CN112300026B - 4-苯并五元环-苯基酮肟酯类化合物及其制备方法和应用 - Google Patents
4-苯并五元环-苯基酮肟酯类化合物及其制备方法和应用 Download PDFInfo
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- CN112300026B CN112300026B CN202011031860.3A CN202011031860A CN112300026B CN 112300026 B CN112300026 B CN 112300026B CN 202011031860 A CN202011031860 A CN 202011031860A CN 112300026 B CN112300026 B CN 112300026B
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- 238000006243 chemical reaction Methods 0.000 description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 27
- 239000000543 intermediate Substances 0.000 description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 22
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- 125000000217 alkyl group Chemical group 0.000 description 17
- 239000000047 product Substances 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000004809 thin layer chromatography Methods 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- OYVXVLSZQHSNDK-UHFFFAOYSA-N n-methoxy-n-methylacetamide Chemical compound CON(C)C(C)=O OYVXVLSZQHSNDK-UHFFFAOYSA-N 0.000 description 6
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- 229910052763 palladium Inorganic materials 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- CJNIXHIUHZMCJX-UHFFFAOYSA-N 3-cyclopentyl-n-methoxy-n-methylpropanamide Chemical compound CON(C)C(=O)CCC1CCCC1 CJNIXHIUHZMCJX-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004287 oxazol-2-yl group Chemical group [H]C1=C([H])N=C(*)O1 0.000 description 4
- 230000008569 process Effects 0.000 description 4
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- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical group NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 3
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 3
- 150000003935 benzaldehydes Chemical class 0.000 description 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical group [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000009396 hybridization Methods 0.000 description 3
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical class C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- 239000012074 organic phase Substances 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 3
- 238000007699 photoisomerization reaction Methods 0.000 description 3
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- 238000002390 rotary evaporation Methods 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- 235000021286 stilbenes Nutrition 0.000 description 3
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000006272 (C3-C7) cycloalkyl group Chemical group 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
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- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
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- 238000001514 detection method Methods 0.000 description 2
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
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- QRNTVFDUZBJJCO-UHFFFAOYSA-N 1-[4-(1H-inden-2-yl)phenyl]propan-1-one Chemical compound CCC(C(C=C1)=CC=C1C1=CC2=CC=CC=C2C1)=O QRNTVFDUZBJJCO-UHFFFAOYSA-N 0.000 description 1
- UWSLBNRXAZLILY-UHFFFAOYSA-N 1-bromo-4-[2-(2-ethynylphenyl)ethynyl]benzene Chemical compound C#CC(C=CC=C1)=C1C#CC(C=C1)=CC=C1Br UWSLBNRXAZLILY-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- JHFAEUICJHBVHB-UHFFFAOYSA-N 1h-indol-2-ol Chemical compound C1=CC=C2NC(O)=CC2=C1 JHFAEUICJHBVHB-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
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- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
- C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
- C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D263/57—Aryl or substituted aryl radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
- C07D307/81—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
- C07D333/58—Radicals substituted by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
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Abstract
4‑苯并五元环‑苯基酮肟酯类化合物及其制备方法和应用。本申请涉及下述式(I)所示的4‑苯并五元环‑苯基肟酯衍生物、光固化组合物以及式(I)所示的4‑苯并五元环‑苯基酮肟酯衍生物的制备方法。本发明的式(I)所示的4‑苯并五元环‑苯基酮肟酯衍生物分子的吸收波长红移,光引发效率好,而且合成步骤简单,在UV‑Vis‑LED可激发的光固化涂料或油墨工业化领域的有广泛的应用前景。
Description
技术领域
本发明属于新材料有机化学品技术领域,具体涉及一种4-苯并五元环-苯基酮肟酯类化合 物及其制备方法和应用。
背景技术
光固化反应是指在光照(紫外或可见光)下,引发剂产生活性种(自由基或者阳离子等)引发 多官能度的低聚物和/或活性稀释剂进行链式聚合反应,快速形成高度交联的聚合物网络,因 此其具有快速高效、操作简便、可以实现时间-空间可控等优点,在被广泛应用于涂料、胶黏 剂以及生物医药、3D打印等领域中,具有极高的商业价值。实现光固化的配方中通常含有光 引发剂、活性稀释剂、低聚物和各种助剂,而配方体系中大多数单体都不能在光照作用下产生 有效的引发活性种,因此,光引发剂成为光固化配方中至关重要的组分,其活性直接影响光固 化速率、固化程度以及终端产品性能。
但是传统的光固化采用汞灯作为光源,能耗较高,而且会产生臭氧,破坏环境,不利于实 现可持续发展,但是新兴的LED光源较汞灯波长较长,与传统的光引发剂吸收波长并不匹配, 难以实现高效的光引发效率,为此开发一系列高效的LED光引发剂成为了新的研究热点。二 苯乙烯及其衍生物由于具有良好的平面共轭结构,可以实现波长的红移,有望成为高感光性、 高稳定性、且易于制备的LED光引发剂,如下结构所示。
这些分子结构的吸光基团由共轭的二苯乙烯结构组成,在LED发射光谱波段有很高的摩 尔消光系数。但是,也不是没有缺点,二苯乙烯类结构中存在的双键在被光辐照时会发生光致 异构化,与肟酯的氮氧键光解竞争,导致其吸收的能量有一部分无法用于分子激发断键,极大 地影响了其光引发的效率。
因此,解决二苯乙烯类光引发剂双键光致异构化化导致引发效率受影响的问题,合成无光 致异构化二苯乙烯类结构的对LED光源敏感的、在光固化领域中具有高感光性、稳定性高、 且易于制备的光引发剂是我们要做的技术挑战。
发明内容
本发明人等针对现有分子结构中的不足进行了深入研究后发现,通过将五元环引入到肟酯 中获得的本发明的式(I)所示的4-苯并五元环-苯基酮肟酯及其衍生物,可以保持双键的同时, 其中五元环可以扼制双键的异构,从而解决二苯乙烯类光引发剂引发效率受影响的问题。又从 C=C双键出发,引入了C=N双键等结构,进一步拓展了类似二苯乙烯类的分子结构。由此, 本发明的式(I)所示的4-苯并五元环-苯基酮肟酯及其衍生物有望成为新的高效率商品化的LED 光源的光引发剂。
进一步,本发明的式(I)所示的4-苯并五元环-苯基酮肟酯及其衍生物的制备方法不仅方法 简便,并且产率高、原料易于获得,适合工业化的生产和应用。本发明的式(I)所示的4-苯并五 元环-苯基酮肟酯及其衍生物作为光生酸剂具有良好应用前景。
具体地,本发明提供下述方案:
第一方面,本发明提供下述的式(I)所示的4-苯并五元环-苯基酮肟酯及其衍生物,其通式 如下:
其中:
R1,R2,R3,R4,R5,R6,R7,R8分别独立地选自被1-4个Ra取代的C1-6的烷基、-F、-Cl、 -Br、-I、-CN、-CF2CF3、-CF3、-NO2、-NRbRb、-ORb、-SRb、-C(=O)Rb、-CO2Rb、-OC(=O)Rb、 -NRbC(=O)Rb、-S(=O)Rb、-S(=O)2Rb;两者同时存在时也可以组成环状结构的苯并芳环、苯并芳杂环、苯并二氧五环;
R9和R10分别选自C1-20烷基或者被1-5个R11取代的苄基或者被1-5个R11取代的苯基;
R11选自:被1-5个Ra取代的C1-6的烷基、-F、-Cl、-Br、-I、-CN、-CF2CF3、-CF3、-NO2、 -NRbRb、-ORb、-SRb、-C(=O)Rb、-CO2Rb、-OC(=O)Rb、-NRbC(=O)Rb、-S(=O)Rb、-S(=O)2Rb, 或者被1-5个Rc取代的碳环,或者被1-5个Rd取代的杂环、P(=O)(ORb)2;
Ra选自C1-6烷基、(CH2)rC3-6环烷基或者-(CH2)r苯基;
Rb选自H或者被1-5个Re取代的C1-6烷基或者被1-5个Re取代的-(CH2)rPh;
Rc选自被1-5个Re取代的C1-6烷基或者被1-5个Re取代的(CH2)rPh;
Rd选自被1-5个Re取代的C1-6烷基或者被1-5个Re取代的(CH2)rPh;
Re选自-F、-Cl、-Br、-I、-OH、-NO2、-CN,-CF3、-CF2CF3、C1-4烷基、C1-4烷氧基、C3-7环烷基、苯基、苄基、苯乙基、萘基、杂环芳基、或者、酮基;
r为0、1、2、3或者4;
X、Y各自独立地选自CH、CH2、O、N、NH、NRf、S、SO、SO2、Se或者SeO2;
Rf选自C1-12烷基、C3-7环烷基、苯基、苄基、苯乙基、萘基或者杂环芳基。第二方面,本发明提供一种光固化组合物,其含有本发明的式(I)所示的4-苯并五元环-苯基酮肟酯及其衍 生物和可聚合成分,所述可聚合成分包含具有烯键或者环氧基的单体或聚合物。
所述的4-苯并五元环-苯基酮肟酯衍生物,其中,含X、Y的五元环选自下述的结构式之 一;
第三方面,所述的4-苯并五元环-苯基酮肟酯衍生物的制备方法,其包括如下步骤(b)~(d):
步骤(b):所述含有溴代苯基团取代的4-苯并五元环衍生物I-(a)在烷基锂或金属镁条件下 反应,得到含有烷基酮苯基团取代的苯并五元环中间体I-(b):
所述步骤(c):所述含有烷基酮苯基团取代的4-苯并五元环中间体I-(b)在酸性条件下和亚 硝酸酯进行反应,得到酮肟产物I-(c):
所属步骤(d):所述酮肟产物I-(c)与酰氯或者酸酐在碱性作用下进行反应,得到4-苯并五 元环-苯基酮肟酯衍生物(I):
所述R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、X、Y的定义与权利要求1和2中相 同。
所述的4-苯并五元环-苯基酮肟酯及其衍生物的制备方法,所述五元杂化中X和Y为CH 和CH2时,增加获得所述式(I)-b所示的化合物的制备方法,即增加步骤(a):
所述步骤(a)中炔基衍生物在催化剂和水环境中反应得到(I)-a,反应温度为0℃~室温20℃。
所述的4-苯并五元环-苯基酮肟酯及其衍生物的制备方法,所述五元杂化中X或者Y包括 CH或CH2时,增加获得所述式(I)-b所示的化合物的制备方法,,即增加包括下述步骤(a’):
所述步骤(a’)中苯并五元环衍生物和溴代芳基衍生物在钯催化剂和锂的作用下反应,得到 中间体(I)-a,反应温度为室温20℃~200℃;
所述的4-苯并五元环-苯基酮肟酯及其衍生物的制备方法,所述五元杂化中X是N时,增 加获得所述式(I)-a所示的化合物的制备方法,即增加包括下述步骤(a”):
所述步骤(a”)中,取代茚酮/氨基酚与硼酸取代物/取代苯醛在催化剂碱性条件下反应得到 (I)-a所示化合物,反应温度为室温20℃~90℃。
一种光固化组合物,其含有权利要求1~6的任一项所述的4-苯并五元环-苯基酮肟酯及其 衍生物和可聚合成分,所述可聚合成分包含具有烯键或者环氧基的单体或聚合物。
所述的光固化组合物,配比为:相对于所述可聚合成分的总量100重量份,所述式(I)所示 的肟酯的含量为0.1~15重量份。
本发明的式(I)所示的4-苯并五元环-苯基酮肟酯及其衍生物作为光生酸剂具有良好应用前 景,其能够用作光引发剂应用于光固化组合物中,也可以作为合成其他化合物的中间体。另外, 本发明的4-苯并五元环-苯基酮肟酯及其衍生物还作为辐射固化光敏引发剂能够在辐射固化配 方产品中应用,特别是在UV-Vis-LED可激发的光固化涂料或油墨等场合应用。
本发明的式(I)所示的4-苯并五元环-苯基酮肟酯及其衍生物的制造方法,分子的合成步骤 简便,原材料容易获得,适合工业化的生产和应用。
前述术语“C1-12的烷基”是指碳原子数为1~12个的烷基,其可以为直链或支链的烷基, 没有特别的限定。作为“C1-12的烷基”的实例,可以列举出例如甲基、乙基、正丙基、异丙基、 正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、叔戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基等。
前述术语“C1-6的烷基”是指碳原子数为1~6个的烷基,其可以为直链或支链的烷基,没 有特别的限定。作为“C1-6的烷基”的实例,可以列举出例如甲基、乙基、正丙基、异丙基、 正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、叔戊基、己基等。
前述术语“C1-20的烷基”是指碳原子数为1~20个的烷基,其可以为直链或支链的烷基, 没有特别的限定。作为“C1-12的烷基”的实例,可以列举出例如甲基、乙基、正丙基、异丙基、 正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、叔戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十九烷基等。
前述术语“杂环芳基”是指具有芳香特性的杂环基,作为芳香杂环基的实例,可以列举出 呋喃基、咪唑基、吡啶基等。
前述术语“苯并芳香杂环基”是指苯环与杂环稠合而成的芳香杂环基,作为“苯并芳香杂 环基”的实例,例如有喹啉基、吲哚基、嘌呤基等。
前述术语“C3-7环烷基”是指碳原子数为3~7个的环烷基,作为“C3-7环烷基”的实例, 例如有环丙基、甲基环丙基、环丁基、环戊基、甲基环丁基、二甲基环丁基、环己基等。
前述术语“C1-4烷基”是指碳原子数为1~4个的烷基,作为“C1-4的烷基”的实例,可以 列举出例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基。
前述术语“C1-4烷氧基”是指碳原子数为1~4个的含氧原子的烷基,作为“C1-4的烷基” 的实例,可以列举出例如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁 氧基、叔丁氧基。
前述的“Ph”表示苯基。
本发明的式(I)所示的4-苯并五元环-苯基酮肟酯及其衍生物中,优选地,R9、R10各自独 立地选自甲基、乙基、环丙基、甲基环戊基、苯基、苄基、4-氰基苄基、或者、4-三氟甲基苄 基。由此,所获得的式(I)所示的4-苯并五元环-苯基酮肟酯及其衍生物不仅制造成本低,进一 步,这样的肟酯在光解后产生自由基、阳离子,可以引发自由基聚合、阳离子聚合。
本发明的式(I)所示的4-苯并五元环-苯基酮肟酯及其衍生物中,含X、Y的五元环选自下 述的结构式之一:
本发明式(I)所述的4-苯并五元环-苯基酮肟酯衍生物,其还选自下述的结构式所示的化合 物组成的组:
[光固化组合物]
本发明的光固化组合物含有前述的本发明的4-苯并五元环-苯基酮肟酯及其衍生物和可聚 合成分,前述可聚合成分包含具有烯键或者环氧基的单体或聚合物。
本发明的光固化组合物中,优选地,相对于所述可聚合成分的总量100重量份,前述式(I) 所示的4-苯并五元环-苯基酮肟酯及其衍生物的含量为0.1~15重量份。更优选地,前述式(I) 所示的4-苯并五元环-苯基酮肟酯及其衍生物的含量为0.5~10重量%。
作为前述的具有烯键的单体,例如可以列举出例如,(甲基)丙烯酸酯,丙烯醛,烯烃, 共轭双烯烃,苯乙烯,马来酸酐,富马酸酐,乙酸乙烯酯,乙烯基吡咯烷酮,乙烯基咪唑,(甲 基)丙烯酸,(甲基)丙烯酸衍生物例如(甲基)丙烯酰胺,乙烯基卤化物,亚乙烯基卤化物 等。
作为前述的具有环氧基的单体,例如可以列举出例如单官能缩水甘油醚类、多官能脂肪族 缩水甘油醚类、多官能芳香族缩水甘油醚类、缩水甘油酯类、脂肪族环氧化合物等。
作为单官能缩水甘油醚类,例如可以列举出,烯丙基缩水甘油醚、丁基缩水甘油醚、苯基 缩水甘油醚、2-乙基己基缩水甘油醚、仲丁基苯基缩水甘油醚、叔丁基苯基缩水甘油醚、2-甲 基辛基缩水甘油醚等。
作为多官能脂肪族缩水甘油醚类,可以列举出例如,1,6-己二醇缩水甘油醚、三羟甲基丙 烷三缩水甘油醚、新戊二醇二缩水甘油醚、甘油二缩水甘油醚、甘油三缩水甘油醚、乙二醇二 缩水甘油醚、聚乙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚等。
作为多官芳香族缩水甘油醚类,可以列举出例如,双酚A缩水甘油醚、双酚F缩水甘油 醚、溴化双酚A缩水甘油醚、联苯酚缩水甘油醚、四甲基联苯酚缩水甘油醚、间苯二酚缩水 甘油醚等。
作为缩水甘油酯类,可以列举出例如,丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、邻苯 二甲酸二缩水甘油酯、六氢邻苯二甲酸二缩水甘油酯等。
作为脂肪族环氧化合物,可以列举出例如,3,4-环氧环己基甲基-3,4-环氧环己基甲酸酯、 3,4-环氧环己基乙基-3,4-环氧环己基甲酸酯、乙烯环己烯基二氧化物、丙烯基环己烯基二氧化 物、3,4-环氧-4-甲基环己基-2-丙烯基氧化物等。
本发明的光固化组合物中,前述的可聚合成分也可以为低聚物或预聚物等聚合物的形式, 或者是由单体、低聚物、预聚物中的至少一种形成的共聚物。另外,也可以是水性分散体的形 式。
作为这样的含烯键的聚合物,可以列举出例如(甲基)丙烯酰官能基的(甲基)丙烯酸共 聚物,聚氨酯甲酸酯(甲基)丙烯酸酯,聚酯(甲基)丙烯酸酯,不饱和聚酯,聚醚(甲基)丙烯酸酯,硅氧烷(甲基)丙烯酸酯,环氧树脂(甲基)丙烯酸酯等,以及上述物质的水溶性或水分散性的类似物。
作为前述的含环氧基的聚合物,例如可以是含有环氧基的聚合物或者树脂,如双酚A环 氧树脂、二环戊二烯型环氧树脂、二氨基二苯基甲烷型环氧树脂、氨基苯酚型环氧树脂、萘型 环氧树脂、酚醛清漆型环氧树脂、联苯型环氧树脂、氢化联苯型环氧树脂、脂肪式环氧树脂等。 [4-苯并五元环-苯基酮肟酯及其衍生物的制备方法]
本发明提供式(I)所示的4-苯并五元环-苯基酮肟酯及其衍生物的制备方法,其包括如下 的步骤(b)~(d):
步骤(b):所述含有溴代苯基团取代的苯并五元环衍生物I-(a)在烷基锂或金属镁条件下反 应,得到含有烷基酮苯基团取代的苯并五元环中间体I-(b):
所述步骤(c):所述含有烷基酮苯基团取代的苯并五元环中间体I-(b)在酸性条件下和亚硝 酸酯进行反应,得到酮肟产物I-(c):
所属步骤(d):所述酮肟产物I-(c)与酰氯或者酸酐在碱性作用下进行反应,得到4-苯并五 元环-苯基酮肟酯衍生物(I):
所述R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、X、Y的定义与前述的式(I)所示的 4-苯并五元环-苯基酮肟酯及其衍生物中的定义相同。
作为前述步骤(b)~(d)的一个例子,可以列举出例如:
(b)在N2保护下,以四氢呋喃(THF)作为溶剂将式(I)-a所示化合物和镁屑进行反应,再 加入N-甲氧基-N-甲基乙酰胺,反应完成后加入饱和氯化铵溶液终止反应,经萃取和硅胶柱层 析得到目标产物(I)-b。
(c)以四氢呋喃(THF)作为溶剂,加入(I)-b(10mmol)和浓盐酸,搅拌下滴加亚硝酸异戊 酯,反应结束后倒入水中,萃取后得到目标产物(I)-c。
(d)在N2保护下,以无水二氯甲烷(DMC)作为溶剂,加入(I)-c,室温下搅拌加入三乙 胺和乙酸酐,反应完成后加入去离子水进行萃取,用HCl、NaHCO3水溶液调pH至中性;硅胶柱层析制得本发明的式(I)所示的4-苯并五元环-苯基酮肟酯及其衍生物,即为目标产物。
所述步骤(b)中反应温度为0℃~室温,前述步骤(b)的反应时间可以为例如0~1小时,优选 为10-20min;
作为前述步骤(b),可选地,还可以在其他有机溶剂的体系中下进行。优选地,前述有机 溶剂选自乙腈、DMF、DMAc、二氯甲烷等。
所述步骤(c)中反应温度为-5℃~室温,前述步骤(c)的反应时间可以为例,如1~24小时, 优选为6~12h;
作为前述步骤(c),可选地,还可以在其他有机溶剂和酸的体系中下进行。优选地,前述 有机溶剂选自乙腈、DMF、DMAc、二氯甲烷等。酸优选为浓盐酸、硫酸、硝酸等。
所述步骤(d)中反应温度为-10℃~室温,前述步骤(c)的反应时间可以为例如1~24小时,优 选为6~12h;
作为前述步骤(d),可选地,还可以在其他有机溶剂和缚酸剂的体系中下进行。优选地, 前述有机溶剂选自乙腈、DMF、DMAc、二氯甲烷等。缚酸剂优选为三乙胺、吡啶、N,N-二异 丙基乙胺、4-二甲氨基吡啶、三乙醇胺、四丁基溴化铵等。
根据上述的4-苯并五元环-苯基酮肟酯及其衍生物的制备方法,当式(I)所示的五元杂化 中X和Y为CH和CH2时,所述式(I)-b所示的化合物的制备方法为下述步骤(a):
所述步骤(a)中炔衍生物在金催化剂下和水反应,得到中间体(I)-a,反应温度为0℃~室温;
前述步骤(a),溶剂选自水、乙腈、乙醇、DMAc等,反应时间为2-48h,优选地为2-8h。
根据上述的4-苯并五元环-苯基酮肟酯及其衍生物的制备方法,当式(I)所示的五元杂化 中X或者Y包括CH或CH2时,所述式(I)-b所示的化合物的制备方法包括下述步骤(a’):
所述步骤(a’)中苯并五元环衍生物和溴代芳基衍生物在钯催化剂和锂的作用下反应,得到 中间体(I)-a,反应温度为室温~200℃;
前述步骤(a’),溶剂选自乙醚、乙腈、DMF、DMAc、二氯甲烷等,反应时间为8-48h,优选地为12-24h。钯催化剂优选为Pd/C、Pd(dba)2、Pd2(dba)3、四三苯基膦钯、[1,1-(双二苯基膦基)二茂铁]二氯化钯、醋酸钯、二(三叔丁基膦)钯等,锂优选为碳酸锂、高氯酸锂、四 氟硼酸锂、六氟磷酸锂、草酸锂等。
根据上述的4-苯并五元环-苯基酮肟酯及其衍生物的制备方法,当式(I)所示的五元杂化 中X是N时,所述式(I)-a所示的化合物的制备方法包括下述步骤(a”):
所述步骤(a”)中,取代茚酮/氨基酚与硼酸取代物/取代苯醛在催化剂和碱性条件下反应得到 (I)-a所示化合物,反应温度为室温~90℃
前述步骤(a”),对取代茚酮与硼酸取代物反应溶剂选自乙醇、甲醇、三氯甲烷、乙腈、DMAc 等,反应时间为1-12h,优选地为4-8h,催化剂优选为Pd/C、[1,1-(双二苯基膦基)二茂铁] 二氯化钯、醋酸钯、二(三叔丁基膦)钯等,碱优选为碳酸钾、碳酸铯、碳酸钠、三乙胺等。
前述步骤(a”),对氨基酚与取代苯醛反应溶剂选自DMSO、DMF、THF、DMC、乙醚、 乙腈、DMAc等,反应时间为12-48h,优选地为10-24h,催化剂优选为Na2S·5H2O、S、(NH4)2S 等。
实施例
为了更清楚地说明本公开,下面结合优选实施例对本公开做进一步的说明。本领域技术 人员应当理解,下面所具体描述的内容是说明性的而非限制性的,不应以此限制本公开的保 护范围。
实施例1:化合物(I)-1的制备
(a)中间体2-(4-溴苯基)-1H-茚的制备:室温下,将H2O(5当量)和催化剂IPrAuNTf2(5mol%)加入到烧瓶中的1-((4-溴苯基)乙炔基)-2-乙炔基苯(1当量)的THF溶液中, 给装置充入N2,搅拌反应6h,用薄层色谱法监测反应过程,确定反应完成后,旋蒸浓缩混合 物,用硅胶柱层析得到目标产物(I)-1a,产率60%。
(b)中间体1-(4-(1H-茚-2-基)苯基)丙-1-酮的制备:
在N2保护下,在100mL的圆底烧瓶中加入镁屑(20mmol),再加入2mL干燥的四氢呋喃 (THF),搅拌下将(I)-1a(2mmol)溶于5mL THF后用针管注入,用电吹风加热,使混合溶液保持微沸腾状态2min后,再把剩余的(I)-1a(18mmol)和N-甲氧基-N-甲基乙酰胺(20mmol)溶于10mL的THF溶液缓慢滴加到反应体系中,保持微沸的状态,加完后补加10mL THF,室 温继续搅拌反应,薄层色谱法监测反应完全后,向反应液中加入10mL饱和氯化铵溶液,搅拌10min后用乙酸乙酯萃取三次,分出有机相用无水硫酸钠干燥,蒸去溶剂后用硅胶柱层析得到 目标产物(I)-1b。产率:80%。
(c)中间体1-(4-(1H-茚-2-基)苯基)-2-(羟基亚氨基)丙-1-酮:
向三口烧瓶中投入1当量的芳基酮(I)-1b(10mmol),溶液四氢呋喃形成2mol/L的溶液, 加入1.05当量的浓盐酸,搅拌下滴加1.05当量的亚硝酸异戊酯,室温搅拌至薄层色谱检测反 应结束,将反应物倒入100ml水中,使用二氯甲烷萃取,无水MgSO4干燥。蒸干得到粘稠物 状产物加入石油醚后析出固体,抽滤得到产物,产率83%。可以直接用于下一步反应。
(d)化合物(I)-1的制备:
暗室中,在N2气保护下,在三口烧瓶中依次投入(5mmol)酮肟(I)-1c、15mL无水二氯 甲烷,室温下搅拌5min后加入10mmol的三乙胺,再滴加5mmol乙酸酐,约30min滴加完毕,继续搅拌2h。把反应体系加入50mL去离子水,二氯甲烷萃取,分别用2mol/L的HCl、5%的NaHCO3水溶液洗,调pH至中性;无水NaSO4干燥,减压蒸馏除去溶剂;过硅胶柱色谱纯化, 最后得到(I)-1,产率95%。
实施例2:化合物(I)-2的制备
(a)中间体2-(4-溴苯基)苯并呋喃的制备:
将S-(4-溴苯基)氯硫氰酸酯(1mmol)、苯并呋喃(1.5mmol)、Li2CO3(6mmol,0.444g)、1,4-二氧六环(2mL)和钯碳催化剂(0.05mmol)依次添加到烘干的烧瓶中。通过真空-N2循环(5次)排空反应混合物,并在150℃油浴下搅拌反应16h。薄层色谱法监测反应完全后,将反应冷却到室温,旋蒸浓缩粗产物后用硅胶柱层析法纯化粗混合物,得到(I)-2a,产率81%。
(b)1-(4-(苯并呋喃-2-基)苯基)丙-1-酮、(c)中间体1-(4-(苯并呋喃-2-基)苯基) -2-(羟基亚氨基)丙-1-酮和(d)化合物(I)-2的制备过程具体操作见实施例1,总产率62.38%。
实施例3:化合物(I)-9的制备
(a)中间体2-(4-溴苯基)-1H-吲哚的制备:
向H2O和EtOH(7:3)的混合溶液中添加2-羟基吲哚(3.0mmol)、NEt3(6.0当量)和PyBroP(1.2当量)并搅拌10min。再向该反应混合物中添加Pd/C催化剂(0.01mol)并在室 温下搅拌30min,然后添加KOH(5mmol)和(4-溴苯基)硼酸(4.0mmol)。用薄层色谱 法对反应过程进行监测。确定反应完成后,将产物混合物冷却至室温;添加乙酸乙酯并进行离 心分离使催化剂沉淀,并用水彻底清洗以除去无机盐,最终得到(I)-9a,产率75.12%。
(b)中间体1-(4-(1H-吲哚-2-基)苯基)-3-环戊基丙烷-1-酮制备过程与实施例1操作 相同,仅需要把N-甲氧基-N-甲基乙酰胺改为3-环戊基-N-甲氧基-N-甲基丙酰胺;
(c)中间体1-(4-(1H-吲哚-2-基)苯基)-3-环戊基-2-(羟基亚氨基)丙-1-酮和(d)化 合物(I)-9的制备过程具体操作见实施例1,总产率59.67%。
实施例4:化合物(I)-10的制备:
(a)中间体2-(4-溴苯基)苯并[d]恶唑的制备:
在500mL的三口烧瓶中加入对溴甲醛、2-氨基苯酚和硫元素各20mmol以及10%molNa2S·5H2O,然后加入DMSO(1.5当量),将装置放入70℃的油浴中进行加热搅拌,在空 气下反应约16h,用薄层色谱法检测应完全后,向混合溶液中加入DCM,充分混合后,用水 萃取三遍,分出有机相,用无水硫酸钠干燥,蒸去溶剂后用硅胶柱层析得到目标产物(I)-10a, 得产率:61%-78%。
(b)中间体1-(4-(苯并[d]恶唑-2-基)苯基)-3-环戊基丙烷-1-酮制备过程与实施例1 操作相同,仅需要把N-甲氧基-N-甲基乙酰胺改为3-环戊基-N-甲氧基-N-甲基丙酰胺;
(c)中间体1-(4-(苯并[d]恶唑-2-基)苯基)-3-环戊基-2-(羟基亚氨基)丙-1-酮和(d) 化合物(I)-9的制备过程具体操作见实施例1,总产率59.67%。
实施例5:化合物(I)-35的制备
(a)中间体2-(4-溴苯基)苯并噻吩的制备:
将S-(4-溴苯基)氯硫氰酸酯(1mmol)、苯并噻吩(1.5mmol)、Li2CO3(6mmol,0.444g)、1,4-二氧六环(2mL)和钯碳催化剂(0.05mmol)依次添加到烘干的烧瓶中。通过真空-N2循环(5次)排空反应混合物,并在150℃油浴下搅拌反应16h。薄层色谱法监测反应完全后,将反应冷却到室温,旋蒸浓缩粗产物后用硅胶柱层析法纯化粗混合物,得到(I)-35a,产率81%。
(b)1-(4-(苯并[b]噻吩-2-基)苯基)-3-环戊基丙烷-1-酮制备过程与实施例1操作相同, 仅需要把N-甲氧基-N-甲基乙酰胺改为3-环戊基-N-甲氧基-N-甲基丙酰胺;
(c)中间体1-(4-(苯并[b]噻吩-2-基)苯基)-3-环戊基-2-(羟基亚氨基)丙-1-酮操作 同实施例1
(d)化合物(I)-35的制备过程具体操作见实施例1,仅需要把乙酸酐换为苯甲酸酐,总产 率59.64%。
实施例6:化合物(I)-50的制备:
(a)中间体2-(4-溴苯基)-6-甲氧基苯并[d]恶唑的制备:
在500mL的三口烧瓶中加入对溴甲醛、2-氨基-4-甲氧基苯酚和硫元素各20mmol以及 10%mol Na2S·5H2O,然后加入DMSO(1.5当量),将装置放入70℃的油浴中进行加热搅拌,在空气下反应约16h,用薄层色谱法检测应完全后,向混合溶液中加入DCM,充分混合后,用水萃取三遍,分出有机相,用无水硫酸钠干燥,蒸去溶剂后用硅胶柱层析得到目标产物 (I)-50a,得产率:50%-71%。
(b)中间体1-(4-(苯并[d]恶唑-2-基)苯基)-3-环戊基丙烷-1-酮制备过程与实施例1 操作相同,仅需要把N-甲氧基-N-甲基乙酰胺改为3-环戊基-N-甲氧基-N-甲基丙酰胺;
(c)中间体1-(4-(苯并[d]恶唑-2-基)苯基)-3-环戊基-2-(羟基亚氨基)丙-1-酮具体 操作见实施例1;
(d)化合物(I)-50的制备过程,仅需要把乙酸酐换为苯甲酸酐,总产率62.07%。
实施例7:其余肟酯的制备及表征
其余各种肟酯的中间体的制备除了原材料变化外,其它过程方法都是一致的,这里不再重 复。制备的肟酯总产率以及质谱数据如下表所示。
实施例10:(I)-1~(I)-14的LED光固化实验以及涂料性质测试
含丙烯酸酯基团样品体系按下列配方制作(以重量百分比计)
三羟甲基丙烷三丙烯酸酯(TMPTA):97%
光引发剂((I)-1~(I)-14):3%
将上述配制实施例混合物涂覆于卡纸板上形成约25-30微米的涂层,以广州和光同盛科技 有限公司生产的单位功率为1000mW/cm2的发射波长为365纳米的LED光源(3厘米宽和80 厘米长LED面光源)为激发光源,放置于变速传送带。以指甲反复压刻刮擦不产生印迹为光 聚合固化完成的判据。
结果表明含有本实施例的化合物均以高于25米/分钟的速度高效固化。
对上述通过光固化得到的涂层通过手摇铅笔硬度计进行硬度测试,测得其硬度为4H。
实施例11:((I)-33~(I)-45)的LED光固化实验以及涂料性质测试
含双丙烯酸酯基团样品体系按下列配方制作(以重量百分比计)
己二醇二丙烯酸酯(HDDA):98.5%
光引发剂((I)-33~(I)-45):1.5%
将上述配制实施例混合物涂覆于卡纸板上形成约30-35微米的涂层,以广州和光同盛科技 有限公司生产的单位功率为1000mW/cm2的发射波长为365纳米的LED光源(3厘米宽和80 厘米长LED面光源)为激发光源,放置于变速传送带。以指甲反复压刻刮擦不产生印迹为光 聚合固化完成的判据。
结果表明含有本实施例的化合物均以高于30米/分钟的速度高效固化。
对上述通过光固化得到的涂层通过手摇铅笔硬度计进行硬度测试,测得其硬度为4H。
上述对实施例的描述是为了便于该技术领域的普通技术人员能理解和使用本发明。熟悉本 领域技术人员显然可以容易的对这些实施例做出各种修改,并把在此说明的一般原理应用到其 他实施例中,而不必经过创造性的劳动。因此,本发明不限于上述实施例。本领域技术人员根 据本发明的原理,不脱离本发明的范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (5)
2.一种光固化组合物,其含有权利要求1所述的4-苯并五元环-苯基酮肟酯和可聚合成分,所述可聚合成分包含具有烯键或者环氧基的单体或聚合物。
3.根据权利要求2所述的光固化组合物,配比为:相对于所述可聚合成分的总量100重量份,所述4-苯并五元环-苯基酮肟酯的含量为0.1~15重量份。
4.根据权利要求3所述的光固化组合物作为辐射固化光敏引发剂在辐射固化配方产品中的应用。
5.根据权利要求4所述的光固化组合物作为辐射固化光敏引发剂在辐射固化配方产品中的应用,其中辐射固化配方产品是UV-Vis-LED可激发的光固化涂料或油墨。
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