amino aromatic ketone is synthesized by aromatic carboxylic acids |
| CN109824530B (en) * | 2019-04-04 | 2021-09-28 | 南京大学 | Method for synthesizing o-amino aromatic ketone from aromatic carboxylic acid |
| CN111072478A (en) * | 2019-12-31 | 2020-04-28 | 南京大学 | Synthetic method of fenofibrate drug molecule |
| CN111943826A (en) * | 2020-08-19 | 2020-11-17 | 河南师范大学 | Preparation method of novel deuterated aromatic aldehyde compound |
| CN112778238A (en) * | 2020-12-31 | 2021-05-11 | 大连理工大学 | Method for preparing amide from carboxylic acid by using iridium and cobalt complex as catalyst under blue light irradiation |
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