CN100469841C - Coumarin dye connected by stilbene, and synthetic method and application thereof - Google Patents
Coumarin dye connected by stilbene, and synthetic method and application thereof Download PDFInfo
- Publication number
- CN100469841C CN100469841C CNB2005101352314A CN200510135231A CN100469841C CN 100469841 C CN100469841 C CN 100469841C CN B2005101352314 A CNB2005101352314 A CN B2005101352314A CN 200510135231 A CN200510135231 A CN 200510135231A CN 100469841 C CN100469841 C CN 100469841C
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- China
- Prior art keywords
- group
- amido
- organic solvent
- dyestuff
- alcohol
- 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.)
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- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 235000001671 coumarin Nutrition 0.000 title claims abstract description 50
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 title claims abstract description 20
- 229960000956 coumarin Drugs 0.000 title claims abstract description 13
- 238000010189 synthetic method Methods 0.000 title claims description 6
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 title abstract 3
- 235000021286 stilbenes Nutrition 0.000 title abstract 3
- 239000000975 dye Substances 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 239000012074 organic phase Substances 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 12
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000004440 column chromatography Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000011630 iodine Substances 0.000 claims abstract description 7
- 239000012043 crude product Substances 0.000 claims abstract description 5
- 238000009835 boiling Methods 0.000 claims abstract description 3
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 61
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 48
- 150000004775 coumarins Chemical class 0.000 claims description 37
- -1 methoxyl group Chemical group 0.000 claims description 33
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 32
- 235000019441 ethanol Nutrition 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000012046 mixed solvent Substances 0.000 claims description 18
- 229960001701 chloroform Drugs 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 14
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 238000001953 recrystallisation Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001555 benzenes Chemical class 0.000 claims description 7
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000010025 steaming Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- 239000004258 Ethoxyquin Substances 0.000 claims description 6
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical group C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 6
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229940093500 ethoxyquin Drugs 0.000 claims description 6
- 235000019285 ethoxyquin Nutrition 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 6
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 150000004714 phosphonium salts Chemical class 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004915 dibutylamino group Chemical group C(CCC)N(CCCC)* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 claims description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N ortho-diethylbenzene Natural products CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 150000003839 salts Chemical group 0.000 claims description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N monoethyl amine Natural products CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims 2
- 238000001914 filtration Methods 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 8
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract 3
- 125000001424 substituent group Chemical group 0.000 abstract 3
- 238000010438 heat treatment Methods 0.000 abstract 2
- 239000012071 phase Substances 0.000 abstract 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 150000003003 phosphines Chemical class 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 7
- 239000012362 glacial acetic acid Substances 0.000 description 6
- 206010034972 Photosensitivity reaction Diseases 0.000 description 5
- 239000006059 cover glass Substances 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910052594 sapphire Inorganic materials 0.000 description 5
- 239000010980 sapphire Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 235000021251 pulses Nutrition 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- MTBDYOYIPBPAPV-UHFFFAOYSA-N 7-methyl-3-prop-2-enoylchromen-2-one Chemical compound C(=O)(C=C)C=1C(OC2=CC(=CC=C2C1)C)=O MTBDYOYIPBPAPV-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- VHVFGLLLPYYEJT-UHFFFAOYSA-N ICC1=CC=CC=C1.P Chemical compound ICC1=CC=CC=C1.P VHVFGLLLPYYEJT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- LVOXJBXYXGNHBS-UHFFFAOYSA-N bromomethylbenzene;phosphane Chemical compound P.BrCC1=CC=CC=C1 LVOXJBXYXGNHBS-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical class CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical compound OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 1
- UBRNWFAJPPGJGV-UHFFFAOYSA-N 3-acetyl-7-methylchromen-2-one Chemical class C1=C(C)C=C2OC(=O)C(C(=O)C)=CC2=C1 UBRNWFAJPPGJGV-UHFFFAOYSA-N 0.000 description 1
- XQZVPBWXGOXJBQ-UHFFFAOYSA-N C(C)C(=O)CC.C1(CCCCC1)C1=CC=CC=C1 Chemical compound C(C)C(=O)CC.C1(CCCCC1)C1=CC=CC=C1 XQZVPBWXGOXJBQ-UHFFFAOYSA-N 0.000 description 1
- LVAFXZPABJCMJK-UHFFFAOYSA-N COClCC1=CC=CC=C1 Chemical compound COClCC1=CC=CC=C1 LVAFXZPABJCMJK-UHFFFAOYSA-N 0.000 description 1
- QDQMANQLAVEZOW-UHFFFAOYSA-N CO[Cl+]CC1=CC=CC=C1.P Chemical compound CO[Cl+]CC1=CC=CC=C1.P QDQMANQLAVEZOW-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 244000309466 calf Species 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical class [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention belongs to the field of two-photon polymerization initiation systems, and particularly relates to a high-efficiency synthesis method of coumarin dyes connected by stilbene and application of the coumarin dyes in two-photon polymerization. Will be provided with A1Dissolving the coumarin dye intermediate in organic solvent, adding alkaline catalyst water solution, and mixing with the intermediate1With A at equimolar ratio of the radical coumarin dye2Dropwise adding an organic solvent solution of the phosphine salt of the group into a reaction system, heating to the boiling point of the solvent for refluxing, cooling, separating an organic phase from a water phase, and extracting the water phase by using the organic solvent; drying and rotary evaporating an organic phase, separating a crude product by using column chromatography, and heating by using iodine with a catalytic amount to obtain coumarin dye which is used as a photosensitizer in two-photon polymerization and is connected by stilbene, wherein the coumarin dye is of the following structure; in the formula: a. the1、A2The substituent is the same substituent or different substituent, and is selected from alkyl, alkoxy, amino, heterocycle or substituted phenyl.
Description
Invention field
The invention belongs to two-photon polymerized initiator system field, particularly relate to the synthetic method of the coumarins dyestuff that a class connects with toluylene efficiently and the purposes in two-photon polymerized thereof.
Background technology
Two-photon polymerized technology is along with the development of two-photon technology produces, it has the advantage that penetrativity is strong, spatial resolution is high, therefore two-photon polymerized technology is stored at magnanimity information, the retrofit of nanometer, micron and submicrometer structure, fields such as photonic crystal have a wide range of applications.The Kawata research group of Osaka, Japan university has reported that on " nature " magazine using two-photon polymerized technology processes 7 microns high as calendar year 2001,10 microns long three-dimensional calf (exercise question: the retrofit of functionalization micro element, Nature, vol.412,697～698).In two-photon polymerized technology, the design and use of photosensitized initiation system are its keys, and wherein initiator system has big two photon absorption cross section and high efficiency of initiation is two important factors.Though used two-photon dyestuff has big two photon absorption cross section at present, but efficiency of initiation is low, and dyestuff is synthetic complicated, if when adopting efficient ultraviolet-visible initiator as two-photon polymerized initiator, though efficiency of initiation is improved, two photon absorption cross section is little.So employed dyestuff exists photo sensitized initiation efficient and two photon absorption cross section shortage unity in two-photon polymerized technology at present, thereby cause problem long owing to the time shutter, that incident intensity causes material damage by force.So not only had big two photon absorption cross section but also had efficiently with simple method is synthetic that the two-photon dyestuff of photo sensitized initiation efficient has become problem anxious to be solved in the present two-photon polymerized technology.
Summary of the invention
A purpose of the present invention is to solve the lower problem of two photon absorption cross section that common coumarine dye exists, and provides a class both to have photo sensitized initiation efficient efficiently, has the coumarins dyestuff with the toluylene connection of bigger two photon absorption cross section again.
Another object of the present invention provides a kind of synthetic method of the coumarins dyestuff that connects with toluylene, and this method is simple, and dyestuff makes easily, and can use with common light trigger coupling.
A further object of the present invention provides the purposes of coumarins dyestuff in two-photon polymerized that connects with toluylene.
The coumarins dyestuff that connects with toluylene of the present invention has following molecular structure:
In the formula: A
1, A
2For containing the group of electron donor(ED) character or electron acceptor(EA) character, as alkyl, alkoxyl group, amido, heterocycle or substituted-phenyl etc.A
1And A
2Can be identical substituting group, also can be substituting group inequality.
Described alkyl is methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, amyl group or carbonatoms less than alkyl of 15 etc.
Described alkoxyl group is methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy or carbonatoms less than alkoxyl group of 15 etc.
Described amido is methylamino, ethylamino-, butylamine base, ethanol amido, propyl alcohol amido, dimethylin, diethylin, dipropyl amido, dibutyl amino, di-alcohol amido, dipropanolamine base, dimethylbenzene amido, diethylbenzene amido, hexichol amido, substituted diphenylamine or quaternary ammonium salt base etc.
Described heterocyclic radical is pyridine, pyrroles, thiazole or carbazole etc.
The substituting group of described substituted-phenyl be adjacent,, contraposition alkyl or alkoxyl group.
The synthetic method of the coumarins dyestuff that connects with toluylene of the present invention may further comprise the steps:
(1) has A
1Synthesizing of the coumarine dye intermediate of group
Reaction equation:
Concrete steps:
To have A
1The coumarin compound of group and the terephthalaldehyde ratio of 1:2～5 in molar ratio join in the reaction vessel, and adding mol ratio then is the described A of having
1The solvent that the coumarin compound of group is 50～500 times, solvent are acetate or ethanol/acetonitrile mixed solvent, and wherein ethanol accounts for 20～80% of mixed solvent mass percentage concentration.And then the adding mol ratio is the described A of having
1The basic catalyst that the coumarin compound of group is 0.05～0.5 times reacted 8～40 hours under 25 ℃～150 ℃ conditions, and cooled and filtered goes out precipitation, obtains being with A
1The coumarine dye intermediate of group is used the corresponding A of ethanol/acetonitrile mixed solvent recrystallization then
1The coumarine dye intermediate of group, standby.
(2) have A
2Synthesizing of the phosphonium salt of group
Reaction equation:
Perhaps
X is Cl, Br or I
Concrete steps:
Method one: (3732 pages of methods of reference literature " Chem.Ber. " 1973 106 volume are synthetic) etc. the A of mol ratio
2Group substituted benzene, potassium halide, triphenylphosphine and formaldehyde add in the reactor of a suitable size, and adding mol ratio then is A
2The acetate that the group substituted benzene is 2～5 times, mol ratio are A
2The water that the group substituted benzene is 8～20 times, mol ratio are A
2The chloroform that the group substituted benzene is 3～10 times stirred for three weeks under the room temperature, reaction is revolved steaming after finishing, crude product with behind twice of methyl alcohol or the ethyl alcohol recrystallization pure product.
Method two: (synthetic with reference to " Reactionsand Syntheses in the organic chemistry laboratory " the 180th page of method that Lutz-Friedijan Tietze and Theophil Eicher write) will wait the contraposition A of mol ratio
2The benzyl halogenide and the triphenylphosphine that replace add in the reactor of a suitable size, and adding mol ratio again is A
2The organic solvent that the benzyl halogenide that replaces is 30～100 times, reflux 2～8 hours, reaction finishes postcooling to room temperature, and suction filtration is directly used in after the products obtained therefrom oven dry in next step reaction.
(3) the coumarins dyestuff that connects with toluylene is synthetic
Reaction equation:
Concrete steps:
What in reactor step (1) is made has an A
1It is to have A that the coumarine dye intermediate of group is dissolved in mol ratio
1In the organic solvent that the group coumarine dye is 50～100 times, adding mol ratio then is to have A
1The alkaline catalyst solution that the group coumarine dye is 0.02～0.50 times, again will with have A
1Step (2) synthetic of mol ratios such as group coumarine dye has A
2The organic solvent solution of the phosphonium salt of group drops in the reaction system, is heated to solvent boiling point and refluxes 1～4 hour, and the cooling back separates the water organic solvent extraction to organic phase and water.The organic phase drying, revolve after steaming, crude product separate twice with column chromatography,, can obtain the pure trans coumarins dyestuff that connects with toluylene of the present invention with the iodine heat treated of catalytic amount.
More than the described basic catalyst of reaction is sodium hydroxide, potassium hydroxide, Anhydrous potassium carbonate, anhydrous sodium carbonate, hexahydropyridine or their any mixture etc.
Described organic solvent is methylene dichloride, chloroform, toluene, dimethylbenzene, acetate, acetonitrile, alcohol solvent or their any mixture etc.
The application of coumarins dyestuff in two-photon polymerized that connects with toluylene of the present invention:
The coumarins dyestuff that connects with toluylene of the present invention, they are as photosensitizers in two-photon polymerized, can with couplings such as light trigger such as salt compounded of iodine, sulfosalt, hexa-aryl bi-imidazole, benzophenone, ferrocene, organoboron compound, amine, thioxanthone, form photosensitized initiation system efficiently, adopt two-photon polymerized technology can carry out accurate solid processing and meticulous graphic making.
The coumarins dyestuff that connects with toluylene of the present invention cooperates the component and the consumption that cause the vinyl monomer double photon photopolymerization as follows as photosensitizers with light trigger:
Light reactive resin 10%～60wt%
Multi-functional acrylate's linking agent 10%～50wt%
Simple function group reactive monomer 5%～40wt%
Organic solvent 10%～50wt%
Light trigger 0.1%～5wt%
Chain-transfer agent 0%～5wt%
Photosensitizers (coumarine dye of the present invention) 0.01%～0.1wt%
In the above-mentioned prescription, described light reactive resin is epoxy acrylate, epoxy soybean oil acrylate, polyester acrylate, urethane acrylate or their any mixture etc.
Described multi-functional acrylate's linking agent is Viscoat 295, pentaerythritol triacrylate, double pentaerythritol C5 methacrylate, ethoxyquin pentaerythritol triacrylate, ethoxyquin Viscoat 295, the third oxidation Viscoat 295 or their any mixture etc.
Described simple function group reactive monomer is methyl methacrylate, hydroxyl ethyl ester, hydroxypropyl acrylate, 2-benzene oxygen ethyl propylene acid esters, vinylbenzene, N-vinylcarbazole, vinyl-acetic ester, N-vinyl pyrrolidone or their any mixture etc.
Described organic solvent is ethers such as halogenated hydrocarbons such as aromatic hydrocarbons such as naphthenic hydrocarbon, benzene, toluene, methylene dichloride, trichloromethane, chlorobenzene, ethylene glycol monomethyl ether, alcohols, ketone, acetonitrile, dimethyl sulfoxide (DMSO) or their any mixture etc.
Described light trigger is that organoboron compounds such as organometallic compound, butyl triphenyl borate, Benzophenones, various alkyl such as two glyoxaline compounds such as salt compounded of iodine, sulfosalt class salt compound, hexa-aryl bi-imidazole, ferrocene compounds, ferrocene salt, aluminate complex compound replace thioxanthone, Alpha-hydroxy-acetophenone derivs such as phenylcyclohexane ethyl ketone, amine or their any mixture etc.
Described chain-transfer agent is sulfur alcohol compounds such as lauryl mercaptan.
The making method of preparation with double photon photopolymerization system that coumarins dyestuff that toluylene connects makes photosensitizers of the present invention and fine pattern is as follows:
In reaction vessel, the coumarine dye that adds 0.01%～0.1wt%, the chain-transfer agent of 0%～5wt% and the light trigger of 0.1%～5wt% are dissolved in the organic solvent of 10%～50wt%, then it is joined 10%～60wt% light reactive resin, 10%～50wt% multi-functional acrylate linking agent, in the mixture of 5%～40wt% simple function group reactive monomer, under the lucifuge condition, stir, at room temperature solvent evaporates is fallen, then the sample liquid for preparing is applied on the cover glass of hydrophilic treatment, with the Ti-Sapphire femto-second laser is light source, excitation wavelength is 800nm, the point by point scanning sample, at last unpolymerized part is washed off with solvent, just can be obtained micro-machined figure.
The coumarins dyestuff that connects with toluylene of the present invention has following outstanding feature:
(1) the synthetic and separation method of coumarins dyestuff of the present invention is fairly simple, and raw material sources conveniently are easy to get, and wherein contain A
1The coumarin ketone of group with contain A
2The phosphonium salt of group all can be synthetic by ordinary method, only needs then above-mentioned two components are carried out the Wittig condensation, just can make coumarins dyestuff of the present invention, and productive rate is higher.
(2) coumarins dyestuff of the present invention can be by changing A
1Group or A
2The molecular structure of group is adjusted the two photon absorption cross section value of dyestuff easily according to service requirements.
(3) coumarins dyestuff of the present invention is a sensitizing dye efficiently, has big two photon absorption cross section, it can with multiple Photoepolymerizationinitiater initiater coupling, form light initiation system and cause two-photon polymerized efficiently.
Embodiment
Embodiment 1
A
1, A
2Be coumarins dyestuff (K1) synthetic of diethylin
(1) add 10 mmole 3-ethanoyl-7-diethylin tonka bean camphor, 20 mmole terephthalaldehydes and 50ml Glacial acetic acid in the 100ml there-necked flask, the back that stirs adds the 0.5ml hexahydropyridine, is heated to 120 ℃ and refluxes 12 hours.After the reactant cooling, suction filtration, filter cake is washed with 10ml ethanol.Thick product gets 3-[3-(4-carboxaldehyde radicals) phenyl with ethanol/acetonitrile (m/m=1:1) mixed solvent recrystallization twice] acryl-7-diethylin tonka bean camphor intermediate, productive rate 64.8%.
(2) with 50 mmole potassiumiodides, 50 mmole triphenylphosphines, 50 mmole Diethyl Anilines, 40% formalin 3.75g, chloroform 40ml, water 20ml, Glacial acetic acid 10g are mixed in the 250ml round-bottomed flask, stir for 3 weeks under the room temperature, reaction is revolved steaming after finishing, the solid that obtains obtains diethylin benzyl iodide phosphonium salt, productive rate 80% with ethyl alcohol recrystallization twice.
(3) in the 100ml there-necked flask, add tonka bean camphor intermediate and the 20ml methylene dichloride that 1 mmole above-mentioned steps (1) makes, the dissolving back adds the aqueous sodium hydroxide solution of 40ml 2M, the dichloromethane solution 20ml of right-diethylin benzyl iodide phosphonium salt that dropping 1 mmole above-mentioned steps (2) makes under the room temperature, after adding, be heated to 40 ℃ and refluxed 2 hours.Reaction finishes postcooling to room temperature, and organic phase and water are separated, and water merges organic phase with chloroform extraction twice, uses anhydrous sodium sulfate drying, revolves to steam to obtain thick product oily matter.Thick product separates twice through column chromatography, and eluent is the mixed solvent (m:m=96:4) of chloroform and ethyl acetate, and products obtained therefrom obtains pure trans A after 10 milligrams of iodine heat treated
1, A
2Be the coumarins dyestuff (K1) of diethylin, productive rate 48.6%.This product is identified through nucleus magnetic hydrogen spectrum, mass spectrum, ultimate analysis.
1H?NMR(CDCl
3，300MHz)δ:1.21(t，J＝7.14Hz，6H)，1.23(t，J＝6.99Hz，6H)，3.38(q，J＝7.14Hz，4H)，3.46(q，J＝7.14Hz，4H)，6.50(d，J＝2.13Hz，1H)，6.62(m，3H)，6.91(d，J＝16.20Hz，1H)，7.09(d，J＝16.20Hz，1H)，7.45(m，5H)，7.64(d，J＝8.16Hz，2H)，7.86(d，J＝15.66Hz，1H)，8.12(d，J＝15.66Hz，1H)，8.56(1H，s)；MS?m/z?520.3；Anal.Calcd.for?C
34H
36N
2O
3:C?78.43，H?6.97，N?5.38；Found：C?78.19，H?6.83，N?5.41。
Embodiment 2
A1, A2 are coumarins dyestuff (K2) synthetic of methoxyl group
(1) add 20 mmole 3-ethanoyl-ayapanins, 50 mmole terephthalaldehydes and 90ml Glacial acetic acid in the 100ml there-necked flask, the back that stirs adds the 2ml hexahydropyridine, is heated to 120 ℃ and refluxes 25 hours.Reactant cooling back suction filtration, filter cake is with 10 milliliters of washing with alcohol.Thick product gets 3-[3-(4-carboxaldehyde radicals) phenyl with 30 milliliters of ethanol/acetonitrile (m/m=1:1) mixed solvent recrystallization twice] acryl-ayapanin intermediate, productive rate 85.2%
(2) with 10 mmoles to methoxy-benzyl chlorine, 10 mmole triphenylphosphines join in the 100ml round-bottomed flask, add 30 milliliters of hexanaphthenes, reflux 2 hours, reaction finishes postcooling to room temperature, suction filtration, and filter cake washs with the 15ml ether, obtain to methoxy-benzyl chlorine phosphonium salt being directly used in after air-dry in next step reaction productive rate 83%.
(3) in the 100ml there-necked flask, add 3-[3-(4-carboxaldehyde radicals) phenyl that 20 mmoles above-mentioned (1) make] acryl-ayapanin intermediate and 40ml methylene dichloride, the dissolving back adds 80ml
0.5M wet chemical, drip the dichloromethane solution 50ml of right-methoxy-benzyl phosphine villaumite that 20 mmoles above-mentioned (2) make under the room temperature, after adding, be heated to 40 ℃ and refluxed 8 hours.Reaction finishes postcooling to room temperature, and organic phase and water are separated, and water merges organic phase with chloroform extraction twice, uses anhydrous sodium sulfate drying, revolves to steam to obtain thick product oily matter.Thick product separates twice through column chromatography, and eluent is the mixed solvent (m:m=97:3) of chloroform and ethyl acetate, and products obtained therefrom is obtaining pure trans product (K2) after the photo-irradiation treatment in the presence of 5 milligrams of iodine, productive rate 78.4%.This product is identified through nucleus magnetic hydrogen spectrum, mass spectrum, ultimate analysis.
1H?NMR(300MHz，CDCl
3)δ?3.73(s，3H)，3.84(s，3H)，6.51(s，J＝8.52Hz，1H)，6.27(d，J＝8.85Hz，1H)，6.90(d，J＝8.52Hz，2H)，7.01(d，J＝16.47Hz，1H)，7.12(d，＝16.41Hz，1H)，7.47(m，5H)，7.66(d，J＝8.04Hz，2H)，7.86(d，J＝15.63Hz，1H)，8.14(d，J＝15.60Hz，1H)，8.57(s，1H)；MS(m/z)：438.3.Anal.Calcd(％)for?C
28H
22O
5：C，76.70；H，5.06；Found：C，76.54；H，5.08。
Embodiment 3
A
1Be dimethylin, A
2Synthetic for the coumarins dyestuff (K3) of diethylin
(1) adding 20 mmole 3-ethanoyl-7-dimethylin tonka bean camphor, 50 mmole terephthalaldehydes and 50ml volume ratio in the 100ml there-necked flask is acetonitrile/alcohol mixed solvent of 1:1; back adding 1ml acetic acid stirs; the 1ml hexahydropyridine, reflux 30 hours.After the reactant cooling, suction filtration, filter cake washs with 8ml acetonitrile/alcohol mixed solvent.Thick product gets 3-[3-(4-carboxaldehyde radicals) phenyl with ethanol/acetonitrile (m/m=1:1) mixed solvent recrystallization twice] acryl-7-dimethylin tonka bean camphor intermediate, productive rate 86.3%
(2) with 0.1 mole of Potassium Bromide, 0.1 the mole triphenylphosphine, 0.1 mole of Diethyl Aniline, 40% formalin 37.5g, chloroform 150ml, water 100ml, Glacial acetic acid 50g are mixed in the 500ml round-bottomed flask, stir for 3 weeks under the room temperature, reaction is revolved steaming after finishing, the solid that obtains obtains diethylin bromotoluene phosphonium salt, productive rate 89.5% with recrystallizing methanol twice.
(3) in the 100ml there-necked flask, add 3-[3-(4-carboxaldehyde radicals) phenyl that 3 mmoles above-mentioned (1) make] acryl-7-dimethylin tonka bean camphor intermediate and 10ml methylene dichloride; the dissolving back adds the potassium hydroxide aqueous solution of 10ml1M; the dichloromethane solution 10ml of right-diethylin bromotoluene phosphonium salt that dropping 3 mmoles above-mentioned (2) make under the room temperature; after adding, be heated to 40 ℃ and refluxed 1 hour.Reaction finishes postcooling to room temperature, and organic phase and water are separated, and water merges organic phase with chloroform extraction twice, uses anhydrous sodium sulfate drying, revolves to steam to obtain thick product oily matter.Thick product separates twice through column chromatography, and eluent is chloroform and ethyl acetate mixed solvent (m:m=98:2), and products obtained therefrom obtains pure trans A after 5 milligrams of iodine heat treated
1Be dimethylin, A
2Be the coumarins dyestuff (K3) of diethylin, productive rate 74.8%.This product is identified through nucleus magnetic hydrogen spectrum, mass spectrum, ultimate analysis.
1H?NMR(300MHz，CDCl
3)δ?1.26(t，J＝7.14Hz，6H)，3.02(s，6H)，3.46(q，J＝7.08Hz，4H)，6.50(d，J＝2.22Hz，1H)，6.65(m，3H)，6.97(d，J＝16.20Hz，1H)，7.11(d，J＝16.20Hz，1H)，7.45(m，5H)，7.65(d，J＝8.25Hz，2H)，7.86(d，J＝15.72Hz，1H)，8.13(d，J＝15.66Hz，1H)，8.57(s，1H)；MS(m/z):492.4.Anal.Calcd(％)for?C
32H
32N
2O
3:C，78.02；H，6.55；N，5.69.Found:C，77.85；H，6.62；N，5.53。
Embodiment 4
A
1Be methyl, A
2Synthetic for the coumarins dyestuff (K4) of hexichol amido
(1) add 10 mmole 3-ethanoyl-7-methylcoumarins, 40 mmole terephthalaldehydes and 50ml Glacial acetic acid in the 100ml there-necked flask, the back that stirs adds the 0.5ml hexahydropyridine, is heated to 120 ℃ and refluxes 15 hours.Reactant cooling back suction filtration, filter cake washs with 8ml acetonitrile/alcohol mixed solvent.Thick product gets 3-[3-(4-carboxaldehyde radicals) phenyl with ethanol/acetonitrile (m/m=1:1) mixed solvent recrystallization twice] acryl-7-methylcoumarin intermediate, productive rate 64.8%.
(2) with 0.1 mole of Repone K, 0.1 the mole triphenylphosphine, 0.1 mole of triphenylamine, 40% formalin 37.5g, chloroform 200ml, water 150ml, Glacial acetic acid 70g are mixed in the 500ml round-bottomed flask, stir for 3 weeks under the room temperature, reaction is revolved steaming after finishing, the solid that obtains obtains right-hexichol amido benzyl chloride phosphonium salt, productive rate 92.1% with Virahol recrystallization twice.
(3) in the 100ml there-necked flask, add 3-[3-(4-carboxaldehyde radicals) phenyl that 1 mmole above-mentioned (1) makes] acryl-7-methylcoumarin intermediate and 20ml methylene dichloride; the dissolving back adds the aqueous sodium hydroxide solution of 40ml 2M; the dichloromethane solution 20ml of right-hexichol amido benzyl chloride phosphonium salt that dropping 1 mmole above-mentioned (2) makes under the room temperature; after adding, be heated to 40 ℃ and refluxed 2 hours.Reaction finishes postcooling to room temperature, and organic phase and water are separated, and water merges organic phase with chloroform extraction twice, uses anhydrous sodium sulfate drying, revolves to steam to obtain thick product oily matter.Thick product separates twice through column chromatography, and eluent is the mixed solvent (m:m=99:1) of chloroform and ethyl acetate, and products obtained therefrom obtains pure trans A after 6 milligrams of iodine heat treated
1Be methyl, A
2Be the coumarins dyestuff (K4) of hexichol amido, productive rate 78.6%.This product is identified through nucleus magnetic hydrogen spectrum, mass spectrum, ultimate analysis.
1H?NMR(300MHz，CDCl
3)2.35(s，3H)，6.50(m，5H)，6.65(m，3H)，6.97(m，7H)，7.11(d，J＝16.20Hz，1H)，7.45(m，5H)，7.65(d，J＝8.25Hz，2H)，7.86(d，J＝15.72Hz，1H)，8.13(d，.J＝15.66Hz，1H)，8.57(s，1H)；MS(m/z)：559.01.Anal.Calcd(％)for?C
39H
29NO
3：C，83.70；H，5.22；N，2.50.Found：C，83.52；H，5.01；N，2.35。
Embodiment 5
Coumarins dyestuff K1 is as two-photon polymerized photosensitizers
Epoxy acrylate 4g
Pentaerythritol triacrylate 3g
N-vinylcarbazole 3g
Methylene dichloride 5ml
Adjacent chlorine hexa-aryl bi-imidazole 0.04g
Dodecyl Mercaptan 0.1g
Coumarine dye K1 0.004g
With 0.004g K1,0.04g adjacent chlorine hexa-aryl bi-imidazole, 0.1g Dodecyl Mercaptan is dissolved in the 5ml methylene dichloride, then itself and the 3gN-vinylcarbazole, 3g pentaerythritol triacrylate, the 4g epoxy acrylate monomer that are pre-mixed are stirred, lucifuge is drained solvent wherein with water circulating pump.The polymer fluid for preparing is applied on the cover glass that passes through hydrophilic treatment in advance, utilize the Ti-Sapphire femto-second laser, excitation wavelength is 800nm, output rating is 10～20mw, pulse width is the LASER Light Source of 130 femtoseconds, carry out three-dimensional little processing by two-photon polymerized, after having the polymeric part to wash off, promptly do not obtain the retrofit figure with acetone.
Embodiment 6
Coumarins dyestuff k2 is as two-photon polymerized photosensitizers
Epoxy acrylate 5g
Tri methylol triacrylate 3g
2-benzene oxygen ethyl propylene acid esters 2g
Acetone 4ml
The phenylbenzene hexafluoro closes phosphoric acid salt compounded of iodine 0.05g
Coumarine dye K2 0.003g
With 0.003g K2,0.05g closing the phosphoric acid salt compounded of iodine, the phenylbenzene hexafluoro is dissolved in the 4ml acetone, with itself and the 2g2-benzene oxygen ethyl propylene acid esters that is pre-mixed, 3g tri methylol triacrylate, 5g epoxy acrylate monomer stir then, and lucifuge is drained solvent wherein with water circulating pump.The polymer fluid for preparing is applied on the cover glass that passes through hydrophilic treatment in advance, utilize the Ti-Sapphire femto-second laser, excitation wavelength is 800nm, output rating is 5～30mw, pulse width is the LASER Light Source of 130 femtoseconds, carry out three-dimensional little processing by two-photon polymerized, obtain poly-good figure after not having the polymeric part to wash off with acetone.
Embodiment 7
Coumarins dyestuff K3 is as two-photon polymerized photosensitizers
Epoxy soybean oil acrylate 6g
Dipentaerythritol five acrylate 3g
Hydroxyethyl methylacrylate 1g
Toluene 6ml
Ferrocene 0.05g
Coumarine dye K3 0.003g
With 0.003g K3,0.05g ferrocene is dissolved in the 6ml toluene, then itself and the 1g hydroxyethyl methylacrylate, 3g Dipentaerythritol five acrylate, the 6g epoxy soybean oil acrylate monomer that are pre-mixed are stirred, lucifuge is drained solvent wherein with water circulating pump.The polymer fluid for preparing is applied on the cover glass that passes through hydrophilic treatment in advance, utilize the Ti-Sapphire femto-second laser, excitation wavelength is 800nm, output rating is 5～30mw, pulse width is the LASER Light Source of 130 femtoseconds, carry out three-dimensional little processing by two-photon polymerized, obtain poly-good figure after not having the polymeric part to wash off with acetone
Embodiment 8
Coumarins dyestuff K4 is as two-photon polymerized photosensitizers
Polyester acrylate 12g
Ethoxyquin tetramethylol methane tetraacrylate 6g
Methyl methacrylate 2g
Ethanol 8ml
Triphenyl tetrafluoride boron sulfosalt 0.08g
Coumarine dye K4 0.006g
With 0.006g k4,0.08g triphenyl tetrafluoride boron vitriol is dissolved in the 8ml ethanol, then itself and the 2g methyl methacrylate, 6g ethoxyquin tetramethylol methane tetraacrylate, the 12g polyester acrylate monomer that are pre-mixed are stirred, lucifuge is drained solvent wherein with water circulating pump.The polymer fluid for preparing is applied on the cover glass that passes through hydrophilic treatment in advance, utilize the Ti-Sapphire femto-second laser, excitation wavelength is 800nm, output rating is 5～30mw, pulse width is the LASER Light Source of 130 femtoseconds, carry out three-dimensional little processing by two-photon polymerized, obtain poly-good figure after not having the polymeric part to wash off with acetone.
Claims (10)
1. coumarins dyestuff that connects with toluylene, it is characterized in that: this dyestuff has following molecular structure:
In the formula: A
1, A
2Substituting group be identical substituting group or substituting group inequality, be selected from alkyl, alkoxyl group or amido.
2. coumarins dyestuff according to claim 1 is characterized in that: described alkyl is methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, amyl group or carbonatoms less than 15 alkyl;
Described alkoxyl group is methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy or carbonatoms less than 15 alkoxyl group;
Described amido is methylamino, ethylamino-, butylamine base, ethanol amido, propyl alcohol amido, dimethylin, diethylin, dipropyl amido, dibutyl amino, di-alcohol amido, dipropanolamine base, dimethylbenzene amido, diethylbenzene amido, hexichol amido, substituted diphenylamine or quaternary ammonium salt base.
3. the synthetic method according to each described coumarins dyestuff of claim 1～2 is characterized in that, this method may further comprise the steps:
(1) has A
1Synthesizing of the coumarine dye intermediate of group
To have A
1The coumarin compound of group and the terephthalaldehyde ratio of 1:2～5 in molar ratio join in the reaction vessel, add acetate or ethanol/acetonitrile mixed solvent then, and adding mol ratio again is the described A of having
1The basic catalyst that the coumarin compound of group is 0.05～0.5 times reacts under 25 ℃～150 ℃ conditions, and after reaction was finished, cold filtration went out precipitation, obtains being with A
1The coumarine dye intermediate of group is used the corresponding A of ethanol/acetonitrile mixed solvent recrystallization then
1The coumarine dye intermediate of group, standby;
(2) have A
2Synthesizing of the phosphonium salt of group
With etc. the A of mol ratio
2Group substituted benzene, potassium halide, triphenylphosphine and formaldehyde add in the reactor, and adding mol ratio then is A
2The acetate that the group substituted benzene is 2～5 times, water and mol ratio are A
2Stir under the chloroform that the group substituted benzene is 3～10 times, room temperature, revolve steaming after reaction finishes, crude product with behind twice of methyl alcohol or the ethyl alcohol recrystallization pure product; Or
With etc. the contraposition A of mol ratio
2The benzyl halogenide and the triphenylphosphine that replace add in the reactor, add organic solvent again, reflux, and reaction finishes postcooling to room temperature, and suction filtration is directly used in after the products obtained therefrom oven dry in next step reaction;
(3) the coumarins dyestuff that connects with toluylene is synthetic
What in reactor step (1) is made has an A
1The coumarine dye intermediate of group is dissolved in the organic solvent, and adding mol ratio then is to have A
1The alkaline catalyst solution that the group coumarine dye is 0.02～0.50 times, again will with have A
1Step (2) synthetic of mol ratios such as group coumarine dye has A
2The organic solvent solution of the phosphonium salt of group drops in the reaction system, is heated to solvent boiling point and refluxes, and the cooling back separates the water organic solvent extraction to organic phase and water; The organic phase drying, revolve after steaming, crude product separate with column chromatography,, obtain the coumarins dyestuff that connects with toluylene with the iodine heat treated of catalytic amount; Molecular structure:
In the formula: A
1, A
2Substituting group be identical substituting group or substituting group inequality, be selected from alkyl, alkoxyl group or amido.
4. method according to claim 3 is characterized in that: described alkyl is methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, amyl group or carbonatoms less than 15 alkyl;
Described alkoxyl group is methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy or carbonatoms less than 15 alkoxyl group;
Described amido is methylamino, ethylamino-, butylamine base, ethanol amido, propyl alcohol amido, dimethylin, diethylin, dipropyl amido, dibutyl amino, di-alcohol amido, dipropanolamine base, dimethylbenzene amido, diethylbenzene amido, hexichol amido, substituted diphenylamine or quaternary ammonium salt base.
5. method according to claim 3 is characterized in that: in the described ethanol/acetonitrile mixed solvent, ethanol accounts for 20～80% of mixed solvent mass percentage concentration.
6. method according to claim 3 is characterized in that: it is 1～4 hour that described step (3) refluxes.
7. method according to claim 3 is characterized in that: described basic catalyst is sodium hydroxide, potassium hydroxide, Anhydrous potassium carbonate, anhydrous sodium carbonate, hexahydropyridine or their any mixture.
8. method according to claim 3 is characterized in that: described organic solvent is methylene dichloride, chloroform, toluene, dimethylbenzene, acetate, acetonitrile, alcohol solvent or their any mixture.
9. purposes according to each described coumarins dyestuff of claim 1～2 is characterized in that: described coumarins dyestuff in two-photon polymerized as photosensitizers.
10. purposes according to claim 9 is characterized in that: described coumarins dyestuff as photosensitizers, cooperates the component and the consumption that cause the vinyl monomer double photon photopolymerization to be with light trigger in two-photon polymerized:
Light reactive resin 10%～60wt%
Multi-functional acrylate's linking agent 10%～50wt%
Simple function group reactive monomer 5%～40wt%
Organic solvent 10%～50wt%
Light trigger 0.1%～5wt%
Chain-transfer agent 0%～5wt%
Coumarine dye photosensitizers 0.01%～0.1wt%
Described light reactive resin is epoxy acrylate, epoxy soybean oil acrylate, polyester acrylate, urethane acrylate or their any mixture;
Described multi-functional acrylate's linking agent is Viscoat 295, pentaerythritol triacrylate, double pentaerythritol C5 methacrylate, ethoxyquin pentaerythritol triacrylate, ethoxyquin Viscoat 295, the third oxidation Viscoat 295 or their any mixture;
Described simple function group reactive monomer is methyl methacrylate, hydroxyl ethyl ester, hydroxypropyl acrylate, 2-benzene oxygen ethyl propylene acid esters, vinylbenzene, N-vinylcarbazole, vinyl-acetic ester, N-vinyl pyrrolidone or their any mixture;
Described organic solvent is naphthenic hydrocarbon, benzene, toluene, methylene dichloride, trichloromethane, chlorobenzene, ethylene glycol monomethyl ether, alcohol, ketone, acetonitrile, dimethyl sulfoxide (DMSO) or their any mixture;
Described light trigger is salt compounded of iodine, sulfosalt, hexa-aryl bi-imidazole, ferrocene compounds, ferrocene salt, aluminate complex compound, butyl triphenyl borate, benzophenone, alkyl replacement thioxanthone, Alpha-hydroxy-phenylcyclohexane ethyl ketone, amine or their any mixture;
Described chain-transfer agent is a lauryl mercaptan.
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| CN101759815B (en) * | 2008-12-25 | 2011-12-28 | 中国科学院理化技术研究所 | Application of coumarin and/or benzal naphthenic hydrocarbon ketone dye in preparing two-photon polymerized resin |
| CN101885922B (en) * | 2009-05-14 | 2012-03-28 | 中国科学院理化技术研究所 | Polymer material with two-photon amplitude limiting characteristic and preparation method and application thereof |
| CN102766349B (en) * | 2011-05-05 | 2013-11-20 | 中国科学院理化技术研究所 | Lipid-water amphiphilic coumarin dye, preparation method thereof and application thereof in preparation of photodynamic therapy photosensitive drugs |
| CN103131206A (en) * | 2011-12-02 | 2013-06-05 | 中国科学院理化技术研究所 | Pyrazolopyridine benzocoumarin dye derivative and synthesis method and application thereof |
| CN104119690B (en) * | 2014-06-27 | 2016-06-29 | 安徽大学 | Seven-substituted coumarin derivative two-photon fluorescent dye and preparation method thereof |
| CN104892556B (en) * | 2015-05-29 | 2017-01-04 | 合肥工业大学 | One class stilbene coumarin derivatives and preparation method thereof and purposes |
| CN110028671B (en) * | 2019-04-23 | 2021-06-01 | 湘潭大学 | Benzimidazole-linked triphenyl imidazole polymer and preparation method and application thereof |
| CN110951413B (en) * | 2019-12-17 | 2020-12-18 | 江苏学泰印务有限公司 | Preparation method of waterborne polyurethane surface sizing agent |
| CN114196226B (en) * | 2021-11-21 | 2024-02-13 | 大连理工大学 | Coumarin dye, composite initiator for ultrasonic curing, preparation method and application thereof |
| CN115236936B (en) * | 2022-09-22 | 2022-12-06 | 之江实验室 | Femtosecond laser cured and crosslinked polyamic acid photoresist and preparation method, use method and application thereof |
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