CN110105166A - Alpha-hydroxy ketones and its preparation method and application containing talan - Google Patents
Alpha-hydroxy ketones and its preparation method and application containing talan Download PDFInfo
- Publication number
- CN110105166A CN110105166A CN201910360588.4A CN201910360588A CN110105166A CN 110105166 A CN110105166 A CN 110105166A CN 201910360588 A CN201910360588 A CN 201910360588A CN 110105166 A CN110105166 A CN 110105166A
- Authority
- CN
- China
- Prior art keywords
- alpha
- talan
- hydroxy ketones
- preparation
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- HDWLUGYOLUHEMN-UHFFFAOYSA-N Dinobuton Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1OC(=O)OC(C)C HDWLUGYOLUHEMN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 241000425573 Talanes Species 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 238000006467 substitution reaction Methods 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 14
- 239000005977 Ethylene Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000003847 radiation curing Methods 0.000 claims description 10
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- YGJORYBAYKUDBH-UHFFFAOYSA-N ethene;n-phenylaniline Chemical group C=C.C=1C=CC=CC=1NC1=CC=CC=C1 YGJORYBAYKUDBH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 6
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000003935 benzaldehydes Chemical class 0.000 claims description 4
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical group [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 3
- 230000021615 conjugation Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical class C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 238000007171 acid catalysis Methods 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- SPVWMKHJURDVSJ-UHFFFAOYSA-N cyanophosphonous acid Chemical compound OP(O)C#N SPVWMKHJURDVSJ-UHFFFAOYSA-N 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 abstract description 4
- 238000000862 absorption spectrum Methods 0.000 abstract description 3
- 238000001782 photodegradation Methods 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 3
- 238000004896 high resolution mass spectrometry Methods 0.000 description 34
- 239000007787 solid Substances 0.000 description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- -1 talan Class compound Chemical class 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BHWABVQSIIDAON-UHFFFAOYSA-N 2-(3-oxo-1,3-diphenylpropyl)cyclohexan-1-one Chemical compound C=1C=CC=CC=1C(=O)CC(C=1C=CC=CC=1)C1CCCCC1=O BHWABVQSIIDAON-UHFFFAOYSA-N 0.000 description 2
- JOWNMNFMYXUNHY-UHFFFAOYSA-N 2-methyl-2-trimethylsilyloxypropanenitrile Chemical compound N#CC(C)(C)O[Si](C)(C)C JOWNMNFMYXUNHY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical class BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- PJANXHGTPQOBST-QXMHVHEDSA-N cis-stilbene Chemical compound C=1C=CC=CC=1/C=C\C1=CC=CC=C1 PJANXHGTPQOBST-QXMHVHEDSA-N 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- FVYXIJYOAGAUQK-UHFFFAOYSA-N honokiol Chemical compound C1=C(CC=C)C(O)=CC=C1C1=CC(CC=C)=CC=C1O FVYXIJYOAGAUQK-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- GQIYWKDVGPFXOP-UHFFFAOYSA-N (4-bromophenyl)methyl diethyl phosphite Chemical compound CCOP(OCC)OCC1=CC=C(Br)C=C1 GQIYWKDVGPFXOP-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- OCVLMHBFYUSVPU-UHFFFAOYSA-N 1-trimethylsilyloxycyclohexane-1-carbonitrile Chemical compound C[Si](C)(C)OC1(C#N)CCCCC1 OCVLMHBFYUSVPU-UHFFFAOYSA-N 0.000 description 1
- UUZYFBXKWIQKTF-UHFFFAOYSA-N 2-(3-bromophenyl)acetonitrile Chemical compound BrC1=CC=CC(CC#N)=C1 UUZYFBXKWIQKTF-UHFFFAOYSA-N 0.000 description 1
- MFHFWRBXPQDZSA-UHFFFAOYSA-N 2-(4-bromophenyl)acetonitrile Chemical compound BrC1=CC=C(CC#N)C=C1 MFHFWRBXPQDZSA-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- BMWPHWOFNJEMGM-UHFFFAOYSA-N BrC1=CC=C(CP(O)(O)O)C=C1 Chemical compound BrC1=CC=C(CP(O)(O)O)C=C1 BMWPHWOFNJEMGM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- HFXKQSZZZPGLKQ-UHFFFAOYSA-N cyclopentamine Chemical compound CNC(C)CC1CCCC1 HFXKQSZZZPGLKQ-UHFFFAOYSA-N 0.000 description 1
- 229960003263 cyclopentamine Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007337 electrophilic addition reaction Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N trans-Stilbene Natural products C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/2635—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions involving a phosphorus compound, e.g. Wittig synthesis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/24—Halogenated aromatic hydrocarbons with unsaturated side chains
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/40—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by doubly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
- C07C49/835—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups having unsaturation outside an aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The present invention provides a kind of alpha-hydroxy ketones and its preparation method and application containing talan, the R in the alpha-hydroxy ketones0And R1It is respectively selected from halogen atom, R, OR, SR, SOR and SO2R, R2Selected from hydrogen, CN and COOR, R3And R4It is respectively selected from alkyl, aryl and alkoxy, R is selected from C1‑C24Straight chained alkyl, C1‑C24Branched alkyl and-C6‑C24Aryl, integer of the m in 0-4, integer of the n in 0-5, the position of substitution of alpha-alcohol ketone on phenyl ring are selected from contraposition or meta position；Alpha-hydroxy ketones of the invention are by being introduced into talan conjugated system in alpha-alcohol ketone structure, advantage is that one side molecule has good comprehensive performance, talan group makes the absorption spectrum of molecule that red shift occur, and research finds to introduce the photodegradation that electron-withdrawing group is more advantageous to alpha-alcohol ketone in conjugated structure.
Description
Technical field
The invention belongs to new material organic chemicals technical fields, and in particular to a kind of alpha-alcohol ketone containing talan
Class compound and its preparation method and application.
Background technique
Photoepolymerizationinitiater initiater class compound is a kind of important Fine Organic Chemical product material, they can be under light excitation
It decomposes and generates reactive species to cause the polymerization of corresponding monomer.Free radical type initiator and sun can be divided on the whole
Ionic initiator, these compounds generate free radical or cation activity object under the radiation parameter of ultraviolet light or visible light
Kind, it is to induce the unsaturated system containing alkene or epoxy etc. to carry out the key species of efficient photopolymerization reaction, therefore be important spoke
Penetrate one of curing formula component.
In the numerous photoinitiator products for having obtained business application, alpha-alcohol ketone photoinitiator occupies outstanding
Status, mainstream product, such as Irgacure 1173,184 (molecular structure is as follows), these molecules are in black light area
There are good absorbing properties in domain, and photodegradation speed is a kind of freedom being widely used in fields such as coating, ink quickly
Fundamental mode photoinitiator is still the very big photoinitiator of dosage up to now, especially require it is colourless, yellowing-resistant
Curing field purposes is very extensive, the molecular structure of above-mentioned alpha-alcohol ketone photoinitiator are as follows:
On the other hand, for photocuring light source usually using mercury lamp, mercuryvapour does not meet world's energy conservation and environmental protection industry development
Strategic new trend, thus in recent years LED (i.e. Light-Emitting Diode) light source obtain increasingly extensive attention and
Quickly development, and the application of LED light curing technology considerably reduces energy consumption and ozone generates, industry sustainable growth is dynamic
Power is powerful.LED system is solidified, it is also desirable to both be directed to LED longwave transmissions wavelength (365-420 nanometers, especially 395-405
The LED light source of nanometer is most mature, and industrialization cost is minimum) there is the photoinitiator of sensitive absorption.Therefore, it designs, research and develop, industry
Change novel photoinitiator compound, is the key technique challenge that current this field faces.
But the alpha-alcohol ketone photoinitiator of a phenyl ring, maximum absorption wave strong point are only had as shown in above formula
In the region UVA, the wavelength of LED light source transmitting cannot be absorbed.It challenges in view of the above technology, invention is a kind of quick to LED light source
Feel and the radical photoinitiator with efficiency light capacity of decomposition is very important.In addition, such initiator synthesis
Step should have many advantages, such as that easy, cost is relatively low and synthesis process is environmentally friendly, the three wastes are few.Such photoinitiator can and freely
Base solidified resin is effectively compatible and compounds to form storage stable light-curable ink or coating, prints to the coating of woodenware green, environmental protection
The fields such as brush, inkjet printing, 3D printing and energy-saving material possess far-reaching influence.
Summary of the invention
Aiming at the shortcomings in the prior art, primary and foremost purpose of the invention is to provide a kind of alpha-alcohol ketone containing talan
Class compound.
A second object of the present invention is to provide a kind of preparation methods of alpha-hydroxy ketones containing talan.
Third object of the present invention is to provide the purposes of the above-mentioned alpha-hydroxy ketones containing talan.
In order to achieve the above objectives, solution of the invention is:
A kind of alpha-hydroxy ketones containing talan, general formula are as follows:
Wherein, R0And R1It is respectively selected from halogen atom, R, OR, SR, SOR and SO2One or more of R.
R2Selected from one or more of hydrogen, CN and COOR.
R3And R4It is respectively selected from one or more of alkyl, aryl and alkoxy.
R is selected from C1-C24Straight chained alkyl, C1-C24Branched alkyl and-C6-C24One or more of aryl.
Specifically, hydrogen atom can be replaced to form fluorocarbon chain structure with fluorine atom in R structure；It can also contain in R structure
1-6 discrete S, O, N element not only include carbochain in i.e. 2 R structures, can also in carbochain introducing hetero-atoms, thus
Such as C-C-O-C-C, C-C-S-C-C etc. are formed, i.e., is no longer that only pure carbochain can contain heteroatomic carbochain as substituent group
It can be used as substituent group.2 R can form the ring system structure of a 3-6 member when existing simultaneously, such as ring butylamine base, cyclopentamine base,
Cyclohexylamino etc..
Integer of the m in 0-4, integer of the n in 0-5, the position of substitution of alpha-alcohol ketone on phenyl ring are selected from contraposition
Or meta position.
A kind of preparation method of the above-mentioned alpha-hydroxy ketones containing talan comprising following steps:
(1)、R0The methyl bromobenzene that substituted benzaldehyde and the X with electron-withdrawing group replace is anti-under alkali (Base) effect
It answers, TLC is monitored after reaction, obtains R using methanol or ethyl alcohol recrystallization through washing, suction filtration and drying0Substituted diphenylamine
Ethylene is conjugated product (I)-a (trans stilbene structure):
(2)、R0Substituted diphenylamine ethylene is conjugated product (I)-a and prepares lithium salts or benefit at -78 DEG C in lithium alkylide (LiR)
Grignard reagent is prepared under room temperature or slightly heating state with magnesium metal, reacts (the reaction process with Weinreb amide one-step method
Basic anhydrous and oxygen-free is needed to operate, the gas of oxygen free operation is selected from inert gas, high-purity argon gas or nitrogen), obtain first
Intermediate (I)-b containing talan:
(3), the first intermediate (I)-b containing talan is reacted (wherein, carbon with the trimethylsilyl ethers of cyano-containing
Electrophilic addition to cyano occurs for anion), obtain second intermediate (I)-c containing talan:
(4), reaction is hydrolyzed in second intermediate (I)-c containing talan under acid catalysis, obtains containing hexichol
α-hydroxy ketone compounds of ethylene:
Further, R0And R1It is respectively selected from halogen atom, R, OR, SR, SOR and SO2One or more of R.
R2Selected from one or more of hydrogen, CN and COOR.
R3And R4It is respectively selected from one or more of alkyl, aryl and alkoxy.
R is selected from C1-C24Straight chained alkyl, C1-C24Branched alkyl and-C6-C24One or more of aryl.
Integer of the m in 0-4, integer of the n in 0-5, the position of substitution of alpha-alcohol ketone on phenyl ring are selected from contraposition
Or meta position.
Further, in step (1), alkali is selected from one or more of sodium methoxide, sodium ethoxide, potassium tert-butoxide and sodium hydride.
It in addition, common inorganic base also can be used, but can include cis-stilbene in substituted diphenylamine ethylene conjugation product (I)-a
Structure.
Further, in step (1), R0Substituted benzaldehyde, the methyl bromobenzene of X substitution and the molar ratio of alkali is 1:1:
(1.0-1.2)。
Further, in step (1), the temperature of reaction is 0-25 DEG C, and the time of reaction is 1-6h.
Further, in step (1), X is selected from cyano (CN), phosphite ester (PO (OR)2) and carboxylate (COOR) in
More than one.
Further, in step (2), lithium alkylide is n-BuLi.The addition of lithium alkylide or magnesium metal is also required to anhydrous nothing
The operation of oxygen, to improve conversion ratio and purity.
Further, in step (4), acid is selected from one or more of hydrochloric acid or aqueous hydrochloric acid solution, and the temperature of reaction is 25-
60 DEG C, the time of reaction is 1-10h.
Specifically, in step (2), substituted diphenylamine ethylene is conjugated product (I)-a (1 equivalent substituted phenyl-bromide) and lithium alkylide low
Prepare corresponding carbanion under temperature is lower or magnesium metal heats up at 25 DEG C (1-1.2 equivalents) or slightly, be not required to it is to be separated, directly
Row is tapped into react in next step.
Specifically, in step (3), the trimethylsilyl ethers with cyano is dissolved in the organic solvent (preferably four of anhydrous and oxygen-free
Hydrogen furans) in, it is injected into the above-mentioned reaction system of equivalent in low temperature or at room temperature, after being stirred to react 1-10h, TLC prison
Surveying reaction terminates, and does not need to be separated, directly progress next step reaction.
Further, in step (4), acid is selected from one or more of hydrochloric acid or aqueous hydrochloric acid solution, and the temperature of reaction is 25-
60 DEG C, the time of reaction is 1-10h.
Specifically, in step (4), second intermediate (I)-c containing talan, which can suitably be concentrated, distills part
Tetrahydrofuran, can also be directly added into the hydrochloric acid of 1-5 equivalent, stirred at 25 DEG C or 25-60 DEG C at stir 1-10h after, extraction,
Anhydrous sodium sulfate is dry, silica gel column chromatography or recrystallization.
A kind of purposes of above-mentioned alpha-hydroxy ketones for containing talan as radiation curing photoinitiator.
Specifically, the purposes as the radical photopolymerization system initiator containing unsaturated double-bond.
In fact, realizing that its light is split by introducing alpha-alcohol ketone group in the substituted-phenyl of talan conjugated structure
The function of solution type radical photopolymerization initiator and sensitizer, the introducing of especially talan group make it in commercialization LED
The lower photocuring for realizing double bond of excitation, has wide practical use in ultraviolet-visible photocuring field.
Further, the light source of radiation curing photoinitiator is selected from one or more of ultraviolet light and visible light.
Further, the light source of radiation curing photoinitiator be selected from can emitting ultraviolet light, the mercury lamp of visible light, LED
One or more of light source, LDI light source.
Further, radiation curing photoinitiator includes the Alpha-hydroxy ketone that 0.01-30 parts by weight contain talan
Compound and 100 parts by weight contain ethylene linkage (C=C) unsaturated compound.
Further, radiation curing photoinitiator includes the Alpha-hydroxy ketone that 0.5-10 parts by weight contain talan
It closes object and 100 parts by weight contains ethylene linkage (C=C) unsaturated compound.
In fact, radiation curing photoinitiator is in addition to including alpha-hydroxy ketones containing talan and containing alkene
Except key (C=C) unsaturated compound, can also containing according to actual needs add inorganic filler, organic filler,
Any components such as toner, other additives and solvent.
Wherein, colorant is selected from pigments or dyes.
Other additives include ultraviolet absorbing agent, light stabilizer, fire retardant, levelling agent or defoaming agent.
Further, unsaturated compound containing ethylene linkage refer to compound that ethylene linkage is crosslinked by Raolical polymerizable or
Mixture.
Further, unsaturated compound containing ethylene linkage be selected from monomer, oligomer or prepolymer or three mixture or
Copolymer or the water-borne dispersions of three.
The monomer such as polymerisable monomer containing ethylene linkage of suitable free radical polymerization, including but not limited to (methyl) acrylic acid
Ester, methacrylaldehyde, alkene, conjugated diolefin, styrene, maleic anhydride, fumaric acid anhydride, vinyl acetate, vinyl pyrrolidone,
Vinyl imidazole, (methyl) acrylic acid, (methyl) acrylic acid derivative such as (methyl) acrylamide, vinyl halide and Asia
Vinyl halide etc..
Suitable prepolymer containing ethylene linkage and oligomer include but is not limited to (methyl) propylene of (methyl) acryloyl functional group
Acid copolymer, polyurethane formic acid esters (methyl) acrylate, polyester (methyl) acrylate, unsaturated polyester (UP), polyethers (methyl)
The water solubility of acrylate, siloxanes (methyl) acrylate, epoxy resin (methyl) acrylate etc. and above-mentioned substance or
The analog of water dispersible.
It is above-mentioned either to contain alkene monomer or oligomer, prepolymer or copolymer, to this profession working technical staff
Speech, be all it is well known, be not particularly limited.
The exemplary compounds for meeting logical formula (I) structure are listed below:
By adopting the above scheme, the beneficial effects of the present invention are:
Alpha-hydroxy ketones containing talan of the invention are compared with existing initiator, by hexichol second
Alkene conjugated system is introduced into alpha-alcohol ketone structure, and advantage is that one side molecule has good comprehensive performance, talan
Group makes the absorption spectrum of molecule that red shift occur, and research finds that electron-withdrawing group is introduced in conjugated structure is more advantageous to alpha-alcohol ketone
Photodegradation；In addition, these molecular structure synthetic methods are simple, step is few, and the three wastes are low, and purification is convenient；Its absorption spectrum and LED
The emission spectrum of this kind of cheap light source has preferable overlapping, consistent with the developing direction of UV curing technology.
Detailed description of the invention
Fig. 1 is the general structure of the alpha-hydroxy ketones of the invention containing talan.
Specific embodiment
As shown in Figure 1, the present invention provides a kind of alpha-hydroxy ketones containing talan, and preparation method thereof
And application.
The present invention is further illustrated with reference to embodiments.
Embodiment 1: the preparation method of the alpha-hydroxy ketones (1) containing talan of the present embodiment includes as follows
Step:
(a) in dry there-necked flask, under nitrogen protection, by benzaldehyde (10mmol) and 4- bromobenzyl diethyl phosphite
(10mmol) is added in the dry tetrahydrofuran (THF) of 50mL, is placed under ice bath and is cooled to 0-5 DEG C, by potassium tert-butoxide
(10mmol) is added portionwise, and system color becomes glassy yellow, and 30min is stirred at room temperature after adding, and TLC monitors raw material and disappears, subtracts
THF is concentrated in pressure, and 100mL deionized water is added in system, filters the precipitating of precipitation, is recrystallized after dry with dehydrated alcohol, product
For yellowish solid, yield 90.3%.HR-MS(C14H11Br): m/e:258.0044；Experimental result: 259.0120 (M+H+)。
(b) it in dry there-necked flask, under nitrogen protection, is added 4- bromine talan (5mmol), it is anhydrous to be dissolved in 30mL
In THF, -78 DEG C are cooled to, with the n-BuLi hexane solution of syringe injection equivalent, low temperature 30min, TLC
Raw material are monitored to disappear；
(c) equivalent 2- methyl -2- (trimethylsiloxy group) propionitrile (2-methyl-2- (trimethylsilyloxy)
Propanenitrile it) is dissolved in the anhydrous THF of 20mL, is added dropwise in above-mentioned (b) system with syringe, 1h is added dropwise to complete
Afterwards, it is warming up to and 2h is stirred at room temperature, TLC monitoring reaction terminates, directly progress next step reaction；
(d) it is slowly added to two equivalent of 2mol/L HCl solution (10mmol) in the above system, stirring at normal temperature 6h uses dichloro
Methane is extracted twice, and sodium bicarbonate aqueous solution washing, after saturated salt solution and deionized water washs respectively, anhydrous sodium sulfate is done
Dry, product obtains yellowish product with silica gel column chromatography (ethyl acetate: cyclohexane volume ratio 1:2), three step gross production rates, and 65%.
HR-MS(C18H18O2): m/e:266.1307；Experimental result: 267.1384 (M+H+)。
Embodiment 2: alpha-hydroxy ketones (3), (5), (7), (9), (11), (13) and (15) preparation process:
The preparation method of these initiators is similar with initiator alpha-hydroxy ketones (1), and mainly raw material are different,
First is that benzaldehyde is replaced with fluorine-substituted benzaldehyde, second is that replacing 4- bromobenzyl phosphorous acid two with 3- bromobenzyl diethyl phosphite
Ethyl ester, to prepare the alpha-alcohol ketone photoinitiator with electrophilic fluorine atom and meta position substitution.
(3), yield 64%, light yellow solid.HR-MS(C18H18O2): m/e:266.1307；Experimental result: 267.1385
(M+H+)。
(5), yield 62%, light yellow solid.HR-MS(C18H17FO2): m/e:284.1213；Experimental result: 285.1290
(M+H+)。
(7), yield 61%, light yellow solid.HR-MS(C18H17FO2): m/e:284.1213；Experimental result: 285.1291
(M+H+)。
(9), yield 57%, light yellow solid.HR-MS(C18H15F3O2): m/e:320.1024；Experimental result:
321.1101 (M+H+)。
(11), yield 57%, light yellow solid.HR-MS(C18H15F3O2): m/e:320.1024；Experimental result:
321.1102 (M+H+)。
(13), yield 67%, light yellow solid.HR-MS(C18H13F5O2): m/e:356.0836；Experimental result:
357.0914 (M+H+)。
(15), yield 68%, light yellow solid.HR-MS(C18H13F5O2): m/e:356.0836；Experimental result:
357.0913 (M+H+)。
Embodiment 3: the preparation of alpha-hydroxy ketones (2), (4), (6), (8), (10), (12), (14) and (16)
Journey:
The preparation of these initiators is with the initiator of above-mentioned odd numbered sequences the difference is that the structure of alpha-alcohol ketone, these points
The structure of son is therefore 184 derivative such as the step of embodiment 1 in (c), utilizes 1- (trimethyl silyl) hexamethylene
(1- (trimethylsilyloxy) cyclohexanecarbonitrile) replaces 2- methyl -2- (trimethylsiloxy group) propionitrile
(2-methyl-2- (trimethylsilyloxy) propanenitrile), to prepare with the similar of cyclohexane group
Product.
(2), yield 60%, light yellow solid.HR-MS(C21H22O2): m/e:306.1620；Experimental result: 307.1695
(M+H+)。
(4), yield 59%, light yellow solid.HR-MS(C21H22O2): m/e:306.1620；Experimental result: 307.1696
(M+H+)。
(6), yield 58%, light yellow solid.HR-MS(C21H21FO2): m/e:324.1526；Experimental result: 325.1604
(M+H+)。
(8), yield 54%, light yellow solid.HR-MS(C21H21FO2): m/e:324.1526；Experimental result: 325.1603
(M+H+)。
(10), yield 54%, light yellow solid.HR-MS(C21H19F3O2): m/e:360.1337；Experimental result:
361.1414 (M+H+)。
(12), yield 52%, light yellow solid.HR-MS(C21H19F3O2): m/e:360.1337；Experimental result:
361.1414 (M+H+)。
(14), yield 54%, light yellow solid.HR-MS(C21H17F5O2): m/e:396.1149；Experimental result:
397.1226 (M+H+)。
(16), yield 50%, light yellow solid.HR-MS(C21H17F5O2): m/e:396.1149；Experimental result:
397.1225 (M+H+)。
Embodiment 4: the preparation process of the alpha-hydroxy ketones (21) containing talan of the present embodiment:
(a) in dry there-necked flask, under nitrogen protection, by 4- fluorobenzaldehyde (10mmol) and 4- bromobenzylcyanide
(10mmol) is added in the dry tetrahydrofuran (THF) of 50mL, is placed under ice bath and is cooled to 0-5 DEG C, by potassium tert-butoxide
(10mmol) is added portionwise, and system color becomes glassy yellow, and 30min is stirred at room temperature after adding, and TLC monitors raw material and disappears, subtracts
TFH is concentrated in pressure, and 100mL deionized water is added in system, filters the precipitating of precipitation, is recrystallized after dry with dehydrated alcohol, product
For yellowish solid, yield 95.3%.HR-MS(C14H11Br): m/e:258.0044；Experimental result: 259.0120 (M+H+)。
(b) it in dry there-necked flask, under nitrogen protection, is added step (a) product (5mmol), it is anhydrous to be dissolved in 30mL
In THF, -78 DEG C are cooled to, with the n-BuLi hexane solution of syringe injection equivalent, low temperature 30min, TLC
Raw material are monitored to disappear；
(c) equivalent 2- methyl -2- (trimethylsiloxy group) propionitrile (2-methyl-2- (trimethylsilyloxy)
Propanenitrile it) is dissolved in the anhydrous THF of 20mL, is added dropwise in above-mentioned (b) system with syringe, 1h is added dropwise to complete
Afterwards, it is warming up to and 2h is stirred at room temperature, TLC monitoring reaction terminates, directly progress next step reaction；
(d) it is slowly added to two equivalent of 2mol/L HCl solution (10mmol) in the above system, stirring at normal temperature 6h uses dichloro
Methane is extracted twice, and sodium bicarbonate aqueous solution washing, after saturated salt solution and deionized water washs respectively, anhydrous sodium sulfate is done
Dry, product obtains yellowish product with silica gel column chromatography (ethyl acetate: cyclohexane volume ratio 1:2), three step gross production rates, and 70%.
HR-MS(C19H16FNO2): m/e:309.1165；Experimental result: 310.1232 (M+H+)。
Embodiment 5: alpha-hydroxy ketones (17)-alpha-hydroxy ketones (20), alpha-hydroxy ketones
(22) preparation process of-alpha-hydroxy ketones (32):
The preparation of these photoinitiators with cyano (CN), step (a) is similar to alpha-hydroxy ketones (21),
If it is metacompaund, then raw material utilize 3- bromobenzylcyanide, remaining adjusts reactant according to molecular structure, can prepare
All relevant molecular structures.C22H20FNO2: m/e:349.1478 (100.0%), 350.1512 (23.8%), 351.1545
(2.7%).
(17), yield 54%, light yellow solid.HR-MS(C19H17NO2): m/e:291.1259；Experimental result:
292.1346 (M+H+)。
(18), yield 50%, light yellow solid.HR-MS(C22H21NO2): m/e:331.1572；Experimental result:
332.1659 (M+H+)。
(19), yield 54%, light yellow solid.HR-MS(C19H17NO2): m/e:291.1259；Experimental result:
292.1347 (M+H+)。
(20), yield 50%, light yellow solid.HR-MS(C22H21NO2): m/e:331.1572；Experimental result:
332.1658 (M+H+)。
(22), yield 54%, light yellow solid.HR-MS(C22H20FNO2): m/e:349.1478；Experimental result:
350.1553 (M+H+)。
(23), yield 50%, light yellow solid.HR-MS(C19H16FNO2): m/e:309.1165；Experimental result:
310.1232 (M+H+)。
(24), yield 54%, light yellow solid.HR-MS(C22H20FNO2): m/e:349.1478；Experimental result:
350.1554 (M+H+)。
(25), yield 50%, light yellow solid.HR-MS(C19H14F3NO2): m/e:345.0977；Experimental result:
346.1055 (M+H+)。
(26), yield 54%, light yellow solid.HR-MS(C22H18F3NO2): m/e:385.1290；Experimental result:
386.1367 (M+H+)。
(27), yield 50%, light yellow solid.HR-MS(C19H14F3NO2): m/e:345.0977；Experimental result:
346.1053 (M+H+)。
(28), yield 54%, light yellow solid.HR-MS(C22H18F3NO2): m/e:385.1290；Experimental result:
386.1366 (M+H+)。
(29), yield 50%, light yellow solid.HR-MS(C19H12F5NO2): m/e:381.0788；Experimental result:
382.0875 (M+H+)。
(30), yield 54%, light yellow solid.HR-MS(C22H16F5NO2): m/e:421.1101；Experimental result:
422.1278 (M+H+)。
(31), yield 50%, light yellow solid.HR-MS(C19H12F5NO2): m/e:381.0788；Experimental result:
382.0876 (M+H+)。
(32), yield 54%, light yellow solid.HR-MS(C22H16F5NO2): m/e:421.1101；Experimental result:
422.1277 (M+H+)。
<experiment>
It is tested as follows respectively with the product of above-described embodiment.
<experiment 1>
Film polymer reaction:
Photocuring test sample: epoxy acrylate: 28 parts is prepared according to following weight percent；Polyester acrylic
Ester: 32 parts；Hexanediyl ester: 6 parts；Pentaerythritol triacrylate: 24 parts；Titanium dioxide dyestuff: 16 parts；It chooses
Embodiment photoinitiator: 4 parts.
It is coated on white ABS substrate after taking part said mixture to be fully ground uniformly, forms about 20 μm under air
Figure layer.It is irradiated at sample 2cm with 365nm and 385nm LED solidity test machine (and light is with Sheng, Guangzhou), transmits belt speed
Degree is 20m/min.Finger pressure scrapes hair and determines that situation is fully cured in coating.F atom and CN base are had in above-described embodiment compound
Photoinitiator cause film layer be fully cured, especially metacompaund (the embodiment molecule of serial number even number) is shown more excellent
Cause performance.
<experiment 2>
Thick film polymerization reaction:
Formula is the same as experiment 1.
It is coated on after taking part said mixture to be fully ground on white ABS substrate, forms about 200 μm of figure under air
Layer.It is irradiated at sample 2cm with 365nm and 385nm LED solidity test machine (and light is with Sheng, Guangzhou), conveyor belt speed is
10m/min.Pressure scrapes hair and determines that situation is fully cured in coating.Serial number even number and meta position substitution in above-described embodiment compound
, the photoinitiator with strong electron-withdrawing group group causes film layer and is fully cured, it is shown that good Photoinitiation Property.
The above-mentioned description to embodiment is that this hair can be understood and used for the ease of those skilled in the art
It is bright.Those skilled in the art obviously readily can make various modifications to these embodiments, and described herein one
As principle be applied in other embodiments, without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments.
Those skilled in the art's principle according to the present invention, not departing from improvement that scope of the invention is made and modification all should be at this
Within the protection scope of invention.
Claims (10)
1. a kind of alpha-hydroxy ketones containing talan, it is characterised in that: its general formula is as follows:
Wherein, R0And R1It is respectively selected from halogen atom, R, OR, SR, SOR and SO2One or more of R；
R2Selected from one or more of hydrogen, CN and COOR；
R3And R4It is respectively selected from one or more of alkyl, aryl and alkoxy；
R is selected from C1-C24Straight chained alkyl, C1-C24Branched alkyl and-C6-C24One or more of aryl；
Integer of the m in 0-4, integer of the n in 0-5, the position of substitution of alpha-alcohol ketone on phenyl ring be selected from contraposition or
Position.
2. a kind of preparation method of the alpha-hydroxy ketones according to claim 1 containing talan, feature
Be: it includes the following steps:
(1)、R0The methyl bromobenzene that substituted benzaldehyde and X replace reacts under alkali effect, obtains R0Substituted diphenylamine ethylene conjugation produces
Object (I)-a:
(2), the R0Substituted diphenylamine ethylene conjugation product (I)-a is reacted under the conditions of lithium alkylide or magnesium metal, obtains first
Intermediate (I)-b containing talan:
(3), the described first intermediate (I)-b containing talan is reacted with the trimethylsilyl ethers of cyano-containing, obtains
Two intermediate (I)-c containing talan:
(4), reaction is hydrolyzed in described second intermediate (I)-c containing talan under acid catalysis, obtains containing hexichol
The alpha-hydroxy ketones of ethylene:
3. preparation method according to claim 2, it is characterised in that: R0And R1Be respectively selected from halogen atom, R, OR, SR,
SOR and SO2One or more of R；
R2Selected from one or more of hydrogen, CN and COOR；
R3And R4It is respectively selected from one or more of alkyl, aryl and alkoxy；
R is selected from C1-C24Straight chained alkyl, C1-C24Branched alkyl and-C6-C24One or more of aryl；
Integer of the m in 0-4, integer of the n in 0-5, the position of substitution of alpha-alcohol ketone on phenyl ring be selected from contraposition or
Position.
4. preparation method according to claim 2, it is characterised in that: in step (1), the alkali is selected from sodium methoxide, ethyl alcohol
One or more of sodium, potassium tert-butoxide and sodium hydride；And/or
In step (1), R0Substituted benzaldehyde, the methyl bromobenzene of X substitution and the molar ratio of alkali is 1:1:(1.0-1.2)；And/or
In step (1), the temperature of reaction is 0-25 DEG C, and the time of reaction is 1-6h；And/or
In step (1), X is selected from one or more of cyano, phosphite ester and carboxylate.
5. preparation method according to claim 2, it is characterised in that: in step (2), the lithium alkylide is n-BuLi.
6. preparation method according to claim 2, it is characterised in that: in step (4), the acid is hydrochloric acid, the reaction
Temperature be 25-60 DEG C, time of the reaction is 1-10h.
7. one kind contains the alpha-hydroxy ketones of talan as the photosensitive initiation of radiation curing as described in claim 1
The purposes of agent.
8. purposes according to claim 7, it is characterised in that: the light source of the radiation curing photoinitiator is selected from ultraviolet
One or more of light and visible light.
9. purposes according to claim 8, it is characterised in that: the radiation curing photoinitiator includes 0.01-30 weight
Measure alpha-hydroxy ketones of the part containing talan and 100 parts by weight unsaturated compounds containing ethylene linkage；
Preferably, the radiation curing photoinitiator includes the Alpha-hydroxy ketone chemical combination that 0.5-10 parts by weight contain talan
Object and 100 parts by weight unsaturated compounds containing ethylene linkage.
10. purposes according to claim 9, it is characterised in that: the unsaturated compound containing ethylene linkage refers to that ethylene linkage passes through
The compound or mixture that Raolical polymerizable is crosslinked；
Preferably, the unsaturated compound containing ethylene linkage is selected from the mixture or total of monomer, oligomer or prepolymer or three
Polymers or the water-borne dispersions of three.
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