CN110330501B - Long-wavelength coumarin oxime ester compounds and preparation and application thereof - Google Patents
Long-wavelength coumarin oxime ester compounds and preparation and application thereof Download PDFInfo
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- CN110330501B CN110330501B CN201910554491.7A CN201910554491A CN110330501B CN 110330501 B CN110330501 B CN 110330501B CN 201910554491 A CN201910554491 A CN 201910554491A CN 110330501 B CN110330501 B CN 110330501B
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- radical
- alkyl
- compound
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- alkoxy
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- -1 coumarin oxime ester compounds Chemical class 0.000 title claims abstract description 178
- 238000002360 preparation method Methods 0.000 title claims description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 199
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229960000956 coumarin Drugs 0.000 claims abstract description 21
- 235000001671 coumarin Nutrition 0.000 claims abstract description 21
- 238000000016 photochemical curing Methods 0.000 claims abstract description 15
- 230000005855 radiation Effects 0.000 claims abstract description 8
- 150000003254 radicals Chemical class 0.000 claims description 288
- 150000002367 halogens Chemical class 0.000 claims description 85
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 84
- 229910052736 halogen Inorganic materials 0.000 claims description 77
- 238000000034 method Methods 0.000 claims description 52
- 125000001424 substituent group Chemical group 0.000 claims description 47
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 44
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- 125000003545 alkoxy group Chemical group 0.000 claims description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 36
- 238000006146 oximation reaction Methods 0.000 claims description 33
- 239000000460 chlorine Substances 0.000 claims description 32
- 229910052801 chlorine Inorganic materials 0.000 claims description 32
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 32
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 29
- 229910052731 fluorine Inorganic materials 0.000 claims description 28
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 27
- 229910052794 bromium Inorganic materials 0.000 claims description 27
- 239000011737 fluorine Substances 0.000 claims description 27
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 238000005886 esterification reaction Methods 0.000 claims description 26
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 19
- 238000006482 condensation reaction Methods 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 16
- 150000003512 tertiary amines Chemical class 0.000 claims description 16
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 16
- 125000004414 alkyl thio group Chemical group 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 125000001624 naphthyl group Chemical group 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 230000032050 esterification Effects 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 8
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 8
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 8
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012312 sodium hydride Substances 0.000 claims description 8
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 8
- 125000005270 trialkylamine group Chemical group 0.000 claims description 8
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims description 5
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 5
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 claims description 4
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- SKRDXYBATCVEMS-UHFFFAOYSA-N isopropyl nitrite Chemical compound CC(C)ON=O SKRDXYBATCVEMS-UHFFFAOYSA-N 0.000 claims description 4
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical group CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 235000011447 Geum Nutrition 0.000 claims description 3
- 241000220313 Geum Species 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 229930194542 Keto Natural products 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 11
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims 4
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims 3
- 125000001153 fluoro group Chemical group F* 0.000 claims 3
- 125000005907 alkyl ester group Chemical group 0.000 claims 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims 2
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract description 6
- 230000036211 photosensitivity Effects 0.000 abstract description 6
- 238000003847 radiation curing Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 3
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 168
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 34
- 150000002431 hydrogen Chemical class 0.000 description 25
- 238000001723 curing Methods 0.000 description 22
- 239000002904 solvent Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 16
- 229910052753 mercury Inorganic materials 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 150000002576 ketones Chemical class 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- 238000007639 printing Methods 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- SEEVRZDUPHZSOX-WPWMEQJKSA-N [(e)-1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(\C)=N\OC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-WPWMEQJKSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000000000 cycloalkoxy group Chemical group 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 125000003544 oxime group Chemical group 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- PYRKKGOKRMZEIT-UHFFFAOYSA-N 2-[6-(2-cyclopropylethoxy)-9-(2-hydroxy-2-methylpropyl)-1h-phenanthro[9,10-d]imidazol-2-yl]-5-fluorobenzene-1,3-dicarbonitrile Chemical compound C1=C2C3=CC(CC(C)(O)C)=CC=C3C=3NC(C=4C(=CC(F)=CC=4C#N)C#N)=NC=3C2=CC=C1OCCC1CC1 PYRKKGOKRMZEIT-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000002015 acyclic group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- 150000002826 nitrites Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 206010034960 Photophobia Diseases 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000003848 UV Light-Curing 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
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 150000004775 coumarins Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 208000013469 light sensitivity Diseases 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IYLGZMTXKJYONK-ACLXAEORSA-N (12s,15r)-15-hydroxy-11,16-dioxo-15,20-dihydrosenecionan-12-yl acetate Chemical compound O1C(=O)[C@](CC)(O)C[C@@H](C)[C@](C)(OC(C)=O)C(=O)OCC2=CCN3[C@H]2[C@H]1CC3 IYLGZMTXKJYONK-ACLXAEORSA-N 0.000 description 1
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 1
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- ZXCBDJZHOVXGIX-UHFFFAOYSA-N 1-(4-hydroxy-6-methyldibenzofuran-3-yl)ethanone Chemical compound CC1=C2C(=CC=C1)C3=C(O2)C(=C(C=C3)C(=O)C)O ZXCBDJZHOVXGIX-UHFFFAOYSA-N 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
- 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 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
- 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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- BARRBVRPLCTVSP-UHFFFAOYSA-N C(C)(=O)O.CC1=CC=CC=C1C(=O)C1=CC(=CC=2C3=CC=CC=C3N(C12)CC)C(C)=NO Chemical compound C(C)(=O)O.CC1=CC=CC=C1C(=O)C1=CC(=CC=2C3=CC=CC=C3N(C12)CC)C(C)=NO BARRBVRPLCTVSP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
- C07D491/052—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being six-membered
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- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The present invention relates to a coumarin (ketoxime) ester compound of formula (I) comprising a structural moiety of formula (I-1) wherein X, A1、A2、A3、A4、R3、R4、R5、R6、R8、R9And R10And n is as defined in the specification. The compound has strong ultraviolet absorption within the range of 300-500nm, can rapidly generate energy transfer after absorbing light energy and continuously initiate polymerization, has obvious advantages in the aspects of photosensitivity and pattern integrity, and is very suitable for radiation curing of a UV-LED light source. In addition, the compounds of formula (I) also have good thermal stability. The invention also relates to a method for producing the compounds of formula (I) and to the use of said compounds, which are suitable as photoinitiators in UV-LED photocuring systems, and which are suitable for the radiation wavelength of UV-LED photocuring.
Description
Technical Field
The invention relates to coumarin 3- (ketone) oxime ester compounds suitable for an ultraviolet-visible LED exposure light source, which can be used as a photoinitiator. The invention also relates to a preparation method of the coumarin 3- (ketone) oxime ester compound and an application of the coumarin 3- (ketone) oxime ester compound as a photoinitiator.
Background
The photoinitiator is also called photosensitizer, and is a compound which can absorb energy with certain wavelength in an ultraviolet region (250-400nm) or a visible light region (400-600nm) to generate free radicals, cations and the like so as to initiate the polymerization, crosslinking and curing of the monomer. In the light curing system, the content is low, but is a key component, and plays a role in determining the light curing speed. It is related to the rapid crosslinking and curing of the oligomer and diluent upon exposure of the formulation to light, thereby changing from a liquid to a solid. At present, the photocuring technology is widely applied to the traditional fields of coatings, printing ink, microelectronics, printing and the like, and is also applied to the novel fields of laser video recording, three-dimensional elements and the like. As an important component of the photocuring system, photoinitiators must meet the needs of different photocuring conditions and applications. In the field of free radical photoinitiators, the main goals are: the method has the advantages of improving the light sensitivity, improving the surface curing efficiency (oxygen inhibition resistance), improving the deep curing performance, improving the solubility of the photoinitiator in monomers and resin, reducing the toxicity and the smell, reducing the mobility of the uncured initiator after curing and reducing the yellowing property.
The oxime ester photoinitiator is a photoinitiator which is gradually paid attention in recent years due to excellent photosensitive property, wherein the BASF products OXE-01 and OXE-02 are two oxime ester representative products commonly seen in the market at present, the two products have higher photosensitivity, but the ultraviolet absorption wavelengths of the two products are shorter (250 and 350nm), and the oxime ester photoinitiator is not suitable for the requirements of ultraviolet-visible LED light sources (the emission wavelengths of 365nm, 385nm, 395nm, 405nm, 420nm, 430nm and 450 nm). There are also some patents related to oxime ester photoinitiators in China, for example, CN10277552A discloses a diphenyl sulfide ketoxime ester photoinitiator and a preparation method thereof, and CN102492059A discloses a substituted diphenyl sulfide ketoxime ester photoinitiator and the like. However, most initiators have ultraviolet absorption wavelength of 250-350nm and cannot be matched with increasingly developed LED light sources, so that the application of oxime ester photoinitiators is greatly limited. LED point light sources, line light sources, and surface light sources have begun to be used in the light curing industry, and LED light sources have absolute advantages over conventional UV curing equipment.
(1) The service life is long. The service life of the mercury lamp is only 800-. The LED system can be lit up only instantaneously when ultraviolet light is required, and the life of the LED system is 30 to 40 times as long as that of the mercury lamp system when the duty is 1/5 (the preparation time is 1 × 5). Therefore, the LED mode reduces the time for replacing the bulb, improves the production efficiency and simultaneously saves energy. When the traditional mercury lamp mode curing equipment works, the mercury lamp is started slowly, is opened and closed to influence the service life of a bulb and must be always lighted, so that unnecessary power consumption is caused, and the service life of the mercury lamp is shortened.
(2) No heat radiation. High power leds emit no infrared radiation. The temperature rise of the surface of the irradiated product is only below 5 ℃, but the surface temperature of the irradiated product is generally raised by 60-90 ℃ by a traditional ultraviolet curing machine in a mercury lamp mode, so that the positioning of the product is displaced, and the product is poor.
(3) Environmental protection and no pollution. The traditional curing machine adopting the mercury lamp mode adopts the mercury lamp light-emitting mode, mercury is contained in a bulb, waste treatment and transportation are very troublesome, and serious pollution can be caused to the environment due to improper treatment. And the LED type curing machine adopts semiconductor light emission, so that no factor of environmental pollution is caused. Therefore, the LED curing machine is more environment-friendly.
(4) The illumination is ultra strong. The high-power LED chip and the special optical design are adopted, so that the ultraviolet light can reach high-precision and high-intensity irradiation; the ultraviolet light output can reach 8600mW/m2The irradiation intensity of (2). By adopting the latest optical technology and manufacturing process, the high-intensity output and uniformity which are more optimized than those of the traditional mercury lamp irradiation mode are realized, and almost 2 times of the irradiation luminosity of the traditional mercury lamp mode is realized, so that the UV adhesive is cured more quickly, the production time is shortened, and the production efficiency is greatly improved. When the irradiation channels are increased in the conventional mercury lamp point light source curing machine, the output energy of each irradiation channel is reduced due to the increase of the channels. And the LED type irradiation is adopted, each irradiation head independently emits light, and the irradiation energy is not influenced by the increase of channels and is always kept at the maximum value. Compared with mercury lamps, the UV-LED lamp shortens the irradiation time of operation and improves the production efficiency due to the super-strong concentrated illuminance.
(5) The energy consumption is low. The UV-LED mode has the effective luminous efficiency which is more than 10 times higher than that of the mercury lamp mode. Meanwhile, in the mercury lamp system, the mercury lamp needs to be continuously turned on regardless of whether effective irradiation is performed, and power is always consumed. The UV-LED mode consumes power only during irradiation and almost zero during standby. A simple calculation can be made, and the electric energy saved by each point light source curing machine is as follows: 270 watts by 8 hours 365 days 800 kilowatt hours, it follows that each can save thousands of dollars per year in electricity consumption. Moreover, by saving electric energy, the emission of carbon dioxide can be indirectly reduced by 1.4 tons every year, which is equivalent to the annual exhaust of a car.
The visible light is cured more deeply and at lower temperature compared with the ultraviolet light, and the visible light curing mode is the preferable mode under the condition that the conditions allow. Both the UV led area light source and the UV led line light source contain the UV spectrum in the visible portion), visible light curing will have less energy loss. The main advantage of visible light curing is that it can cure glue through a substrate that blocks ultraviolet light and that translucent colored materials can be chosen. The improvement of safety is another important advantage of the visible light curing device. Visible light is output, and ultraviolet light related occlusion and protection can be minimized. Therefore, the development of the photoinitiator suitable for the ultraviolet-visible LED light source can greatly meet the requirement of wide application of the ultraviolet-visible LED exposure light source in the photocuring industry.
CN1889960A discloses that coumarin ketoxime ester compounds can be used in pharmaceutical compositions or cosmetic compositions for preventing and treating diseases, including immune diseases, chronic inflammation, nerve diseases and skin diseases, tumor diseases, specific virus (especially SARS), etc. In this sense, such compounds are safe and non-toxic.
Therefore, there is still a need for photoinitiators with absorption wavelengths suitable for UV-visible LED light sources and with good thermal stability.
Disclosure of Invention
In view of the problems in the prior art, the inventors of the present invention conducted extensive and intensive studies on photoinitiators suitable for radiation curing by UV-visible LED light sources (emission wavelength 300-. The inventor finds that the modified coumarin (ketone) oxime ester compound obtained by fusing a benzene five-membered ring on the benzene ring of the coumarin (ketone) oxime ester compound has strong ultraviolet absorption in the range of 300-500nm, particularly 350-450nm, and has good thermal stability, so that the modified coumarin (ketone) oxime ester compound is suitable for being used as a photoinitiator for ultraviolet-visible LED light source radiation curing. The object of the present invention is achieved based on the above findings.
Therefore, the invention aims to provide a coumarin (ketoxime) ester compound, which has an absorption wavelength suitable for ultraviolet-visible LED light source radiation curing and has good thermal stability.
It is another object of the present invention to provide a process for the preparation of the coumarin (ketoxime) ester compounds of the present invention.
It is a further object of the present invention to provide the use of the coumarin (ketoxime) ester compounds of the present invention as photoinitiators.
The technical solution for achieving the above object of the present invention can be summarized as follows:
1. a coumarin (keto) oxime ester compound of formula (I) comprising a moiety of formula (I-1):
wherein:
x is O, S, NR1Or CR2aR2bWherein R is1、R2aAnd R2bEach independently is H, C1-C20Alkyl radical, C3-C10Cycloalkyl radical, C3-C10Cycloalkyl radical C1-C8Alkyl radical, C1-C8Alkyl radical C3-C10Cycloalkyl radical, C1-C20Alkoxy (thio) radical, C3-C10Cycloalkoxy (thio) radical, C3-C10Cycloalkyl radical C1-C8Alkoxy (thio) radical, C1-C8Alkyl radical C3-C10Cycloalkoxy (thio) radical, C6-C18Aryl or C6-C18Aryloxy (thio) wherein each of the foregoing groups other than H may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6An alkoxy (thio) group;
R3、R4、R5、R6independently of one another, hydrogen, halogen, nitro, cyano, C1-C20Alkyl radical, C3-C10Cycloalkyl radical, C3-C10Cycloalkyl radical C1-C8Alkyl radical, C1-C8Alkyl radical C3-C10Cycloalkyl radical, C1-C20Alkoxy (thio) radical, C3-C10Cycloalkoxy (thio) radical, C3-C10Cycloalkyl radical C1-C8Alkoxy (thio) radical, C1-C8Alkyl radical C3-C10Cycloalkoxy (thio) radical, C6-C18Aryl or C6-C18Aryloxy (thio) wherein each of the foregoing groups, except hydrogen, halogen, nitro and cyano, may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6An alkoxy (thio) group;
and are a moiety of formula (I-1) and A in the compound of formula (I)1And A2、A2And A3Or A3And A4The attachment site of (a);
A1、A2、A3、A4wherein two of the moieties of formula (I-1) are carbon atoms and the remaining two are the same or different and are independently CH or CR7Wherein R is7Is H, halogen, C1-C6Alkyl or C1-C6Alkoxy (thio) radical, in which the aforementioned C1-C6Alkyl and C1-C6The alkoxy (thio) group may contain one or more halogen substituents, which may be the same or different;
R8is H, halogen, C1-C6Alkyl or C1-C6Alkoxy (thio) radical, in which the aforementioned C1-C6Alkyl and the aforementioned C1-C6The alkoxy (thio) group may contain one or more halogen substituents, which may be the same or different;
R9is hydrogen, halogen, nitro, cyano, C1-C20Alkyl radical, C3-C10Cycloalkyl radical, C3-C10Cycloalkyl radical C1-C8Alkyl radical, C1-C8Alkyl radical C3-C10Cycloalkyl radical, C1-C20Alkoxy (thio) radical, C3-C10Cycloalkoxy (thio) radical, C3-C10Cycloalkyl radical C1-C8Alkoxy (thio) radical, C1-C8Alkyl radical C3-C10Cycloalkoxy (thio) radical, C6-C18Aryl or C6-C18Aryloxy (thio) wherein each of the foregoing groups other than H, halogen, nitro and cyano may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6An alkoxy (thio) group;
R10is C1-C20Alkyl or C6-C18Aryl radical, wherein C1-C20Alkyl and C6-C18The aryl group may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6An alkoxy (thio) group; and
n is 0 or 1.
2. The compound according to item 1, wherein
R1、R2aAnd R2bEach independently is H, C1-C10Alkyl radical, C3-C8Cycloalkyl radical, C3-C8Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkyl radical C3-C8Cycloalkyl radical, C1-C6Alkoxy (thio) radical, C3-C8Cycloalkoxy (thio) radical, C3-C8Cycloalkyl radical C1-C6Alkoxy (thio) radical, C1-C6Alkyl radical C3-C8Cycloalkoxy (thio) radical, C6-C10Aryl or C6-C10Aryloxy (thio) wherein each of the foregoing groups other than H may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6Alkoxy (thio) radical, preferably R1、R2aAnd R2bEach independently is H, C1-C8Alkyl radical, C5-C6Cycloalkyl radical, C5-C6Cycloalkyl radical C1-C4Alkyl radical, C1-C4Alkyl radical C5-C6Cycloalkyl radical, C1-C4Alkoxy (thio) radical, C5-C6Cycloalkoxy (thio) radical, C3-C6Cycloalkyl radical C1-C4Alkoxy (thio) radical, C1-C4Alkyl radical C5-C6Cycloalkoxy (thio) radical, C6-C10Aryl or C6-C10Aryloxy (thio) wherein each of the foregoing groups other than H may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C4Alkyl and C1-C4An alkoxy (thio) group; and/or
R3、R4、R5、R6Independently of one another, hydrogen, halogen, nitro, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl radical, C3-C8Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkyl radical C3-C8Cycloalkyl radical, C1-C6Alkoxy (thio) radical, C3-C8Cycloalkoxy (thio) radical, C3-C8Cycloalkyl radical C1-C6Alkoxy (thio) radical, C1-C6Alkyl radical C3-C10Cycloalkoxy (thio) radical, C6-C10Aryl or C6-C10Aryloxy (thio) wherein each of the foregoing groups, except hydrogen, halogen, nitro and cyano, may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6Alkoxy (thio) radical, preferably R3、R4、R5、R6Independently of one another, hydrogen, halogen, nitro, cyano, C1-C4Alkyl radical, C5-C6Cycloalkyl radical, C5-C6Cycloalkyl radical C1-C4Alkyl radical, C1-C4Alkyl radical C5-C6Cycloalkyl radical, C1-C4Alkoxy (thio) radical, C5-C6Cycloalkoxy (thio) radical, C5-C6Cycloalkyl radical C1-C4Alkoxy (thio) radical, C1-C4Alkyl radical C5-C6A cycloalkoxy (thio) group, a phenyl group, or a phenoxy (thio) group, wherein each of the foregoing groups other than hydrogen, halogen, nitro, cyano may comprise one or more substituents independently selected from the group consisting of: fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4Alkyl and C1-C4An alkoxy (thio) group; and/or
R7Is H, fluorine, chlorine, bromine, C1-C4Alkyl or C1-C4Alkoxy (thio) radical, in which the aforementioned C1-C4Alkyl and C1-C4The alkoxy (thio) group may contain one or more identical or different substituents selected from fluorine, chlorine, bromine; and/or
R8Is H, fluorine, chlorine, bromine, C1-C4Alkyl or C1-C4Alkoxy (thio) radical, in which the aforementioned C1-C4Alkyl and C1-C4The alkoxy (thio) group may contain one or more identical or different substituents selected from fluorine, chlorine, bromine; and/or
R9Is hydrogen, halogen, nitro, cyano, C1-C8Alkyl radical, C3-C8Cycloalkyl radical, C3-C8Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkyl radical C3-C8Cycloalkyl radical, C1-C6Alkoxy (thio) radical, C3-C8Cycloalkoxy (thio) radical, C3-C8Cycloalkyl radical C1-C6Alkoxy (thio) radical, C1-C6Alkyl radical C3-C8Cycloalkoxy (thio) radical, C6-C10Aryl or C6-C10Aryloxy (thio) wherein each of the foregoing groups other than H, halogen, nitro and cyano may comprise one or more substituents independently selected from the group consisting of: halogen, nitroAmino, cyano, C1-C6Alkyl and C1-C6Alkoxy (thio) radical, preferably R9Is hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C8Alkyl radical, C5-C6Cycloalkyl radical, C5-C6Cycloalkyl radical C1-C4Alkyl radical, C1-C4Alkyl radical C5-C6Cycloalkyl radical, C1-C4Alkoxy (thio) radical, C5-C6Cycloalkoxy (thio) radical, C5-C6Cycloalkyl radical C1-C4Alkoxy (thio) radical, C1-C4Alkyl radical C5-C6A cycloalkoxy (thio) group, a phenyl group, or a phenoxy (thio) group, wherein each of the foregoing groups other than hydrogen, fluorine, chlorine, bromine, nitro, and cyano may comprise one or more substituents independently selected from the group consisting of: fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4Alkyl and C1-C4An alkoxy (thio) group; and/or
R10Is C1-C6Alkyl or C6-C10Aryl radical, wherein C1-C6Alkyl and C6-C10The aryl group may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6Alkoxy (thio) radical, preferably R10Is C1-C4Alkyl or phenyl, wherein C1-C4The alkyl and phenyl groups may comprise one or more substituents independently selected from the group consisting of: fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4Alkyl and C1-C4An alkoxy (thio) group.
3. The compound according to item 1, wherein
X is O, S, NR1Or CR2aR2bWherein R is1Is C1-C8Alkyl, phenyl or naphthyl, wherein the phenyl or naphthyl may contain one or more of the same or different C1-C4An alkyl substituent; and R2aAnd R2bSame or differentAnd each independently is H, C1-C6Alkyl radical, C5-C6Cycloalkyl radical C1-C4Alkyl or C1-C4Alkoxy radical C1-C4An alkyl group;
R3、R4、R5、R6independently of one another, hydrogen, nitro, C1-C4Alkyl radical, C1-C4Alkoxy (thio) or phenyl;
A1、A2、A3、A4wherein two of the moieties of formula (I-1) are carbon atoms and the remaining two are the same or different and are independently CH or CR7Wherein R is7H or C1-C4An alkyl group;
R8is H or C1-C4An alkyl group;
R9is cyano, C1-C7Alkyl, halo C1-C6Alkyl or C5-C6Cycloalkyl radical C1-C4An alkyl group; and
R10is C1-C4Alkyl or phenyl.
4. The compound according to item 1, wherein the compound is selected from the group consisting of compounds 1-64.
5. A process for the preparation of a compound as claimed in any one of claims 1 to 4, comprising the steps of:
(1) oximation reaction: when n is 0, subjecting the compound of formula (II) to oximation reaction with hydroxylamine, hydroxylamine hydrochloride or any combination thereof to obtain the compound of formula (IIIa)
(iii) subjecting the compound of formula (II) to an oximation reaction with nitrous acid, a nitrite salt, an alkyl nitrite, or any combination thereof, when n is 1, to give a compound of formula (IIIb):
wherein A in the formulae (II), (IIIa) and (IIIb)1、A2、A3、A4、R8And R9As defined in any one of items 1 to 4; and (2) esterifying the compound of formula (IIIa) or (IIIb) to obtain the compound of formula (I).
6. The method according to item 5, wherein
When n is 0:
the oximation reaction is carried out in the presence of sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide or a mixture thereof as a catalyst; and/or the temperature of the oximation reaction is 60-120 ℃; and/or the molar ratio of the compound of formula (II) to the compound selected from hydroxylamine and/or hydroxylamine hydrochloride is from 1:1.5 to 1.5:1, preferably from 1:1.2 to 1.2: 1; or
When n is 1, the compound is a compound of formula (I),
the oximation reaction is carried out in the presence of concentrated hydrochloric acid; and/or the temperature of the oximation reaction is-30 to 20 ℃, preferably 5-20 ℃; and/or the molar ratio of the compound of the formula (II) to the compound selected from nitrous acid, nitrite and/or alkyl nitrite is from 1:1.5 to 1.5:1, preferably from 1:1.2 to 1.2: 1.
7. The method according to item 5 or 6, wherein
Alkyl nitrite is nitrous acid C1-C6Alkyl esters such as methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, isoamyl nitrite; and/or the presence of a gas in the gas,
the esterification of step (2) is carried out using an esterifying reagent selected from the group consisting of compounds of the following formulae (IVa), (IVb) and (IVc):
wherein X is halogen, especially chlorine, and R7As defined in any one of items 1 to 4.
8. The process according to any one of items 5 to 7, wherein the esterification reaction is carried out in the presence of one or more catalysts selected from the group consisting of: sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride and tertiary amines, for example trialkylamines, such as trimethylamine and triethylamine.
9. The process according to item 7 or 8, wherein the molar ratio of the compound of formula (IIIa) or (IIIb) to the esterifying reagent selected from the group consisting of compounds (IVa), (IVb) and (IVc) is from 1:1.5 to 1.5:1, preferably from 1:1.2 to 1.2: 1.
10. The method according to any one of items 5-9, further comprising: carrying out Nowenge geum condensation reaction on the compound of formula (V) and the compound of formula (VI) to obtain a compound of formula (II),
wherein A in the compound of formula (V)1、A2、A3、A4And R8As defined in any one of items 1 to 4, and R in the compound of formula (VI)9As defined in any of items 1 to 4, and R11Is C1-C12Alkyl, preferably C1-C6An alkyl group.
11. The method according to item 10, wherein
The knoevenageous condensation reaction is carried out in the presence of piperidine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride, tetramethylammonium hydroxide, tertiary amines (e.g., trialkylamines such as trimethylamine and triethylamine), or any combination thereof; and/or the presence of a gas in the gas,
the temperature of the Nowenge Bayer Algorithm condensation reaction is 0-150 ℃, preferably 0-100 ℃; and/or
The molar ratio of the compound of formula (V) to the compound of formula (VI) is 1:1.5 to 1.5:1, preferably 1:1.2 to 1.2: 1.
12. Use of a compound of the formula (I) as claimed in any of claims 1 to 4 as photoinitiator, in particular in UV-LED photocuring systems, in particular in photocuring systems with a radiation wavelength of 300-450 nm, in particular 350-450nm, in particular 365-450 nm.
Drawings
FIG. 1 is a schematic representation of a Ugra (Ugra) printing test strip, wherein
1-a continuous density ladder section,
2-concentric circle coil segment with equal line of yin and yang micron,
3-a full tone dot segment,
4-ghost control segment, and
5-highlight, dark tone control section.
Detailed Description
According to a first aspect of the present invention there is provided a coumarin (ketoxime) ester compound of formula (I) comprising a moiety of formula (I-1):
wherein:
x is O, S, NR1Or CR2aR2bWherein R is1、R2aAnd R2bEach independently is H, C1-C20Alkyl radical, C3-C10Cycloalkyl radical, C3-C10Cycloalkyl radical C1-C8Alkyl radical, C1-C8Alkyl radical C3-C10Cycloalkyl radical, C1-C20Alkoxy (thio) radical, C3-C10Cycloalkoxy (thio) radical, C3-C10Cycloalkyl radical C1-C8Alkoxy (thio) radical, C1-C8Alkyl radical C3-C10Cycloalkoxy (thio) radical, C6-C18Aryl or C6-C18Aryloxy (thio) wherein each of the foregoing groups other than H may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6An alkoxy (thio) group;
R3、R4、R5、R6independently of each otherRepresents hydrogen, halogen, nitro, cyano, C1-C20Alkyl radical, C3-C10Cycloalkyl radical, C3-C10Cycloalkyl radical C1-C8Alkyl radical, C1-C8Alkyl radical C3-C10Cycloalkyl radical, C1-C20Alkoxy (thio) radical, C3-C10Cycloalkoxy (thio) radical, C3-C10Cycloalkyl radical C1-C8Alkoxy (thio) radical, C1-C8Alkyl radical C3-C10Cycloalkoxy (thio) radical, C6-C18Aryl or C6-C18Aryloxy (thio) wherein each of the foregoing groups, except hydrogen, halogen, nitro and cyano, may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6An alkoxy (thio) group;
and are a moiety of formula (I-1) and A in the compound of formula (I)1And A2、A2And A3Or A3And A4The attachment site of (a);
A1、A2、A3、A4wherein two of the moieties of formula (I-1) are carbon atoms and the remaining two are the same or different and are independently CH or CR7Wherein R is7Is H, halogen, C1-C6Alkyl or C1-C6Alkoxy (thio) radical, in which the aforementioned C1-C6Alkyl and C1-C6The alkoxy (thio) group may contain one or more halogen substituents, which may be the same or different;
R8is H, halogen, C1-C6Alkyl or C1-C6Alkoxy (thio) radical, in which the aforementioned C1-C6Alkyl and the aforementioned C1-C6The alkoxy (thio) group may contain one or more halogen substituents, which may be the same or different;
R9is hydrogen, halogen, nitro, cyano, C1-C20Alkyl radical, C3-C10Cycloalkyl radical, C3-C10Cycloalkyl radicalsC1-C8Alkyl radical, C1-C8Alkyl radical C3-C10Cycloalkyl radical, C1-C20Alkoxy (thio) radical, C3-C10Cycloalkoxy (thio) radical, C3-C10Cycloalkyl radical C1-C8Alkoxy (thio) radical, C1-C8Alkyl radical C3-C10Cycloalkoxy (thio) radical, C6-C18Aryl or C6-C18Aryloxy (thio) wherein each of the foregoing groups other than H, halogen, nitro and cyano may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6An alkoxy (thio) group;
R10is C1-C20Alkyl or C6-C18Aryl radical, wherein C1-C20Alkyl and C6-C18The aryl group may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6An alkoxy (thio) group; and
n is 0 or 1.
The compound of the formula (I) comprises a coumarin (ketone) oxime ester structure part and a benzo five-membered ring structure fused with the coumarin (ketone) oxime ester structure part. The structure enables the compound to have strong ultraviolet absorption in the range of 300-500nm, preferably 350-450nm, can rapidly generate energy transfer after absorbing light energy, continuously initiates polymerization, has obvious advantages in the aspects of photosensitivity and pattern integrity, is very suitable for an ultraviolet-visible LED light source, is safe and nontoxic, and can be used in the fields of food packaging and the like. In addition, the compounds of formula (I) have good thermal stability.
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 branched or unbranched saturated hydrocarbon radical having n-m, for example from 1 to 20, preferably from 1 to 12, more preferably from 1 to 8, particularly preferably from 1 to 6, particularly preferably from 1 to 4, carbon atoms, for example 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-methylpentyl, 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.
The term "C" as used herein3-CmCycloalkyl "means a saturated alicyclic monocyclic group having 3 to m, such as 3 to 20, preferably 3 to 8, more preferably 5 to 6, ring carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
The term "C3-CmCycloalkyl radical Cn-CmAlkyl "represents by C3-CmCycloalkyl-substituted Cn-CmAlkyl, in which case the two m's may be the same or different, wherein Cn-CmAlkyl and C3-CmCycloalkyl groups are as defined herein. C3-CmCycloalkyl radical Cn-CmThe alkyl group may be C3-C10Cycloalkyl radical C1-C8Alkyl, preferably C3-C6Cycloalkyl radical C1-C6Alkyl, more preferably C3-C6Cycloalkyl radical C1-C4Alkyl radicals, e.g. cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclobutylsHexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl, and the like.
The term "Cn-CmAlkyl radical C3-CmCycloalkyl being represented by Cn-CmAlkyl substituted C3-CmCycloalkyl in which case the two m's may be the same or different, wherein Cn-CmAlkyl and C3-CmCycloalkyl groups are as defined herein. Cn-CmAlkyl radical C3-CmCycloalkyl may be C1-C8Alkyl radical C3-C10Cycloalkyl, preferably C1-C6Alkyl radical C3-C6Cycloalkyl, more preferably C1-C4Alkyl radical C3-C6Cycloalkyl groups such as 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 higher aromatic hydrocarbon group containing 6 to m carbon atoms, for example 6 to 18, preferably 6 to 10 carbon atoms. As C6-CmAs examples of the aryl group, there may be mentioned phenyl, tolyl, ethylphenyl, propylphenyl, butylbenzyl, xylyl, methylethylphenyl, diethylphenyl, methylpropylphenyl, naphthyl and the like; phenyl or naphthyl, especially phenyl, is preferred.
The term "C" alone or in combinationn-CmAlkoxy (thio) radicals "including" Cn-CmAlkoxy "and" Cn-CmAlkylthio "means at Cn-CmOpen chain C corresponding to alkyln-CmC having an oxygen or sulfur atom as a linking group bonded to any carbon atom of the alkanen-CmAlkyl radicals, e.g. C1-C20Alkoxy (thio) radicals, preferably C1-C12Alkoxy (thio) radical, more preferably C1-C8Alkoxy (C)Sulfur) group, particularly preferably C1-C6Alkoxy (thio) radicals, particularly preferably C1-C4An alkoxy (thio) 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-C8The alkylthio group may be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, 2-butylthio, t-butylthio, pentylthio, isopentylthio, hexylthio, heptylthio, octylthio, isooctylthio and isomers thereof.
The term "C" alone or in combination3-CmCycloalkoxy (thio) radicals "including" C3-CmCycloalkoxy "and" C3-CmCycloalkylthio "is defined at C3-CmCycloalkyl corresponds to C3-CmC having an oxygen or sulfur atom as a linking group bonded to any ring carbon atom in the cycloalkane3-CmCycloalkyl radicals, e.g. C3-C20A cycloalkoxy (thio) group, preferably C3-C8A cycloalkoxy (thio) group, more preferably C5-C6A cycloalkoxy (thio) group such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecyloxy and isomers thereof, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cycloheptylthio, cyclooctylthio, cyclodecylthio and isomers thereof.
The term "C3-CmCycloalkyl radical Cn-CmAlkoxy (thio) radicals "including" C3-CmCycloalkyl radical Cn-CmAlkoxy "and" C3-CmCycloalkyl radical Cn-CmAlkylthio "refers to a group consisting of3-CmCycloalkyl-substituted Cn-CmAlkoxy (thio) radicals, in which case the two m radicals may be identical or different, where C3-CmCycloalkyl and Cn-CmAlkoxy (thio) groups are as defined herein. C3-CmCycloalkyl radical Cn-CmThe alkoxy (thio) group may be C3-C10Cycloalkyl radical C1-C8Alkoxy (thio) radicals, preferably C3-C6Cycloalkyl radical C1-C6Alkoxy (thio) radical, more preferably C3-C6Cycloalkyl radical C1-C4Alkoxy (thio) groups such as cyclopropylmethoxy, cyclopropylethoxy, cyclopropylpropoxy, cyclopropylbutoxy, cyclobutylmethoxy, cyclobutylethoxy, cyclobutylpropoxy, cyclobutylbutoxy, cyclopentylmethoxy, cyclopentylethoxy, cyclopentylpropoxy, cyclopentylbutoxy, cyclohexylmethoxy, cyclohexylethoxy, cyclohexylpropoxy, cyclohexylbutoxy, cyclopropylmethylthio, cyclopropylethylthio, cyclopropylpropylthio, cyclopropylbutylthio, cyclobutylmethylthio, cyclobutylethylthio, cyclobutylpropylthio, cyclobutylbutylbutylbutylbutylbutylbutylthio, cyclopentylmethylthio, cyclopentylethylthio, cyclopentylpropylthio, cyclopentylbutylthio, cyclohexylmethylthio, cyclohexylethylthio, cyclohexylpropylthio, cyclohexylbutylthio and the like.
The term "Cn-CmAlkyl radical C3-CmCycloalkoxy "is represented by Cn-CmAlkyl substituted C3-CmCycloalkoxy, in which case the two m's may be the same or different, wherein Cn-CmAlkyl and C3-CmCycloalkoxy is as defined herein. Cn-CmAlkyl radical C3-CmThe cycloalkoxy group may be C1-C8Alkyl radical C3-C10Cycloalkoxy, preferably C1-C6Alkyl radical C3-C6Cycloalkoxy, more preferably C1-C4Alkyl radical C3-C6Cycloalkoxy groups such as methylcyclopropoxy, ethylcyclopropoxy, propylcyclopropoxy, butylcyclopropoxy, methylcyclobutoxy, ethylcyclobutoxy, propylcyclobutoxy, butylcyclobutoxy, methylcyclopentoxy, ethylcyclopentoxy, propylcyclopentoxy, butylcyclopentoxy, methylcyclohexoxy, ethylcyclohexoxy, propylcyclohexoxy, butylcyclohexoxy and the like.
The term "C" as used herein6-CmAryloxy (thio) radicals "including" C6-CmAryloxy radical "and" C6-CmArylthio "is defined at C6-CmAryl radical corresponding to C6-CmC having an oxygen or sulfur atom as a linking group bonded to any aromatic carbon atom in the aromatic hydrocarbon6-CmAryl groups such as phenylthio, phenoxy, tolyloxy, tolylthio, naphthylthio, naphthyloxy and the like.
In the present invention, n is 0 or 1. When n is 0, the compound of formula (I) is referred to as a coumarin oxime ester compound; when n is 1, the compound of formula (I) is referred to as a coumarin ketoxime ester compound. These two compounds are collectively referred to as coumarin (ketoxime) ester compounds.
In the present invention, X is O, S, NR1Or CR2aR2bWherein R is1、R2aAnd R2bEach independently is H, C1-C20Alkyl radical, C3-C10Cycloalkyl radical, C3-C10Cycloalkyl radical C1-C8Alkyl radical, C1-C8Alkyl radical C3-C10Cycloalkyl radical, C1-C20Alkoxy (thio) radical, C3-C10Cycloalkoxy (thio) radical, C3-C10Cycloalkyl radical C1-C8Alkoxy (thio) radical, C1-C8Alkyl radical C3-C10Cycloalkoxy (thio) radical, C6-C18Aryl or C6-C18Aryloxy (thio) wherein each of the foregoing groups other than H may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6An alkoxy (thio) group.
Preferably, R is1、R2aAnd R2bEach independently is H, C1-C10Alkyl radical, C3-C8Cycloalkyl radical, C3-C8Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkyl radical C3-C8Cycloalkyl radical, C1-C6Alkoxy radical(thio) group, C3-C8Cycloalkoxy (thio) radical, C3-C8Cycloalkyl radical C1-C6Alkoxy (thio) radical, C1-C6Alkyl radical C3-C8Cycloalkoxy (thio) radical, C6-C10Aryl or C6-C10Aryloxy (thio) wherein each of the foregoing groups other than H may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6An alkoxy (thio) group.
It is particularly preferred that R1、R2aAnd R2bEach independently is H, C1-C8Alkyl radical, C5-C6Cycloalkyl radical, C5-C6Cycloalkyl radical C1-C4Alkyl radical, C1-C4Alkyl radical C5-C6Cycloalkyl radical, C1-C4Alkoxy (thio) radical, C5-C6Cycloalkoxy (thio) radical, C3-C6Cycloalkyl radical C1-C4Alkoxy (thio) radical, C1-C4Alkyl radical C5-C6Cycloalkoxy (thio) radical, C6-C10Aryl or C6-C10Aryloxy (thio) wherein each of the foregoing groups other than H may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C4Alkyl and C1-C4An alkoxy (thio) group.
In particular, R1Is C1-C8Alkyl, phenyl or naphthyl, wherein the phenyl or naphthyl may contain one or more of the same or different C1-C4An alkyl substituent; and R2aAnd R2bAre the same or different and are each independently H, C1-C6Alkyl radical, C5-C6Cycloalkyl radical C1-C4Alkyl or C1-C4Alkoxy radical C1-C4An alkyl group.
In the present invention, R3、R4、R5、R6Independently of one another represent hydrogenHalogen, nitro, cyano, C1-C20Alkyl radical, C3-C10Cycloalkyl radical, C3-C10Cycloalkyl radical C1-C8Alkyl radical, C1-C8Alkyl radical C3-C10Cycloalkyl radical, C1-C20Alkoxy (thio) radical, C3-C10Cycloalkoxy (thio) radical, C3-C10Cycloalkyl radical C1-C8Alkoxy (thio) radical, C1-C8Alkyl radical C3-C10Cycloalkoxy (thio) radical, C6-C18Aryl or C6-C18Aryloxy (thio) wherein each of the foregoing groups other than hydrogen, halogen, nitro, cyano may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6An alkoxy (thio) group.
Preferably, R is3、R4、R5、R6Independently of one another, hydrogen, halogen, nitro, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl radical, C3-C8Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkyl radical C3-C8Cycloalkyl radical, C1-C6Alkoxy (thio) radical, C3-C8Cycloalkoxy (thio) radical, C3-C8Cycloalkyl radical C1-C6Alkoxy (thio) radical, C1-C6Alkyl radical C3-C10Cycloalkoxy (thio) radical, C6-C10Aryl or C6-C10Aryloxy (thio) wherein each of the foregoing groups, except hydrogen, halogen, nitro and cyano, may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6An alkoxy (thio) group.
It is particularly preferred that R3、R4、R5、R6Independently of one another, hydrogen, halogen, nitro, cyano, C1-C4Alkyl radical, C5-C6Cycloalkyl radicals、C5-C6Cycloalkyl radical C1-C4Alkyl radical, C1-C4Alkyl radical C5-C6Cycloalkyl radical, C1-C4Alkoxy (thio) radical, C5-C6Cycloalkoxy (thio) radical, C5-C6Cycloalkyl radical C1-C4Alkoxy (thio) radical, C1-C4Alkyl radical C5-C6A cycloalkoxy (thio) group, a phenyl group, or a phenoxy (thio) group, wherein each of the foregoing groups other than hydrogen, halogen, nitro, cyano may comprise one or more substituents independently selected from the group consisting of: fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4Alkyl and C1-C4An alkoxy (thio) group.
In particular, R3、R4、R5、R6Independently of one another, hydrogen, nitro, C1-C4Alkyl radical, C1-C4Alkoxy (thio) or phenyl.
In the present invention, A1、A2、A3、A4Wherein two of the moieties of formula (I-1) are carbon atoms and the remaining two are the same or different and are independently CH or CR7Wherein R is7Is H, halogen, C1-C6Alkyl or C1-C6Alkoxy (thio) radical, in which the aforementioned C1-C6Alkyl and C1-C6The alkoxy (thio) group may contain one or more identical or different halogen substituents.
Preferably, R is7Is H, fluorine, chlorine, bromine, C1-C4Alkyl or C1-C4Alkoxy (thio) radical, in which the aforementioned C1-C4Alkyl and C1-C4The alkoxy (thio) group may contain one or more identical or different substituents selected from fluorine, chlorine, bromine.
In particular, R7Is H or C1-C4An alkyl group.
In the present invention, R8Is H, halogen, C1-C6Alkyl or C1-C6Alkoxy (thio) radical, in which the aforementioned C1-C6Alkyl and C6The alkoxy (thio) group may contain one or more identical or different halogen substituents.
Preferably, R is8Is H, fluorine, chlorine, bromine, C1-C4Alkyl or C1-C4Alkoxy (thio) radical, in which the aforementioned C1-C4Alkyl and C1-C4The alkoxy (thio) group may contain one or more identical or different substituents selected from fluorine, chlorine, bromine. Especially R8Is H.
In particular, R8Is H or C1-C4An alkyl group.
In the present invention, R9Is hydrogen, halogen, nitro, cyano, C1-C20Alkyl radical, C3-C10Cycloalkyl radical, C3-C10Cycloalkyl radical C1-C8Alkyl radical, C1-C8Alkyl radical C3-C10Cycloalkyl radical, C1-C20Alkoxy (thio) radical, C3-C10Cycloalkoxy (thio) radical, C3-C10Cycloalkyl radical C1-C8Alkoxy (thio) radical, C1-C8Alkyl radical C3-C10Cycloalkoxy (thio) radical, C6-C18Aryl or C6-C18Aryloxy (thio) wherein each of the foregoing groups other than H, halogen, nitro and cyano may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6An alkoxy (thio) group.
Preferably, R is9Is hydrogen, halogen, nitro, cyano, C1-C8Alkyl radical, C3-C8Cycloalkyl radical, C3-C8Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkyl radical C3-C8Cycloalkyl radical, C1-C6Alkoxy (thio) radical, C3-C8Cycloalkoxy (thio) radical, C3-C8Cycloalkyl radical C1-C6Alkoxy (thio) radical, C1-C6Alkyl radical C3-C8Cycloalkoxy (thio) radical, C6-C10Aryl or C6-C10Aryloxy (thio) wherein each of the foregoing groups other than H, halogen, nitro and cyano may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6An alkoxy (thio) group.
It is particularly preferred that R9Is hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C8Alkyl radical, C5-C6Cycloalkyl radical, C5-C6Cycloalkyl radical C1-C4Alkyl radical, C1-C4Alkyl radical C5-C6Cycloalkyl radical, C1-C4Alkoxy (thio) radical, C5-C6Cycloalkoxy (thio) radical, C5-C6Cycloalkyl radical C1-C4Alkoxy (thio) radical, C1-C4Alkyl radical C5-C6A cycloalkoxy (thio) group, a phenyl group, or a phenoxy (thio) group, wherein each of the foregoing groups other than hydrogen, fluorine, chlorine, bromine, nitro, and cyano may comprise one or more substituents independently selected from the group consisting of: fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4Alkyl and C1-C4An alkoxy (thio) group.
In particular, R9Is cyano, C1-C7Alkyl, halo C1-C6Alkyl or C5-C6Cycloalkyl radical C1-C4An alkyl group.
In the present invention, R10Is C1-C20Alkyl or C6-C18Aryl radical, wherein C1-C20Alkyl and C6-C18The aryl group may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6An alkoxy (thio) group.
Preferably, R is10Is C1-C6Alkyl or C6-C10Aryl radical, wherein C1-C6Alkyl and C6-C10The aryl group may comprise one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl and C1-C6An alkoxy (thio) group.
It is particularly preferred that R10Is C1-C4Alkyl or phenyl, wherein C1-C4The alkyl and phenyl groups may comprise one or more substituents independently selected from the group consisting of: fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4Alkyl and C1-C4An alkoxy (thio) group.
In particular, R10Is C1-C4Alkyl or phenyl.
In some preferred embodiments of the invention, wherein
X is O, S, NR1Or CR2aR2bWherein R is1Is C1-C8Alkyl, phenyl or naphthyl, wherein the phenyl or naphthyl may contain one or more of the same or different C1-C4An alkyl substituent; and R2aAnd R2bAre the same or different and are each independently H, C1-C6Alkyl radical, C5-C6Cycloalkyl radical C1-C4Alkyl radical, C1-C4Alkoxy radical C1-C4An alkyl group;
R3、R4、R5、R6independently of one another, hydrogen, nitro, C1-C4Alkyl radical, C1-C4Alkoxy (thio) or phenyl;
A1、A2、A3、A4wherein two of the moieties of formula (I-1) are carbon atoms and the remaining two are the same or different and are independently CH or CR7Wherein R is7H or C1-C4An alkyl group;
R8is H or C1-C4An alkyl group;
R9is cyano, C1-C7Alkyl, halo C1-C6Alkyl or C5-C6Cycloalkyl radical C1-C4An alkyl group; and
R10is C1-C4Alkyl or phenyl.
In some particularly preferred embodiments of the present invention, the compound of formula (I) is selected from compounds 1-64. Compounds 1-64 were prepared in examples 1-64, respectively.
According to a second aspect of the present invention there is provided a process for the preparation of a compound of formula (I) according to the invention, comprising the steps of:
(1) oximation reaction: when n is 0, subjecting the compound of formula (II) to oximation reaction with hydroxylamine, hydroxylamine hydrochloride or any combination thereof to obtain the compound of formula (IIIa)
(iii) subjecting the compound of formula (II) to an oximation reaction with nitrous acid, a nitrite salt, an alkyl nitrite, or any combination thereof, when n is 1, to give a compound of formula (IIIb):
wherein A in the formulae (II), (IIIa) and (IIIb)1、A2、A3、A4、R8And R9As defined for compounds of formula (I); and
(2) esterifying the compound of formula (IIIa) or (IIIb) to obtain the compound of formula (I).
In order to prepare the compound of formula (I) of the present invention, oximation reaction is first performed to introduce an oxime group, and then a hydroxyl group in the oxime group is converted into a corresponding ester group through esterification reaction, so as to obtain the coumarin (ketoxime) ester compound of the present invention.
Oximation reaction
The oximation reaction usually starts from a carbonyl compound. To this end, when n is 0, subjecting the compound of formula (III) to an oximation reaction with hydroxylamine, hydroxylamine hydrochloride or any combination thereof to obtain a compound of formula (IIIa):
a in the formulae (II) and (IIIa)1、A2、A3、A4、R8And R9As defined for the compounds of formula (I). For converting the acyclic carbonyl group in the compound of the formula (II) into an oxime group, hydroxylamine hydrochloride (NH) is generally used2OH & HCl), hydroxylamine (NH)2OH) or mixtures thereof as an oximation agent. The oximation reaction is usually carried out in an organic solvent, preferably in an organic polar solvent. Examples of solvents which can be used are ethanol or aqueous ethanol. To promote completion of the oximation reaction, a base such as sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide, or a mixture thereof is typically added. Among these, pyridine, piperidine, triethylamine can also be used as a base and/or a solvent or co-solvent. The temperature of the oximation reaction is generally the reflux temperature of the solvent and is generally in the range of 60 to 120 ℃. The oximation reaction time is also not particularly limited, and is usually carried out for 0.1 to 20 hours, preferably 0.5 to 10 hours. The relative amounts of the compound of formula (II) and the compound selected from hydroxylamine and/or hydroxylamine hydrochloride are not particularly limited, and in general they are used in approximately equimolar amounts, e.g. in a molar ratio of 1:1.5 to 1.5:1, preferably 1:1.2 to 1.2: 1.
(iii) subjecting the compound of formula (II) above to an oximation reaction with nitrous acid, a nitrite salt, an alkyl nitrite, or any combination thereof, when n is 1, to give a compound of formula (IIIb):
wherein, A in the formula (IIIb)1、A2、A3、A4、R8And R9As defined for formula (I). For converting the acyclic carbonyl group in the compound of formula (II) into a ketoxime group, nitrous acid, nitrite, alkyl nitrite or mixtures thereof are generally used as oximation agents. The reagent is toNitrosation is carried out with "active" (methylene) (α - (methylene), i.e. (methylene) next to the acyclic carbonyl group). As the nitrite, sodium nitrite is generally used. The alkyl nitrite can be nitrous acid C1-C6Alkyl esters, for example methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, isoamyl nitrite. The oximation reaction is usually carried out in an organic solvent, preferably in an organic polar solvent. Examples of solvents which can be used are tetrahydrofuran, ethanol or aqueous ethanol. In order to promote the completion of the oximation reaction, concentrated hydrochloric acid is generally added, the concentration of which is usually 20 to 40%. Concentrated hydrochloric acid may also be used as an acid and/or a solvent or co-solvent. The temperature of the oximation reaction is low and is generally in the range from-30 to 20 ℃ and preferably from 5 to 20 ℃. The oximation reaction time is also not particularly limited, and is usually carried out for 0.1 to 20 hours, preferably 0.5 to 10 hours. The relative amounts of the compound of formula (II) and the compound selected from nitrous acid, nitrite and/or alkyl nitrite are not particularly limited, and in general they are used in approximately equimolar amounts, e.g. in a molar ratio of 1:1.5 to 1.5:1, preferably 1:1.2 to 1.2: 1.
Two configurations for each oxime ester group are possible, either the (Z) or (E) form. The isomers can be separated by conventional methods, but mixtures of isomers can also be used as photoinitiating substances. The invention therefore also relates to mixtures of configurational isomers of the respective compounds of the formula (I). Esterification reaction
Esterification of the compounds of formula (IIIa) and (IIIb) is conventional, by which the hydroxyl group in the oxime group is converted to an ester group to obtain the compound of formula (I). The esterification reagent is not particularly limited as long as the hydroxyl group in the oxime group of the compounds of the formulae (IIIa) and (IIIb) 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. These compounds may be represented by formulas (IVa), (IVb) and (IVc), respectively:
wherein X is a halogen atom or a halogen atom,especially chlorine, and R10As defined for the compounds of formula (I).
In order to accelerate the esterification reaction, the above-mentioned esterification reaction is usually carried out in the presence of a catalyst suitable for the esterification reaction. As the catalyst, either an acidic catalyst or a basic catalyst may be used. As the catalyst, sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride, tetramethylammonium hydroxide, tertiary amines (e.g., trialkylamines such as trimethylamine and triethylamine), or any combination thereof may be used. The amount of catalyst used is conventional and can be determined by conventional knowledge in the art or by several routine preliminary experiments.
In order to increase the yield of the compound of formula (I), it is advantageous to remove the water of esterification during the esterification reaction. This can be done, for example, by distillative condensation.
The esterification reaction is usually carried out in a solvent, preferably an organic solvent. As the type of the solvent, there is no particular limitation as long as the compound of formula (IIIa) or (IIIb) and the esterification reagent can be dissolved and chemically inert to the esterification reaction, i.e., do not participate in the esterification reaction. As examples of the solvent, tetrahydrofuran, benzene, toluene, N-dimethylformamide, dichloromethane, and acetone may be mentioned. The solvent may be used singly or as a mixture of two or more solvents.
The relative amounts of compound of formula (IIIa) or (IIIb) and the esterification reagent selected from compounds (IVa), (IVb) and (IVc) are not particularly limited, and they are generally used in approximately equimolar amounts, e.g. in a molar ratio of 1:1.5 to 1.5:1, preferably 1:1.2 to 1.2: 1.
The esterification reaction can be carried out over a very wide temperature range. Advantageously according to the invention, the esterification reaction is carried out at a temperature of from-10 ℃ to 150 ℃, preferably from 0 ℃ to 100 ℃, preferably at ambient temperature. The esterification reaction time is also not particularly limited, and is usually carried out for 1 to 24 hours, preferably 1 to 12 hours.
After the esterification reaction is complete, a reaction mixture comprising the compound of formula (I) is obtained. Therefore, the reaction mixture needs to be worked up to obtain a purified compound of formula (I). In general, the reaction mixture obtained by the esterification reaction is first filtered, and a filtrate portion is taken out. Then, the filtrate was washed to remove the catalyst and unreacted raw materials. The washing liquid is not particularly limited as long as the catalyst and unreacted raw materials can be removed. As examples of the washing liquid, dilute hydrochloric acid (aqueous solution), saturated aqueous sodium bicarbonate solution and water may be mentioned. The concentration of the dilute hydrochloric acid is not particularly limited, and a dilute hydrochloric acid having a concentration of 5 to 12% is generally used. Washing with the washing liquid can be carried out once or for multiple times; in the case of multiple runs, a single wash solution may be used, or different wash solutions may be used sequentially. Advantageously according to the invention, the filtrate obtained by filtration of the reaction mixture obtained in the esterification reaction is washed successively with dilute hydrochloric acid, saturated aqueous sodium bicarbonate solution and water. Of course, after each washing with a wash liquid, it is necessary to pour off the aqueous phase and then wash the organic phase with the next wash liquid. After washing, drying is required to remove residual water. For this purpose, drying may be usually carried out using anhydrous sodium sulfate. After drying, the residual organic solvent is removed again. The means for removing the organic solvent is not particularly limited, and the organic solvent can be removed by distillation under reduced pressure. After removal of the residual organic solvent, the crude compound of formula (I) is obtained. If it is desired to further increase the purity of the compound of formula (I), the compound may be further purified, for example by recrystallization. The choice of the recrystallization solvent is conventional and is not particularly limited. According to the invention, the crude product of the compound of formula (I) is advantageously recrystallized from methanol.
The compounds of formula (II) are commercially available and can also be prepared by methods conventional in the art. In some preferred embodiments of the method of the present invention, further comprising the steps of: reacting a compound of formula (V) with a compound of formula (VI) to give a compound of formula (II). Performing Knoevenagel condensation reaction between the compound of formula (V) and the compound of formula (VI) to obtain the compound of formula (II)
Wherein A in the compound of formula (V)1、A2、A3、A4And R8As defined for the compounds of formula (I), and R in the compounds of formula (VI)9As defined for the compounds of formula (I), and R11Is C1-C12Alkyl, preferably C1-C6An alkyl group.
The Knoevenagel condensation reaction described above is typically carried out in the presence of a catalyst suitable for the condensation reaction. As the catalyst, a basic catalyst is usually used. For example, piperidine, pyridine, piperidine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride, tetramethylammonium hydroxide, tertiary amines (e.g., trialkylamines such as trimethylamine and triethylamine), or any combination thereof may be used. The amount of catalyst used is conventional and can be determined by conventional knowledge in the art or by several routine preliminary experiments.
The condensation reaction is usually carried out in a solvent, preferably an organic solvent. As the type of solvent, there is no particular limitation as long as the compounds of formula (V) and formula (VI) can be dissolved and are chemically inert to the condensation reaction, i.e., do not participate in the condensation reaction. As examples of the solvent, ethanol, methanol, t-butanol, tetrahydrofuran, benzene, toluene, dichloromethane, and acetone may be mentioned. The solvent may be used singly or as a mixture of two or more solvents.
The relative amounts of the compound of formula (V) and the compound of formula (VI) are not particularly limited, and in general they are used in approximately equimolar amounts, e.g. in a molar ratio of 1:1.5 to 1.5:1, preferably 1:1.2 to 1.2: 1.
The above condensation reaction can be carried out over a very wide temperature range. Advantageously according to the invention, the condensation reaction is carried out at a temperature of from 0 ℃ to 150 ℃, preferably from 0 ℃ to 100 ℃, preferably at the reflux temperature of the solvent. The condensation reaction time is also not particularly limited, and is usually carried out for 1 to 24 hours, preferably 1 to 12 hours.
After completion of the condensation reaction, a reaction mixture comprising the compound of formula (II) is obtained. Therefore, the reaction mixture needs to be worked up to obtain a purified compound of formula (II). This work-up makes it possible, as is customary, for example, to first filter the reaction mixture obtained and then recrystallize it. The choice of the recrystallization solvent is conventional and is not particularly limited. According to the invention, it is advantageous to recrystallize the crude product of the compound of formula (II) from methanol, ethanol or a mixture thereof.
The compound of formula (I) has strong absorption in the wavelength range of 300-500nm, especially 350-450nm, especially 365-450nm, and thus can be applied to UV-visible LED photocuring systems. The preparation raw materials of the compound shown in the formula (I) are coumarin ketone compounds with low toxicity, and compared with the traditional photoinitiator, the harm degree to human bodies and the environment is reduced.
Thus, according to a third aspect of the present invention, there is provided the use of a compound of formula (I) according to the present invention as a photoinitiator. The compound of formula (I) can be used as a photoinitiator in an ultraviolet-visible LED photocuring system, and can effectively initiate curing reaction. Particularly preferred is the use of the compounds of the formula (I) according to the invention as photoinitiators in photocuring systems with radiation wavelengths of 300-500nm, in particular 350-450nm, especially 365-450 nm. The compounds of formula (I) are useful as photoinitiators or photosensitizers in coatings, inks, microelectronics, printing and the like. When the compounds of the formula (I) are used as photoinitiators, their amounts are customary or can be determined by routine preliminary experiments.
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.
Example 1: preparation of Compound 1
The synthetic route for compound 1 is as follows:
synthesis of intermediate Compound 1a
Adding 3, 9-dimethyl-9H-carbazolyl-1-hydroxy-2-formaldehyde (0.05mol, 11.95g) into a 250mL three-neck round-bottom flask containing 50mL ethanol, stirring uniformly, and heating the mixed solution to 35 ℃ to completely dissolve reactants in the ethanol. Hexahydropyridine (0.01mol, 1mL) and ethyl acetoacetate (0.06mol, 7.8g) were then added and the reaction mixture was heated to reflux and stirred for 1 h. After the reaction was complete, the mixture was cooled to room temperature, filtered to give a yellow solid, which was then recrystallized from ethanol to give 13g of the product, identified as compound 1a, in 90% yield. 1H-NMR (400MHz, CDCl)3)δ2.27(s，3H)，3.48(s，3H)，3.82(s，3H)，7.02(s，1H)，7.30(d，1H)，7.42-7.45(m，2H)，8.17(d，1H)，8.45(s,1H)。
Synthesis of intermediate Compound 1b
Intermediate Compound 1a (11.64g, 0.04mol) and 50mL of a mixed solution of ethanol and water (V)Ethanol：VWater (W)2:1) was poured into a 100mL three-necked round-bottomed flask, and hydroxylamine hydrochloride (2.76g, 0.04mol) and sodium acetate (3.28g, 0.04mol) were added. Stirring and reacting for 0.5h at 70 ℃, filtering reaction liquid, then carrying out vacuum rotary evaporation on the filtrate to obtain light yellow solid, and recrystallizing with ethanol to obtain 11.2g of a product, wherein the yield is 92 percent, and the compound is identified as a compound 1 b. 1H-NMR (400MHz, CDCl)3)δ2.27(s，3H)，3.48(s，3H)，3.82(s，3H)，7.02(s，1H)，7.30(d，1H)，7.42-7.45(m，2H)，8.17(d，1H)，8.45(s,1H)，8.45(s,1H)，8.70(s,1H)。
Synthesis of target product 1
The above intermediate compound 1b (9.18g, 0.03mol) and 30mL of tetrahydrofuran were charged into a 100mL three-necked round-bottomed flask, followed by addition of acetyl chloride (2.81g, 0.036mol) and triethylamine (4.67g, 0.045mol), and the reaction was stirred at ordinary temperature for 1 hour. Terminating the reaction, filtering the reaction solution to obtain filtratePouring into water, extracting with ethyl acetate, collecting organic phase, washing with dilute hydrochloric acid solution, saturated sodium carbonate aqueous solution and distilled water, collecting organic phase, and washing with MgSO4Dry overnight. After filtration and distillation under reduced pressure of the organic phase, 9.4g of a yellow powdery solid was obtained, and the yield was 90.0%, and the compound was identified as compound 1. 1H-NMR (400MHz, CDCl)3)δ2.20(s，3H)，2.48(s，3H)，3.11(s，3H)，3.82(s，3H)，7.26(s，1H)，7.33(t，1H)，7.44(t，1H)，7.54(s，1H)，7.59(d，1H)，8.17(d，1H)
Examples 2 to 43: preparation of Compounds 2 to 43
The procedure of example 1 was repeated, with appropriate changes in the reaction raw materials, to obtain compounds 2 to 43 shown in Table 1 below and nuclear magnetic data thereof, respectively.
Example 44: preparation of Compound 44
Compound 44a was synthesized first, the synthetic route is as follows:
synthesis of intermediate Compound 44a
4-methyl-6-hydroxy-7-methylcarbonyldibenzofuran (0.05mol, 12g) was added to a 250mL three-necked round-bottomed flask containing 50mL of ethanol, and after stirring, the mixture was heated to 35 ℃ to dissolve all the reactants in ethanol. Hexahydropyridine (0.01mol, 1mL) and ethyl acetoacetate (0.06mol, 7.8g) were then added and the reaction mixture was heated to reflux and stirred for 1 h. After the reaction was complete, the mixture was cooled to room temperature, filtered to give a yellow solid, which was then recrystallized from ethanol to give 12.5g of the product, 81.6% yield, and identified as compound 44 a. 1H-NMR (400MHz, CDCl)3)δ2.27(s，3H)，3.48(s，3H)，3.82(s，3H)，7.02(d，1H)，7.30(d，1H)，7.38(d，2H)，7.45(m，1H)。
The other procedure was similar to compound 1, in which compound 44a was substituted for compound 1a, to give compound 44, whose nuclear magnetic data are shown in table 1 below.
Preparation of Compounds 45-51
The procedure of example 1 was repeated, with appropriate changes in the reaction raw materials, to obtain compounds 45 to 51 shown in Table 1 below and nuclear magnetic data thereof, respectively.
TABLE 1
Example 52 preparation of Compound 52
The synthetic route for compound 52 is as follows:
synthesis of intermediate Compound 52a
Adding 1-hydroxy-3-methyl-9-ethyl-9H-carbazolyl-2-formaldehyde (0.05mol, 11.95g) into 250mL of three-port round-bottom baked cake containing 50mL of ethanolAfter stirring the mixture in a bottle, the mixture was heated to 35 ℃ to dissolve all the reactants in ethanol. Hexahydropyridine (0.01mol, 1mL) and ethyl capryloacetate (0.06mol, 12.84g) were then added, and the reaction mixture was heated to reflux and stirred for 1 h. After the reaction was complete, the mixture was cooled to room temperature, filtered to give a yellow solid, which was then recrystallized from ethanol to give 20.7g of the product, 92% yield, identified as compound 52 a. 1H-NMR (400MHz, CDCl)3)δ0.88(t，3H)，1.31-1.36(m，10H)，1.29(t，3H)，2.48(s，3H)，2.94(t，2H)，4.53(q，2H)，7.02(s，1H)，7.42(m，2H)，7.59(d，1H)，8.17(d，1H)，8.45(s，1H)。
Synthesis of intermediate Compound 52b
Intermediate compound 52a (7.51g, 0.02mol) was added to a 100ml three-necked flask containing 30ml tetrahydrofuran, 15g concentrated hydrochloric acid (35%) was added, and after stirring for 0.5h, isoamyl nitrite (2.36g, 0.02mol) was added dropwise at 5 ℃ and after completion of the addition, the reaction was continued at 10 ℃ for 3 h. After the reaction is finished, pouring the reaction solution into water, extracting with ethyl acetate, collecting an organic phase, and washing the organic phase to be neutral. The organic phase was dried, the organic solvent removed by rotary evaporation, recrystallized from 10g of petroleum ether and filtered at low temperature to give 5.3g of a white solid, a yield of 63% and identified as compound 52 b. 1H-NMR (400MHz, CDCl)3)δ0.88(t，3H)，1.31-1.36(m，8H)，1.44(t，2H)，1.29(t，3H)，2.48(s，3H)，4.53(q，2H)，7.02(s，1H)，7.42(m，2H)，7.59(d，1H)，8.17(d，1H)，8.45(s，1H)，8.70(s，1H)。
Synthesis of end product 52
The above intermediate compound 52b (4.19g, 0.01mol) and 30mL of tetrahydrofuran were charged into a 100mL three-necked round-bottomed flask, followed by the addition of acetyl chloride (0.78g, 0.01mol) and triethylamine (1.35g, 0.013mol), and the reaction was stirred at ordinary temperature for 1 hour. Terminating the reaction, filtering the reaction solution, pouring the filtrate into water, extracting with ethyl acetate, collecting the organic phase, washing with dilute hydrochloric acid, saturated aqueous sodium carbonate solution and distilled water in sequence, collecting the organic phase, and using MgSO4Dry overnight. After filtration and distillation under reduced pressure of the organic phase, 4.42g of a white solid was obtained, and the yield was 95.0%, which was identified as compound 52.
1H-NMR(400MHz,CDCl3)δ0.88(t，3H)，1.31-1.36(m，8H)，1.44(t，2H)，1.29(t，3H)，2.28(s，3H),2.48(s，3H)，4.53(q，2H)，7.02(s，1H)，7.42(m，2H)，7.59(d，1H)，8.17(d，1H)，8.45(s，1H)。
Examples 53 to 64: preparation of Compounds 53-64
The procedure of example 52 was repeated, with appropriate changes in the reaction materials, to obtain compounds 53 to 64 shown in Table 2 below and nuclear magnetic data thereof, respectively.
TABLE 2
Thermal stability test
Testing the initial temperature at which the photoinitiator initiates polymerization of the polymerizable monomer using differential thermal analysis (DSC) is an effective measure of the thermal stability of the photoinitiator. Using this method, tripropylene glycol diacrylate (TPGDA) was used as a monomer, and the initiation temperature of each of the compounds 1,3, 17, and 55 and the coumarin oxime ester compound COXE-15 disclosed in the commercial oxime ester photoinitiator OXE-02 and CN201710620077.2 patents were tested. The results of the differential thermal analysis are shown in Table 3.
TABLE 3
As can be seen from Table 3, the initial temperatures at which compounds 1,3, 17, and 55 each initiated polymerization of TPGDA were higher than the initial temperatures at which OXE-02 (see below for its structure) and COXE-15 (see below for its structure) each initiated polymerization of TPGDA.
The structure of COXE-15 is shown below:
in addition, the above thermal stability experiment was repeated with each of compounds 2, 4-16, 18-54, and 56-64. The results show that the initial temperatures at which compounds 2, 4-16, 18-54, and 56-64 each initiate polymerization of TPGDA are all above 120 ℃.
Therefore, the stability of the compounds 1 to 64 according to the present invention in acrylate monomers is significantly higher than that of the commercial products OXE-02 and COXE-15, and thus the compounds 1 to 64 of the present invention have better thermal stability.
The application example is as follows: and (3) testing the photosensitive performance:
the photosensitivity of the photoinitiators was tested using a Ugra (Ugra) plate test strip as a mask. The sections of the ugra strip are shown in fig. 1. The black-grid printing test strip is divided into 5 control sections, which are respectively from left to right: a continuous density ladder section (1); a yin-yang micron isoline concentric circle segment (2); a full tone dot section (3); a ghost control section (4); a highlight and dark tone control section (5). A first stage: the continuous density scale segment is divided into 13 gradients for controlling exposure and development. And a second stage: yin-yang micron isopleth concentric circle segment: the concentric circle line graphs composed of 12 yin-yang micron isochrones are respectively 4, 6, 8, 10, 12, 15, 20, 25, 30, 40, 55 and 70, and are used for detecting exposure and development conditions when the PS plate is exposed. A third stage: full tone dot segment: the film printing and proofing system consists of 10-100% evaluation nets with the range difference of 10%, and is arranged in an upper row and a lower row and used for measuring the transfer conditions of printing-down, proofing and printing branches and measuring the change curve graphs of film manufacturing branches and printing-down, proofing and printing net shops. A fourth stage: a ghost control section: the line is composed of fine lines with the line width of 60 lines/cm and the area rate of 60 percent, and is divided into 4 small blocks, lines arranged at three angles of 0 degrees, 45 degrees and 90 degrees, and small lines arranged at two sides of 90 degrees, a middle small block of 45 degrees and upper and lower 90 degrees in D small blocks with 1/4. A fifth stage: and the fine screen dot section is formed by correspondingly arranging small highlight screen dots and dark-tone deep screen dots and is used for finely controlling the accuracy of printing exposure and development. A photosensitive composition containing a photoinitiator was coated on an aluminum substrate, followed by exposure and development, and the sensitivity was evaluated from the continuous scale of the obtained image, and the accuracy was evaluated from the area of the micro-line test block, thereby evaluating the merits of the formulation of the photosensitive composition.
Specifically, the photosensitivity of the compound of formula (I) was tested as follows.
(1) A photosensitive composition containing a photoinitiator was prepared according to the following composition:
the photoinitiator in the composition is selected from coumarin (ketone) oxime ester compounds shown in the formula (I) of the invention or photoinitiators known in the prior art (for comparison). The acrylate resin was a resin sold under the trade name FS2600K from Shanghai Kabushiki International trade company, Inc., having a functionality of 2 and a number average molecular weight of 1400. Dipentaerythritol hexaacrylate is a product purchased from Shanghai under the trade designation GM66G0C from International trade company, Inc. The crystal violet dye is a product purchased from Shanghai national medicine under the trade name hexamethyl rhodanidine hydrochloride.
Test of light sensitivity
(2) The compositions are stirred and mixed evenly under yellow light, and are coated on a PS aluminum plate base which is pretreated in advance and meets the following conditions by a centrifugal machine in a rotating way:
the base size of the aluminum plate is as follows: 1030mm x 800mm
Thickness of the aluminum substrate: 0.28-0.3mm
Specification of the sand mesh: ra is 0.5-0.6 μm
Rh＝0.3-0.35μm
Weight of anodic oxide film: 3-3.5g/m2
Controlling the rotation speed of the centrifugal coating machine to ensure that the coating weight (calculated by solid content) coated on the aluminum plate base is 1.0-2.5g/m2And after primary drying on a centrifugal coating machine, transferring the plate to a blast drier at 100 ℃ for drying for 3 minutes to obtain the purple laser CTP original plate. Then, using Ugra test stripsAnd (4) making a mask to test the photosensitive performance of the plate, and developing the plate by using a 1% NaOH aqueous solution after exposing the plate for a period of time.
In the exposed areas, the photopolymerizable compound is polymerized in the presence of an initiator, insoluble in the developer, while the unexposed areas are soluble, thus giving a negative image. The sensitivity of the photoinitiator was evaluated from the continuous scale of the resulting image by exposure development. The sensitivity of the initiator system is characterized by the retention of the highest number of gray levels (i.e., polymerized) after development. The higher the number of gray levels, the higher the sensitivity of the test system. The results are shown in Table 4.
TABLE 4
In Table 4, OXE-01 represents 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyloxime), OXE-02 represents 1- (6-methylbenzoyl-9-ethylcarbazol-3-yl) - (3-ethanone) -1-oxime acetate, the structural formulae of which are respectively as follows:
as is apparent from the experimental results in Table 4, the number of gray levels of the photoinitiators 1-64 of the invention at 365nm, 385nm, 395nm and 405nm and visible light 420, 436 and 450nm is higher than that of the commercially available photoinitiators OXE-01 and OXE-02. Namely, the coumarin (ketone) oxime ester photoinitiator has more excellent photosensitivity at 365nm, 385nm, 395nm, 405nm and visible light wavelengths of 420, 436 and 450nm, is suitable for LED light sources of 365nm, 385nm, 395nm, 405nm and visible light wavelengths of 420, 436 and 450nm, and has wider application range.
In summary, the coumarin (ketone) oxime ester photoinitiator shown in the formula (I) has better sensitization performance at 365nm, 385nm, 395nm and 405nm and visible light wavelengths of 420, 436 and 450nm, and is superior to the commercially available ketoxime ester photoinitiators such as OXE-01, OXE-02 and the like at the present stage. In addition, the compound disclosed by the invention is simple in production process, high in yield and very suitable for industrial production. The compound has good matching property with 365nm, 385nm, 395nm, 405nm and visible light 420, 436 and 450nm LED light sources, and can be widely applied to fields related to ultraviolet visible LED light curing, such as coating, ink, microelectronics, printing and the like, and used as a photoinitiator. The substance has good market prospect. In view of the fact that the variety of the existing photoinitiator applicable to the ultraviolet-visible LED is small, and the popularization and application of the ultraviolet-visible LED light source in the ultraviolet curing field are limited to a certain extent, the photoinitiator can make a contribution to promoting the wide application of the environment-friendly ultraviolet-visible LED light source in the UV curing industry.
Claims (48)
1. A coumarin (keto) oxime ester compound of formula (I) comprising a moiety of formula (I-1):
wherein:
x is O, S, NR1Or CR2aR2bWherein R is1、R2aAnd R2bEach independently is H, C1-C20Alkyl radical, C3-C10Cycloalkyl radical, C3-C10Cycloalkyl radical C1-C8Alkyl radical, C1-C8Alkyl radical C3-C10Cycloalkyl radical, C1-C20Alkoxy radical, C1-C20Alkylthio radical, C3-C10Cycloalkoxy, C3-C10Cycloalkylthio radical, C3-C10Cycloalkyl radical C1-C8Alkoxy radical, C3-C10Cycloalkyl radical C1-C8Alkylthio radical, C1-C8Alkyl radical C3-C10Cycloalkoxy, C1-C8Alkyl radical C3-C10Cycloalkylthio radical, C6-C18Aryl radical, C6-C18Aryloxy radical or C6-C18Arylthio, wherein each of the foregoing groups other than H may be substituted with one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl radical, C1-C6Alkoxy and C1-C6An alkylthio group;
R3、R4、R5、R6independently of one another, hydrogen, halogen, nitro, cyano, C1-C20Alkyl radical, C3-C10Cycloalkyl radical, C3-C10Cycloalkyl radical C1-C8Alkyl radical, C1-C8Alkyl radical C3-C10Cycloalkyl radical, C1-C20Alkoxy radical, C1-C20Alkylthio radical, C3-C10Cycloalkoxy, C3-C10Cycloalkylthio radical, C3-C10Cycloalkyl radical C1-C8Alkoxy radical, C3-C10Cycloalkyl radical C1-C8Alkylthio radical, C1-C8Alkyl radical C3-C10Cycloalkoxy, C1-C8Alkyl radical C3-C10Cycloalkylthio radical, C6-C18Aryl radical, C6-C18Aryloxy radical or C6-C18Arylthio, wherein each of the foregoing groups other than hydrogen, halogen, nitro and cyano may be substituted with one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl radical, C1-C6Alkoxy and C1-C6An alkylthio group;
and are a moiety of formula (I-1) and A in the compound of formula (I)1And A2、A2And A3Or A3And A4The attachment site of (a);
A1、A2、A3、A4wherein two of the moieties of formula (I-1) are carbon atoms and the remaining two are the same or different and are independently of each otherIs CH or CR7Wherein R is7Is H, halogen, C1-C6Alkyl radical, C1-C6Alkoxy or C1-C6Alkylthio group wherein the foregoing C1-C6Alkyl radical, C1-C6Alkoxy and C1-C6Alkylthio groups may be substituted by one or more identical or different halogen substituents;
R8is H, halogen, C1-C6Alkyl radical, C1-C6Alkoxy or C1-C6Alkylthio group wherein the foregoing C1-C6Alkyl group, the foregoing C1-C6Alkoxy and the aforementioned C1-C6Alkylthio groups may be substituted by one or more identical or different halogen substituents;
R9is hydrogen, halogen, nitro, cyano, C1-C20Alkyl radical, C3-C10Cycloalkyl radical, C3-C10Cycloalkyl radical C1-C8Alkyl radical, C1-C8Alkyl radical C3-C10Cycloalkyl radical, C1-C20Alkoxy radical, C1-C20Alkylthio radical, C3-C10Cycloalkoxy, C3-C10Cycloalkylthio radical, C3-C10Cycloalkyl radical C1-C8Alkoxy radical, C3-C10Cycloalkyl radical C1-C8Alkylthio radical, C1-C8Alkyl radical C3-C10Cycloalkoxy, C1-C8Alkyl radical C3-C10Cycloalkylthio radical, C6-C18Aryl radical, C6-C18Aryloxy radical or C6-C18Arylthio, wherein each of the foregoing groups other than H, halogen, nitro and cyano may be substituted with one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl radical, C1-C6Alkoxy and C1-C6An alkylthio group;
R10is C1-C20Alkyl or C6-C18Aryl radical ofC in1-C20Alkyl and C6-C18The aryl group may be substituted with one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl radical, C1-C6Alkoxy and C1-C6An alkylthio group; and
n is 0 or 1.
2. The compound of claim 1, wherein
R1、R2aAnd R2bEach independently is H, C1-C10Alkyl radical, C3-C8Cycloalkyl radical, C3-C8Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkyl radical C3-C8Cycloalkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C3-C8Cycloalkoxy, C3-C8Cycloalkylthio radical, C3-C8Cycloalkyl radical C1-C6Alkoxy radical, C3-C8Cycloalkyl radical C1-C6Alkylthio radical, C1-C6Alkyl radical C3-C8Cycloalkoxy, C1-C6Alkyl radical C3-C8Cycloalkylthio radical, C6-C10Aryl radical, C6-C10Aryloxy radical or C6-C10Arylthio, wherein each of the foregoing groups other than H may be substituted with one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl radical, C1-C6Alkoxy and C1-C6An alkylthio group; and/or
R3、R4、R5、R6Independently of one another, hydrogen, halogen, nitro, cyano, C1-C6Alkyl radical, C3-C8Cycloalkyl radical, C3-C8Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkyl radical C3-C8Cycloalkyl radical, C1-C6Alkoxy radical,C1-C6Alkylthio radical, C3-C8Cycloalkoxy, C3-C8Cycloalkylthio radical, C3-C8Cycloalkyl radical C1-C6Alkoxy radical, C3-C8Cycloalkyl radical C1-C6Alkylthio radical, C1-C6Alkyl radical C3-C10Cycloalkoxy, C1-C6Alkyl radical C3-C10Cycloalkylthio radical, C6-C10Aryl radical, C6-C10Aryloxy radical or C6-C10Arylthio, wherein each of the foregoing groups other than hydrogen, halogen, nitro and cyano may be substituted with one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl radical, C1-C6Alkoxy and C1-C6An alkylthio group; and/or
R7Is H, fluorine, chlorine, bromine, C1-C4Alkyl radical, C1-C4Alkoxy or C1-C4Alkylthio group wherein the foregoing C1-C4Alkyl radical, C1-C4Alkoxy and C1-C4The alkylthio group may be substituted by one or more same or different substituents selected from the group consisting of fluorine, chlorine, bromine; and/or
R8Is H, fluorine, chlorine, bromine, C1-C4Alkyl radical, C1-C4Alkoxy or C1-C4Alkylthio group wherein the foregoing C1-C4Alkyl radical, C1-C4Alkoxy and C1-C4The alkylthio group may be substituted by one or more same or different substituents selected from the group consisting of fluorine, chlorine, bromine; and/or
R9Is hydrogen, halogen, nitro, cyano, C1-C8Alkyl radical, C3-C8Cycloalkyl radical, C3-C8Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkyl radical C3-C8Cycloalkyl radical, C1-C6Alkoxy radical, C1-C6Alkylthio radical, C3-C8Cyclic alkoxy radicalBase, C3-C8Cycloalkylthio radical, C3-C8Cycloalkyl radical C1-C6Alkoxy radical, C3-C8Cycloalkyl radical C1-C6Alkylthio radical, C1-C6Alkyl radical C3-C8Cycloalkoxy, C1-C6Alkyl radical C3-C8Cycloalkylthio radical, C6-C10Aryl radical, C6-C10Aryloxy radical or C6-C10Arylthio, wherein each of the foregoing groups other than H, halogen, nitro and cyano may be substituted with one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl radical, C1-C6Alkoxy and C1-C6An alkylthio group; and/or
R10Is C1-C6Alkyl or C6-C10Aryl radical, wherein C1-C6Alkyl and C6-C10The aryl group may be substituted with one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6Alkyl radical, C1-C6Alkoxy and C1-C6An alkylthio group.
3. The compound of claim 2, wherein
R1、R2aAnd R2bEach independently is H, C1-C8Alkyl radical, C5-C6Cycloalkyl radical, C5-C6Cycloalkyl radical C1-C4Alkyl radical, C1-C4Alkyl radical C5-C6Cycloalkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C5-C6Cycloalkoxy, C5-C6Cycloalkylthio radical, C3-C6Cycloalkyl radical C1-C4Alkoxy radical, C3-C6Cycloalkyl radical C1-C4Alkylthio radical, C1-C4Alkyl radical C5-C6Cycloalkoxy, C1-C4Alkyl radical C5-C6Cycloalkylthio radical, C6-C10Aryl radical, C6-C10Aryloxy radical or C6-C10Arylthio, wherein each of the foregoing groups other than H may be substituted with one or more substituents independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C4Alkyl radical, C1-C4Alkoxy and C1-C4An alkylthio group.
4. The compound of claim 2, wherein
R3、R4、R5、R6Independently of one another, hydrogen, halogen, nitro, cyano, C1-C4Alkyl radical, C5-C6Cycloalkyl radical, C5-C6Cycloalkyl radical C1-C4Alkyl radical, C1-C4Alkyl radical C5-C6Cycloalkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C5-C6Cycloalkoxy, C5-C6Cycloalkylthio radical, C5-C6Cycloalkyl radical C1-C4Alkoxy radical, C5-C6Cycloalkyl radical C1-C4Alkylthio radical, C1-C4Alkyl radical C5-C6Cycloalkoxy, C1-C4Alkyl radical C5-C6Cycloalkylthio, phenyl, phenoxy or phenylthio, wherein each of the foregoing groups other than hydrogen, halogen, nitro, cyano may be substituted with one or more substituents independently selected from the group consisting of: fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4Alkyl radical, C1-C4Alkoxy and C1-C4An alkylthio group.
5. The compound of claim 2, wherein
R9Is hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C8Alkyl radical, C5-C6Cycloalkyl radical, C5-C6Cycloalkyl radical C1-C4Alkyl radical, C1-C4Alkyl radical C5-C6Cycloalkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C5-C6Cycloalkoxy, C5-C6Cycloalkylthio radical, C5-C6Cycloalkyl radical C1-C4Alkoxy radical, C5-C6Cycloalkyl radical C1-C4Alkylthio radical, C1-C4Alkyl radical C5-C6Cycloalkoxy, C1-C4Alkyl radical C5-C6Cycloalkylthio, phenyl, phenoxy or phenylthio, wherein each of the foregoing groups other than hydrogen, fluoro, chloro, bromo, nitro and cyano may be substituted with one or more substituents independently selected from the group consisting of: fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4Alkyl radical, C1-C4Alkoxy and C1-C4An alkylthio group.
6. The compound of claim 2, wherein
R10Is C1-C4Alkyl or phenyl, wherein C1-C4The alkyl and phenyl groups may be substituted with one or more substituents independently selected from the group consisting of: fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4Alkyl radical, C1-C4Alkoxy and C1-C4An alkylthio group.
7. The compound of claim 1, wherein
X is O, S, NR1Or CR2aR2bWherein R is1Is C1-C8Alkyl, phenyl or naphthyl, wherein the phenyl or naphthyl may be substituted by one or more identical or different C1-C4Alkyl substituent group substitution; and R2aAnd R2bAre the same or different and are each independently H, C1-C6Alkyl radical, C5-C6Cycloalkyl radical C1-C4Alkyl or C1-C4Alkoxy radicalRadical C1-C4An alkyl group;
R3、R4、R5、R6independently of one another, hydrogen, nitro, C1-C4Alkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio or phenyl;
A1、A2、A3、A4wherein two of the moieties of formula (I-1) are carbon atoms and the remaining two are the same or different and are independently CH or CR7Wherein R is7Is H or C1-C4An alkyl group;
R8is H or C1-C4An alkyl group;
R9is cyano, C1-C7Alkyl, halo C1-C6Alkyl or C5-C6Cycloalkyl radical C1-C4An alkyl group; and
R10is C1-C4Alkyl or phenyl.
8. The compound according to claim 1, wherein the compound is selected from the group consisting of:
9. a process for the preparation of a compound according to any one of claims 1 to 8, comprising the steps of:
(1) oximation reaction: when n is 0, subjecting the compound of formula (II) to oximation reaction with hydroxylamine, hydroxylamine hydrochloride or any combination thereof to obtain the compound of formula (IIIa)
(iii) subjecting the compound of formula (II') to oximation reaction with nitrous acid, nitrite, alkyl nitrite, or any combination thereof when n is 1 to give a compound of formula (IIIb):
wherein A in the formulae (II), (II'), (IIIa) and (IIIb)1、A2、A3、A4、R8And R9As defined in any one of claims 1 to 8; and
(2) esterifying the compound of formula (IIIa) or (IIIb) to obtain the compound of formula (I).
10. The method of claim 9, wherein
When n is 0:
the oximation reaction is carried out in the presence of sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide or a mixture thereof as a catalyst; and/or the temperature of the oximation reaction is 60-120 ℃; and/or the molar ratio of the compound of formula (II) to the compound selected from hydroxylamine and/or hydroxylamine hydrochloride is from 1:1.5 to 1.5: 1; or
When n is 1, the compound is a compound of formula (I),
the oximation reaction is carried out in the presence of concentrated hydrochloric acid; and/or the temperature of the oximation reaction is-30 to 20 ℃; and/or the molar ratio of the compound of formula (II') to the compound selected from nitrous acid, nitrite and/or alkyl nitrite is from 1:1.5 to 1.5: 1.
11. The method of claim 10, wherein
When n is 0:
the molar ratio of the compound of formula (II) to the compound selected from hydroxylamine and/or hydroxylamine hydrochloride is 1:1.2 to 1.2: 1.
12. The method of claim 10, wherein
When n is 1, the compound is a compound of formula (I),
the temperature of the oximation reaction is 5-20 ℃.
13. The method of claim 10, wherein
When n is 1, the compound is a compound of formula (I),
the molar ratio of the compound of the formula (II') to the compound selected from nitrous acid, nitrite and/or alkyl nitrite is from 1:1.2 to 1.2: 1.
14. The method of claim 9, wherein
Alkyl nitrite is nitrous acid C1-C6An alkyl ester; and/or the presence of a gas in the gas,
the esterification of step (2) is carried out using an esterifying reagent selected from the group consisting of compounds of the following formulae (IVa), (IVb) and (IVc):
wherein X is halogen, and R10As defined in any one of claims 1 to 8.
15. The method of claim 14, wherein the alkyl nitrite is methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, or isoamyl nitrite.
16. The method of claim 14, wherein X is chlorine.
17. The method of claim 10, wherein
Alkyl nitrite is nitrous acid C1-C6An alkyl ester; and/or the presence of a gas in the gas,
the esterification of step (2) is carried out using an esterifying reagent selected from the group consisting of compounds of the following formulae (IVa), (IVb) and (IVc):
wherein X is halogen, and R10As defined in any one of claims 1 to 8.
18. The method of claim 17, wherein the alkyl nitrite is methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, or isoamyl nitrite.
19. The method of claim 17, wherein X is chlorine.
20. The process of any one of claims 9-19, wherein the esterification reaction is carried out in the presence of one or more catalysts selected from the group consisting of: sulfuric acid, perchloric acid, zinc chloride, ferric trichloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride and tertiary amines.
21. The method of claim 20, wherein the tertiary amine is a trialkylamine.
22. The method of claim 20, wherein the tertiary amines are trimethylamine and triethylamine.
23. The process of any one of claims 14-19, wherein the molar ratio of compound of formula (IIIa) or (IIIb) to esterifying reagent selected from compounds of formula (IVa), (IVb) and (IVc) is from 1:1.5 to 1.5: 1.
24. The process of any one of claims 14-19, wherein the molar ratio of compound of formula (IIIa) or (IIIb) to esterifying reagent selected from compounds of formula (IVa), (IVb) and (IVc) is from 1:1.2 to 1.2: 1.
25. The method of any of claims 9-19 and 21-22, further comprising: carrying out Nowenge geum condensation reaction on the compound of formula (V) and the compound of formula (VI) to obtain a compound of formula (II),
wherein A in the compound of formula (V)1、A2、A3、A4And R8R as defined in any of claims 1 to 8, and in compounds of the formula (VI)9As defined in any one of claims 1 to 8, and R11Is C1-C12An alkyl group.
26. The method of claim 25, wherein R11Is C1-C6An alkyl group.
27. The method of claim 20, further comprising: carrying out Nowenge geum condensation reaction on the compound of formula (V) and the compound of formula (VI) to obtain a compound of formula (II),
wherein A in the compound of formula (V)1、A2、A3、A4And R8R as defined in any of claims 1 to 8, and in compounds of the formula (VI)9As defined in any one of claims 1 to 8, and R11Is C1-C12An alkyl group.
28. The method of claim 27, whereinR11Is C1-C6An alkyl group.
29. The method of claim 25, wherein
The knoevenageous Bayer condensation reaction is carried out in the presence of piperidine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride, tetramethylammonium hydroxide, tertiary amine or any combination thereof; and/or the presence of a gas in the gas,
the temperature of the Nowenge Bayer Algorithm condensation reaction is 0-150 ℃; and/or
The molar ratio of the compound of formula (V) to the compound of formula (VI) is 1:1.5 to 1.5: 1.
30. The method of claim 29, wherein the tertiary amine is a trialkylamine.
31. The method of claim 29, wherein the tertiary amines are trimethylamine and triethylamine.
32. The method of claim 29 wherein the temperature of the knoevenagel condensation reaction is from 0 ℃ to 100 ℃.
33. The process of claim 29, wherein the molar ratio of the compound of formula (V) to the compound of formula (VI) is 1:1.2-1.2: 1.
34. The method of claim 26, wherein
The knoevenageous Bayer condensation reaction is carried out in the presence of piperidine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride, tetramethylammonium hydroxide, tertiary amine or any combination thereof; and/or the presence of a gas in the gas,
the temperature of the Nowenge Bayer Algorithm condensation reaction is 0-150 ℃; and/or
The molar ratio of the compound of formula (V) to the compound of formula (VI) is 1:1.5 to 1.5: 1.
35. The method of claim 34, wherein the tertiary amine is a trialkylamine.
36. The method of claim 34, wherein tertiary amines are trimethylamine and triethylamine.
37. The method of claim 34 wherein the temperature of the knoevenagel condensation reaction is from 0 ℃ to 100 ℃.
38. The process of claim 34, wherein the molar ratio of the compound of formula (V) to the compound of formula (VI) is 1:1.2-1.2: 1.
39. The method of claim 27 or 28, wherein
The knoevenageous Bayer condensation reaction is carried out in the presence of piperidine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride, tetramethylammonium hydroxide, tertiary amine or any combination thereof; and/or the presence of a gas in the gas,
the temperature of the Nowenge Bayer Algorithm condensation reaction is 0-150 ℃; and/or
The molar ratio of the compound of formula (V) to the compound of formula (VI) is 1:1.5 to 1.5: 1.
40. The method of claim 39, wherein the tertiary amine is a trialkylamine.
41. The method of claim 39, wherein the tertiary amines are trimethylamine and triethylamine.
42. The method of claim 39 wherein the temperature of the knoevenagel condensation reaction is from 0 to 100 ℃.
43. The process of claim 39, wherein the molar ratio of the compound of formula (V) to the compound of formula (VI) is from 1:1.2 to 1.2: 1.
44. Use of a compound of formula (I) as defined in any one of claims 1 to 8 as a photoinitiator.
45. Use of a compound of formula (I) according to any one of claims 1 to 8 as photoinitiator in a UV-LED photocuring system.
46. Use of a compound of the formula (I) as claimed in any of claims 1 to 8 as photoinitiator in a photocuring system with a radiation wavelength of 300-500 nm.
47. Use of a compound of formula (I) as claimed in any of claims 1 to 8 as photoinitiator in a photocuring system with a radiation wavelength of 350-450 nm.
48. Use of a compound of the formula (I) as claimed in any of claims 1 to 8 as photoinitiator in a photocuring system with a radiation wavelength of 365-450 nm.
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