CN109983037A - 光引发剂 - Google Patents
光引发剂 Download PDFInfo
- Publication number
- CN109983037A CN109983037A CN201780070745.7A CN201780070745A CN109983037A CN 109983037 A CN109983037 A CN 109983037A CN 201780070745 A CN201780070745 A CN 201780070745A CN 109983037 A CN109983037 A CN 109983037A
- Authority
- CN
- China
- Prior art keywords
- alkylidene
- linker
- photoinitiator according
- alkyl
- photoinitiator
- 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.)
- Granted
Links
- 125000005647 linker group Chemical group 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 13
- -1 sulphonic acid ester Chemical class 0.000 claims description 13
- 125000000623 heterocyclic group Chemical group 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- 150000003456 sulfonamides Chemical class 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229930006711 bornane-2,3-dione Natural products 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 13
- 125000004429 atom Chemical group 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 125000001118 alkylidene group Chemical group 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- LSEVJUQNMUCFKW-UHFFFAOYSA-N 2,2,5-trimethyl-1,3-dioxane Chemical compound CC1COC(C)(C)OC1 LSEVJUQNMUCFKW-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- MXMGFUNWQUEXIL-UHFFFAOYSA-N (7,7-dimethyl-2,3-dioxo-4-bicyclo[2.2.1]heptanyl)methanesulfonyl chloride Chemical compound C1CC2(CS(Cl)(=O)=O)C(=O)C(=O)C1C2(C)C MXMGFUNWQUEXIL-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 125000004450 alkenylene group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VQHWAOZYKVGMQX-UHFFFAOYSA-N (7,7-dimethyl-2,3-dioxo-4-bicyclo[2.2.1]heptanyl)methanesulfonic acid Chemical compound C1CC2(CS(O)(=O)=O)C(=O)C(=O)C1C2(C)C VQHWAOZYKVGMQX-UHFFFAOYSA-N 0.000 description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000006418 Brown reaction Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 150000002012 dioxanes Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- HGTTYFKDCTYIIZ-UHFFFAOYSA-N 2,2,5-trimethyl-1,3-dioxan-5-amine Chemical compound CC1(N)COC(C)(C)OC1 HGTTYFKDCTYIIZ-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- YLYPIBBGWLKELC-RMKNXTFCSA-N 2-[2-[(e)-2-[4-(dimethylamino)phenyl]ethenyl]-6-methylpyran-4-ylidene]propanedinitrile Chemical compound C1=CC(N(C)C)=CC=C1\C=C\C1=CC(=C(C#N)C#N)C=C(C)O1 YLYPIBBGWLKELC-RMKNXTFCSA-N 0.000 description 1
- WEQPBCSPRXFQQS-UHFFFAOYSA-N 4,5-dihydro-1,2-oxazole Chemical compound C1CC=NO1 WEQPBCSPRXFQQS-UHFFFAOYSA-N 0.000 description 1
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical compound C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 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 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910004879 Na2S2O5 Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241000534944 Thia Species 0.000 description 1
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical compound C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- HSDAJNMJOMSNEV-UHFFFAOYSA-N benzyl chloroformate Chemical compound ClC(=O)OCC1=CC=CC=C1 HSDAJNMJOMSNEV-UHFFFAOYSA-N 0.000 description 1
- 125000002362 bornane-2,3-dione group Chemical group 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 235000013325 dietary fiber Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- WGBBUURBHXLGFM-UHFFFAOYSA-N hexan-2-amine Chemical compound CCCCC(C)N WGBBUURBHXLGFM-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000005958 tetrahydrothienyl group Chemical group 0.000 description 1
- 125000001984 thiazolidinyl group Chemical group 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000004568 thiomorpholinyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/28—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
-
- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/82—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
- C07C311/10—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/517—Saturated compounds containing a keto group being part of a ring containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
提供了一种光引发剂，所述光引发剂包含樟脑醌光引发剂部分。
Description
背景技术
固化有机材料可以例如通过用紫外线或可见光照射来完成。实现适当的照射固化需要引发负责固化过程的化学反应的有效方法。光引发剂可用于通过在例如用UV光照射后产生自由基种类来进行有机材料的固化。
对于医疗领域中使用的材料，患者安全考虑因素限制了可以从给定材料中浸出(＝释放)的物质的量和类型。
需要其中可以减少或甚至消除小分子的浸出的光引发剂。附加的重要考虑因素包括待固化材料的固化时间、固化方法和光引发剂与所述材料的其他组分的相容性。
发明内容
因此提供了一种光引发剂，所述光引发剂包含樟脑醌光引发剂部分，即，具有式(I)的光引发剂
其中R3、R4、R5和R6选自H或C1-C6烷基；
其中R1、R2、R7或R8之一具有式(Ia)的结构：
其中：
Z1是包含一个或多个选自以下各项的连接基单元的连接基：单键、-O-、-S-、任选取代的-(C1-C12亚烷基)-、任选取代的-(C1-C12亚烯基)-、-SO2-、-CO-、-NR’-、-Si(R’)2-、任选取代的杂环基和任选取代的芳基，其中R'是H或C1-C6烷基；
其中连接基-Z1-，任选与-Z2-组合，包含至少一个磺酰胺、磺酸酯、羧酰胺或羧酸酯部分；
Z2是三价氮原子或Z2是C(R”)，其中R”是H或C1-C6烷基；前提是-当Z2是氮原子时-与Z2相邻的Z1中的连接基单元是-SO2-或-CO-；
X1和X2中的每一个独立地选自单键，或包含一个或多个选自以下各项的连接基单元的连接基：-O-、-S-、任选取代的-(C1-C12亚烷基)-、任选取代的-(C1-C12亚烯基)-、-SO2-、-CO-、-NR’-、任选取代的杂环基和任选取代的芳基，其中R'是H或C1-C6烷基；
并且其中X1和X2可以彼此连接或与Z1连接以形成一个或多个环结构；
并且其中剩余的R1、R2、R7和R8选自H或C1-C6烷基。
在以下说明和从属权利要求中提出了本发明的其他方面。
具体实施方式
定义
在下文中，当将分子的一部分描述为“任选地取代的”时，这表示所述部分可以被选自以下的一个或多个取代基取代：C1-C6直链、支链或环状烷基、芳基、-OH、-CN、-NO2、卤素、胺、酰胺、醇、醚、硫醚、砜及其衍生物、亚砜及其衍生物、碳酸酯、异氰酸酯、硝酸盐和丙烯酸酯。优选的取代基是C1-C6直链烷基、-OH、卤素、胺和醇。
术语“杂环基”是指非芳香族单环或多环的环体系，其包含约3至约10个环原子、优选约5至约10个环原子，其中环体系中的一个或多个原子单独或组合地是除碳之外的元素，例如氮、氧或硫。优选的杂环基含有约5至约6个环原子。在杂环基根名称之前的前缀氮杂、氧杂或硫杂是指至少氮、氧或硫原子分别作为环原子存在。杂环基可以任选地如以上所述那样取代。杂环基的氮或硫原子可以任选地被氧化成相应的N-氧化物、S-氧化物或S,S-二氧化物。合适的单环杂环基环的非限制性实例包括哌啶基、吡咯烷基、哌嗪基、吗啉基、硫代吗啉基、噻唑烷基、1,3-二氧杂环戊基、1,4-二氧杂环己基、四氢呋喃基、四氢噻吩基、以及四氢噻喃基。
术语“亚烷基”在下文中用来说明衍生自链烷的部分，其中已经移除两个H原子以形成双自由基种类。最简单的亚烷基是亚甲基-CH2-，并且其他亚烷基包括亚乙基-CH2-CH2-、亚丙基-C3H6-和亚丁基-C4H8-。术语“亚烷基”包括支链、直链和环状亚烷基，其中直链亚烷基是最优选的。为C1-C12亚烷基的亚烷基是含有1与12之间个碳原子的亚烷基。优选的亚烷基含有1与6之间个碳原子(即，C1-C6亚烷基)。
术语“亚烯基”在下文中用来说明衍生自烯的部分，其中已经移除两个H原子以形成双自由基种类。实例包括亚乙烯基-CH2＝CH2-和亚丙烯基-C3H4-部分。术语“亚烯基”包括支链、直链和环状亚烯基，其中直链亚烯基是最优选的。
术语“芳基”用来定义在环周围含有离域π电子体系的不饱和环体系。芳基可以包含4-12个原子，适当地6-8个原子，最适当地6个原子。“芳基”优选包含碳环，并且优选为苯基(-C6H5)。
在本发明中，术语“芳基”也用来包括芳香族杂环，即，其中环内一个或多个原子(例如1-3个原子)是N、S、P或O的环。芳香族杂环包括吡咯、呋喃、噻吩、咪唑、咪唑啉、吡唑、吡唑啉、噁唑、噁唑啉、异噁唑、异噁唑啉、噻唑、噻唑啉、异噻唑、异噻唑啉(5元环)、吡啶、吡喃、噻喃(6元环)。术语“芳基”也包括稠合环体系。
当指连接基(例如，Z、X1、X2)时，术语“芳基”用来定义衍生自芳烃的部分，其中已经移除两个H原子以形成双自由基种类(即，亚芳基)。实例包括1,2-亚苯基、1,3-亚苯基和1,4-亚苯基。
在一个方面，提供了一种光引发剂，所述光引发剂包含樟脑醌光引发剂部分。
樟脑醌部分有效地将来自可见光源的光转化为反应性自由基，所述反应性自由基可以夺取氢原子和其他不稳定原子并且因此实现交联。
自由基光引发剂部分可以分类为可裂解的(诺里什I型反应)或不可裂解的(其中诺里什II型反应是特殊情况，参见例如A.Gilbert,J.Baggott：“Essentials of MolecularPhotochemistry[分子光化学要点]”，布莱克韦尔(Blackwell)，伦敦，1991)。激发时，可裂解的光引发剂部分自发地分解成两个自由基，其中至少一个的活性足以从大部分基质中夺取氢原子。
樟脑醌是可裂解的光引发剂部分(I型)的实例。不需要向此类体系中加入电子供体(如胺)，但可以提高可裂解的光引发剂部分的总效率。
所述光引发剂具有通式(I)：
在式(I)中，R3、R4、R5和R6选自H或C1-C6烷基。适当地，R3、R4、R5和R6选自H或甲基，更优选H。
在式(I)中，R1、R2、R7或R8之一具有式(Ia)的结构：
而剩余的R1、R2、R7和R8选自H或C1-C6烷基。此外，R1和R2二者都可以是甲基。
适当地，它是R2、R7或R8，优选R7或R8，其具有式(Ia)的结构。
在式(Ia)中，Z1是包含一个或多个选自以下各项的连接基单元的连接基：单键、-O-、-S-、任选取代的-(C1-C12亚烷基)-、任选取代的-(C1-C12亚烯基)-、-SO2-、-CO-、-NR’-、-Si(R’)2-、任选取代的杂环基和任选取代的芳基，其中R'是H或C1-C6烷基。适当地，Z1中的至少一个连接基单元选自-SO2-、-O-或-CO-，优选-SO2-或-CO-。
连接基-Z1-，任选与-Z2-组合，包含至少一个磺酰胺、磺酸酯、羧酰胺或羧酸酯部分。此部分形成连接基结构本身的一部分，而不是侧链或侧接部分的一部分。
在式(Ia)中，Z2是三价氮原子或Z2是C(R”)，其中R”是H或C1-C6烷基；前提是-当Z2是氮原子时-与Z2相邻的Z1中的连接基单元是-SO2-或-CO-。
用于-Z1-Z2-的合适的结构可选自包含以下各项的组：
-SO2-N-；
-CO-N-；
-CO-O-CR”-；
-O-CO-CR”-；
-(C1-C12亚烷基)-SO2-N-；
-(C1-C12亚烷基)-CO-N-；
-(C1-C12亚烷基)-CO-O-CR”-；
-(C1-C12亚烷基)-O-CO-CR”-，
-(C1-C12亚烷基)-SO2-O-(C1-C12亚烷基)-Z2-；
-(C1-C12亚烷基)-SO2-NR’-(C1-C12亚烷基)-Z2-；
-(C1-C12亚烷基)-O-SO2-(C1-C12亚烷基)-Z2-；
-(C1-C12亚烷基)-NR’-SO2-(C1-C12亚烷基)-Z2-；
-(C1-C12亚烷基)-CO-O-(C1-C12亚烷基)-Z2-；
-(C1-C12亚烷基)-O-CO-(C1-C12亚烷基)-Z2-；
-(C1-C12亚烷基)-CO-NR’-(C1-C12亚烷基)-Z2-；或
-(C1-C12亚烷基)-NR’-CO-(C1-C12亚烷基)-Z2-；
优选选自
-SO2-N-；
-CO-N-；
-CO-O-CR”-；
-O-CO-CR”；
-(C1-C12亚烷基)-SO2-N-；
-(C1-C12亚烷基)-CO-N-；
-(C1-C12亚烷基)-CO-O-CR”-；
-(C1-C12亚烷基)-O-CO-CR”-；
-(C1-C12亚烷基)-SO2-O-(C1-C12亚烷基)-Z2-；
-(C1-C12亚烷基)-SO2-NR’-(C1-C12亚烷基)-Z2-；
-(C1-C12亚烷基)-CO-O-(C1-C12亚烷基)-Z2-；
-(C1-C12亚烷基)-CO-NR’-(C1-C12亚烷基)-Z2-；或
更优选选自
-SO2-N-；
-CO-N-；
-(C1-C12亚烷基)-SO2-N-；
-(C1-C12亚烷基)-CO-N-；
-(C1-C12亚烷基)-SO2-O-(C1-C12亚烷基)-Z2-；或
-(C1-C12亚烷基)-CO-O-(C1-C12亚烷基)-Z2-。
在一个方面，Z2是N。在另一方面，Z2是C(R”)，其中R”是H、甲基或乙基或丙基。在其他方面，Z1中的-(C1-C12亚烷基)-连接基单元是-(C1-C6亚烷基)-，例如亚丙基、亚乙基或亚甲基。
适当地，连接基Z1具有小于10000Da、适当地小于5000Da、最适当地小于1000Da的分子量。连接基Z1优选地包含不多于50个原子、优选地不多于30个原子。
在式(Ia)中，X1和X2中的每一个独立地选自单键，或包含一个或多个选自以下各项的连接基单元的连接基：-O-、-S-、任选取代的-(C1-C12亚烷基)-、任选取代的-(C1-C12亚烯基)-、-SO2-、-CO-、-NR’-、任选取代的杂环基和任选取代的芳基，其中R'是H或C1-C6烷基；并且X1和X2可以彼此连接或与Z1连接以形成一个或多个环结构。
在一个方面，X1和X2是独立的连接基，这些独立的连接基包含一个或多个选自以下各项的连接基单元：-O-、-S-、任选取代的-(C1-C12亚烷基)-、-SO2-、-CO-、以及-NR’-，其中R'是H或C1-C6烷基-；优选一个或多个选自以下各项的连接基单元：-O-、-S-和任选取代的-(C1-C12亚烷基)-。X1和X2中的-(C1-C12亚烷基)-连接基单元可以是-(C1-C6亚烷基)-，例如亚丙基、亚乙基或亚甲基。在优选的方面，X1和X2独立地是-(C1-C12亚烷基)-；优选-(C1-C6亚烷基)-，例如亚丙基、亚乙基或亚甲基。适当地，X1和X2是相同的。
在特定的方面，R1、R2、R3、R4、R5、R6、R7或R8之一选自由以下各项组成的组：
特定的光引发剂可选自包含以下各项的组：
实例
实验程序
10-樟脑磺酸.......................54.01g
二氧化硒..........................38.7g(1.5当量)
二噁烷(HPLC级)...........250mL
将固体10-樟脑磺酸悬浮在二噁烷溶剂中，并且将搅拌的混合物回流120小时(温度从回流减少至60℃过夜)。获得强亮黄色溶液和黑色固体。滤出灰色/黑色固体并且将澄清的黄色溶液蒸发为浓稠的油状残余物。将残余物溶于水(200mL)中，用40mL水+20mL 37％HCl酸化。向搅拌的略微混浊的黄色/橙色溶液中加入以下过夜：在100mL水中的30g亚硫酸氢钠(Na2S2O5/NaHSO3)。获得浑浊的红棕色悬浮液。将悬浮液温热至80℃保持1小时以将硒转化为黑色可过滤形式。滤出金属硒并且将水性滤液蒸发为油状物，所述油状物在冰箱中过夜完全固化。用甲醇(250mL)萃取亮黄色固体。滤出白色无机物并且将亮黄色滤液蒸发至干。黄色固体在NMR上示出非常好的纯度。通过以下方式除去其他无机残余物：将固体悬浮在温热的四氢呋喃(1000mL)中并且过滤。这提供了亮黄色溶液，将其蒸发至干以提供10-樟脑醌磺酸(45.8g；80％产率)。
1H NMR(400MHz,DMSO-d6)：3.01(d,J＝14.6Hz,1H),2.73(m,1H),2.72(d,J＝14.6Hz,1H),2.61(d,J＝5.3Hz,1H),2.15(m,1H),1.70(m,1H),1.51(m,1H),1.11(s,3H),0.83(s,3H)。
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樟脑醌-10-磺酰氯的合成描述于：C.S.Pande,M.Pelzig,J.D.Glass,Proc.Natl.Acad.Sci.USA[美国科学院院报]，第77卷，第2期，第895-899页，1980年2月。
修改后的程序如下进行：
·在20min内将60mL亚硫酰氯逐滴添加到100mL冷DMF(冰/水冷却的)中。
·将溶液在0℃下搅拌30min。
·在30min内将樟脑醌-10-磺酸(42g)作为固体加入到极淡黄色溶液中。
·将黄棕色反应混合物在环境温度下搅拌3h。
·将轻度混浊的黄棕色反应混合物逐滴加入到快速搅拌的冰(800g)和水(400mL)的混合物中。
·在0℃下快速滤出沉淀的砂黄色固体(相当淡黄色液体)并且允许其在环境温度下在高真空下干燥。获得砂黄色粉末产物。m＝314.1–280.5＝33.6g(74％)。
·将产物储存在冷冻器中并且在10天内进一步反应。
1H NMR(400MHz,CDCl3)：4.36(d,J＝14.7Hz,1H),3.89(d,J＝14.7Hz,1H),2.74(d,J＝5.3Hz,1H),2.70-2.63(m,1H),2.38-2.29(m,1H),2.08-2.01(m,1H),1.81-1.74(m,1H),1.24(s,3H),1.02(s,3H)。
13C NMR(100MHz,CDCl3)：198.91,198.74,77.16,62.86,59.59,57.41,44.52,25.56,22.00,20.97,18.24。
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文献参考：J.Nat.Prod.[天然产物杂志]1999,62,963–968。
2-氨基-2-甲基丙烷-1,3-二醇...............16.5849g
DMF(无水)................................104mL
在搅拌下将2-氨基-2-甲基丙烷-1,3-二醇溶解在干DMF中。在冰/水冷却下在大约20min内逐滴加入氯甲酸苄酯(23.7mL)。观察到强烈的放热并且释放出HCl气体。将无色反应混合物在氯化钙水分排除下在环境温度下搅拌过夜。向无色澄清溶液中加入2,2-二甲氧基丙烷(45mL)和对甲苯磺酸吡啶鎓(1.24g)并且在环境温度下搅拌48小时。将反应混合物缓慢加入碳酸氢钠(40g)在水/冰(800mL)中的溶液中。通过TLC(AcOEt 100％)检查产物的纯度。将水相再次用AcOEt(2x 200mL)萃取，将有机相用水再萃取以除去起始氨基二醇、干燥并且蒸发至干。将油状残余物在70℃下在真空中干燥以除去大部分苄基氯副产物。油状物在60h内在冰箱中部分结晶。加入己烷(50mL)以完成产物的固化，将无色晶体滤出并且用己烷(100mL)洗涤。通过在烧结体的周围环境中使空气通过来干燥产物。这提供了作为细晶无色针状物的所希望的产物(2,2,5-三甲基-1,3-二氧杂环己烷-5-基)氨基甲酸苄酯。产量＝16.756g(38％)。
1H NMR(400MHz,CDCl3)：7.37-7.29(m,5H),5.35(bs,1H),5.07(s,2H),3.90(d,J＝11.7Hz,2H),3.66(d,J＝11.7Hz,2H),1.43(s,3H),1.42(s,3H),1.28(s,3H)。
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来自前一步骤的(2,2,5-三甲基-1,3-二氧杂环己烷-5-基)氨基甲酸苄酯..................................................16.756g
甲酸铵......................................19.1g
甲醇(HPLC)..................................250mL
碳负载钯(10％)..............................1.75g
将固体(2,2,5-三甲基-1,3-二氧杂环己烷-5-基)氨基甲酸苄酯加入到甲醇中(大部分固体不溶解)，然后加入Pd/C。在快速搅拌下，将多部分固体甲酸铵在氮气流下在大约30min内加入反应混合物中(轻微放出气体，没有可见的放热)。允许反应在环境温度下搅拌过夜。TLC(AcOEt/己烷3:10)证实起始材料完全消失。将Pd/C滤出，用甲醇洗涤并且将无色滤液蒸发至干。获得的油状物迅速固化。将固体重新溶于水(150mL)中，用NaOH将pH调节至13并且用硫酸钠使溶液饱和。用乙酸乙酯(5x 100mL)萃取混合物。蒸发提供了作为无色液体的2,2,5-三甲基-1,3-二氧杂环己烷-5-胺。m＝7.2g(83％产率)。
1H NMR(400MHz,CDCl3)：3.74(d,J＝11.5Hz,1H),3.42(d,J＝11.5Hz,1H),1.76(bs,2H),1.44(s,3H),1.43(s,3H),1.00(s,3H)。
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来自先前反应的2,2,5-三甲基-1,3-二氧杂环己烷-5-胺...........2.08g
吡啶无水)..................................................40mL
樟脑醌-10-磺酰氯(97％，购自卡博森斯公司(Carbosynth Ltd.))...1.2897g
在20min内在冷却下将樟脑醌-10-磺酰氯固体装入2,2,5-三甲基-1,3-二氧杂环己烷-5-胺的吡啶溶液中，然后允许其在环境温度下搅拌过夜。将亮黄色反应混合物用乙酸乙酯(100mL)稀释并且用水(3x100mL)萃取。将黄色有机萃取物干燥并且蒸发以提供亮黄色玻璃状固体，其不经进一步纯化用于下一步骤。
1H NMR(400MHz,CDCl3)：5.87(s,1H),3.98(dd,J＝12.5,2.9Hz,1H),3.87-3.83(m,2H),3.74(dd,J＝12.3,1.8Hz,2H),3.26(d,J＝14.9Hz,1H),2.68(d,J＝5.1Hz,1H),2.58-2.46(m,1H),2.29-2.18(m,2H),1.75-1.68(m,1H),1.45(s,3H),1.36(s,3H),1.34(s,3H),1.14(s,3H),0.99(s,3H)。
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水/THF.....................................................25mL/25mL
甲磺酸.....................................................0.4mL
将来自前一步骤的粗材料溶解在THF/水混合物中，并且将澄清的亮黄色溶液在环境温度下搅拌，同时避光过夜。TLC(AcOEt/DCM1:5)证实接近定量转化为1种极性产物。向反应混合物中加入碳酸氢钠(5g)以中和酸。搅拌5min后，将反应混合物在水(150mL)与乙酸乙酯(150mL)之间分配。将浅黄色水相(pH 8)再次用乙酸乙酯(100mL)萃取，将有机相合并、干燥(Na2SO4)并且蒸发至干。将粘性残余物溶解在二氯甲烷中并且在二氧化硅上进行色谱分析(洗脱液：AcOEt/DCM 1:10→1:0)。收集主要的黄色带并且将其蒸发至干。m＝0.9g(经两步55％产率)。这产生了作为亮黄色玻璃状材料的所希望的产物N-(1,3-二羟基-2-甲基丙烷-2-基)-1-(7,7-二甲基-2,3-二氧代双环[2.2.1]庚-1-基)甲磺酰胺，其在静置时凝固。
熔点(在1.0℃/min下)：108℃-117℃
1H NMR(400MHz,CD3OD)：0.95(s,3H),1.18(s,3H),1.34(s,3H),1.62-1.69(m,1H),1.92-2.00(m,1H),2.25-2.34(m,1H),2.59-2.67(m,2H),3.44(d,J＝15.0Hz,1H),3.60-3.67(m,4H),3.78(d,J＝15.0Hz,1H)。
13C NMR(100MHz,CD3OD)：18.17,19.60,21.30,22.88,26.90,44.97,53.00,58.78,60.48,62.28,66.50,66.57,202.27,202.66。
(在甲醇中在461nm处)
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在氮气下将10-樟脑醌磺酸(30g)溶解在无水DMF(100mL)中，并且将溶液用冰/水冷却。在冰冷却和避光的情况下，在1小时内加入亚硫酰氯(100mL)。将反应混合物在环境温度下搅拌16小时并且然后在30分钟内小心地逐滴加入到冰/水(2000mL)中。用二氯甲烷(2*300mL)萃取冰冷的悬浮液，将有机相干燥并且过滤以除去任何固体。获得了亮黄色澄清溶液。在30分钟内将此粗10-樟脑醌磺酰氯溶液加入冰冷却的、快速搅拌的二乙醇胺(58.4g)和二氯甲烷(50mL)的混合物中。然后允许将反应混合物在环境温度下搅拌16小时。通过TLC证实10-樟脑醌磺酰氯接近完全转化。将反应混合物在二氯甲烷与水/NaCl之间分配。将有机相分离、干燥并且蒸发至干。通过柱色谱法纯化提供了作为粘稠黄色油状物的所希望的产物(6.1g；15％)。
Claims (15)
1.一种具有式(I)的光引发剂
其中R3、R4、R5和R6选自H或C1-C6烷基；
其中R1、R2、R7或R8之一具有式(Ia)的结构：
其中：
Z1是包含一个或多个选自以下各项的连接基单元的连接基：单键、-O-、-S-、任选取代的-(C1-C12亚烷基)-、任选取代的-(C1-C12亚烯基)-、-SO2-、-CO-、-NR’-、-Si(R’)2-、任选取代的杂环基和任选取代的芳基，其中R'是H或C1-C6烷基；
其中连接基-Z1-，任选与-Z2-组合，包含至少一个磺酰胺、磺酸酯、羧酰胺或羧酸酯部分；
Z2是三价氮原子或Z2是C(R”)，其中R”是H或C1-C6烷基；前提是-当Z2是氮原子时-与Z2相邻的Z1中的连接基单元是-SO2-或-CO-；
X1和X2中的每一个独立地选自单键，或包含一个或多个选自以下各项的连接基单元的连接基：-O-、-S-、任选取代的-(C1-C12亚烷基)-、任选取代的-(C1-C12亚烯基)-、-SO2-、-CO-、-NR’-、任选取代的杂环基和任选取代的芳基，其中R'是H或C1-C6烷基；
并且其中X1和X2可以彼此连接或与Z1连接以形成一个或多个环结构；
并且其中剩余的R1、R2、R7和R8选自H或C1-C6烷基。
2.根据权利要求1所述的光引发剂，其中R2、R7或R8，优选R7或R8，具有式(Ia)的结构。
3.根据前述权利要求中任一项所述的光引发剂，其中R3、R4、R5和R6选自H或甲基，并且全部优选为H。
4.根据前述权利要求中任一项所述的光引发剂，其中R1和R2二者都是甲基。
5.根据前述权利要求中任一项所述的光引发剂，其中Z1中的至少一个连接基单元选自-SO2-、-O-或-CO-，优选-SO2-或-CO-。
6.根据前述权利要求中任一项所述的光引发剂，其中-Z1-Z2-具有选自包含以下各项的组的结构；-SO2-N-；-CO-N-；-CO-O-CR”-；-O-CO-CR”-；-(C1-C12亚烷基)-SO2-N-；-(C1-C12亚烷基)-CO-N-；-(C1-C12亚烷基)-CO-O-CR”-；-(C1-C12亚烷基)-O-CO-CR”-，-(C1-C12亚烷基)-SO2-O-(C1-C12亚烷基)-Z2-；-(C1-C12亚烷基)-SO2-NR’-(C1-C12亚烷基)-Z2-；-(C1-C12亚烷基)-O-SO2-(C1-C12亚烷基)-Z2-；-(C1-C12亚烷基)-NR’-SO2-(C1-C12亚烷基)-Z2-；-(C1-C12亚烷基)-CO-O-(C1-C12亚烷基)-Z2-；-(C1-C12亚烷基)-O-CO-(C1-C12亚烷基)-Z2-；-(C1-C12亚烷基)-CO-NR’-(C1-C12亚烷基)-Z2-；或-(C1-C12亚烷基)-NR’-CO-(C1-C12亚烷基)-Z2-；优选选自-SO2-N-；-CO-N-；-CO-O-CR”-；-O-CO-CR”；-(C1-C12亚烷基)-SO2-N-；-(C1-C12亚烷基)-CO-N-；-(C1-C12亚烷基)-CO-O-CR”-；-(C1-C12亚烷基)-O-CO-CR”-；-(C1-C12亚烷基)-SO2-O-(C1-C12亚烷基)-Z2-；-(C1-C12亚烷基)-SO2-NR’-(C1-C12亚烷基)-Z2-；-(C1-C12亚烷基)-CO-O-(C1-C12亚烷基)-Z2-；-(C1-C12亚烷基)-CO-NR’-(C1-C12亚烷基)-Z2-；或更优选选自-SO2-N-；-CO-N-；-(C1-C12亚烷基)-SO2-N-；-(C1-C12亚烷基)-CO-N-；-(C1-C12亚烷基)-SO2-O-(C1-C12亚烷基)-Z2-；或-(C1-C12亚烷基)-CO-O-(C1-C12亚烷基)-Z2-。
7.根据前述权利要求中任一项所述的光引发剂，其中Z2是N。
8.根据权利要求1-6中任一项所述的光引发剂，其中Z2是C(R”)，其中R”是H、甲基或乙基或丙基。
9.根据前述权利要求中任一项所述的光引发剂，其中Z1中的-(C1-C12亚烷基)-连接基单元是-(C1-C6亚烷基)-，例如亚丙基、亚乙基或亚甲基。
10.根据前述权利要求中任一项所述的光引发剂，其中X1和X2是独立的连接基，这些独立的连接基包含一个或多个选自以下各项的连接基单元：-O-、-S-、任选取代的-(C1-C12亚烷基)-、-SO2-、-CO-、以及-NR’-，其中R'是H或C1-C6烷基-；优选一个或多个选自以下各项的连接基单元：-O-、-S-和任选取代的-(C1-C12亚烷基)-。
11.根据前述权利要求中任一项所述的光引发剂，其中X1和X2中的-(C1-C12亚烷基)-连接基单元是-(C1-C6亚烷基)-，例如亚丙基、亚乙基或亚甲基。
12.根据前述权利要求中任一项所述的光引发剂，其中X1和X2独立地是-(C1-C12亚烷基)-；优选-(C1-C6亚烷基)-，例如亚丙基、亚乙基或亚甲基。
13.根据前述权利要求中任一项所述的光引发剂，其中X1和X2是相同的。
14.根据权利要求1-13中任一项所述的光引发剂，其中R1、R2、R3、R4、R5、R6、R7或R8之一选自由以下各项组成的组：
15.根据前述权利要求中任一项所述的光引发剂，所述光引发剂选自包含以下各项的组：
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| CN102408500A (zh) * | 2010-09-21 | 2012-04-11 | 北京化工大学 | 一种新型含硅大分子光引发剂及其制备方法 |
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| CN102408500A (zh) * | 2010-09-21 | 2012-04-11 | 北京化工大学 | 一种新型含硅大分子光引发剂及其制备方法 |
| WO2012062332A2 (en) * | 2010-11-12 | 2012-05-18 | Coloplast A/S | Novel photoinitiators |
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| GOKHAN TEMELA, ET AL.: "Photopolymerization and photophysical properties of amine linked benzophenone photoinitiator for free radical polymerization", 《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A:CHEMISTRY》 * |
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