CN113336876A - Use of gamma, delta-unsaturated oxime ester compounds as photoinitiators - Google Patents
Use of gamma, delta-unsaturated oxime ester compounds as photoinitiators Download PDFInfo
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- CN113336876A CN113336876A CN202110659660.0A CN202110659660A CN113336876A CN 113336876 A CN113336876 A CN 113336876A CN 202110659660 A CN202110659660 A CN 202110659660A CN 113336876 A CN113336876 A CN 113336876A
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- alkyl
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- aryl
- amino
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- -1 oxime ester compounds Chemical class 0.000 title claims abstract description 168
- 150000001875 compounds Chemical class 0.000 claims abstract description 81
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 150000003254 radicals Chemical class 0.000 claims description 126
- 125000001072 heteroaryl group Chemical group 0.000 claims description 104
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 96
- 229910052739 hydrogen Inorganic materials 0.000 claims description 52
- 239000001257 hydrogen Substances 0.000 claims description 52
- 229910052736 halogen Inorganic materials 0.000 claims description 50
- 150000002367 halogens Chemical class 0.000 claims description 50
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 49
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 48
- 125000003118 aryl group Chemical group 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 27
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 22
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 19
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 18
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000000016 photochemical curing Methods 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 238000010146 3D printing Methods 0.000 claims description 8
- 125000004641 (C1-C12) haloalkyl group Chemical group 0.000 claims description 7
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- 125000005418 aryl aryl group Chemical group 0.000 claims description 3
- 238000006146 oximation reaction Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 13
- 230000000977 initiatory effect Effects 0.000 abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 60
- 238000006243 chemical reaction Methods 0.000 description 51
- 150000002431 hydrogen Chemical class 0.000 description 30
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000000178 monomer Substances 0.000 description 18
- 238000002390 rotary evaporation Methods 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 238000004611 spectroscopical analysis Methods 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 229940126214 compound 3 Drugs 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 8
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 7
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 7
- 229940125904 compound 1 Drugs 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 125000006024 2-pentenyl group Chemical group 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 125000006022 2-methyl-2-propenyl group Chemical group 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 229940125782 compound 2 Drugs 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000006029 2-methyl-2-butenyl group Chemical group 0.000 description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000012312 sodium hydride Substances 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 125000006063 1,2-dimethyl-3-butenyl group Chemical group 0.000 description 3
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 3
- KYGSYTRHCDNSGS-UHFFFAOYSA-N 1-phenylpent-4-en-1-one Chemical compound C=CCCC(=O)C1=CC=CC=C1 KYGSYTRHCDNSGS-UHFFFAOYSA-N 0.000 description 3
- 125000006077 2-ethyl-2-butenyl group Chemical group 0.000 description 3
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 125000001188 haloalkyl group Chemical group 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
- 239000005457 ice water Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 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
- 150000002576 ketones Chemical class 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- HBQOBNFVZMZRGC-UHFFFAOYSA-N n-(1-phenylpent-4-enylidene)hydroxylamine Chemical compound C=CCCC(=NO)C1=CC=CC=C1 HBQOBNFVZMZRGC-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- JDKQTIKEGOOXTJ-UHFFFAOYSA-N pent-4-enoyl chloride Chemical compound ClC(=O)CCC=C JDKQTIKEGOOXTJ-UHFFFAOYSA-N 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 125000006062 1,2-dimethyl-2-butenyl group Chemical group 0.000 description 2
- 125000006066 1,3-dimethyl-3-butenyl group Chemical group 0.000 description 2
- 125000006080 1-ethyl-1-methyl-2-propenyl group Chemical group 0.000 description 2
- 125000006039 1-hexenyl group Chemical group 0.000 description 2
- 125000006019 1-methyl-1-propenyl group Chemical group 0.000 description 2
- 125000006028 1-methyl-2-butenyl group Chemical group 0.000 description 2
- 125000006021 1-methyl-2-propenyl group Chemical group 0.000 description 2
- 125000006023 1-pentenyl group Chemical group 0.000 description 2
- 125000006017 1-propenyl group Chemical group 0.000 description 2
- 125000006078 2-ethyl-3-butenyl group Chemical group 0.000 description 2
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006040 2-hexenyl group Chemical group 0.000 description 2
- 125000006026 2-methyl-1-butenyl group Chemical group 0.000 description 2
- 125000006031 2-methyl-3-butenyl group Chemical group 0.000 description 2
- 125000006056 2-methyl-4-pentenyl group Chemical group 0.000 description 2
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 2
- 125000006041 3-hexenyl group Chemical group 0.000 description 2
- 125000006057 3-methyl-4-pentenyl group Chemical group 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 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
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 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
- 125000003544 oxime group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 1
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- 125000006061 1,2-dimethyl-1-butenyl group Chemical group 0.000 description 1
- 125000006034 1,2-dimethyl-1-propenyl group Chemical group 0.000 description 1
- 125000006035 1,2-dimethyl-2-propenyl group Chemical group 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 125000006064 1,3-dimethyl-1-butenyl group Chemical group 0.000 description 1
- 125000006065 1,3-dimethyl-2-butenyl group Chemical group 0.000 description 1
- 125000006073 1-ethyl-1-butenyl group Chemical group 0.000 description 1
- 125000006036 1-ethyl-1-propenyl group Chemical group 0.000 description 1
- 125000006074 1-ethyl-2-butenyl group Chemical group 0.000 description 1
- 125000006081 1-ethyl-2-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000006082 1-ethyl-2-methyl-2-propenyl group Chemical group 0.000 description 1
- 125000006037 1-ethyl-2-propenyl group Chemical group 0.000 description 1
- 125000006075 1-ethyl-3-butenyl group Chemical group 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006025 1-methyl-1-butenyl group Chemical group 0.000 description 1
- 125000006044 1-methyl-1-pentenyl group Chemical group 0.000 description 1
- 125000006048 1-methyl-2-pentenyl group Chemical group 0.000 description 1
- 125000006030 1-methyl-3-butenyl group Chemical group 0.000 description 1
- 125000006052 1-methyl-3-pentenyl group Chemical group 0.000 description 1
- 125000006055 1-methyl-4-pentenyl group Chemical group 0.000 description 1
- 125000006018 1-methyl-ethenyl group Chemical group 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
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 125000006068 2,3-dimethyl-1-butenyl group Chemical group 0.000 description 1
- 125000006069 2,3-dimethyl-2-butenyl group Chemical group 0.000 description 1
- 125000006070 2,3-dimethyl-3-butenyl group Chemical group 0.000 description 1
- 125000006076 2-ethyl-1-butenyl group Chemical group 0.000 description 1
- 125000006045 2-methyl-1-pentenyl group Chemical group 0.000 description 1
- 125000006049 2-methyl-2-pentenyl group Chemical group 0.000 description 1
- 125000006053 2-methyl-3-pentenyl group Chemical group 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 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 1
- 125000006027 3-methyl-1-butenyl group Chemical group 0.000 description 1
- 125000006046 3-methyl-1-pentenyl group Chemical group 0.000 description 1
- 125000006050 3-methyl-2-pentenyl group Chemical group 0.000 description 1
- 125000006032 3-methyl-3-butenyl group Chemical group 0.000 description 1
- 125000006054 3-methyl-3-pentenyl group Chemical group 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- 125000006042 4-hexenyl group Chemical group 0.000 description 1
- 125000006047 4-methyl-1-pentenyl group Chemical group 0.000 description 1
- 125000006051 4-methyl-2-pentenyl group Chemical group 0.000 description 1
- 125000003119 4-methyl-3-pentenyl group Chemical group [H]\C(=C(/C([H])([H])[H])C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006058 4-methyl-4-pentenyl group Chemical group 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000006440 butyl cyclopropyl group Chemical group 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004850 cyclobutylmethyl group Chemical group C1(CCC1)C* 0.000 description 1
- 125000002188 cycloheptatrienyl group Chemical group C1(=CC=CC=CC1)* 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000006437 ethyl cyclopropyl group Chemical group 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000006431 methyl cyclopropyl group Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000006434 propyl cyclopropyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Images
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- 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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- 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
- C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
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- 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
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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
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- 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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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- 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
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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Abstract
The invention relates to the use of gamma, delta-unsaturated oxime ester compounds of formula (I) wherein the variables are as defined in the description, as photoinitiators. The invention also relates to a preparation method of the gamma, delta-unsaturated oxime ester compound. The gamma, delta-unsaturated compounds of the inventionAnd oxime ester compounds have excellent initiation efficiency as photoinitiators.
Description
Technical Field
The invention relates to the field of photoinitiators, in particular to application of a gamma, delta-unsaturated oxime ester compound as a photoinitiator.
Background
The photocuring technology with the 5E characteristic (high efficiency, wide adaptability, economy, energy conservation and environmental protection) is widely applied to the traditional fields of coatings, adhesives, printing ink and the like and the high and new technologies of photoresist, 3D printing and the like. The photo-curing system mainly comprises oligomer, monomer, photoinitiator, auxiliary agent and the like, wherein the photoinitiator is a core component of the photo-curing system and has the function of generating active species (free radicals, cations and the like) after absorbing light energy and initiating the monomer and the oligomer in the system to carry out polymerization crosslinking, so that the activity of the photoinitiator has a decisive influence on the photo-curing rate and the curing degree.
Oxime ester photoinitiators are excellent high-sensitivity photoinitiators, which can generate active free radicals to initiate polymerization through irreversible decarboxylation after absorbing light energy, and currently, the most widely used commercial oxime ester photoinitiators are OXE-1 and OXE 2. It is to be noted that the photosensitivity of a photoinitiator is not only dependent on its absorption properties, but also its quantum yield of active radicals is an important determinant. The quantum yield of active free radicals of the oxime ester photoinitiator reported at present is lower than that of the traditional I-type UV photoinitiator, such as alpha-dialkoxy acetophenone, alpha-hydroxy alkyl benzophenone, alpha-amino alkyl benzophenone and the like. Therefore, how to break through the quantum yield limit of active free radicals of the oxime ester photoinitiator is the key for effectively improving the sensitivity of the photoinitiator.
Disclosure of Invention
In order to solve the problems, the invention provides the application of gamma, delta-unsaturated oxime ester serving as a photoinitiator. The oxime ester initiator of the present invention has excellent initiation efficiency when used as a photoinitiator due to its specific molecular structure.
Accordingly, it is an object of the present invention to provide a use of a γ, δ -unsaturated oxime ester compound as a photoinitiator, which has excellent initiation efficiency.
It is another object of the present invention to provide a process for preparing the gamma, delta-unsaturated oxime ester compounds of the present invention. The method is simple and easy to implement, mild in condition, easy to obtain raw materials and low in price.
The technical solution for achieving the above object of the present invention can be summarized as follows:
1. use of a gamma, delta-unsaturated oxime ester compound of formula (I) as a photoinitiator,
wherein R is1、R2、R3、R4And R5Independently of one another, hydrogen, halogen, nitro, cyano, amino, mono (C)1-C6Alkyl) amino, di (C)1-C6Alkyl) amino, C1-C20Alkoxy radical, C1-C20Alkyl radical, C1-C20Haloalkyl, C3-C10Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C4-C20Alkyl cycloalkyl radical, C3-C10Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C2-C20Alkenyl radical, C6-C18Aryl of (C)7-C20Aralkyl radical, C7-C20Alkylaryl and C6-C20An aryloxy group;
R6is represented by C1-C20Alkyl radical, C1-C20Haloalkyl, C3-C10Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C4-C20Alkyl cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl and C7-C20An alkylaryl group; and
ar represents an aryl group or a heteroaryl group.
2. The use according to item 1, wherein R1、R2、R3、R4And R5Independently of one another, hydrogen, halogen, nitro, cyano, amino, mono (C)1-C6Alkyl) amino, di (C)1-C6Alkyl) amino, C1-C12Alkoxy radical, C1-C12Alkyl radical, C1-C12Haloalkyl, C3-C8Cycloalkyl radical, C4-C12Cycloalkylalkyl radical, C4-C12Alkyl cycloalkyl radical, C3-C8Cycloalkoxy, C4-C12Cycloalkylalkoxy radical, C2-C6Alkenyl radical, C6-C10Aryl of (C)7-C12Aralkyl radical, C7-C12Alkylaryl and C6-C10An aryloxy group;
preferably, R is1、R2、R3、R4And R5Independently of one another, hydrogen, halogen, amino, mono (C)1-C4Alkyl) amino, di (C)1-C4Alkyl) amino, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C4-C8Alkyl cycloalkyl radical, C2-C6Alkenyl radical, C6-C10Aryl and C7-C12An alkylaryl group;
more preferably R1、R2、R3、R4And R5Independently of one another, hydrogen, halogen, amino, mono (C)1-C4Alkyl) amino, di (C)1-C4Alkyl) amino, C1-C6Haloalkyl and C1-C6An alkyl group.
3. The use according to item 1 or 2, wherein R6Is represented by C1-C12Alkyl radical, C1-C12Haloalkyl, C3-C8Cycloalkyl radical, C4-C12Cycloalkylalkyl radical, C4-C12Alkyl cycloalkyl radical, C6-C10Aryl radical, C7-C11Aralkyl and C7-C11An alkylaryl group;
preferably, R is6Is represented by C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C4-C8Alkyl cycloalkyl radical, C6-C10Aryl radical, C7-C11Aralkyl and C7-C11An alkylaryl group;
more preferably, R6Is represented by C1-C6Alkyl radical, C1-C6Haloalkyl, C5-C6Cycloalkyl radicals, quilt C5-C6Cycloalkyl-substituted C1-C6Alkyl, phenyl or C substituted by phenyl1-C6An alkyl group;
most preferred is R6Is C1-C6An alkyl group.
4. Use according to any one of items 1 to 3, wherein Ar represents C6-C30Aryl or heteroaryl having 5 to 18 ring members, wherein said aryl or heteroaryl is unsubstituted or substituted with one or more groups independently selected from the group consisting of: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino;
preferably Ar represents C6-C20Aryl or heteroaryl having 5 to 18 ring members, wherein said aryl or heteroaryl is unsubstituted or substituted with one or more groups independently selected from the group consisting of: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino;
more preferably Ar represents C6-C14Aryl or heteroaryl having 5 to 14 ring members, wherein said aryl or heteroaryl is unsubstituted or substituted with one or more groups independently selected from the group consisting of: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5 to 8 ring members or amino,
in particular Ar is a heteroaryl group having two or three fused rings and having 8 to 14, or 9 to 14 or 9 to 13 ring members, the heteroaryl group having 1 or 2N atoms as ring members, the heteroaryl group being unsubstituted or substituted by one or more groups independently selected from: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino.
5. Use according to any one of items 1 to 4, wherein the variables in the compound of formula (I) have the following definitions:
R1、R2、R3、R4and R5Independently of one another, hydrogen, halogen, amino, mono (C)1-C4Alkyl) amino, di (C)1-C4Alkyl) amino, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C4-C8Alkyl cycloalkyl radical, C2-C6Alkenyl radical, C6-C10Aryl and C7-C12An alkylaryl group;
R6is represented by C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C4-C8Alkyl cycloalkyl radical, C6-C10Aryl radical, C7-C11Aralkyl and C7-C11An alkylaryl group; and
ar represents C6-C20Aryl or heteroaryl having 5 to 18 ring members, wherein said aryl or heteroaryl is unsubstituted or substituted with one or more groups independently selected from the group consisting of: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino.
6. Use according to any one of items 1 to 5, wherein the variables in the compound of formula (I) have the following definitions:
R1、R2、R3、R4and R5Independently of one another, hydrogen, halogen, amino, mono (C)1-C4Alkyl) amino, di (C)1-C4Alkyl) amino and C1-C6An alkyl group;
R6is represented by C1-C6Alkyl radical, C5-C6Cycloalkyl radicals, quilt C5-C6Cycloalkyl-substituted C1-C6Alkyl, phenyl or C substituted by phenyl1-C6An alkyl group; and
ar represents C6-C14Aryl radicals or radicalsHeteroaryl having 5 to 14 ring members, wherein said aryl or heteroaryl is unsubstituted or substituted with one or more groups independently selected from the group consisting of: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino.
7. Use according to any one of items 1 to 6, wherein the compound of formula (I) is selected from the following compounds:
8. use according to any one of items 1 to 7 for the irradiation of a photocuring system with a wavelength of 300-550nm, preferably 350-525nm, in particular for 3D printing.
9. A γ, δ -unsaturated oxime ester compound of formula (I):
wherein R is1、R2、R3、R4、R5And R6As defined in any of items 1 to 7, and
ar is a heteroaryl group having two or three fused rings and having 8-14, or 9-14 or 9-13 ring members, the heteroaryl group having 1 or 2N atoms as ring members, the heteroaryl group being unsubstituted or substituted with one or more groups independently selected from: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl having 5-10 ring members of heteroaryl, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino.
10. A compound according to item 9, which is
11. A process for the preparation of a compound of formula (I) as defined in any one of claims 1 to 10, which comprises reacting a compound of formula (E)
Wherein R is1、R2、R3、R4、R5And Ar is as defined in any one of items 1 to 10,
reacting with a compound of formula (F) to give a compound of formula (I)
Wherein X1Is halogen, hydroxy or-C (═ O) -R6And R6As defined in any one of items 1 to 10.
12. The process according to item 11, which comprises subjecting the compound of formula (C) to oximation reaction with hydroxylamine and/or hydroxylamine hydrochloride to obtain a compound of formula (E)
Wherein R is1、R2、R3、R4、R5And Ar is as defined in any one of items 1 to 10.
13. A method according to item 12, which comprises reacting a compound of formula (A)
Ar-H
(A)
Wherein Ar is as defined in any one of items 1 to 10,
with a compound of formula (B) to prepare a compound of formula (C)
Wherein R is1、R2、R3、R4、R5And Ar is as defined in any one of items 1 to 10, and X2Is halogen.
14. A photocurable composition comprising at least one γ, δ -unsaturated oxime ester compound of formula (I) according to any one of items 1 to 10.
15. A cured material obtainable from the photocurable composition of item 14.
Drawings
Fig. 1 shows uv-vis absorption spectra of compound 2 and compound 3 in examples of the present invention.
FIG. 2 is a graph of the real-time infrared conversion of monomers for an acrylate system comprising Compound 1 of example 1 of the present invention and a reference compound, respectively.
Fig. 3 is a digital photograph of a 3D print molded structure obtained using compound 3 of example 3 of the present invention as a photoinitiator.
FIG. 4 is a bar graph of monomer conversion in samples using compounds 1,2, or 3.
Detailed Description
In a first aspect the present invention provides the use of a gamma, delta-unsaturated oxime ester compound of formula (I):
wherein R is1、R2、R3、R4And R5Independent of each otherAnd represents hydrogen, halogen, nitro, cyano, amino, mono (C)1-C6Alkyl) amino, di (C)1-C6Alkyl) amino, C1-C20Alkoxy radical, C1-C20Alkyl radical, C1-C20Haloalkyl, C3-C10Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C4-C20Alkyl cycloalkyl radical, C3-C10Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C2-C20Alkenyl radical, C6-C18Aryl of (C)7-C20Aralkyl radical, C7-C20Alkylaryl and C6-C20An aryloxy group;
R6is represented by C1-C20Alkyl radical, C1-C20Haloalkyl, C3-C10Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C4-C20Alkyl cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl and C7-C20An alkylaryl group; and
ar represents an aryl group or a heteroaryl group.
In the present invention, the prefix "Cn-Cm"in each case denotes that the number of carbon atoms contained in the radical is n to m.
"halogen" refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferred that the halogen comprises F, Cl or a combination thereof.
The term "C" as used hereinn-CmAlkyl "means a saturated hydrocarbon radical having n to m, for example 1 to 20, preferably 1 to 12, more preferably 1 to 8, particularly preferably 1 to 6, particularly preferably 1 to 4, carbon atoms, which may be branched or unbranched. Examples include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpropylCyclopentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, 1,2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and isomers thereof. C1-C8The alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, and isomers thereof. C1-C6The alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, t-butyl, pentyl, isopentyl, hexyl and isomers thereof. C1-C4The alkyl group may be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, and isomers thereof.
“C1-C20Haloalkyl "includes C1-C12Haloalkyl, C1-C8Haloalkyl, C1-C6Haloalkyl, C1-C4A haloalkyl group. Halogen and alkyl in haloalkyl are as defined herein for halogen and alkyl.
The term "C" as used herein2-CmAlkenyl "means an unsaturated open-chain hydrocarbon group having 2 to m, for example 2 to 20, 2 to 12, preferably 2 to 6, more preferably 2 to 4 carbon atoms and having one or more double bonds located anywhere, which may be branched or unbranched. Examples include ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 2-propenyl, 2-butenyl, 2-methyl-butenyl, 2-pentenyl, 2-methyl-butenyl, 2-pentenyl, 2-butenyl, 2-methyl-pentenyl, 2-methyl-pentenyl, 2-methyl-butenyl, 2-methyl-pentenyl, 2-butenyl, 2-pentenyl, 2-butenyl, 2-pentenyl, 2-methyl-butenyl, and the like, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-Propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1-dimethyl-2-butenyl, 1-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl, 1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1, 3-dimethyl-1-butenyl, 1, 3-dimethyl-2-butenyl, 1, 3-dimethyl-3-butenyl, 2-dimethyl-3-butenyl, 2-methyl-3-butenyl, 1, 2-dimethyl-2-butenyl, 1, 3-dimethyl-3-butenyl, 1, 2-dimethyl-3-butenyl, 1, 2-methyl-4-pentenyl, 3-pentenyl, 4-pentenyl, 3-methyl-4-pentenyl, 4-butenyl, 1, 2-dimethyl-3-butenyl, 1, 2-dimethyl-butenyl, 2-dimethyl-2-butenyl, 2-dimethyl-2-butenyl, 2-dimethyl-butenyl, 2, and the like, 2, 3-dimethyl-1-butenyl, 2, 3-dimethyl-2-butenyl, 2, 3-dimethyl-3-butenyl, 3-dimethyl-1-butenyl, 3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-ethyl-3-butenyl, 2-ethyl-2-butenyl, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 2-methyl-2-butenyl, 2-ethyl-2-butenyl, 2-methyl-propenyl, 2-methyl-2-propenyl, 2-methyl-propenyl, 2-propenyl, 2-methyl-2-propenyl, 2-ethyl-butyl, 2-propenyl, 2, 1-ethyl-2-methyl-2-propenyl and isomers thereof. C2-C6The alkenyl group may be vinyl, propenyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, neopentynyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, isohexenyl, neohexenyl and isomers thereof. C2-C4The alkenyl group may be vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, and isomers thereof.
The term "C" as used herein3-CmCycloalkyl "means a saturated alicyclic monocyclic group having 3 to m, such as 3 to 10, preferably 3 to 8, more preferably 5 to 6, ring carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
The term "C4-CmCycloalkylalkyl radical tableAlkyl substituted by cycloalkyl and containing a total of 4 to m carbon atoms, for example 4 to 20 carbon atoms, 4 to 12, preferably 4 to 10, 4 to 8 or 4 to 8 carbon atoms. Alkyl and cycloalkyl groups are suitably defined herein, and examples include cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl and the like.
The term "C4-CmAlkylcycloalkyl "denotes cycloalkyl substituted by alkyl and contains a total of 4 to m carbon atoms, for example 4 to 20 carbon atoms, 4 to 12, preferably 4 to 10, 4 to 8 or 4 to 8 carbon atoms. Alkyl and cycloalkyl groups are suitably defined herein, and examples include methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, butylcyclopropyl, methylcyclobutyl, ethylcyclobutyl, propylcyclobutyl, butylcyclobutyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, butylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl, and the like.
The term "C" as used herein6-CmAryl "means a monocyclic, bicyclic or tricyclic aromatic hydrocarbon radical containing from 6 to m carbon atoms, for example from 6 to 18, preferably from 6 to 10 carbon atoms. As C6-CmAs examples of aryl groups, mention may be made of phenyl, azulenyl, cycloheptatrienyl, biphenylene, dicyclopentadiene acenyl, fluorenyl, phenanthryl, triphenylene, pyrenyl, tetracenyl, chrysenyl, biphenyl, anthracenyl, indenyl, pentalenyl and naphthyl. The aryl group may be unsubstituted or substituted. Suitable substituents include, for example, hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino.
The term "C7-CmAralkyl "means an alkyl group substituted with an aryl group and contains 7 to m, for example, 7 to 20 carbon atoms, 7 to 12, preferably 7 to 10 carbon atoms, and more preferably 7 to 8 carbon atoms in total. Wherein alkyl and aryl are as defined herein, examples include benzyl, phenethyl, naphthylmethyl, naphthylethyl and the like.
The term "C7-CmAlkylaryl "denotes an aryl group substituted by an alkyl group and containing a total of 7 to m, such as 7 to 20, carbon atoms, for example 7 to 12, preferably 7 to 10, more preferably 7 to 8 carbon atoms. Wherein alkyl and aryl are as defined herein, examples include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, methylnaphthyl, ethylnaphthyl and the like.
The term "Cn-CmAlkoxy "means at Cn-CmOpen chain C corresponding to alkyln-CmC having an oxygen atom as a linking group bonded to any carbon atom of the alkanen-CmAlkyl radicals, e.g. C1-C20Alkoxy, preferably C1-C12Alkoxy, more preferably C1-C8Alkoxy, particularly preferably C1-C6Alkoxy, particularly preferably C1-C4An alkoxy group. C1-C8The alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, isooctoxy and isomers thereof. C1-C4The alkoxy group may be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and isomers thereof.
The term "C3-CmCycloalkoxy "is defined as being in C3-CmCycloalkyl corresponds to C3-CmC having an oxygen atom as a linking group bonded to any ring carbon atom in the cycloalkane3-CmCycloalkyl radicals, examplesSuch as C3-C10Cycloalkoxy, preferably C3-C8Cycloalkoxy, more preferably C5-C6Cycloalkoxy groups, such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecyloxy and isomers thereof.
The term "C4-CmCycloalkylalkoxy "means an alkoxy group substituted with a cycloalkyl group and containing a total of 4 to m carbon atoms, for example 4 to 20, 4 to 12 carbon atoms, preferably 4 to 8 carbon atoms. Where cycloalkyl is suitably defined herein, examples include cyclopropylmethoxy, cyclopropylethoxy, cyclopropylpropoxy, cyclopropylbutoxy, cyclobutylmethoxy, cyclobutylethoxy, cyclobutylpropoxy, cyclobutylbutoxy, cyclopentylmethoxy, cyclopentylethoxy, cyclopentylpropoxy, cyclopentylbutoxy, cyclohexylmethoxy, cyclohexylethoxy, cyclohexylpropoxy, cyclohexylbutoxy and the like.
The term "C" as used herein6-CmAryloxy "means in C6-CmAryl radical corresponding to C6-CmC having an oxygen atom as a linking group bonded to any aromatic carbon atom in the aromatic hydrocarbon6-CmAryl groups such as phenoxy, tolyloxy, naphthyloxy and the like.
The term heterocycloalkyl is understood to mean a saturated radical comprising n-m ring members, such as 3-8, 3-7, 3-6 or 4-8, 4-7, 4-6, or 5, 6 or 7 ring members and one or more, such as 1-5, 1-3, 1 or 2 heteroatoms selected from N, O or S, as ring members.
Heteroaryl is understood as meaning a group having 5 to 18 ring members, for example 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18, such as 5 to 16, 5 to 14, 5 to 10 or 5 to 8, or 8 to 14, 9 to 14 or 9 to 13 ring members. At least one ring atom of the heteroaryl group is a heteroatom, preferably a heteroatom selected from N, O and S, more preferably N. Heteroaryl groups preferably have 1 to 3, e.g. one or two, heteroatoms. More preferably, heteroaryl is a ring system having two or three fused rings with 8-14, 9-14 or 9-13 ring members. Examples of heteroaryl groups include carbazole, pyridinePyrrole, furan, pyrazole, imidazole and thiophene. The aryl group may be unsubstituted or substituted. Suitable substituents include, for example, hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino.
In one embodiment of the invention, R1、R2、R3、R4And R5Independently of one another, hydrogen, halogen, nitro, cyano, amino, mono (C)1-C6Alkyl) amino, di (C)1-C6Alkyl) amino, C1-C12Alkoxy radical, C1-C12Alkyl radical, C1-C12Haloalkyl, C3-C8Cycloalkyl radical, C4-C12Cycloalkylalkyl radical, C4-C12Alkyl cycloalkyl radical, C3-C8Cycloalkoxy, C4-C12Cycloalkylalkoxy radical, C2-C6Alkenyl radical, C6-C10Aryl of (C)7-C12Aralkyl radical, C7-C12Alkylaryl and C6-C10An aryloxy group.
In a preferred embodiment of the invention, R1、R2、R3、R4And R5Independently of one another, hydrogen, halogen, amino, mono (C)1-C4Alkyl) amino, di (C)1-C4Alkyl) amino, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C4-C8Alkyl cycloalkyl radical, C2-C6Alkenyl radical, C6-C10Aryl and C7-C12An alkylaryl group.
In a preferred embodiment of the invention, R1、R2、R3、R4And R5Independently of one another, hydrogen, halogen, amino, mono (C)1-C4Alkyl) amino, di (C)1-C4Alkyl) amino, C1-C6Haloalkyl and C1-C6An alkyl group.
In a preferred embodiment of the invention, R6Is represented by C1-C12Alkyl radical, C1-C12Haloalkyl, C3-C8Cycloalkyl radical, C4-C12Cycloalkylalkyl radical, C4-C12Alkyl cycloalkyl radical, C6-C10Aryl radical, C7-C11Aralkyl and C7-C11An alkylaryl group.
In a preferred embodiment of the invention, R6Is represented by C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C4-C8Alkyl cycloalkyl radical, C6-C10Aryl radical, C7-C11Aralkyl and C7-C11An alkylaryl group.
In a preferred embodiment of the invention, R6Is represented by C1-C6Alkyl radical, C5-C6Cycloalkyl radicals, quilt C5-C6Cycloalkyl-substituted C1-C6Alkyl, phenyl or C substituted by phenyl1-C6An alkyl group. Most preferred is R6Is C1-C6An alkyl group.
In one embodiment of the present invention, wherein Ar represents C6-C30Aryl or heteroaryl having 5 to 18 ring members, wherein the aryl or heteroaryl is unsubstituted or substituted with one or more (e.g., 1 to 5, 1 to 4, 1 to 3, 1 or 2) groups independently selected from the group consisting of: hydroxy, halogen, cyano, C1-C6Alkyl, aryl, heteroaryl, and heteroaryl,C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino.
In a preferred embodiment of the invention, Ar represents C6-C20Aryl or heteroaryl having 5 to 18 ring members, wherein the aryl or heteroaryl is unsubstituted or substituted with one or more (e.g., 1 to 5, 1 to 4, 1 to 3, 1 or 2) groups independently selected from the group consisting of: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino.
In a preferred embodiment of the invention, Ar represents C6-C14Aryl or heteroaryl having 5 to 14 ring members, wherein the aryl or heteroaryl is unsubstituted or substituted with one or more (e.g., 1 to 5, 1 to 4, 1 to 3, 1 or 2) groups independently selected from the group consisting of: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl, and heteroaryl,Heteroaryl or amino having 5 to 8 ring members.
Ar may be, for example, phenyl, naphthyl or carbazole, which may be selected by one or more (e.g. 1-5, 1-4, 1-3, 1 or 2) independently of one another from C1-C6Alkyl, C (O) R 'wherein R' is hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, or C6-C10And (4) an aryl group.
In a preferred embodiment of the invention, the variables in the compounds of formula (I) have the following definitions:
R1、R2、R3、R4and R5Independently of one another, hydrogen, halogen, amino, mono (C)1-C4Alkyl) amino, di (C)1-C4Alkyl) amino, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C4-C8Alkyl cycloalkyl radical, C2-C6Alkenyl radical, C6-C10Aryl and C7-C12An alkylaryl group;
R6is represented by C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C4-C8Alkyl cycloalkyl radical, C6-C10Aryl radical, C7-C11Aralkyl and C7-C11An alkylaryl group; and
ar represents C6-C20Aryl or heteroaryl having 5 to 18 ring members, wherein said aryl or heteroaryl is unsubstituted or substituted with one or more groups independently selected from the group consisting of: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ', wherein R ', R ' andr' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino.
In a preferred embodiment of the invention, the variables in the compounds of formula (I) have the following definitions:
R1、R2、R3、R4and R5Independently of one another, hydrogen, halogen, amino, mono (C)1-C4Alkyl) amino, di (C)1-C4Alkyl) amino, C1-C6Alkyl and C1-C6A haloalkyl group;
R6is represented by C1-C6Alkyl radical, C1-C6Haloalkyl, C5-C6Cycloalkyl radicals, quilt C5-C6Cycloalkyl-substituted C1-C6Alkyl, phenyl or C substituted by phenyl1-C6An alkyl group; and
ar represents C6-C14Aryl or heteroaryl having 5 to 14 ring members, wherein said aryl or heteroaryl is unsubstituted or substituted with one or more groups independently selected from the group consisting of: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino.
In a preferred embodiment of the invention, the variables in the compounds of formula (I) have the following definitions:
R1、R2、R3、R4and R5Independently of each other, hydrogen, amino, mono (C)1-C4Alkyl) amino, di (C)1-C4Alkyl) amino and C1-C6An alkyl group;
R6is represented by C1-C6An alkyl group; and
ar represents C6-C14Aryl or heteroaryl having 5 to 14 ring members, wherein said aryl or heteroaryl is unsubstituted or substituted with one or more groups independently selected from the group consisting of: c1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', wherein R' is C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl or heteroaryl having 5 to 8 ring members.
Specific examples of compounds of formula (I) may be mentioned:
one aspect of the present invention relates to a γ, δ -unsaturated oxime ester compound of formula (I):
wherein R is1、R2、R3、R4、R5And R6Each as defined above, and
ar is a heteroaryl group having two or three fused rings and having 8 to 14, or 9 to 14 or 9 to 13 ring members, the heteroaryl group having 1 or 2N atoms as ring members, the heteroaryl group being unsubstituted or substituted with one or more (e.g. 1 to 5, 1 to 3 or 1 or 2) groups independently selected fromGroup substitution: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino.
In a preferred embodiment, Ar is a carbazole, which is unsubstituted or substituted by one or more (e.g. 1 to 5 or 1 to 3) substituents as defined above, preferably by one or more (e.g. 1 to 5, 1 to 4, 1 to 3, 1 or 2) substituents independently selected from C1-C6Alkyl, C (O) R 'wherein R' is hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, or C6-C10And (4) an aryl group.
In one embodiment, the compound of formula (I) is
A second aspect of the invention relates to a process for the preparation of a compound of formula (I) according to the invention, which comprises reacting a compound of formula (E)
Wherein R is1、R2、R3、R4、R5And Ar is as defined above, and (C) Ar are as defined above,
reacting with a compound of formula (F) to give a compound of formula (I)
Wherein X1Is halogen, hydroxy or-C (═ O) -R6And R6As defined above.
In the reaction of the compound of formula (E) with the compound of formula (F), the hydroxyl group in the oxime group is converted to an ester group, thereby obtaining the compound of formula (I). The esterification reagent is not particularly limited as long as the hydroxyl group in the oxime group of the compound of the formula (III) can be converted into an ester group. As esterification reagents, the corresponding acid halides, such as acid chlorides, the corresponding carboxylic acids and the corresponding acid anhydrides can be used.
The reaction of the compound of formula (E) with the compound of formula (F) is usually carried out in the presence of a catalyst, for example, the compound of formula (E) and the compound of formula (F) are dispersed in an organic solvent in the presence of a catalyst. As the catalyst, any one or a mixture of two or more of triethylamine, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide and sodium hydride may be mentioned. The molar ratio of the compound of formula (E) to the compound of formula (F) may be 1:2 to 1: 5; the molar ratio of compound of formula (E) to catalyst may be from 1:2 to 1: 15. Said ratio contributes to an increase in the yield of the product. In the reaction of the compound of formula (E) with the compound of formula (F), the reaction temperature may be 10 to 100 ℃ and the reaction time may be 1 to 8 hours, such as 1 to 5 hours.
According to the invention, the compounds of the formula (E) are obtainable by oximation of compounds of the formula (C) with hydroxylamine and/or hydroxylamine hydrochloride
Wherein R is1、R2、R3、R4、R5And Ar is as defined above.
The reaction of the compound of the formula (C) with hydroxylamine and/or hydroxylamine hydrochloride may be carried out in the presence of a catalyst. The catalyst can be any one or more of sodium bicarbonate, sodium carbonate or sodium acetate. The molar ratio of the compound of formula (C) to hydroxylamine and/or hydroxylamine hydrochloride may be 1:2 to 1: 5. The molar ratio of compound of formula (C) to catalyst may be from 1:2 to 1: 15.
According to the invention, the compounds of the formula (C) can be prepared by reacting compounds of the formula (A)
Ar-H
(A)
Wherein Ar is as defined above, and wherein,
with a compound of formula (B)
Wherein R is1、R2、R3、R4、R5And Ar is as defined above, and X2Is halogen.
The reaction of the compound of formula (a) with the compound of formula (B) may be carried out in the presence of a catalyst. As examples of the catalyst, there may be mentioned any one of aluminum trichloride, aluminum tribromide, ferric trichloride, boron trifluoride and zinc dichloride or a mixture of two or more thereof. The reaction is a friedel-crafts acylation reaction. The reaction temperature can be 50-150 ℃, and the reaction time can be 1-10 hours.
The reaction of the compound of the formula (A) with the compound of the formula (B), the reaction of the compound of the formula (C) with hydroxylamine and/or hydroxylamine hydrochloride, and the reaction of the compound of the formula (E) with the compound of the formula (F) may be carried out in the presence of an organic solvent. The organic solvent can be any one or the mixture of more than two of dichloromethane, chloroform, methanol, ethanol, toluene, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide or triethylamine.
The compound of formula (I) can be used as a photoinitiator in a UV-vis photocuring system, and can effectively initiate a curing reaction. The compounds of formula (I) according to the invention can be used as photoinitiators in photocuring systems with radiation wavelengths of 300-550nm, preferably 350-525 nm. The compounds of formula (I) of the present invention may also be used as photoinitiators for 3D printing.
Another aspect of the present invention relates to photocurable compositions comprising at least one inventive gamma, delta-unsaturated oxime ester compound of formula (I).
The amount of the compounds of the formula (I) according to the invention is generally from 0.01 to 10% by weight, for example from 0.02% by weight, 0.05% by weight, 0.08% by weight, 0.1% by weight, 0.2% by weight, 0.5% by weight, 0.8% by weight, 1% by weight, 1.2% by weight, 1.5% by weight, 1.8% by weight, 2% by weight, 2.2% by weight, 2.5% by weight, 2.8% by weight, 3% by weight, 3.2% by weight, 3.5% by weight, 3.8% by weight, 4% by weight, 4.5% by weight, 5% by weight, 5.5% by weight, 6% by weight, 6.5% by weight, 7% by weight, 7.5% by weight, 8% by weight, 8.5% by weight, 9% by weight, 9.5% by weight, preferably from 0.1 to 6% by weight, such as from 0.2 to 5% by weight, based on the active ingredient amount of the photocurable composition.
In the context of the disclosure, an active ingredient refers to an ingredient of the photocurable composition excluding the solvent.
The photocurable composition contains a photocurable compound in addition to the photoinitiator of the present invention.
In the present invention, as the photocurable compound, it refers to a monomer or oligomer containing an unsaturated carbon-carbon double bond. After the monomer or the oligomer is irradiated by light, the polymerization reaction can be initiated by a photoinitiator, and then the crosslinking and curing are carried out.
According to an aspect of the present invention, there is provided a cured material obtainable from the photocurable composition of the present invention.
The cured material may be a photo-cured coating, including coatings comprising functional materials, coatings for filters of UV and/or visible light; a sealant; photoetching materials; a holographic recording material; 3D printing materials; a lithographic material; the preparation material of the optical device and the material for improving the mechanical property, such as carbon fiber composite material and/or inorganic nano particles and/or organic nano particles, etc.
The beneficial effects of the gamma, delta-unsaturated oxime ester compounds of formula (I) according to the invention as photoinitiators include:
(1) the initiation efficiency is excellent;
(2) by changing the structure and the variety of the aromatic compound, the absorption wavelength of the photoinitiator can be regulated and controlled, the photoinitiator can be used as an ultraviolet photoinitiator and a visible photoinitiator, and is matched with an energy-saving and environment-friendly LED light source for use, so that the application range is wider;
(3) the photoinitiator can be used for 3D printing to construct an exquisite three-dimensional model.
Examples
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention. The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention.
Example 1: preparation of compound 1:
(1) preparation of phenyl-4-penten-1-one:
the chemical reaction formula is as follows:
after benzene (20mL) and aluminum trichloride (0.956g, 7.17mmol) were added in this order to a 100mL single-neck flask under ice-bath conditions, 4-pentenoyl chloride (0.728g, 6.14mmol) was slowly added dropwise thereto, and after reacting for 2 hours, the reaction mixture was poured into 20mL ice water and extracted with dichloromethane (20 mL. times.3), and the organic phases were combined and dried over anhydrous sodium sulfate. Dichloromethane was removed by rotary evaporation and separated by silica gel column chromatography to give 0.55g of a white solid, yield: 38.7 percent.
The structure of phenyl-4-penten-1-one was confirmed by nuclear magnetic resonance hydrogen spectroscopy:
1H NMR(400MHz,DMSO-d6)δ8.01–7.94(m,2H),7.67–7.60(m,1H),7.57–7.50(m,2H),5.88(ddt,J＝16.8,10.2,6.4Hz,1H),5.08(dq,J＝17.2,1.7Hz,1H),4.98(dq,J＝10.2,1.5Hz,1H),3.13(t,J＝7.3Hz,2H),2.43–2.34(m,2H)。
(2) preparation of phenyl-4-penten-1-one oxime:
the chemical reaction formula is as follows:
a100 mL round-bottom flask was charged with phenyl-4-penten-1-one (0.707g, 4.412mmol), hydroxylamine hydrochloride (0.613g, 8.825mmol), anhydrous sodium acetate (0.723g, 8.825mmol) and 30mL anhydrous ethanol and refluxed for 2 hours. And cooling to room temperature after the reaction is finished, filtering to remove solid impurities, collecting a liquid phase, and removing the solvent by rotary evaporation. Silica gel column chromatography (petroleum ether: ethyl acetate ═ 10:1) afforded a pale yellow solid (0.494 g). Yield: and (3.9).
The structure of phenyl-4-penten-1-one oxime was confirmed by nuclear magnetic resonance hydrogen spectroscopy:
1H NMR(400MHz,DMSO-d6)δ11.19(s,1H),7.65–7.60(m,2H),7.42–7.34(m,3H),5.84(ddt,J＝16.8,10.2,6.5Hz,1H),5.04(dq,J＝17.1,1.7Hz,1H),4.96(ddt,J＝10.2,2.2,1.3Hz,1H),2.84–2.78(m,2H),2.21(dtt,J＝9.3,6.6,1.4Hz,2H)。
(3) preparation of compound 1:
the chemical reaction formula is as follows:
a25 mL round bottom flask was charged with phenyl-4-penten-1-one oxime (28mg, 0.159mmol) and 5mL THF and stirred in an ice bath to add sodium hydride (7.5mg, 0.315mmol) and reacted for 30 min. Acryloyl chloride (43.4mg, 0.479mmol) was then added and the reaction continued for 30 min. After the reaction was completed, the reaction was quenched with deionized water. THF was removed by rotary evaporation and the aqueous phase was extracted three times with ethyl acetate. The organic phases were combined and dried over anhydrous sodium sulfate and ethyl acetate was removed by rotary evaporation. Column chromatography on silica gel (petroleum ether: dichloromethane ═ 1:1.5) gave 30mg of a yellow liquid. The yield was 82.3%.
The structure of compound 1 was confirmed by nuclear magnetic resonance hydrogen spectroscopy.
1H NMR(400MHz,DMSO-d6)δ7.79–7.73(m,2H),7.57–7.47(m,3H),6.48(dd,J＝17.3,1.7Hz,1H),6.40(dd,J＝17.3,10.1Hz,1H),6.10(dd,J＝10.1,1.7Hz,1H),5.81(ddt,J＝16.9,10.1,6.7Hz,1H),5.03(dq,J＝17.1,1.6Hz,1H),4.98(ddt,J＝10.1,2.1,1.2Hz,1H),3.00(dd,J＝8.2,7.1Hz,2H),2.26(dtt,J＝8.5,7.2,1.4Hz,2H).
Example 2: preparation of compound 2:
(1) preparation of N-ethylcarbazol-3- (4-butenyl) ketone:
the chemical reaction formula is as follows:
after methylene chloride (20mL), aluminum trichloride (0.956g, 7.17mmol) and N-ethylcarbazole (1.0g, 5.12mmol) were added in this order to a 50mL single-neck flask under ice-bath conditions, a solution of 4-pentenoyl chloride (0.728g, 6.14mmol) in methylene chloride (10mL) was slowly added dropwise, and after 4 hours of reaction, the reaction solution was poured into 20mL of ice water and extracted with methylene chloride (20 mL. times.3), and the organic phases were combined and dried over anhydrous sodium sulfate. Dichloromethane was removed by rotary evaporation and separated by silica gel column chromatography to give 0.55g of a white solid, yield: 38.7 percent.
The structure of N-ethylcarbazol-3- (4-butenyl) ketone was confirmed by nuclear magnetic resonance hydrogen spectroscopy:
1H NMR(400MHz,DMSO-d6)δ8.91(d,J＝1.6Hz,1H),8.32(dt,J＝7.7,1.0Hz,1H),8.10(dd,J＝8.7,1.7Hz,1H),7.72–7.64(m,2H),7.52(ddd,J＝8.3,7.1,1.2Hz,1H),7.29(ddd,J＝7.9,7.2,0.9Hz,1H),5.94(ddt,J＝16.8,10.2,6.4Hz,1H),5.17–4.96(m,2H),4.48(q,J＝7.1Hz,2H),3.25(t,J＝7.3Hz,2H),2.49–2.40(m,2H),1.32(t,J＝7.1Hz,3H)。
(2) synthesis of N-ethyl carbazole-3- (4-butenyl) ketoxime
The chemical reaction formula is as follows:
n-ethylcarbazole-3- (4-N-butenyl) ketone (0.55g, 1.98mmol), hydroxylamine hydrochloride (0.412g, 5.94mmol), anhydrous sodium acetate (0.487g, 5.94mmol) and anhydrous ethanol (30mL) were added to a 100mL round-bottomed flask, and after refluxing for 2 hours, 20mL of dichloromethane was added and washed with deionized water (20mL × 3), after drying over anhydrous sodium sulfate, dichloromethane was removed by rotary evaporation, and separation by silica gel column chromatography (petroleum ether: ethyl acetate ═ 8: 1) gave 0.461g of a white solid in yield: 79.63 percent.
The structure of N-ethylcarbazole-3- (4-butenyl) ketoxime was confirmed by nuclear magnetic resonance hydrogen spectroscopy:
1H NMR(400MHz,DMSO-d6)δ10.99(s,1H),8.40(d,J＝1.6Hz,1H),8.22(d,J＝7.6Hz,1H),7.79(dd,J＝8.6,1.7Hz,1H),7.61(dd,J＝8.4,4.9Hz,2H),7.47(ddd,J＝8.3,7.1,1.2Hz,1H),7.25–7.19(m,1H),5.90(ddt,J＝16.8,10.2,6.5Hz,1H),5.11–4.94(m,2H),4.45(q,J＝7.1Hz,2H),2.98–2.92(m,2H),2.34–2.25(m,2H),1.33(t,J＝7.1Hz,3H)。
(3) synthesis of Compound 2
The chemical reaction formula is as follows:
n-ethylcarbazole-3- (4-butenyl) ketoxime (0.7g, 2.532mmol), sodium hydride (0.181g, 7.571mmol) and anhydrous tetrahydrofuran (20mL) were charged in a 100mL round-bottom flask under ice-bath conditions, and after 1 hour of reaction, acetyl chloride (0.685g, 7.571mmol) was added to the reaction system and the reaction was continued for 1 hour. After the reaction was completed, the reaction was quenched with saturated sodium bicarbonate solution, and the product was extracted with dichloromethane (20 mL. times.3), and the organic phases were combined and dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporation and separated by silica gel column chromatography (petroleum ether: ethyl acetate 15: 1) to give 0.753g of a yellow viscous liquid, yield: 88.7 percent.
Compound 2: the structure of N-ethylcarbazole-3- (4-butenyl) ketoacetoxime ester was confirmed by nuclear magnetic resonance hydrogen spectroscopy:
1H NMR(400MHz,DMSO-d6)δ8.58(d,J＝1.6Hz,1H),8.29–8.25(m,1H),7.88(dd,J＝8.7,1.8Hz,1H),7.65(dd,J＝14.7,8.5Hz,2H),7.50(ddd,J＝8.2,7.2,1.2Hz,1H),7.28–7.23(m,1H),5.87(ddt,J＝16.8,10.1,6.6Hz,1H),5.10–4.97(m,2H),4.46(q,J＝7.1Hz,2H),3.09(t,J＝7.7Hz,2H),2.36–2.28(m,2H),2.26(s,3H),1.32(t,J＝7.1Hz,3H)。
example 3: preparation of compound 3:
(1) preparation of N-ethylcarbazole-4-butenyl-3- (2-methylphenyl) ketone:
the chemical reaction formula is as follows:
dichloromethane (20mL), aluminum trichloride (0.835g, 6.266mmol) and N-ethylcarbazole-3- (2-methylphenyl) ketone (0.469g, 1.566mmol) were added to a 100mL round bottom flask under ice bath conditions, and a solution of 4-pentenoyl chloride (0.247g, 1.878mmol) in dichloromethane (10mL) was slowly added dropwise to the reaction system and reacted for 4 hours. After completion of the reaction, the reaction mixture was poured into 20mL of ice water. The product was extracted with 20mL x 3 dichloromethane and the organic phases were combined and dried over anhydrous sodium sulfate. Dichloromethane was removed by rotary evaporation and separated by silica gel column chromatography (petroleum ether: ethyl acetate ═ 5: 1) to give 0.53g of a pale yellow solid in yield: 95.2 percent.
The structure of N-ethylcarbazole-4-butenyl-3- (2-methylphenyl) ketone was confirmed by nuclear magnetic resonance hydrogen spectroscopy:
1H NMR(400MHz,DMSO-d6)δ8.87(d,J＝1.6Hz,1H),8.62(d,J＝1.5Hz,1H),8.11(dd,J＝8.6,1.7Hz,1H),7.88(dd,J＝8.6,1.7Hz,1H),7.80(dd,J＝8.7,6.4Hz,2H),7.59(ddd,J＝8.4,5.9,2.9Hz,1H),7.43–7.35(m,3H),5.88(ddt,J＝16.8,10.2,6.4Hz,1H),5.08(dq,J＝17.2,1.7Hz,1H),4.88(dq,J＝10.2,1.5Hz,1H),4.53(q,J＝7.1Hz,2H),3.11(t,J＝7.3Hz,2H),2.59(s,3H),2.43–2.34(m,2H),1.32(t,J＝7.1Hz,3H)。
(2) the chemical reaction formula for synthesizing the N-ethyl carbazole-6- (2-methylbenzoyl) -4-butenyl ketoxime is as follows:
n-ethylcarbazole-4-butenyl-3- (2-methylphenyl) ketone (0.563g, 1.583mmol), hydroxylamine hydrochloride (0.330g, 4.751mmol), anhydrous sodium acetate (0.389g, 4.751mmol) and 25mL of anhydrous ethanol were added to a 100mL round-bottomed flask and refluxed for 3 hours. After the reaction was completed, the liquid phase was collected by filtration, the solvent was removed by rotary evaporation to obtain a crude product, which was dissolved in 20mL of dichloromethane and washed with 20 × 3mL of deionized water, and dried over anhydrous sodium sulfate, and the dichloromethane was removed by rotary evaporation, and separated by silica gel column chromatography (petroleum ether: dichloromethane ═ 1: 3) to obtain 0.594g of a pale yellow solid, yield: 96.6 percent.
The structure of N-ethylcarbazole-6- (2-methylbenzoyl) -4-butenyl ketoxime was confirmed by nuclear magnetic resonance hydrogen spectroscopy:
1H NMR(400MHz,DMSO-d6)δ11.02(s,1H),8.52(d,J＝1.7Hz,1H),8.37(d,J＝1.7Hz,1H),7.72(dd,J＝8.7,1.7Hz,1H),7.64(dd,J＝8.7,1.7Hz,1H),7.51(dd,J＝18.4,8.7Hz,2H),7.49–7.45(m,1H),7.42–7.34(m,3H),5.68(ddt,J＝16.8,10.2,6.4Hz,1H),5.06(dq,J＝17.2,1.7Hz,1H),4.88(dq,J＝10.2,1.5Hz,1H),4.45(q,J＝7.1Hz,2H)，3.11(t,J＝7.3Hz,2H),2.69(s,3H),2.43–2.34(m,2H),1.26(t,J＝7.1Hz,3H)。
(3) synthesis of Compound 3
The chemical reaction formula is as follows:
n-ethylcarbazole-6- (2-methylbenzoyl) -3-methylketoxime (0.594g, 1.529mmol), tetrahydrofuran (20mL) and sodium hydride (0.11g, 4.587mmol) were charged in a 100mL round-bottom flask under ice-bath conditions, and reacted for 1 hour. Then, acetyl chloride (0.415g, 4.587mmol) was added dropwise to the reaction system and the reaction was continued for 1 hour. After the reaction was completed, the reaction was quenched with saturated sodium bicarbonate, and the product was extracted with 20mL of X3 dichloromethane, and the organic phases were combined and dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporation, and separation by silica gel column chromatography (petroleum ether: dichloromethane ═ 1: 3) gave 0.57g of a pale yellow liquid in yield: 90 percent.
The structure of compound 3 was confirmed by nuclear magnetic resonance hydrogen spectroscopy:
1H NMR(400MHz,DMSO-d6)8.62(d,J＝1.7Hz,1H),8.47(d,J＝1.7Hz,1H),7.92(dd,J＝8.7,1.7Hz,1H),7.84(dd,J＝8.7,1.7Hz,1H),7.71(dd,J＝18.4,8.7Hz,2H),7.51–7.45(m,1H),7.42–7.34(m,3H),5.88(ddt,J＝16.8,10.2,6.4Hz,1H),5.08(dq,J＝17.2,1.7Hz,1H),4.98(dq,J＝10.2,1.5Hz,1H),4.55(q,J＝7.1Hz,2H)，3.13(t,J＝7.3Hz,2H),2.43–2.34(m,2H),2.69(s,3H),2.31(s,3H),1.36(t,J＝7.1Hz,3H)。
example 4
The absorption performance of the gamma, delta-unsaturated oxime ester compound is measured
The performance measurements were performed on the compounds 2 and 3 prepared in examples 2 and 3, respectively, by an ultraviolet-visible spectrophotometer at 200-600 nm. The ultraviolet-visible light absorption spectra of the compounds 2 and 3 are shown in fig. 1, which illustrates that the absorption wavelength of the photoinitiator can be adjusted and controlled by changing the structure and the type of the aromatic compound (namely, Ar group), and the ultraviolet-visible light absorption spectra can be matched with a traditional high-pressure mercury lamp and an energy-saving and environment-friendly LED light source, and have a wide application range.
Example 5
Photoinitiation efficiency of gamma, delta-unsaturated oxime ester
10mg of Compound 1 of example 1 was added to 1g of trimethylolpropane triacrylate monomer under exclusion of light, and dissolved completely to give a polymer sample. A polymerized sample of the reference compound was prepared according to the same procedure, wherein the reference compound has the following structure:
irradiating in broad-spectrum high-pressure mercury lamp (100 mW/cm)2250-1000nm and main emission wavelength 365nm) and testing the conversion rate of the monomer by a real-time infrared spectrometer. FIG. 2 is a real-time plot of monomer conversion in a sample. The results in FIG. 2 show that the initiation efficiency of the gamma, delta-unsaturated oxime esters of the present invention is significantly higher than that of the reference compounds which do not contain a gamma, delta-unsaturated carbon-carbon double bond at the end. The polymerization rate and the conversion rate of the initiating monomer of the gamma, delta-unsaturated oxime ester are higher than those of a reference compound without gamma, delta-unsaturated carbon-carbon double bonds at the tail end.
Example 6
Application of gamma, delta-unsaturated oxime ester photoinitiator in 3D printing
Under the dark condition, adding 800mg of compound 3 and 80g of trimethylolpropane triacrylate into a glass container with a stirrer, stirring and oscillating for 24 hours to completely dissolve the compound 3 to obtain the photocuring material for 3D printing, pouring the photocuring material into a printer (mini-fab DLP) resin tank, adjusting the wavelength of a light source used by the printer to be 405nm, calling out a 3D model to be printed, and automatically printing a three-dimensional structure by the printer, wherein the three-dimensional structure is shown in figure 3.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Example 7
10mg of Compound 1 of example 1 was added to 1g of trimethylolpropane triacrylate monomer under exclusion of light, and dissolved completely to give a polymer sample. Polymerization samples containing compound 2 and compound 3 were prepared according to the same method. Broad-spectrum high-pressure mercury lamp irradiation (100 mW/cm)2250-1000nm and main emission wavelength 365nm) and testing the conversion rate of the monomer by a real-time infrared spectrometer. FIG. 4 is a bar graph of monomer conversion after 600s of irradiation for various samples, where the monomer conversion for the system using compound 1 was about 58%, the monomer conversion for the system using compound 2 was about 69%, and the monomer conversion for the system using compound 3 was about 81%. The results in FIG. 4 show that the compounds of the present invention have good polymerization rate and conversion of monomers when used as photoinitiators, and that the initiated monomers of carbazole group-containing γ, δ -unsaturated oxime esters have higher polymerization rate and conversion than phenyl γ, δ -unsaturated oxime esters.
Claims (15)
1. Use of a gamma, delta-unsaturated oxime ester compound of formula (I) as a photoinitiator,
wherein R is1、R2、R3、R4And R5Independently of one another, hydrogen, halogen, nitro, cyano, amino, mono (C)1-C6Alkyl) amino, di (C)1-C6Alkyl) amino, C1-C20Alkoxy radical, C1-C20Alkyl radical, C1-C20Haloalkyl, C3-C10Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C4-C20Alkyl cycloalkyl radical, C3-C10Cycloalkoxy, C4-C20Cycloalkylalkoxy radical, C2-C20Alkenyl radical, C6-C18Aryl of (C)7-C20Aralkyl radical, C7-C20Alkylaryl and C6-C20An aryloxy group;
R6is represented by C1-C20Alkyl radical, C1-C20Haloalkyl, C3-C10Cycloalkyl radical, C4-C20Cycloalkylalkyl radical, C4-C20Alkyl cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl and C7-C20An alkylaryl group; and
ar represents an aryl group or a heteroaryl group.
2. Use according to claim 1, wherein R1、R2、R3、R4And R5Independently of one another, hydrogen, halogen, nitro, cyano, amino, mono (C)1-C6Alkyl) amino, di (C)1-C6Alkyl) amino, C1-C12Alkoxy radical, C1-C12Alkyl radical, C1-C12Haloalkyl, C3-C8Cycloalkyl radical, C4-C12Cycloalkylalkyl radical, C4-C12Alkyl cycloalkyl radical, C3-C8Cycloalkoxy, C4-C12Cycloalkylalkoxy radical, C2-C6Alkenyl radical, C6-C10Aryl of (C)7-C12Aralkyl radical, C7-C12Alkylaryl and C6-C10An aryloxy group;
preferably, R is1、R2、R3、R4And R5Independently of one another, hydrogen, halogen, amino, mono (C)1-C4Alkyl) amino, di (C)1-C4Alkyl) amino, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C4-C8Alkyl cycloalkyl radical, C2-C6Alkenyl radical, C6-C10Aryl and C7-C12An alkylaryl group;
more preferably R1、R2、R3、R4And R5Independently of one another, hydrogen, halogen, amino, mono (C)1-C4Alkyl) amino, di (C)1-C4Alkyl) amino, C1-C6Haloalkyl and C1-C6An alkyl group.
3. Use according to claim 1 or 2, wherein R6Is represented by C1-C12Alkyl radical, C1-C12Haloalkyl, C3-C8Cycloalkyl radical, C4-C12Cycloalkylalkyl radical, C4-C12Alkyl cycloalkyl radical, C6-C10Aryl radical, C7-C11Aralkyl and C7-C11An alkylaryl group;
preferably, R is6Is represented by C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C4-C8Alkyl cycloalkyl radical, C6-C10Aryl radical, C7-C11Aralkyl and C7-C11An alkylaryl group;
more preferably, R6Is represented by C1-C6Alkyl radical, C1-C6Haloalkyl, C5-C6Cycloalkyl radicals, quilt C5-C6CycloalkanesRadical substituted C1-C6Alkyl, phenyl or C substituted by phenyl1-C6An alkyl group;
most preferred is R6Is C1-C6An alkyl group.
4. Use according to any one of claims 1 to 3, wherein Ar represents C6-C30Aryl or heteroaryl having 5 to 18 ring members, wherein said aryl or heteroaryl is unsubstituted or substituted with one or more groups independently selected from the group consisting of: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino;
preferably Ar represents C6-C20Aryl or heteroaryl having 5 to 18 ring members, wherein said aryl or heteroaryl is unsubstituted or substituted with one or more groups independently selected from the group consisting of: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino;
more preferably Ar represents C6-C14Aryl or heteroaryl having 5 to 14 ring members, wherein said aryl or heteroaryl is unsubstituted or substituted with one or more groups independently selected from the group consisting of: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5 to 8 ring members or amino,
in particular Ar is a heteroaryl group having two or three fused rings and having 8 to 14, or 9 to 14 or 9 to 13 ring members, the heteroaryl group having 1 or 2N atoms as ring members, the heteroaryl group being unsubstituted or substituted by one or more groups independently selected from: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino.
5. Use according to any one of claims 1 to 4, wherein the variables in the compound of formula (I) have the following definitions:
R1、R2、R3、R4and R5Independently of one another, hydrogen, halogen, amino, mono (C)1-C4Alkyl) amino, di (C)1-C4Alkyl) amino, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C8Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C4-C8Alkyl cycloalkyl radical, C2-C6Alkenyl radical, C6-C10Aryl and C7-C12An alkylaryl group;
R6is represented by C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C4-C8Cycloalkylalkyl radical, C4-C8Alkyl cycloalkyl radical, C6-C10Aryl radical, C7-C11Aralkyl and C7-C11An alkylaryl group; and
ar represents C6-C20Aryl or heteroaryl having 5 to 18 ring members, wherein said aryl or heteroaryl is unsubstituted or substituted with one or more groups independently selected from the group consisting of: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino.
6. Use according to any one of claims 1 to 5, wherein the variables in the compound of formula (I) have the following definitions:
R1、R2、R3、R4and R5Independently of one another, hydrogen, halogen, amino, mono (C)1-C4Alkyl) amino, di (C)1-C4Alkyl) amino and C1-C6An alkyl group;
R6is represented by C1-C6Alkyl radical, C5-C6Cycloalkyl radicals, quilt C5-C6Cycloalkyl-substituted C1-C6Alkyl, phenyl or C substituted by phenyl1-C6An alkyl group; and
ar represents C6-C14Aryl or heteroaryl having 5 to 14 ring members, wherein said aryl or heteroaryl is unsubstituted or substituted by one or more independentlySubstituted with a group selected from: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino.
7. Use according to any one of claims 1 to 6, wherein the compound of formula (I) is selected from the following compounds:
8. use according to any one of claims 1 to 7, for the irradiation of photocuring systems with wavelengths of 300-550nm, preferably 350-525nm, in particular for 3D printing.
9. A γ, δ -unsaturated oxime ester compound of formula (I):
wherein R is1、R2、R3、R4、R5And R6As defined in any one of claims 1 to 7, and
ar is a heteroaryl group having two or three fused rings and having 8-14, or 9-14 or 9-13 ring members, the heteroaryl group having 1 or 2N atoms as ring members, the heteroaryl group being unsubstituted or substituted with one or more groups independently selected from: hydroxy, halogen, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-10 ring members, amino, -C (O) R ', -C (O) OR ', -OC (O) R ' ", wherein R ', R" and R ' "are each independently hydrogen, C1-C6Alkyl radical, C3-C8Cycloalkyl, heterocycloalkyl having 3 to 8 ring members, C6-C10Aryl, heteroaryl having 5-8 ring members, or amino.
10. A compound according to claim 9 which is
11. A process for the preparation of a compound of formula (I) as defined in any one of claims 1 to 10, which comprises reacting a compound of formula (E)
Wherein R is1、R2、R3、R4、R5And Ar is as defined in any one of claims 1 to 10,
reacting with a compound of formula (F) to give a compound of formula (I)
Wherein X1Is halogen, hydroxy or-C (═ O) -R6And R6As defined in any one of claims 1 to 10.
12. A process according to claim 11, which comprises subjecting the compound of formula (C) to an oximation reaction with hydroxylamine and/or hydroxylamine hydrochloride to give a compound of formula (E)
Wherein R is1、R2、R3、R4、R5And Ar is as defined in any one of claims 1 to 10.
13. A process according to claim 12, which comprises reacting a compound of formula (a)
Ar-H
(A)
Wherein Ar is as defined in any one of claims 1 to 10,
with a compound of formula (B) to prepare a compound of formula (C)
Wherein R is1、R2、R3、R4、R5And Ar is as defined in any one of claims 1 to 10, and X2Is halogen.
14. A photocurable composition comprising at least one γ, δ -unsaturated oxime ester compound of formula (I) according to any one of claims 1 to 10.
15. A cured material obtainable from the photocurable composition of claim 14.
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