CN1229376C - 1,7-二取代的苝-3,4,9,10-四羧酸二酰亚胺,其制备方法及用途 - Google Patents
1,7-二取代的苝-3,4,9,10-四羧酸二酰亚胺,其制备方法及用途 Download PDFInfo
- Publication number
- CN1229376C CN1229376C CNB011194650A CN01119465A CN1229376C CN 1229376 C CN1229376 C CN 1229376C CN B011194650 A CNB011194650 A CN B011194650A CN 01119465 A CN01119465 A CN 01119465A CN 1229376 C CN1229376 C CN 1229376C
- Authority
- CN
- China
- Prior art keywords
- perylene
- group
- general formula
- tetracarboxylic acid
- base
- 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.)
- Expired - Lifetime
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- PONZBUKBFVIXOD-UHFFFAOYSA-N 9,10-dicarbamoylperylene-3,4-dicarboxylic acid Chemical class C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=N)C2=C1C3=CC=C2C(=N)O PONZBUKBFVIXOD-UHFFFAOYSA-N 0.000 title claims description 28
- -1 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic acid diimides Chemical class 0.000 claims abstract description 172
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical class C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 16
- 239000000049 pigment Substances 0.000 claims description 13
- 229910000071 diazene Inorganic materials 0.000 claims description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 239000003880 polar aprotic solvent Substances 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000011368 organic material Substances 0.000 claims description 7
- 239000000990 laser dye Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000000010 aprotic solvent Substances 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 239000000975 dye Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 239000011147 inorganic material Substances 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 238000005401 electroluminescence Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 239000013067 intermediate product Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 97
- 150000003949 imides Chemical class 0.000 description 40
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 33
- 229910052799 carbon Inorganic materials 0.000 description 31
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 31
- 238000002360 preparation method Methods 0.000 description 27
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 26
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 150000001345 alkine derivatives Chemical class 0.000 description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 8
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 6
- 150000003141 primary amines Chemical class 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 241000534944 Thia Species 0.000 description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- VMJNTFXCTXAXTC-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxole-5-carbonitrile Chemical group C1=C(C#N)C=C2OC(F)(F)OC2=C1 VMJNTFXCTXAXTC-UHFFFAOYSA-N 0.000 description 4
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical class [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002223 garnet Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N dimethylbutene Natural products CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- 125000006039 1-hexenyl group Chemical group 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 2
- HRXZRAXKKNUKRF-UHFFFAOYSA-N 4-ethylaniline Chemical compound CCC1=CC=C(N)C=C1 HRXZRAXKKNUKRF-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical group I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZVDBUOGYYYNMQI-UHFFFAOYSA-N dodec-1-yne Chemical compound CCCCCCCCCCC#C ZVDBUOGYYYNMQI-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
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- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical compound CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- YVSFLVNWJIEJRV-UHFFFAOYSA-N 1-undecyne Chemical compound CCCCCCCCCC#C YVSFLVNWJIEJRV-UHFFFAOYSA-N 0.000 description 1
- 125000005808 2,4,6-trimethoxyphenyl group Chemical group [H][#6]-1=[#6](-[#8]C([H])([H])[H])-[#6](-*)=[#6](-[#8]C([H])([H])[H])-[#6]([H])=[#6]-1-[#8]C([H])([H])[H] 0.000 description 1
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 description 1
- KLIDCXVFHGNTTM-UHFFFAOYSA-N 2,6-dimethoxyphenol Chemical group COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 description 1
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical class CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- ZAWLBSATNLQTON-UHFFFAOYSA-N 2-nonynoic acid Chemical compound CCCCCCC#CC(O)=O ZAWLBSATNLQTON-UHFFFAOYSA-N 0.000 description 1
- BQDKCWCMDBMLEH-UHFFFAOYSA-N 2-octynoic acid Chemical compound CCCCCC#CC(O)=O BQDKCWCMDBMLEH-UHFFFAOYSA-N 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- OUEGWZIFRRGOGQ-UHFFFAOYSA-N 3,5-diethylaniline Chemical compound CCC1=CC(N)=CC(CC)=C1 OUEGWZIFRRGOGQ-UHFFFAOYSA-N 0.000 description 1
- MKARNSWMMBGSHX-UHFFFAOYSA-N 3,5-dimethylaniline Chemical group CC1=CC(C)=CC(N)=C1 MKARNSWMMBGSHX-UHFFFAOYSA-N 0.000 description 1
- MJKNHXCPGXUEDO-UHFFFAOYSA-N 3,5-ditert-butylaniline Chemical compound CC(C)(C)C1=CC(N)=CC(C(C)(C)C)=C1 MJKNHXCPGXUEDO-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UIUXJKGIWBOBNV-UHFFFAOYSA-N 4-but-1-ynylbenzoic acid Chemical group C1(=CC=C(C(=O)O)C=C1)C#CCC UIUXJKGIWBOBNV-UHFFFAOYSA-N 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- WRDWWAVNELMWAM-UHFFFAOYSA-N 4-tert-butylaniline Chemical compound CC(C)(C)C1=CC=C(N)C=C1 WRDWWAVNELMWAM-UHFFFAOYSA-N 0.000 description 1
- KDDQRKBRJSGMQE-UHFFFAOYSA-N 4-thiazolyl Chemical compound [C]1=CSC=N1 KDDQRKBRJSGMQE-UHFFFAOYSA-N 0.000 description 1
- CWDWFSXUQODZGW-UHFFFAOYSA-N 5-thiazolyl Chemical group [C]1=CN=CS1 CWDWFSXUQODZGW-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- WJBHDZBQZOMDFF-UHFFFAOYSA-N 7-octynoic acid Chemical compound OC(=O)CCCCCC#C WJBHDZBQZOMDFF-UHFFFAOYSA-N 0.000 description 1
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- CFGDEFAYZGGGLU-UHFFFAOYSA-N 8-phenyloct-7-ynoic acid Chemical compound OC(=O)CCCCCC#CC1=CC=CC=C1 CFGDEFAYZGGGLU-UHFFFAOYSA-N 0.000 description 1
- QGFSQVPRCWJZQK-UHFFFAOYSA-N 9-Decen-1-ol Chemical compound OCCCCCCCCC=C QGFSQVPRCWJZQK-UHFFFAOYSA-N 0.000 description 1
- SILRSAWTHYWMLG-UHFFFAOYSA-N 9-phenylnon-8-ynoic acid Chemical compound OC(=O)CCCCCCC#CC1=CC=CC=C1 SILRSAWTHYWMLG-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- BKTCJEJRCBSGLW-UHFFFAOYSA-N C#CCCCCC.CC1=CC=C(C=C1C(=O)O)C(=O)O Chemical compound C#CCCCCC.CC1=CC=C(C=C1C(=O)O)C(=O)O BKTCJEJRCBSGLW-UHFFFAOYSA-N 0.000 description 1
- AWMHRVHGKOFCNI-UHFFFAOYSA-N C(CCCC)OC(C(C)(C)C)OOCCC(C)C Chemical compound C(CCCC)OC(C(C)(C)C)OOCCC(C)C AWMHRVHGKOFCNI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
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- 238000006887 Ullmann reaction Methods 0.000 description 1
- 241000545067 Venus Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CBMCZKMIOZYAHS-NSCUHMNNSA-N [(e)-prop-1-enyl]boronic acid Chemical compound C\C=C\B(O)O CBMCZKMIOZYAHS-NSCUHMNNSA-N 0.000 description 1
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- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- RZJRJXONCZWCBN-UHFFFAOYSA-N alpha-octadecene Natural products CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- VXVVUHQULXCUPF-UHFFFAOYSA-N cycloheptanamine Chemical compound NC1CCCCCC1 VXVVUHQULXCUPF-UHFFFAOYSA-N 0.000 description 1
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 1
- GCUVBACNBHGZRS-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopenta-2,4-dien-1-yl(diphenyl)phosphane iron(2+) Chemical compound [Fe++].c1cc[cH-]c1.c1cc[c-](c1)P(c1ccccc1)c1ccccc1 GCUVBACNBHGZRS-UHFFFAOYSA-N 0.000 description 1
- HFXKQSZZZPGLKQ-UHFFFAOYSA-N cyclopentamine Chemical compound CNC(C)CC1CCCC1 HFXKQSZZZPGLKQ-UHFFFAOYSA-N 0.000 description 1
- 229960003263 cyclopentamine Drugs 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- XNRAUTMOUDUPET-UHFFFAOYSA-N dodec-11-yn-1-ol Chemical compound OCCCCCCCCCCC#C XNRAUTMOUDUPET-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- YVXHZKKCZYLQOP-UHFFFAOYSA-N hept-1-yne Chemical compound CCCCCC#C YVXHZKKCZYLQOP-UHFFFAOYSA-N 0.000 description 1
- BVRCLEXKQNWTDK-UHFFFAOYSA-N hept-6-yn-1-ol Chemical compound OCCCCCC#C BVRCLEXKQNWTDK-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229950001891 iprotiazem Drugs 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OSSQSXOTMIGBCF-UHFFFAOYSA-N non-1-yne Chemical group CCCCCCCC#C OSSQSXOTMIGBCF-UHFFFAOYSA-N 0.000 description 1
- FKGFCVJJLGSFSB-UHFFFAOYSA-N non-8-en-1-ol Chemical compound OCCCCCCCC=C FKGFCVJJLGSFSB-UHFFFAOYSA-N 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BKEVGGILGWUWSB-UHFFFAOYSA-N nonan-5-amine Chemical compound CCCCC(N)CCCC BKEVGGILGWUWSB-UHFFFAOYSA-N 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- UMIPWJGWASORKV-UHFFFAOYSA-N oct-1-yne Chemical compound CCCCCCC#C UMIPWJGWASORKV-UHFFFAOYSA-N 0.000 description 1
- ATCNYMVVGBLQMQ-UHFFFAOYSA-N oct-7-yn-1-ol Chemical compound OCCCCCCC#C ATCNYMVVGBLQMQ-UHFFFAOYSA-N 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MINRDQDGBLQBGD-UHFFFAOYSA-N pent-2-ynoic acid Chemical group CCC#CC(O)=O MINRDQDGBLQBGD-UHFFFAOYSA-N 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005055 short column chromatography Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- YUQZOUNRPZBQJK-UHFFFAOYSA-N undec-10-yn-1-ol Chemical compound OCCCCCCCCCC#C YUQZOUNRPZBQJK-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
- C07C65/105—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups polycyclic
- C07C65/15—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups polycyclic with carboxyl groups on a condensed ring system containing more than two rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
- C07C65/19—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups having unsaturation outside the aromatic ring
-
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Abstract
公开了用于制备1,7-二取代的苝-3,4,9,10-四羧酸二酐和苝-3,4,9,10-四羧酸的中间体1,7-二取代的苝-3,4,9,10-四羧酸二酰亚胺(VI)及其制备方法和应用,式(VI)中各基团的定义见说明书中。
Description
本申请是国际申请日为1996年12月11日、国际申请号为PCT/EP 96/05525、国家申请号为96199128.3的专利申请的分案申请。
本发明涉及新的通式I的1,7-二取代苝-3,4,9,10-四羧酸二酐和通式Ia的苝-3,4,9,10-四羧酸
其中
L1和L2相互独立地为1,2-亚乙基,1,2-亚乙烯基和1,2-亚乙炔基;
R1和R2相互独立地为氢或C1-C30-烷基,它的碳链可被-个或多个
基团-O-,-S-,-NR3-,-CO-和/或-SO2-***,
以及/或者可被-COOR3,-SO3R3,羟基,氰基,C1-C6-烷氧基,C5-C8-环烷基或芳基或者被由氮原子连接的5-到
7-元杂环基取代一次或多次,该杂环基中可包括其他杂原子以
及/或者该杂环基可是芳香的,R3为氢或C1-C6-烷基,和制备苝-3,4,9,10-四羧酸二酐(I)或酸(Ia)的方法,以及它们作为颜料,激光染料和制备萤光染料,聚合物着色剂,颜料和颜料添加剂前体的用途。
本发明进一步涉及作为苝-3,4,9,10-四羧酸二酐(I)或酸(Ia)中间体的通式VI的新的1,7-二取代苝-3,4,9,10-四羧酸二酰亚胺
其中
X1为溴或-L-R,其中
L为1,2-亚乙基,1,2-亚乙烯基或1,2-亚乙炔基,R为氢或C1-C30-烷基,它的碳链可被一个或多个基团-O-,-S-,-NR3-,-CO-和/或-SO2-***,以及/或者可被-COOR3,-SO3R3,羟基,氰基,C1-C6-烷氧基,C5-C8-环烷基或芳基或者被由氮原子连接的5到7-元杂环基取代一次或多次,该杂环基中可包括其他杂原子以及/或者该杂环基可是芳香的,
R3为氢或C1-C6-烷基;
X2为溴或-L-R;
R4为C4-C30-烷基,它的碳链可被一个或多个基团-O-,-S-或-CO-***,或为可被C1-C6-烷基或C1-C6-烷氧基取代一次或多次的C5-C8-环烷基或芳基,
涉及制备苝-3,4,9,10-四羧酸二酰亚胺(VI)的方法。
已知苝-3,4,9,10-四羧酸及其酐为制备苝基酰亚胺(perylimide)颜料和苝基酰亚胺染料的重要中间体,而且它们本身也可用于高分子量的有机材料的染色或着色。
除了可通过苝-3,4,9,10-四羧酸二酰亚胺在浓硫酸中在约200℃下水解得到的未取代的苝-3,4,9,10-四羧酸外,特别令人感兴趣的是在苝骨架上有取代基的苝四羧酸,通过引入合适的取代基可产生有用的性质,如溶解性,固有的颜色和萤光。
WO-A-94/25504公开了通过相应的二酰亚胺在极性质子溶剂中碱水解制备的1,6,7,12-四芳氧基取代的苝-3,4,9,10-四羧酸二酐。四芳氧基取代的二酰亚胺本身通过四氯化的二酰亚胺与芳基化物反应得到(EP-A-227980)。
到目前为止,还没有文献公开1,7-二取代的苝-3,4,9,10-四羧酸,如新化合物(Ia),它们象所有苝-3,4,9,10-四羧酸一样,通常以二酐形式存在。另外,EP-A-39912和DE-A-412122中所述的二卤化的苝-3,4,9,10-四羧酸二酰亚胺总是产物与不同程度卤化的物质(特别是四-,三-,和单卤化物)的混合物;特定地制备二卤化的二酰亚胺是不可能的。
因此,本发明的一个目的是提供新的1,7-二取代的苝-3,4,9,10-四羧酸和二酐。
我们已经发现通过上面定义的式I和Ia的1,7-二取代的苝-3,4,9,10-四羧酸二酐和相应的酸(下面称为二酐I)可达到这个目的,它们可被对称或不对称地取代。
优选的二酐I为从属权利要求的主题。
我们也已发现制备对称的二酐I的方法,其中包括
a)使1,7-二溴苝-3,4,9,10-四羧酸二酐(II)或1,7-二溴苝-3,4,9,10-四羧酸(IIa)在极性非质子溶剂存在下以及在有或无酰亚胺化催化剂存在下与通式III伯胺反应
R4-NH2 III
其中R4为C4-C30-烷基,它的碳链可被一个或多个基团-O-,-S-或-CO-***,或为可被C1-C6-烷基或C1-C6-烷氧基取代一次或多次的C5-C8-环烷基或芳基,
b)使步骤a)中生成的通式IV的1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺
在非质子溶剂,作为催化剂的钯配合物,作为助催化剂的铜盐和碱的存在下,与通式V的1-炔
H-C≡C-R1 V
以1∶2到1∶4的摩尔比反应,以及
使步骤b)中生成的通式VI′的对称的1,7-二取代的苝-3,4,9,10-四羧酸二酰亚胺水解
如果需要,可在极性质子溶剂和碱的存在下进一步还原L1中的不饱和键,形成对称的二酐I。
我们也已经发现制备不对称二酐I的方法,该方法与步骤a)中制备对称二酐的方法相应,只是在步骤b)中使1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺IV同样在非质子溶剂,作为催化剂的钯配合物,作为助催化剂的铜盐和碱存在下-首先与通式Va的1-炔
H-C≡C-R1 Va
然后与通式Vb的不同1-炔
H-C≡C-R2 Vb
各以1∶1到1∶2的摩尔比反应,然后将所得通式VI″的不对称1,7-二取代的苝-3,4,9,10-四羧酸二酰亚胺
按步骤c)水解,如果需要,可在极性质子溶剂和碱存在下进一步还原L1和L2中的不饱和键,得到不对称的二酐I。
我们还发现了作为二酐I中间体的正如式VI定义的1,7-二取代的苝-3,4,9,10-四羧酸二酰亚胺(称为苝基酰亚胺VI),它同样也可为对称或不对称取代,以及制备苝基酰亚胺VI的方法,其中包括制备相应的二酐I的方法的步骤a)和b)。
优选的苝基酰亚胺VI为从属权利要求中的主题。
另外,我们还发现了二酐I作为颜料,激光染料和制备萤光染料,聚合物着色剂,颜料和颜料添加剂的前体的用途。
最后,我们也发现了苝基酰亚胺VI作为高分子有机材料和无机材料上色的颜料和染料,作为激光染料,以及作为用于电发光应用的有机材料的用途。
式I(包括Ia),III,IV,V(包括Va和Vb)和VI(包括VI′和VI″)中的各个烷基即可为直链的也可为支链的。取代的芳基通常可具有至多三个,优选一或二个,所述的取代基。
除氢外合适的基团R1和R2(以及它们的取代基)的具体实例为:
甲基,乙基,丙基,异丙基,丁基,异丁基,叔丁基,戊基,异戊基,新戊基,叔戊基,己基,2-甲基戊基,庚基,1-乙基戊基,辛基,2-乙基己基,异辛基,壬基,异壬基,癸基,异癸基,十一烷基,十二烷基,十三烷基,异十三烷基,十四烷基,十五烷基,十六烷基,十七烷基,十八烷基,十九烷基和二十烷基(上述名称异辛基,异壬基,异癸基和异十三烷基为俗名,由通过氧化合成所得到的醇衍生而来,-参见Ullmanns Encyklopdie der technischen Chemie,第4版第7卷,215-217,和第11卷,435和436);
2-甲氧基乙基,2-乙氧基乙基,2-丙氧基乙基,2-异丙氧基乙基,2-丁氧基乙基,2-和3-甲氧基丙基,2-和3-乙氧基丙基,2-和3-丙氧基丙基,2-和3-丁氧基丙基,2-和4-甲氧基丁基,2-和4-乙氧基丁基,2-和4-丙氧基丁基,3,6-二氧杂庚基,3,6-二氧杂辛基,4,8-二氧杂壬基,3,7-二氧杂辛基,3,7-二氧杂壬基,4,7-二氧杂辛基,4,7-二氧杂壬基,2-和4-丁氧基丁基,4,8-二氧杂癸基,3,6,9-三氧杂癸基,3,6,9-三氧杂十一烷基,3,6,9-三氧杂十二烷基,3,6,9,12-四氧杂十三烷基和3,6,9,12-四氧杂十四烷基;
2-甲硫基乙基,2-乙硫基乙基,2-丙硫基乙基,2-异丙硫基乙基,2-丁硫基乙基,2-和3-甲硫基丙基,2-和3-乙硫基丙基,2-和3-丙硫基丙基,2-和3-丁硫基丙基,2-和4-甲硫基丁基,2-和4-乙硫基丁基,2-和4-丙硫基丁基,3,6-二硫杂庚基,3,6-二硫杂辛基,4,8-二硫杂壬基,3,7-二硫杂辛基,3,7-二硫杂壬基,4,7-二硫杂辛基,4,7-二硫杂壬基,2-和4-丁硫基丁基,4,8-二硫杂癸基,3,6,9-三硫杂癸基,3,6,9-三硫杂十一烷基,3,6,9-三硫杂十二烷基,3,6,9,12-四硫杂十三烷基和3,6,9,12-四硫杂十四烷基;
2-(N-甲氨基)-和2-(N-乙氨基)乙基,2-(N,N-二甲氨基)乙基,2-和3-(N,N-二甲氨基)丙基,3-(N-异丙氨基)丙基,2-和4-(N-丙氨基)丁基,2-和4-(N,N-二甲氨基)丁基,6-甲基-3,6-二氮杂庚基,3,6-二甲基-3,6-二氮杂庚基,3,6-二氮杂辛基,3,6-二甲基-3,6-二氮杂辛基,9-甲基-3,6,9-三氮杂癸基,3,6,9-三甲基-3,6,9-三氮杂癸基,3,6,9-三氮杂十一烷基,3,6,9-三甲基-3,6,9-三氮杂十一烷基,12-甲基-3,6,9,12-四氮杂十三烷基和3,6,9,12-四甲基-3,6,9,12-四氮杂十三烷基;
丙-2-酮-1-基,丁-3-酮-1-基,丁-3-酮-2-基和2-乙基-戊-3-酮-1-基;
2-甲磺酰基乙基,2-乙磺酰基乙基,2-丙磺酰基乙基,2-异丙磺酰基乙基,2-丁磺酰基乙基,2-和3-甲磺酰基丙基,2-和3-乙磺酰基丙基,2-和3-丙磺酰基丙基,2-和3-丁磺酰基丙基,2-和4-甲磺酰基丁基,2-和4-乙磺酰基丁基,2-和4-丙磺酰基丁基和4-丁磺酰基丁基;
羧甲基,2-羧基乙基,3-羧基丙基,4-羧基丁基,5-羧基戊基,6-羧基己基,8-羧基辛基,10-羧基癸基,12-羧基十二烷基和14-羧基十四烷基;
甲基羧甲基,乙基羧甲基,丙基羧甲基,丁基羧甲基,戊基羧甲基,己基羧甲基,甲基-2-羧基乙基,乙基-2-羧基乙基,丙基-2-羧基乙基,丁基-2-羧基乙基,戊基-2-羧基乙基,己基-2-羧基乙基,甲基-3-羧基丙基,乙基-3-羧基丙基,丙基-3-羧基丙基,丁基-3-羧基丙基,戊基-3-羧基丙基,己基-3-羧基丙基,甲基-4-羧基丁基,甲基-5-羧基戊基,甲基-6-羧基己基,甲基-8-羧基辛基,甲基-10-羧基癸基,甲基-12-羧基十二烷基和甲基-14-羧基十四烷基;
磺基甲基,2-磺基乙基,3-磺基丙基,4-磺基丁基,5-磺基戊基,6-磺基己基,8-磺基辛基,10-磺基癸基,12-磺基十二烷基和14-磺基十四烷基;
甲基磺基甲基,乙基磺基甲基,丙基磺基甲基,丁基磺基甲基,戊基磺基甲基,己基磺基甲基,甲基-2-磺基乙基,乙基-2-磺基乙基,丙基-2-磺基乙基,丁基-2-磺基乙基,戊基-2-磺基乙基,己基-2-磺基乙基,甲基-3-磺基丙基,乙基-3-磺基丙基,丙基-3-磺基丙基,丁基-3-磺基丙基,戊基-3-磺基丙基,己基-3-磺基丙基,甲基-4-磺基丁基,甲基-5-磺基戊基,甲基-6-磺基己基,甲基-8-磺基辛基,甲基-10-磺基癸基,甲基-12-磺基十二烷基和甲基-14-磺基十四烷基;
2-羟基乙基,2-和3-羟基丙基,1-羟基丙基-2-基,2-和4-羟基丁基,1-羟基-丁-2-基和8-羟基-4-氧杂辛基,2-氰基丁基,3-氰基丙基,2-甲基-3-乙基-3-氰基丙基,7-氰基-7-乙基庚基和4-甲基-7-甲基-7-氰基庚基;
甲氧基,乙氧基,丙氧基,异丙氧基,丁氧基,异丁氧基,叔丁氧基,戊氧基,异戊氧基,新戊氧基,叔戊氧基和己氧基;
环戊基,环己基,环庚基,环辛基,2-噁烷基,4-吗啉基,2-和3-四氢呋喃基,1-,2-和3-吡咯烷基和1-,2-,3-和4-哌啶基;
苯基,2-萘基,2-和3-吡咯基,2-,3-和4-吡啶基,2-,4-和5-嘧啶基,3-,4-和5-吡唑基,2-,4-和5-咪唑基,2-,4-和5-噻唑基,3-(1,2,4-三嗪基),2-(1,3,5-三嗪基),6-喹哪啶基,3-,5-,6-和8-喹啉基,2-苯并噁唑基,2-苯并噻唑基,5-苯并噻二唑基,2-和5-苯并咪唑基和1-和5-异喹啉基。
特别优选的基团-L-R(包括-L1-R1和-L2-R2)的实例为未取代或被C1-C18-烷基,特别是C4-C8-烷基取代的乙烯基和乙炔基,该烷基本身可被氰基,羟基,羧基,甲基羧基或乙基羧基取代,特别是端基(在ω位)取代。具体实例为:
乙炔基,1-丙炔基,1-丁炔基,1-戊炔基,3-甲基-1-丁炔基,1-己炔基,3-和4-甲基-1-戊炔基,3,3-二甲基-1-丁炔基,1-庚炔基,3-,4-和5-甲基-1-己炔基,3,3-,3,4-和4,4-二甲基-1-戊炔基,3-乙基-1-戊炔基,1-辛炔基,3-,4-,5-和6-甲基-1-庚炔基,3,3-,3,4-,3,5-,4,4-和4,5-二甲基-1-己炔基,3-,4-和5-乙基-1-己炔基,3-乙基-3-甲基-1-戊炔基,3-乙基-4-甲基-1-戊炔基,3,3,4-和3,4,4-三甲基-1-戊炔基,1-壬炔基,1-癸炔基,1-十一碳炔基和1-十二碳炔基;
4-氰基-1-丁炔基,5-氰基-1-戊炔基,6-氰基-1-己炔基,7-氰基-1-庚炔基和8-氰基-1-辛炔基;
4-羟基-1-丁炔基,5-羟基-1-戊炔基,6-羟基-1-己炔基,7-羟基-1-庚炔基,8-羟基-1-辛炔基,9-羟基-1-壬炔基,10-羟基-1-癸炔基,11-羟基-1-十一碳炔基和12-羟基十二碳炔基;
4-羧基-1-丁炔基,5-羧基-1-戊炔基,6-羧基-1-己炔基,7-羧基-1-庚炔基,8-羧基-1-辛炔基,4-甲羧基-1-丁炔基,5-甲羧基-1-戊炔基,6-甲羧基-1-己炔基,7-甲羧基-1-庚炔基,8-甲羧基-1-辛炔基,4-乙羧基-1-丁炔基,5-乙羧基-1-戊炔基,6-乙羧基-1-己炔基,7-乙羧基-1-庚炔基和8-乙羧基-1-辛炔基;
乙烯基,1-丙烯基,1-丁烯基,1-戊烯基,3-甲基-1-丁炔基,1-己炔基,3-和4-甲基-1-戊烯基,3,3-二甲基-1-丁烯基,1-庚烯基,3-,4-和5-甲基-1-己烯基,3,3-,3,4-和4,4-二甲基-1-戊烯基,3-乙基-1-戊烯基,1-辛烯基,3-,4-,5-和6-甲基-1-庚烯基,3,3-,3,4-,3,5-,4,4-和4,5-二甲基-1-己烯基,3-,4-,和5-乙基-1-己烯基,3-乙基-3-甲基-1-庚烯基,3-乙基-4-甲基-1-庚烯基,3,3,4-和3,4,4-三甲基-1-戊烯基,1-壬烯基,1-癸烯基,1-十一碳烯基和1-十二碳烯基;
4-氰基-1-丁烯基,5-氰基-1-戊烯基,6-氰基-1-己烯基,7-氰基-1-庚烯基和8-氰基-1-辛烯基;
4-羟基-1-丁烯基,5-羟基-1-戊烯基,6-羟基-1-己烯基,7-羟基-1-庚烯基,8-羟基-1-辛烯基,9-羟基-1-壬烯基,10-羟基-1-癸烯基,11-羟基-1-十一碳烯基和12-羟基-1-十二碳烯基;
4-羧基-1-丁烯基,5-羧基-1-戊烯基,6-羧基-1-己烯基,7-羧基-1-庚烯基,8-羧基-1-辛烯基,4-甲基羧基-1-丁烯基,5-甲基羧基-1-戊烯基,6-甲基羧基-1-己烯基,7-甲基羧基-1-庚烯基,8-甲基羧基-1-辛烯基,4-乙基羧基-1-丁烯基,5-乙基羧基-1-戊烯基,6-乙基羧基-1-己烯基,7-甲基羧基-1-庚烯基和8-乙基羧基-1-辛烯基。
合适的R3的例子为氢和上述C1-C6-烷基。
合适的R4的例子为上述C4-C30-烷基,它可被-O-,-S-或-CO-***,以及C5-C8-环烷基和芳基,例如萘基,特别是苯基,它们可被1,2或3个所述的C1-C6-烷基或C1-C6-烷氧基取代,如
2-,3-和4-甲基苯基,2,4-,3,5-和2,6-二甲基苯基,2,4,6-三甲基苯基,2-,3-和4-乙基苯基,2,4-,3,5-和2,6-二乙基苯基,2,4,6-三乙基苯基,2-,3-和4-三丙基苯基,2,4-,3,5-和2,6-二丙基苯基,2,4,6-三丙基苯基,2-,3-和4-异丙基苯基,2,4-,3,5-和2,6-二异丙基苯基,2,4,6-三异丙基苯基,2-,3-和4-丁基苯基,2,4-,3,5-和2,6-二丁基苯基,2,4,6-三丁基苯基,2-,3-和4-异丁基苯基,2,4-,3,5-和2,6-二异丁基苯基,2,4,6-三异丁基苯基,2-,3-和4-仲丁基苯基,2-,3-和4-甲氧基苯基,2,4-,3,5-和2,6-二甲氧基苯基,2,4,6-三甲氧基苯基,2-,3-和4-乙氧基苯基,2,4-,3,5-和2,6-二乙氧基苯基,2,4,6-三乙氧苯基,2-,3-和4-丙氧基苯基,2,4-,3,5-和2,6-二丙氧基苯基,2-,3-和4-异丙氧苯基,2,4-和2,6-二异丙氧基苯基和2-,3-和4-丁氧苯基。
二酐I的新的制备方法为多步骤合成。在步骤a)中,1,7-二溴苝-3,4,9,10-四羧酸二酐(II)与伯胺III反应形成相应的1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺IV,它在步骤b)中与1-炔V(或与不同的1-炔Va和Vb逐步)反应形成苝基酰亚胺VI,它最后在步骤c)中在碱性条件下被水解,如果需要,将桥结构L中的不饱和键进一步还原后,形成二酐I。
新制备方法的原料1,7-二溴苝-3,4,9,10-四羧酸二酐(II)可将苝-3,4,9,10-四羧酸二酐在100%重量的硫酸(单水合物)中选择性溴化而得到。
有利的制备过程包括首先将苝-3,4,9,10-四羧酸二酐在硫酸中搅拌2-16小时,然后加热该混合物,加入卤化催化剂如碘(优选量为每摩尔酐30-40mmol)后升至反应温度(一般为80-90℃)。这时慢慢地滴入溴(通常6-10小时),每摩尔酐优选地使用2-2.5摩尔溴(Br2)。冷却至室温及用氮气置换未反应的溴后,加入水,每次少量,以使硫酸的浓度降低至约85-88%重量。
反应混合物中1,7-二溴苝-3,4,9,10-四羧酸二酐(II)的后处理方法为:滤出沉淀出的产物,用85-88%重量的硫酸洗涤,将其在水中搅拌,再将该混合物过滤,用水洗涤产物,然后将其干燥。
新制备方法的步骤a),1,7-二溴苝-3,4,9,10-四羧酸二酐(II)与伯胺的反应,在极性非质子溶剂的存在下,在有或无酰亚胺化催化剂的存在下进行。
该步骤中合适的极性非质子溶剂具体为非质子含氮杂环化合物如吡啶,嘧啶,喹啉,异喹啉,喹哪啶,N-甲基哌啶,N-甲基哌啶酮以及特别是N-甲基吡咯烷酮。
溶剂的用量本身并不关键,通常为每kg(II)用5-20kg,优选10-15kg。
合适的酰亚胺化催化剂包括有机和无机酸,例如甲酸,乙酸,丙酸和磷酸,优选地使用高浓度形式,以及过渡金属如锌,铁和铜及镁的有机和无机盐,例如乙酸锌,丙酸锌,氧化锌,乙酸铁(II),氯化铁(III),硫酸铁(II),乙酸铜(II),氧化铜(II)和乙酸镁。当然,也可以使用这些催化剂的混合物。
当芳香族胺反应时,酰亚胺化催化剂的存在是特别合适的,当脂环族胺反应时,催化剂的存在也是有利的,而对于短链脂族胺通常不需要催化剂。
基于(II),通常需要使用5-80%重量的催化剂。对于有机酸,优选的量为50-80%,对于过渡金属盐和镁盐,该量为10-40%重量。
可用于新制备方法的伯胺为在反应条件下稳定的且与苝-3,4,9,10-四羧酸二酐反应形成在碱性条件下可被水解的酰二亚胺的所有化合物。
特别优选的伯胺III的例子为十八烷胺,5-壬基胺,环戊胺,环己胺,环庚胺,苯胺,4-甲基苯胺,4-乙基苯胺,4-叔丁基苯胺,3,5-二甲基苯胺,3,5-二乙基苯胺和3,5-二叔丁基苯胺。
胺III与(II)的摩尔比通常为约2∶1到4∶1,优选约2.2∶1到3∶1。
步骤a)通常在40-180℃下进行。脂族和环脂族胺的优选反应温度范围是60-100℃。而芳胺的优选反应温度范围为120-160℃。
在惰性气体气氛下反应(如使用氮气)是有利的。
新方法的步骤a)可在大气压或在高于大气压的压力,通常,至多10bar的压力下进行。当使用挥发性胺(沸点≤约180℃)时,使用高于大气压的压力特别有利。
反应通常进行2-10小时,特别是4-7小时。
步骤a)的具体过程有利地如下:
将1,7-二溴苝-3,4,9,10-四羧酸二酐(II),溶剂,以及,如果使用的话,催化剂加入反应器,在室温及搅拌下加入胺III,使氮气流过反应器约15分钟,并将反应混合物搅拌加热至反应温度并在该温度下保持约4-7小时。冷却至室温后,滤出反应产物,用脂族醇如甲醇洗涤并干燥。
当反应在超过大气压的压力下进行时,反应容器为压力容器,引入各组分后,在该容器中提供约1-2巴压力的氮气,然后将反应***在反应温度下加热所需的时间后冷却,然后使反应器减压。
为了进一步纯化,可将所得1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺IV溶于卤代烃如二氯甲烷,氯仿或四氯乙烷中,将该溶液通过硅胶过滤,并将滤液浓缩至干。如此处理的二酰亚胺IV的纯度通常>98%,因而它可直接用于随后的反应中。
在新制备方法的步骤b)中,在非质子溶剂,作为催化剂的钯配合物,作为助催化剂的铜盐,以及碱的存在下,1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺IV与1-炔V反应。
该步骤中合适的溶剂包括具有至多10个碳原子的线性和环状脂族醚,如***,二-正丙基醚,二-正丁基醚,1,2-二甲氧基乙烷,1,2-二乙氧基乙烷,二噁烷以及,特别是,四氢呋喃。
溶剂的用量本身并不关键,一般为每kg二酰亚胺IV用30-100kg,优选40-60kg溶剂。
加入的碱同时用作助溶剂。特别适用于这种目的的碱为可与醚混合以及熔点低于室温而沸点高于反应温度的有机含氮碱。
优选的碱为具有至多15个碳原子的脂族胺,特别是叔胺如三乙胺,三-正丙基胺和三-正丁基胺,和环状脂族胺如,特别是,哌啶。
通常每kg溶剂加入0.2-1.5kg,优选0.8-1.2kg碱。
所使用的催化剂为与作为助催化剂的铜(I)盐共同使用的钯配合物。
合适的钯配合物的例子为四(三-邻甲苯基膦)钯(O),[1,2-二(二苯基膦基)乙烷]钯(II)氯化物,[1,1′-二(二苯基膦基)二茂铁]钯(II)氯化物,二(三乙基膦)钯(II)氯化物,二(三环己基膦)钯(II)氯化物,二(三苯基膦)钯(II)乙酸盐,(2,2′-二吡啶基)钯(II)氯化物以及,特别是,四(三苯基膦)钯(O)二(三苯基膦)钯(II)氯化物,二(乙腈)钯(II)氯化物和二(苯基腈)钯(II)氯化物。
特别合适的铜(I)盐的例子是碘化铜(I)和溴化铜(I)。
在各种情况下,基于二酰亚胺IV,一般使用2-15mol%,优选5-10mol%的钯配合物,一般使用2-20mol%,优选7-12mol%铜(I)盐。
步骤b)的反应温度通常为20-140℃,尤其40-90℃。
根据所使用的炔,反应可在大气压下或超过大气压的压力,一般在至多50巴的压力下进行。当使用挥发性炔如乙炔时,使用超过大气压的压力是必要的。
当制备对称的苝基酰亚胺VI(VI′)时,原料化合物二酰亚胺IV和炔V的摩尔比一般为1∶2到1∶5,优选1∶2到1∶4。
当制备不对称的苝基酰亚胺VI(VI″)时,首先是苝骨架上两个溴原子中的一个与炔Va反应而被取代,然后第二个溴原子与不同的炔Vb反应而被取代,在各种情况下二酰亚胺与炔V的摩尔比一般为1∶1到1:2,优选1∶1到1∶1.5。
形成对称的苝基酰亚胺VI′的反应通常需要进行1-15小时,特别是2-10小时。相反地,作为反应中形成不对称的苝基酰亚胺VI″的中间体的单取代的单溴苝基酰亚胺的制备一般仅需要15-60分钟,特别是15-30分钟。随后形成二取代的苝基酰亚胺VI″的反应需要的时间与对称的苝基酰亚胺VI′所述的反应时间相等。
根据所选择的反应条件,新制备方法的步骤b)可产生包括作为桥结构L的1,2-亚乙炔基或1,2-亚乙烯基的苝基酰亚胺IV。
为了制备包括不饱和桥结构的苝基酰亚胺VI,在惰性气体(例如氩气或氮气)中反应是有利的。如果反应时间超过4小时和/或反应温度高于100℃,炔键将直接被还原成烯键。
通过随后在氢气氛下搅拌反应混合物可得到包括亚乙基基团L的苝基酰亚胺IV。但是使用如氢气与活性炭上的钯催化也可能随后发生不饱和键的按这类还原常见的步骤进行的还原(参见Larock,ComprehensiveOrganic Transformations,VCH Publishers New York,1989,6-17;March,Advanced Organic Chemistry,John Wiley andSons New York,4th Edition 1992,775-777;Journal ofOrganic Chemistry,Volume 45,4926-4931(1980))。
制备对称的苝基酰亚胺VI′的步骤b)的有利的具体的程序如下:
将搅拌的溶剂和碱(尽可能都是无水的)的混合物中的二酰亚胺IV的溶液或悬浮液装入反应器中,通过用干燥的氮气反复排气和送气而用氮气饱和该悬浮液,将铜(I)盐,钯配合物和1-炔V引入氮气逆流中(挥发性炔烃如乙炔被称量并以气体形式进入密闭的反应器),并将反应混合物在所需的反应温度加热所需的时间(≤4h或>4h)。然后,如果需要,引入氢气并将该混合物在反应温度下再搅拌4-8小时。随后(如果合适使反应器减压后)直接将反应混合物,即无需冷却,强力搅拌下,引入约三倍体积的几乎等重量份的浓盐酸和冰的混合物中,滤出粗产物,用一半浓度的盐酸洗涤,直到洗液无色,然后用水洗涤直到洗液中性,然后干燥。
为了进一步纯化,可将所得苝基VI用合适的溶剂例如卤代烃如二氯甲烷,氯仿或四氯乙烷,或环醚如二噁烷或四氢呋喃重结晶,或将其经硅胶短柱层析,这种情况下,根据R的官能度,可将上述溶剂或其混合物用作洗脱剂。
为了制备不对称的苝基酰亚胺VI″,可优选地按对称的苝基酰亚胺VI′中已描述的具体程序,只是首先加入减少量的1-炔Va,以及将该混合物在所需反应温度下加热15-30分钟。然后首先按上述分离单取代单溴苝基酰亚胺VI,或者直接与第二种1-炔Vb通过在所需反应温度下搅拌2-4小时或更长时间而反应。
反应混合物的后处理及随后粗产物的纯化当然可按上面对称的苝基酰亚胺VI′中所述进行。
按这种方法处理的苝基酰亚胺VI通常具有>98%的纯度,可直接用于随后的反应。不过,它们自身也可被用作有价值的颜料和染料。
新方法的步骤c),苝基酰亚胺VI水解形成二酐I,在极性质子溶剂和碱的存在下进行(如果合适,在苝基酰亚胺还原后)。
该步骤中特别合适的极性质子溶剂为C1-C10-链烷醇如乙醇,丙醇,正丁醇,叔丁醇,2-甲基-2-丁醇,正己醇,正癸醇以及,优选地,异丙醇。为了加速水解通常在每毫摩尔苝基酰亚胺VI中加入0.1-0.2mol水是有利的。
溶剂的用量本身并不关键,每kg苝基酰亚胺VI一般需50-200kg,优选60-80kg。
特别合适的碱为碱金属氢氧化物,如氢氧化钠和氢氧化钾,用量一般为每kg苝基酰亚胺VI使用4-10kg,优选5-7kg碱。
步骤c)的反应温度通常为20-140℃,优选40-90℃。
水解通常需3-10小时,特别是4-6小时。
新制备方法的步骤c)的具体程序有利地如下:
将苝基酰亚胺VI,溶剂和碱的混合物在所需反应温度下加热4-6小时,并冷却至室温,将冷却过程中沉淀出的粗产品滤出并用醇如异丙醇或丙醇洗涤,直到洗涤液无色。为了进一步纯化,优选地将所得二酐I转入30-100倍量的稀无机酸,例如5-10%重量的盐酸,短暂沸腾后冷却并过滤,将产物用水洗至中性并干燥。
使用新的制备方法可以技术简单及经济的工艺得到高产率高纯度(一般>95%)的1,7-二取代的苝-3,4,9,10-四羧酸二酐I。
新的二酐I可有利地用于着色印刷墨水,涂料组合物,特别是日光-萤光着色剂,和塑料,用作激光染料和制备萤光染料,聚合物染色剂,颜料和颜料添加剂的前体。
新的苝基酰亚胺VI也可有利地用作为高分子有机材料和无机材料上色的颜料和染料,用作激光染料,用作供电发光应用的有机材料。
实施例
A)1,7-二溴苝-3,4,9,10-四羧酸二酐(II)的制备
实施例1
将292.5g(0.75mol)苝-3,4,9,10-四羧酸二酐(纯度>98%)和4420g 100%重量的硫酸的混合物在室温下搅拌12小时,然后加入7g碘,并将其加热至85℃。随后在8小时内滴加262.5g(1.64mol)溴。
将反应混合物冷却至室温,用氮气置换过量的溴,然后,每次少量,在1小时内加入670g水,使硫酸的浓度降至86%重量。加入期间,反应混合物又升至85℃:将其冷却,并将沉淀出的产物用G4玻璃料过滤,用3kg 86%重量的硫酸洗涤,然后在5l水中搅拌;再将混合物过滤,将产物洗涤至中性并在120℃减压干燥。
所得到的370g II为亮红色细晶状粉末,熔点>360℃,纯度>98%,相应地产率为90%。
分析数据:
元素分析(%重量计算值/实测值):
C:52.4/52.1;H:1.1/1.1;O:17.45/17.4;Br:29.1/29.4;
IR(KBr):v=1782+1770(s,C=O),1735+1723(s,C=O)cm-1;
UV/VIS(H2SO4):λmax(ε)=408(10309),520(29410),554
(43141)nm.
B)1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺IV的制备
实施例2和3
搅拌下,首先将ag酰亚胺化催化剂K,然后每次少量将381mmol伯胺R4-NH2(III)加入69.9g(127mmol)1,7-二溴苝-3,4,9,10-四羧酸二酐(II)(实施例1)在900ml N-甲基吡咯烷酮中的混合物中。将反应混合物在氮气氛下加热到反应温度T℃,并在该温度下搅拌6小时。
冷却至室温后,将沉淀出的反应产物滤出,用总量2l的甲醇洗涤并在100℃减压干燥。
这些实验的细节和结果收集于表1。
表1
实施例 | R4 | ag | 催化剂K | T℃ | 结果 | |||
产率[g]/[%] | 纯度[%] | 外观 | m.p.[℃] | |||||
2 | 环己基 | 42.8 | 冰乙酸 | 85 | 75.1/83 | 97 | 亮红色,微晶 | >360 |
3 | 3,5-二甲苯基 | 17.5 | 乙酸锌 | 140 | 83.8/87 | 96 | 品红,结晶 | >360 |
实施例2a
为了进一步纯化,将实施例2所得65.3g N,N′-二环己基-1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺(IVa)在800ml二氯甲烷中搅拌1小时,然后将其通过用其2/3容量填充了硅胶的1e G4玻璃料过滤(0.063-0.2mm粒度;用二氯甲烷洗脱)。
减压蒸发滤液除去二氯甲烷,得到58g纯度>99%的橙红色结晶粉末状IVa。
分析数据:
元素分析(%重量计算值/实测值):
c:60.7/60.6;H:4.0/4.0;N:3.9/3.9;O:9.0/9.0;
Br:22.4/22.3;
IR(KBr):v=1698(s,C=O),1655(s,C=O)cm-1;
UV/VIS(CHCl3):λmax(ε)=491(33962),526(50478)nm.
实施例3a
使用热四氯乙烷作为洗脱剂,按与实施例2a相似的方法,将80g实施例3得到的N,N′-二(3′,5′-二甲基苯基)-1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺(IVb)纯化。
得到75g纯度>98%亮红色结晶粉末状IVb。
分析数据:
元素分析(%重量计算值/实测值):
C:63.5/63.3;H:3.2/3.2;N:3.7/3.7;O:8.5/8.6;
Br:21.1/21.2;
质量(FD):m/z=754(M+,100%);
IR(KBr):v=1696(s,C=O),1653(s,C=O)cm-1;
UV/VIs(CHCl3);λmax (ε)=485(29214),532(45100)nm.
C)1,7-二取代的苝-3,4,9,10-四羧酸二酰亚胺VI的制备
实施例4到10
分别将实施例2a和3a所得的2.45mmol纯化的1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺(IV)在氮气逆流中,在搅拌下,引入100ml无水四氢呋喃和100ml新蒸过的哌啶(实施例4到6和9到10)或100ml三乙胺(实施例7和8)的混合物中,然后连续地加入45mg(0.23mmol)碘化铜(I),225mg(0.19mmol)四(三苯基膦)钯(O)和bmg(b′mmol)1-炔V,将该混合物在80℃(实施例4到6和9到10)或60℃(实施例7和8)在氮气氛下加热t小时。将所得黑-紫色(实施例9墨绿色)反应混合物冷却至室温,然后引入搅拌着的600ml一半浓度的盐酸中。将沉淀出的反应产物首先用400ml一半浓度的盐酸洗涤,然后用水洗至中性,并在100℃减压干燥。
将粗产物溶于80ml二氯甲烷中,并以二氯甲烷作为洗脱剂进行硅胶(0.063-0.2mm粒度)层析(柱330×100mm)。
这些实验的进一步细节及其结果收集于表2。
表2
实施例 | X1 | X2 | R4 | ag | 制备二酰亚胺IV的实施例 | bmg | b′mmol | 炔V | th | 结果 | |||
产率[g]/[%] | 纯度[%] | 外观 | 软化点[℃] | ||||||||||
4 | 1-己烯基 | ≡X1 | 环己基 | 1.74 | 2a | 508 | 6 | 1-己炔 | 8 | 0.89/50 | >98 | 黑紫色无定形物 | 70 |
5 | 1-己炔基 | ≡X1 | 环己基 | 1.74 | 2a | 508 | 6 | 1-己炔 | 4 | 1.05/60 | >98 | 黑紫色结晶 | 62 |
6 | 5-氰基-1-戊炔基 | ≡X1 | 环己基 | 1.74 | 2a | 560 | 6 | 5-己炔腈 | 4 | 1.12/62 | >98 | 黑紫色无定形物 | 71 |
7 | 1-十二碳炔基 | ≡X1 | 环己基 | 1.74 | 2a | 1627 | 9.8 | 1-十二碳腈 | 10 | 1.76/81 | >98 | 黑紫色无定形物 | 88 |
8 | 3-乙酰氧基-3-甲基-1-丁炔基 | ≡X1 | 环己基 | 1.74 | 2a | 1236 | 9.8 | 2-甲基-3-丁炔-2-乙酸酯 | 10 | 1.34/68 | >98 | 暗红色结晶 | 237 |
9 | 1-己炔基 | Br | 环己基 | 1.74 | 2a | 288 | 3.4 | 1-己炔 | 0.5 | 0.98/56 | >98 | 黑绿色,有光泽结晶 | 225 |
10 | 1-己烯基 | ≡X1 | 3,5-二-甲基-苯基 | 1.86 | 3a | 508 | 6 | 1-己炔 | 8 | 1.01/54 | >98 | 暗红色结晶 | 122 |
实施例4分析数据:
元素分析(%重量计算值/实测值):
c:80.2/80.0;H:7.0/7.1;N:3.9/3.8;O:8.9/9.1;
质量(FD):m/z=718(M+,100%);
IR(KBr):v=1696(s,C=O),1650(s,C=O)cm-1;
UV/VIS(CHCl3):λmax(ε)=286(22906),342(12569),398
(10544),442(9515),469(17094).540(12179)nm.
实施例5分析数据:
元素分析(%重量计算值/实测值):
C:80.6/79.8;H:6.5/6.7;N:3.9/3.8;O:8.95/9.6;
质量(FD):m/z=714(M+,100%);
IR(KBr):v=2210(w,C≡C),1695(s,C=O),1649
(s,C=O)cm-1;
UV/VIS(CHCl3):λmax(ε)=293(31542),403(15601),441
(7321),471(11359),538(26011)nm.
实施例6分析数据:
元素分析(%重量计算值/实测值):
c:78.2/77.7;H:5.5/5.6;N:7.6/7.5;O:8.7/9.1;
质量(FD):m/z=736(M+,100%);
IR(KBr):v=2238(m,C≡N),1698(s,C=O),1653
(s,C=O)cm-1;
UV/VIS (CHCl3):λmax(8)=292(30108),403(15831),442(6913),472(12003),540(24631)nm.
实施例7分析数据:
元素分析(%重量计算值/实测值):
c:81.6/81.5;H:8.0/8.0;N:3.2/3.2,O:7.25/7.3,
质量(FD):m/z=882(M+,100%);
IR(KBr):v=2206(w,C=C),1695(s,C=O),1650(s,C=O)cm-1;
UV/VIS(CHCl3):λmax(ε)=285(17642),294(19311),471
(6729),505(12936),543(21103)nm.
实施例8分析数据:
元素分析(%重量计算值/实测值):
C:74.8/74.6;H:5.75/5.8;N:3.5/3.5;O:15.95/16.1;
质量(FD):m/z=802(M+,100%);
IR(KBr):v=2209(w,C=C),1741(s,C=O,ester),1695
(s,C=O),1650(s,C=O)cm-1;
UV/VIS(CHCl3):λmax(ε)=288(19733),293(21004),473
(6610),514(14263),565(25317)nm.
实施例9分析数据:
元素分析(%重量计算值/实测值):
C:70.7/71.3;H:5.2/5.3;N:3.9/4.1;
O:9.0/8.7;Br:11.2/10.6;
质量(FD):m/z=712/714(M+,79Br/81Br,100%);
IR(KBr):v=1690(s,C=O),1652(s,C=O)cm-1;
UV/VIS(CHCl3):λmax(ε)=448(11950),629(15300)nm.
实施例10分析数据:
元素分析(%重量计算值/实测值):
C:81.9/81.7;H:6.0/6.1;N:3.7/3.7;O:8.4/8.5:
质量(FD):m/z=762(M+,100%);
IR(KBr):v=1694(s,C=O),1649(s,C=O)cm-1;
UV/VIS(CHCl3):λmax(ε)=290(25703),339(8112),401
(10291),458(15388),559(23900)nm.
实施例11
按与上述相似的方法,使0.8g(1.12mmol)由实施例9制备的N,N′-二环己基-1-己炔基-7-溴苝-3,4,9,10-四羧酸二酰亚胺与0.14g(1.5mmol)5-己腈反应4小时。
经柱层析纯化后,以64%的产率,得到0.52g纯度为98%,软化点为83℃,黑紫色微晶粉末状N,N′-二环己基-1-己炔基-7-(5′-氰基戊炔基)苝-3,4,9,10-四羧酸二酰亚胺(X1:1-己炔基;X2:5-氰基-1-戊炔基)。
分析数据:
元素分析(%重量计算值/实测值):
C:79.4/79.2;H:6.0/6.1;N:5.8/5.8;O:8.8/8.9:
质量(FD):m/z=725(M+,100%);
IR(KBr):v=2236(m,C≡N ),1695(s,C=O),1650
(s,C=O)cm-1;
UV/VIS(CHCl3):λmax(ε)=293(31542),403(15601),441
(7321),471(11359),538(26011)nm.
实施例12
将实施例4得到的1.0g(1.4mmol)N,N′-二环己基-1,7-二己烯基苝-3,4,9,10-四羧酸二酰亚胺溶于150ml甲醇中,将0.5g商品氢化催化剂(5%活性炭上的钯)加入,在1巴的氢气压下在室温下氢化该混合物。
滤除催化剂及蒸发溶剂后,以91%的产率,得到0.92g软化点在112℃,暗红色无定形粉末状N,N′-二环己基-1,7-二己基苝-3,4,9,10-四羧酸二酰亚胺(X1≡X2=己基)。
分析数据:
元素分析(%重量计算值/实测值):
C:79.75/79.7;H:7.55/7.5;N:3.85/3.8;O:8.85/8.9;
质量(FD):m/z=722(M+,100%);
IR(KBr):v=1695(s,C=O),1650(s,C=O)cm-1;
UV/VIs(CHCl3):λmax(ε)=278(19712),339(11823),398
(7210),463(8132),510(20101),554(29300)nm.
D)1,7-二取代苝-3,4,9,10-四羧酸二酐I的制备
实施例13
将10g实施例4制备的N,N′-二环己基-1,7-二己烯基苝-3,4,
9,10-四羧酸二酰亚胺,1l异丙醇,65g氢氧化钾和26g水回流5小时。冷却至室温后,将沉淀出的反应产物滤出,用异丙醇洗涤至洗液无色,然后将其引入搅拌着的1l 10%重量的盐酸,短暂加热煮沸。冷却至室温后,再将产物滤出,用水洗至中性并在100℃减压干燥。该实验中以88%的产率,得到6.8g纯度>98%(使用UV/VIS光谱和以三氯乙酸/甲苯作为流动相的硅胶半定量薄层层析检测),熔点>360℃,暗红色无定形粉末状1,7-二己烯基苝-3,4,9,10-四羧酸二酐(L1=L2=1,2-亚乙基,R1=R2=正-丁基)。
实施例14
按与实施例13相似的方法,使10g由实施例10制备的N,N′-二(3′,5′-二甲基苯基)-1,7-二己烯基苝-3,4,9,10-四羧酸二酰亚胺反应。
该实验以85%的产率得到6.2g质量与实施例13相同的1,7-二己烯基苝-3,4,9,10-四羧酸二酐。
实施例13和14的分析数据:
元素分析(%重量计算值/实测值):
C:77.7/77.6;H:5.1/5.1;O:17.2/17.3;
IR(KBr):v=1769(s,C=O),1722(s,C=O)cm-1;
UV/VIS(CHCl3);λmax(ε)=399(12732),532(46311)nm.
Claims (6)
1.通式VI所示的1,7-二取代的苝-3,4,9,10-四羧酸二酰亚胺
其中
X1为溴或-L-R,其中
L为1,2-亚乙基,1,2-亚乙烯基或1,2-亚乙炔基,以及
R为氢或C1-C30-烷基,它的碳链可被一个或多个基团-O-,-S-,-NR3,-CO-和/或-SO2-***,以及/或者可被-COOR3,-SO3R3,羟基,氰基,C1-C6-烷氧基,C5-C8-环烷基或芳基或者被由氮原子连接的5-到7-元杂环基取代一次或多次,该杂环基中可包括其他杂原子以及/或者该杂环基可是芳香的,
R3为氢或C1-C6-烷基,
X2为溴或-L-R;
R4为可在间位和/或对位被C1-C6-烷基或C1-C6-烷氧基取代的C5-C8-环烷基或苯基。
2.权利要求1所要求的化合物,其中
X1和X2为溴或相同的基团-L-R,其中
L为1,2-亚乙烯基或1,2-亚乙炔基,以及
R为氢或可被-COOR3,羟基,氰基,C1-C6-烷氧基,C5-C8-环烷基或芳基取代一次或多次的C1-C18烷基;
R4为可在间位和/或对位被C1-C6-烷基或C1-C6-烷氧基取代的C5-C8-环烷基或苯基。
3.一种制备权利要求1或2所要求的式VI对称化合物的方法,其中X1和X2为相同的基团-L-R,该方法包括
a)使1,7-二溴苝-3,4,9,10-四羧酸二酐(II)或1,7-二溴苝-3,4,9,10-四羧酸(IIa)在极性非质子溶剂存在下以及在有或无酰亚胺化催化剂的存在下与通式III伯胺反应
R4-NH2 III
以及
b)使步骤a)中生成的通式IV的1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺
在非质子溶剂,作为催化剂的钯配合物,作为助催化剂的铜盐和碱的存在下,与通式V的1-炔
H-C≡C-R1 V
以1∶2到1∶4的摩尔比反应,
其中,R1适用R的定义,
并且如果需要,进一步还原L中的不饱和键。
4.一种制备权利要求1或2所要求的式VI的不对称化合物的方法,
其中X1和X2为不同的基团-L-R,该方法包括
a)使1,7-二溴苝-3,4,9,10-四羧酸二酐(II)或1,7-二溴苝-3,4,9,10-四羧酸(IIa)在极性非质子溶剂存在下以及在有或无酰亚胺化催化剂的存在下与通式III伯胺反应
R4-NH2 III
以及
b)使步骤a)中生成的通式IV的1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺
在非质子溶剂,作为催化剂的钯配合物,作为助催化剂的铜盐和碱的存在下,首先与通式Va的1-炔
H-C≡C-R1 Va
然后再与通式Vb的不同的1-炔
H-C≡C-R2 Vb
各以1∶1到1∶2的摩尔比反应,
其中,R1和R2适用R的定义,但二者是彼此不同的,
并且如果需要,进一步还原L中的不饱和键。
5.一种制备通式IV的1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺的方法
其中R4为可在间位和/或对位被C1-C6-烷基或C1-C6-烷氧基取代的C5-C8-环烷基或苯基,该方法包括使1,7-二溴苝-3,4,9,10-四羧酸二酐(II)或,分别地,1,7-二溴苝-3,4,9,10-四羧酸(IIa)在极性非质子溶剂存在下以及在有或无酰亚胺化催化剂的存在下与通式III伯胺反应
R4-NH2 III.
6.权利要求1或2所要求的化合物作为高分子有机材料和无机材料着色的颜料或染料,作为激光染料或作为用于电发光用途的有机材料的用途。
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US6461543B2 (en) * | 2001-01-17 | 2002-10-08 | Omniglow Corporation | Chemiluminescent solution based on disubstituted perylene tetracarboxylic acids, their dianhydrides and diimides |
ATE344268T1 (de) * | 2001-08-01 | 2006-11-15 | Shell Int Research | Liganden und diese enthaltende katalysatorsysteme fur die herstellung von linearen alpha-olefinen aus ethylen |
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-
1995
- 1995-12-18 DE DE19547210A patent/DE19547210A1/de not_active Withdrawn
-
1996
- 1996-12-11 JP JP52248497A patent/JP4073486B2/ja not_active Expired - Lifetime
- 1996-12-11 US US09/091,263 patent/US6063181A/en not_active Expired - Lifetime
- 1996-12-11 WO PCT/EP1996/005525 patent/WO1997022608A1/de active IP Right Grant
- 1996-12-11 CN CN96199128A patent/CN1084749C/zh not_active Expired - Lifetime
- 1996-12-11 DE DE59605264T patent/DE59605264D1/de not_active Expired - Lifetime
- 1996-12-11 CN CNB011194650A patent/CN1229376C/zh not_active Expired - Lifetime
- 1996-12-11 EP EP96943081A patent/EP0869959B1/de not_active Expired - Lifetime
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1999
- 1999-09-24 US US09/404,534 patent/US6184378B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
CN1084749C (zh) | 2002-05-15 |
JP4073486B2 (ja) | 2008-04-09 |
WO1997022608A1 (de) | 1997-06-26 |
DE59605264D1 (de) | 2000-06-21 |
DE19547210A1 (de) | 1997-06-19 |
EP0869959A1 (de) | 1998-10-14 |
US6063181A (en) | 2000-05-16 |
JP2000502139A (ja) | 2000-02-22 |
US6184378B1 (en) | 2001-02-06 |
EP0869959B1 (de) | 2000-05-17 |
CN1326934A (zh) | 2001-12-19 |
CN1205705A (zh) | 1999-01-20 |
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