JP3559884B2 - Pyrrolidinophenothiazine compound, method for producing the same, method for producing phthalocyanine compound using the same - Google Patents
Pyrrolidinophenothiazine compound, method for producing the same, method for producing phthalocyanine compound using the same Download PDFInfo
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- JP3559884B2 JP3559884B2 JP26519197A JP26519197A JP3559884B2 JP 3559884 B2 JP3559884 B2 JP 3559884B2 JP 26519197 A JP26519197 A JP 26519197A JP 26519197 A JP26519197 A JP 26519197A JP 3559884 B2 JP3559884 B2 JP 3559884B2
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- Prior art keywords
- compound
- alkyl group
- general formula
- pyrrolidinophenothiazine
- producing
- Prior art date
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- -1 Pyrrolidinophenothiazine compound Chemical class 0.000 title claims description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 150000004703 alkoxides Chemical class 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 125000004436 sodium atom Chemical group 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 14
- 229950000688 phenothiazine Drugs 0.000 description 14
- 239000007795 chemical reaction product Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 6
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- 238000004440 column chromatography Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 4
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- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- 230000003287 optical effect Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- COSKNRFORIOBQX-UHFFFAOYSA-N 1,4-bis(3-methylbutoxy)-10h-phenothiazine-2,3-dicarbonitrile Chemical compound C1=CC=C2SC3=C(OCCC(C)C)C(C#N)=C(C#N)C(OCCC(C)C)=C3NC2=C1 COSKNRFORIOBQX-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 2
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 0 CCC(C)(*)CC(C(C)C1C(*)C2NC(CCCC3)=C3SC2C(**)C11)C1=* Chemical compound CCC(C)(*)CC(C(C)C1C(*)C2NC(CCCC3)=C3SC2C(**)C11)C1=* 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003136 n-heptyl 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])* 0.000 description 2
- 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 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- UJEGHEMJVNQWOJ-UHFFFAOYSA-N 1-heptoxyheptane Chemical compound CCCCCCCOCCCCCCC UJEGHEMJVNQWOJ-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- NRITXBDQNSPUDY-UHFFFAOYSA-N CCN1C2=CC=CC=C2SC3=C(C(=C(C(=C31)OCCC(C)C)C#N)C#N)OCCC(C)C Chemical compound CCN1C2=CC=CC=C2SC3=C(C(=C(C(=C31)OCCC(C)C)C#N)C#N)OCCC(C)C NRITXBDQNSPUDY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229940063656 aluminum chloride Drugs 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000006229 isopropoxyethyl group Chemical group [H]C([H])([H])C([H])(OC([H])([H])C([H])([H])*)C([H])([H])[H] 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- QXGWNQBBMBYNCC-UHFFFAOYSA-L manganese(2+) pentane-2,4-dione dichloride Chemical compound [Cl-].[Mn+2].C(C)(=O)CC(C)=O.[Cl-] QXGWNQBBMBYNCC-UHFFFAOYSA-L 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 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
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、新規なピロリジノフェノチアジン化合物及びその製造方法に関し、またこのピロリジノフェノチアジン化合物を用いたフタロシアニン化合物の製造方法に関する。本発明の製造方法により製造されるフタロシアニン化合物は、光カード、有機光導電体、近赤外線吸収フィルター、熱線遮蔽フィルム、光熱変換剤、保護眼鏡、レーザープリンターなどに用いられる近赤外線吸収色素として有用である。
【０００２】
【従来の技術】
ベンゾチアジノ基を有するフタロシアニン化合物は、近赤外線吸収能力、溶剤溶解性、耐久性に優れるため、光カード、有機光導電体、近赤外線吸収フィルター、熱線遮蔽フィルム、光熱変換剤、保護眼鏡、レーザープリンターなどへの応用が近年注目されている。
【０００３】
このようなフタロシアニン化合物として本発明者らが先に出願した特開平８−６０００８号公報には前記一般式（ＩＶ）の構造を有するフタロシアニン化合物が開示されており、その製造方法は特定のジニトリル化合物と金属または金属誘導体から製造する方法である。しかしながら、この方法は収率や反応速度の点で未だ不十分であり、工業的製造方法としての改良が望まれていた。
【０００４】
【発明が解決しようとする課題】
本発明の目的は、近赤外線吸収能力にすぐれるフタロシアニン化合物の製造方法及びこれを製造するための新規な中間体及びその製造方法を提供することである。
【０００５】
【課題を解決するための手段】
前記した課題を解決するために種々検討した結果、本発明者らは、特定の構造を有する新規なピロリジノフェノチアジン化合物を中間体として用いることにより、短い反応時間で収率良く目的のフタロシアニン化合物を得ることができることを見い出した。
【０００６】
本発明は、まず、一般式（Ｉ）で表わされる新規なピロリジノフェノチアジン化合物及びその製造方法に関する。
【０００７】
【化７】
また本発明は、前記一般式（Ｉ）で表わされるピロリジノフェノチアジン化合物と金属または金属誘導体とを反応させることを特徴とする、一般式（ＩＶ）で表わされるフタロシアニン化合物の製造方法に関する。
【０００８】
【化８】
（式中、Ｒ５〜Ｒ１２はアルキル基またはアルコキシアルキル基を示し、Ｘ１〜Ｘ８は硫黄原子または−ＮＲ１３を示し、Ｘ１＝（Ｘ３、Ｘ４のいずれか一方）＝（Ｘ５、Ｘ６のいずれか一方）＝（Ｘ７、Ｘ８のいずれか一方）＝硫黄原子であり、かつＸ２＝（Ｘ３、Ｘ４のもう一方）＝（Ｘ５、Ｘ６のもう一方）＝（Ｘ７、Ｘ８のもう一方）＝−ＮＲ１３である。Ｒ１３は水素原子またはアルキル基を示し、Ｍは２個の水素原子、２価の金属、３価の金属誘導体または４価の金属誘導体を示す。）
【００１０】
【発明の実施の形態】
本発明の第一の発明は、前記一般式（Ｉ）で表わされる新規なピロリジノフェノチアジン化合物である。
【００１１】
一般式（Ｉ）のピロリジノフェノチアジン化合物において、Ｒ１、Ｒ２がアルキル基である場合は、炭素数１〜１２の直鎖或いは分岐のアルキル基が好ましく、炭素数１〜８の直鎖或いは分岐のアルキル基が特に好ましい。例としてはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｎ−ヘキシル基、イソヘキシル基、ｓｅｃ−ヘキシル基、２−エチルブチル基、ｎ−ヘプチル基、イソヘプチル基、ｓｅｃ−ヘプチル基、ｎ−オクチル基、２−エチルヘキシル基が挙げられる。
【００１２】
Ｒ１、Ｒ２がアルコキシアルキル基である場合は、総炭素数２〜６のものが好ましい。例としてメトキシエチル基、メトキシプロピル基、メトキシブチル基、エトキシエチル基、エトキシプロピル基、エトキシブチル基、ｎ−プロポキシエチル基、ｉｓｏ−プロポキシエチル基、ｎ−プロポキシプロピル基が挙げられる。
Ｒ３がアルキル基であるものとしては炭素数１〜１２の直鎖或いは分岐のアルキル基が好ましく、炭素数１〜８の直鎖或いは分岐のアルキル基が特に好ましい。例としてはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｎ−ヘプチル基、イソヘプチル基、ｓｅｃ−ヘプチル基、ｎ−オクチル基、２−エチルヘキシル基が挙げられる。
【００１３】
一般式（Ｉ）で表わされる本発明のピロリジノフェノチアジン化合物の具体例を以下に示す。
【００１４】
【化９】
本発明の第二の発明は、一般式（ＩＩ）で表わされるジニトリル化合物とアンモニアとを、一般式（ＩＩＩ）で表わされるアルコキサイドの存在下に反応させることを特徴とする、一般式（Ｉ）で表わされるピロリジノフェノチアジン化合物の製造方法である。
【００２８】
【化１０】
【化１１】
【００３０】
【化１２】
Ｒ４Ｏ−Ｘ （ＩＩＩ）
（式中、Ｒ４はアルキル基またはアルコキシアルキル基を示し、Ｘはナトリウム原子、カリウム原子を示す。）
一般式（Ｉ）で表わされるピロリジノフェノチアジン化合物の製造方法の詳細を下記に説明する。
【００３１】
一般式（ＩＩＩ）の金属アルコキサイドとしては、ナトリウム或いはカリウムのそれぞれメトキサイド、エトキサイド、ｎ−プロポキサイド、ｎ−ブトキサイド、ｎ−ペントキサイド、ｎ−ヘキシルオキサイド、ｎ−ヘプチルオキサイド、ｎ−オクチルオキサイド、２−メトキシエトキサイド、２−エトキシエトキサイド、２−ｎ−ブトキシエトキサイド等が用いられる。 一般式（ＩＩＩ）の金属アルコキサイドの使用量は化合物（ＩＩ）に対し０．０１〜５モル、好ましくは０．１〜２．０モルである。
【００３２】
一般式（Ｉ）で表わされるピロリジノフェノチアジン化合物の製造においては、反応溶媒であるアルコールに金属ナトリウム、または金属カリウムを添加し、金属アルコキサイドのアルコール溶媒を調整した後、アンモニア及び一般式（ＩＩ）のジニトリル化合物を装入し反応させてもよく、また他の方法としては、アンモニア、一般式（ＩＩ）のジニトリル化合物及び別途調整した金属アルコキサイドを反応溶媒に装入して反応させてもよい。この際、使用する金属量は化合物（ＩＩ）に対し、０．０１〜５．０モル、好ましくは０．１〜２．０モルである。
【００３３】
アンモニアとしてはアンモニアガスを用いてもよいし、液体アンモニアを用いてもよいが、アンモニアガスを用いるのが、取り扱いの点で好ましい。
【００３４】
アンモニアの使用量は化合物（ＩＩ）１モルに対し１〜２０モルで、好ましくは３〜１０モルである。
【００３５】
反応に於いては、溶媒を併用することが好ましく、溶媒としてはアルコール系溶媒が特に好ましい。
【００３６】
アルコール系溶媒の例としては、メタノール、エタノール、ｎ−プロパノール、ｎ−ブタノール、ｎ−ペンタノール、ｎ−ヘキサノール、ｎ−ヘプタノール、ｎ−オクタノール、２−メトキシエタノール、２−エトキシエタノール、２−ｎ−ブトキシエタノール等が用いられる。使用する溶媒の量は化合物（ＩＩ）１モルに対し２００ｍＬ〜１５Ｌ、好ましくは５００ｍＬ〜５Ｌである。
【００３７】
反応温度は０℃〜溶媒の還流温度であり、好ましくは２０℃〜溶媒の還流温度である。
【００３８】
反応時間は３０分〜７２時間が好ましい。
【００３９】
反応後、反応に用いた溶媒を留去し、トルエン等の有機溶媒にて抽出、水洗し、濃縮して一般式（Ｉ）のピロリジノフェノチアジン化合物を得る。
【００４０】
本発明の第三の発明は、前記一般式（Ｉ）のピロリジノフェノチアジン化合物と金属または金属誘導体を反応させることを特徴とするフタロシアニン化合物の製造方法である。
【００４１】
本発明の製造方法で製造される式（ＩＶ）のフタロシアニン化合物の具体例を表１に示す。
【００４２】
表１中、一般式（ＩＶ）において、Ｒ５＝（Ｒ７、Ｒ８のいずれか一方）＝（Ｒ９、Ｒ１０のいずれか一方）＝（Ｒ１１、Ｒ１２のいずれか一方）、かつＲ６＝（Ｒ７、Ｒ８のもう一方）＝（Ｒ９、Ｒ１０のもう一方）＝（Ｒ１１、Ｒ１２のもう一方）である。
【００４３】
【表１】
一般式（ＩＶ）のフタロシアニン化合物の製造方法の詳細を下記に説明する。
金属または金属誘導体としては、Ａｌ、Ｓｉ、Ｔｉ、Ｖ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇｅ、Ｒｕ、Ｒｈ、Ｐｄ、Ｉｎ、Ｓｎ、Ｐｔ、Ｐｂ及びこれらのハロゲン化物、カルボン酸塩、硫酸塩、硝酸塩、カルボニル化合物、酸化物、錯体等が挙げられる。特にこれらのハロゲン化物またはカルボン酸塩が好ましく用いられ、例としては塩化銅、臭化銅、沃化銅、塩化ニッケル、臭化ニッケル、酢酸ニッケル、塩化コバルト、臭化コバルト、酢酸コバルト、塩化鉄、塩化亜鉛、臭化亜鉛、沃化亜鉛、酢酸亜鉛、塩化バナジウム、オキシ三塩化バナジウム、塩化パラジウム、酢酸パラジウム、塩化アルミニウム、塩化マンガン、酢酸マンガン、アセチルアセトンマンガン、塩化マンガン、塩化鉛、酢酸鉛、塩化インジウム、塩化チタン、塩化スズ等が挙げられる。
【００５８】
金属または金属誘導体の使用量は、一般式（Ｉ）のピロリジノフェノチアジン化合物に対して０．１〜０．６倍モル、好ましくは０．２〜０．５倍モルである。
【００５９】
反応温度は６０〜３００℃、好ましくは１００〜２００℃である。
【００６０】
反応に於いては、溶媒を使用することが、好ましい。
【００６１】
反応に使用される溶媒としては沸点６０℃以上、好ましくは８０℃以上の有機溶媒が好ましい。例として、メタノール、エタノール、ｎ−プロピルアルコール、ｎ−ブチルアルコール、イソブチルアルコール、ｔ−ブチルアルコール、ｎ−アミルアルコール、ｎ−ヘキサノール、シクロヘキサノール、２−メチル−１−ペンタノール、１−ヘプタノール、２−ヘプタノール、１−オクタノール、２−エチルヘキサノール、ベンジルアルコール、エチレングリコール、プロピレングリコール、エトキシエタノール、プロポキシエタノール、ブトキシエタノール、ジメチルアミノエタノール、ジエチルアミノエタノール等のアルコール溶媒、トリクロロベンゼン、クロロナフタレン、スルフォラン、ニトロベンゼン、キノリン、尿素等の高沸点溶媒が挙げられる。
【００６２】
溶媒の使用量は一般式（Ｉ）のジニトリル化合物に対して０．５〜５０倍重量、好ましくは１〜１５倍重量である。
【００６３】
反応は触媒の存在下或いは非存在下に進行し、触媒としてはモリブデン酸アンモニウム等の無機触媒、或いはＤＢＵ（１，８−ジアザビシクロ［５．４．０］−７−ウンデセン）、ＤＢＮ（１，５−ジアザビシクロ［４．３．０］−５−ノネン）等の塩基性有機触媒を使用できる。添加量はジニトリル化合物１モルに対して、０．０１〜１０モル、好ましくは０．１〜２モルである。
【００６４】
後処理としては、反応後に溶媒を留去するか、または反応液をフタロシアニン化合物に対する貧溶媒に排出して析出物をろ取することにより反応生成物が得られる。この反応生成物はこのままでも種々の用途に使用し得る程度に充分な純度を有しているが、更に高純度品を得るために、カラムクロマトグラフィー等で精製してもよい。
【００６５】
本発明のピロリジノフェノチアジン化合物より得られたフタロシアニン化合物は、光カード、有機光導電体、近赤外線吸収フィルター、熱線遮蔽フィルム、光熱変換剤、保護眼鏡、レーザープリンターなどの用途に対し十分な純度を要し、収率も高いため、本発明の製造方法は極めて有用な製造方法である。
【００６６】
【実施例】
以下に、実施例により本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、各実施例、比較例においては［部］は［重量部］を示す。
【００６７】
（実施例１） １，３−ジイミノ−４，１１−ジイソペントキシピロリジノ［３，４−ｂ］フェノチアジン（具体例Ｉ−（２９）の化合物）の製造
２５０部のｎ−プロピルアルコールに金属ナトリウム２．４３部を溶解させた液へ室温下、アンモニアガスを１７部導入した。次いで、１，４−ジイソペントキシ−２，３−ジシアノフェノチアジン６３．３部を添加し、６０〜６５℃で１５時間撹拌した。冷却後、ｎ−プロピルアルコールを留去し、残渣へトルエン５００部を加え、３０〜４０℃で加温溶解した。次いで、水３００ｇを加え、分散、静置、分液した。同操作を４回繰り返すことにより、アルカリ分を除去した。次いで、トルエン層よりトルエンを留去し、ｎ−ヘプタン４００部を加え、６０〜６５℃で３０分撹拌後、室温まで冷却した。析出した茶色結晶を濾取、乾燥して下記構造式の１，３−ジイミノ−４，１１−ジイソペントキシピロリジノ［３，４−ｂ］フェノチアジン６２．４部（収率９４・８％）を得た。
【００６８】
【化１３】
この結晶の元素分析値、質量分析値及び融点は、下記の通りであった。この化合物の赤外吸収スペクトルを図１に示す。
（実施例２） １，３−ジイミノ−４，１１−ジ（２−エトキシエトキシ）ピロリジノ［３，４−ｂ］フェノチアジン（具体例Ｉ−（７５）の化合物）の製造
実施例１において、１，４−ジイソペントキシ−２，３−ジシアノフェノチアジン６３．３部の代わりに１，４−ジ（２−エトキシエトキシ）−２，３−ジシアノフェノチアジン７．２３部を用いた以外は実施例１と同様の操作を行って、下記構造式１，３−ジイミノ−４，１１−ジ（２−エトキシエトキシ）ピロリジノ［３，４−ｂ］フェノチアジンの茶色結晶６．６１部（収率８７．９％）を得た。
【００７１】
【化１４】
この結晶の元素分析値、質量分析値及び融点は、下記の通りであった。この化合物の赤外吸収スペクトルを図２に示す。
（実施例３） １，３−ジイミノ−４，１１−ジイソペントキシ−１０−エチルピロリジノ［３，４−ｂ］フェノチアジン（具体例Ｉ−（３０）の化合物）の製造
実施例１において、１，４−ジイソペントキシ−２，３−ジシアノフェノチアジン６３．３部の代わりに１，４−ジイソペントキシ−２，３−ジシアノ−１０−エチルフェノチアジン１５．７部を用いた以外は実施例１と同様の操作を行って、下記構造式１，３−ジイミノ−４，１１−ジイソペントキシ−１０−エチルピロリジノ［３，４−ｂ］フェノチアジンの黄色結晶１７．５部（収率８４．５％）を得た。
【００７４】
【化１５】
この結晶の元素分析値、質量分析値及び融点は、下記の通りであった。この化合物の赤外吸収スペクトルを図３に示す。
（実施例４） フタロシアニン化合物（具体例ＩＶ−（３４）の化合物）の製造
２−ｎ−ブトキシエタノール１５部と実施例１で製造した１，３−ジイミノ−４，１１−ジイソペントキシピロリジノ［３，４−ｂ］フェノチアジン４．３９部の混合物を１３０℃に加熱後、ＤＢＵ０．７６部及び塩化バナジウム０．４７部を添加した。次いで、１５５〜１６０℃で２時間撹拌した後、６０〜７０℃に冷却してメタノール１５０部を添加した。室温まで冷却した後、結晶を濾取、乾燥して下記構造式のフタロシアニン化合物４．１８部（収率９５．５％）を得た。
【００７７】
この反応生成物のトルエン中でのグラム吸光係数（εｇ）及び最大吸収波長（λｍａｘ）は下記の通りであった。
【００７８】
εｇ：９．３×１０４ ｍｌ／ｇ．ｃｍ
λｍａｘ：８３０ｎｍ
この反応生成物をカラムクロマトグラフィーにて精製することにより、高純度の青緑黒色粉末２．７２部（εｇ：１．３０×１０５ ｍｌ／ｇ．ｃｍ、λｍａｘ：８３０ｎｍ）を得た。
【００７９】
【化１６】
（実施例５） フタロシアニン化合物（具体例ＩＶ−（２７）の化合物）の製造
実施例４において、塩化バナジウム０．４７部の代わりに塩化第一銅０．３０部を用い、反応時間を５時間とした以外は実施例４と同様の操作を行って、下記構造式のフタロシアニン化合物４．２８部（収率９７．９％）を得た。
【００８１】
この反応生成物のトルエン中でのグラム吸光係数（εｇ）及び最大吸収波長（λｍａｘ）は下記の通りであった。
【００８２】
εｇ：９．１×１０４ ｍｌ／ｇ．ｃｍ
λｍａｘ：７８９ｎｍ
この反応生成物をカラムクロマトグラフィーにて精製することにより、容易に高純度品を得ることが出来た。
【００８３】
【化１７】
（実施例６） フタロシアニン化合物（具体例ＩＶ−（９３）の化合物）の製造
実施例４において、１，３−ジイミノ−４，１１−ジイソペントキシ−ピロリジノ［３，４−ｂ］フェノチアジン４．３９部の代わりに実施例２で製造した１，３−ジイミノ−４，１１−ジ（２−エトキシエトキシ）ピロリジノ［３，４−ｂ］フェノチアジン４．１５部を用いた以外は実施例４と同様の操作を行って、下記構造式のフタロシアニン化合物３．６５部（収率８８．１％）を得た。
【００８５】
この結晶のトルエン中でのグラム吸光係数（εｇ）及び最大吸収波長（λｍａｘ）下記の通りであった。
【００８６】
εｇ：８．２×１０４ ｍｌ／ｇ．ｃｍ
λｍａｘ：８３０ｎｍ
この反応生成物をカラムクロマトグラフィーにて精製することにより、容易に高純度品を得ることが出来た。
【００８７】
【化１８】
（実施例７） フタロシアニン化合物（具体例ＩＶ−（３６）の化合物）の製造
実施例４において、１，３−ジイミノ−４，１１−ジイソペントキシ−ピロリジノ［３，４−ｂ］フェノチアジン４．３９部、塩化バナジウム０．４７部の代わりに、それぞれ実施例３で製造した１，３−ジイミノ−４，１１−ジイソペントキシ−１０−エチルピロリジノ［３，４−ｂ］フェノチアジン４．６７部、塩化第一銅０．３０部を用い、反応時間を５時間とした以外は実施例４と同様の操作を行って、下記構造式のフタロシアニン化合物の粗製物３．１２部（収率７５．３％）を得た。
【００８９】
この反応生成物のトルエン中でのグラム吸光係数（εｇ）及び最大吸収波長（λｍａｘ）は下記の通りであった。
【００９０】
εｇ：１．１×１０５ ｍｌ／ｇ．ｃｍ
λｍａｘ：７７４ｎｍ
この反応生成物をカラムクロマトグラフィーにて精製することにより、容易に高純度品を得ることが出来た。
【００９１】
【化１９】
【発明の効果】
新規なピロリジノフェノチアジン化合物を中間体として用いることにより近赤外線吸収能力に優れるフタロシアニン化合物を高収率、短時間で製造することができる。また、反応生成物の純度が高いため、容易に高純度品を得ることができる。
【図面の簡単な説明】
【図１】実施例１で製造した１，３−ジイミノ−４，１１−ジイソペントキシピロリジノ［３，４−ｂ］フェノチアジンの赤外吸収スペクトルである。
【図２】実施例２で製造した１，３−ジイミノ−４，１１−ジ（２−エトキシエトキシ）ピロリジノ［３，４−ｂ］フェノチアジンの赤外吸収スペクトルである。
【図３】実施例３で製造した１，３−ジイミノ−４，１１−ジイソペントキシ−１０−エチルピロリジノ［３，４−ｂ］フェノチアジンの赤外吸収スペクトルである。[0001]
[Industrial applications]
The present invention relates to a novel pyrrolidinophenothiazine compound and a method for producing the same, and also relates to a method for producing a phthalocyanine compound using the pyrrolidinophenothiazine compound. The phthalocyanine compound produced by the production method of the present invention is useful as a near-infrared absorbing dye used in optical cards, organic photoconductors, near-infrared absorbing filters, heat ray shielding films, photothermal conversion agents, protective glasses, laser printers and the like. is there.
[0002]
[Prior art]
Phthalocyanine compounds having a benzothiazino group are excellent in near-infrared absorption ability, solvent solubility, and durability, so optical cards, organic photoconductors, near-infrared absorption filters, heat ray shielding films, photothermal conversion agents, protective glasses, laser printers, etc. Application to GaN has recently attracted attention.
[0003]
As such a phthalocyanine compound, a phthalocyanine compound having the structure of the above general formula (IV) is disclosed in Japanese Patent Application Laid-Open No. Hei 8-60008 filed by the present inventors, and its production method is a specific dinitrile compound. And a metal or metal derivative. However, this method is still insufficient in terms of yield and reaction rate, and improvement as an industrial production method has been desired.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing a phthalocyanine compound having excellent near-infrared absorbing ability, a novel intermediate for producing the same, and a method for producing the same.
[0005]
[Means for Solving the Problems]
As a result of various studies to solve the above-described problems, the present inventors have found that by using a novel pyrrolidinophenothiazine compound having a specific structure as an intermediate, the desired phthalocyanine compound can be obtained in a short reaction time and in good yield. I found what I could get.
[0006]
The present invention firstly relates to a novel pyrrolidinophenothiazine compound represented by the general formula (I) and a method for producing the same.
[0007]
Embedded image
The present invention also relates to a method for producing a phthalocyanine compound represented by the general formula (IV), comprising reacting the pyrrolidinophenothiazine compound represented by the general formula (I) with a metal or a metal derivative.
[0008]
Embedded image
(Wherein, R 5 to R 12 represent an alkyl group or an alkoxyalkyl group, X 1 to X 8 represent a sulfur atom or —NR 13 , and X 1 = (one of X 3 and X 4 ) = ( X 5 or X 6 ) = (X 7 or X 8 ) = sulfur atom, and X 2 = (X 3 or X 4 ) = (X 5 or X 6 ) The other) = (the other of X 7 and X 8 ) = — NR 13. R 13 represents a hydrogen atom or an alkyl group, M represents two hydrogen atoms, a divalent metal, or a trivalent metal derivative. Or a tetravalent metal derivative.)
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
The first invention of the present invention is a novel pyrrolidinophenothiazine compound represented by the general formula (I).
[0011]
In the pyrrolidinophenothiazine compound of the general formula (I), when R 1 and R 2 are an alkyl group, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 8 carbon atoms. Branched alkyl groups are particularly preferred. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, sec -Hexyl group, 2-ethylbutyl group, n-heptyl group, isoheptyl group, sec-heptyl group, n-octyl group and 2-ethylhexyl group.
[0012]
When R 1 and R 2 are alkoxyalkyl groups, those having a total carbon number of 2 to 6 are preferred. Examples include methoxyethyl, methoxypropyl, methoxybutyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, n-propoxyethyl, iso-propoxyethyl, and n-propoxypropyl.
When R 3 is an alkyl group, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 8 carbon atoms is particularly preferable. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, n-heptyl, isoheptyl, sec -Heptyl group, n-octyl group and 2-ethylhexyl group.
[0013]
Specific examples of the pyrrolidinophenothiazine compound of the present invention represented by the general formula (I) are shown below.
[0014]
Embedded image
The second invention of the present invention is characterized by reacting a dinitrile compound represented by the general formula (II) with ammonia in the presence of an alkoxide represented by the general formula (III), This is a method for producing a pyrrolidinophenothiazine compound represented by the formula:
[0028]
Embedded image
Embedded image
[0030]
Embedded image
R 4 O-X (III)
(In the formula, R 4 represents an alkyl group or an alkoxyalkyl group, and X represents a sodium atom or a potassium atom.)
The details of the method for producing the pyrrolidinophenothiazine compound represented by the general formula (I) will be described below.
[0031]
Examples of the metal alkoxide of the general formula (III) include sodium or potassium methoxide, ethoxide, n-propoxide, n-butoxide, n-pentoxide, n-hexyl oxide, n-heptyl oxide, n-octyl oxide, -Methoxyethoxide, 2-ethoxyethoxide, 2-n-butoxyethoxide and the like are used. The amount of the metal alkoxide of the general formula (III) to be used is 0.01 to 5 mol, preferably 0.1 to 2.0 mol, relative to compound (II).
[0032]
In the production of the pyrrolidinophenothiazine compound represented by the general formula (I), a metal sodium or a metal potassium is added to an alcohol which is a reaction solvent, an alcohol solvent of the metal alkoxide is adjusted, and then ammonia and the general formula (II) The reaction may be carried out by charging a dinitrile compound of the formula (1), or as another method, by charging ammonia, a dinitrile compound of the general formula (II) and a separately prepared metal alkoxide into a reaction solvent. At this time, the amount of the metal used is 0.01 to 5.0 mol, preferably 0.1 to 2.0 mol, based on compound (II).
[0033]
As the ammonia, ammonia gas or liquid ammonia may be used, but the use of ammonia gas is preferable in terms of handling.
[0034]
The amount of ammonia to be used is 1 to 20 mol, preferably 3 to 10 mol, per 1 mol of compound (II).
[0035]
In the reaction, it is preferable to use a solvent in combination, and as the solvent, an alcohol solvent is particularly preferable.
[0036]
Examples of alcohol solvents include methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-n -Butoxyethanol and the like are used. The amount of the solvent to be used is 200 mL-15 L, preferably 500 mL-5 L, per 1 mol of compound (II).
[0037]
The reaction temperature is from 0 ° C to the reflux temperature of the solvent, preferably from 20 ° C to the reflux temperature of the solvent.
[0038]
The reaction time is preferably 30 minutes to 72 hours.
[0039]
After the reaction, the solvent used in the reaction is distilled off, extracted with an organic solvent such as toluene, washed with water, and concentrated to obtain a pyrrolidinophenothiazine compound of the general formula (I).
[0040]
A third invention of the present invention is a method for producing a phthalocyanine compound, which comprises reacting a pyrrolidinophenothiazine compound of the general formula (I) with a metal or a metal derivative.
[0041]
Table 1 shows specific examples of the phthalocyanine compound of the formula (IV) produced by the production method of the present invention.
[0042]
In Table 1, in the general formula (IV), R 5 = (one of R 7 and R 8 ) = (one of R 9 and R 10 ) = (one of R 11 and R 12 ), And R 6 = (the other of R 7 and R 8 ) = (the other of R 9 and R 10 ) = (the other of R 11 and R 12 ).
[0043]
[Table 1]
The details of the method for producing the phthalocyanine compound of the general formula (IV) will be described below.
Examples of the metal or metal derivative include Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Pd, In, Sn, Pt, Pb, and halides thereof, and carboxylic acids. Examples include salts, sulfates, nitrates, carbonyl compounds, oxides, complexes and the like. In particular, these halides or carboxylate salts are preferably used. Examples thereof include copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate, and iron chloride. , Zinc chloride, zinc bromide, zinc iodide, zinc acetate, vanadium chloride, vanadium oxytrichloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, acetylacetone manganese chloride, manganese chloride, lead chloride, lead acetate, Indium chloride, titanium chloride, tin chloride and the like can be mentioned.
[0058]
The amount of the metal or metal derivative to be used is 0.1 to 0.6 times, preferably 0.2 to 0.5 times, the mol of the pyrrolidinophenothiazine compound of the general formula (I).
[0059]
The reaction temperature is 60 to 300 ° C, preferably 100 to 200 ° C.
[0060]
In the reaction, it is preferable to use a solvent.
[0061]
As a solvent used in the reaction, an organic solvent having a boiling point of 60 ° C. or higher, preferably 80 ° C. or higher is preferable. Examples include methanol, ethanol, n-propyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 1-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol, ethoxyethanol, propoxyethanol, butoxyethanol, dimethylaminoethanol, alcohol solvents such as diethylaminoethanol, trichlorobenzene, chloronaphthalene, sulfolane, High boiling solvents such as nitrobenzene, quinoline, urea and the like can be mentioned.
[0062]
The amount of the solvent to be used is 0.5 to 50 times, preferably 1 to 15 times the weight of the dinitrile compound of the formula (I).
[0063]
The reaction proceeds in the presence or absence of a catalyst. As a catalyst, an inorganic catalyst such as ammonium molybdate, DBU (1,8-diazabicyclo [5.4.0] -7-undecene), DBN (1, Basic organic catalysts such as 5-diazabicyclo [4.3.0] -5-nonene) can be used. The addition amount is 0.01 to 10 mol, preferably 0.1 to 2 mol, per 1 mol of the dinitrile compound.
[0064]
As the post-treatment, the reaction product is obtained by distilling off the solvent after the reaction, or by discharging the reaction solution into a poor solvent for the phthalocyanine compound and collecting the precipitate by filtration. This reaction product has a sufficient purity as it is so that it can be used for various applications, but it may be purified by column chromatography or the like to obtain a higher purity product.
[0065]
The phthalocyanine compound obtained from the pyrrolidinophenothiazine compound of the present invention has sufficient purity for uses such as an optical card, an organic photoconductor, a near-infrared absorption filter, a heat ray shielding film, a photothermal conversion agent, protective glasses, and a laser printer. Therefore, the production method of the present invention is a very useful production method because the production method is high and the yield is high.
[0066]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In each of Examples and Comparative Examples, [parts] indicates [parts by weight].
[0067]
Example 1 Production of 1,3-diimino-4,11-diisopentoxypyrrolidino [3,4-b] phenothiazine (Compound of Specific Example I- (29)) To 250 parts of n-propyl alcohol At room temperature, 17 parts of ammonia gas was introduced into a solution in which 2.43 parts of metallic sodium was dissolved. Next, 63.3 parts of 1,4-diisopentoxy-2,3-dicyanophenothiazine was added, and the mixture was stirred at 60 to 65 ° C. for 15 hours. After cooling, n-propyl alcohol was distilled off, and 500 parts of toluene was added to the residue, followed by heating and dissolving at 30 to 40 ° C. Next, 300 g of water was added, and the mixture was dispersed, allowed to stand, and separated. The same operation was repeated four times to remove alkali components. Next, toluene was distilled off from the toluene layer, 400 parts of n-heptane was added, the mixture was stirred at 60 to 65 ° C for 30 minutes, and then cooled to room temperature. The precipitated brown crystals were collected by filtration, dried, and 62.4 parts of 1,3-diimino-4,11-diisopentoxypyrrolidino [3,4-b] phenothiazine of the following structural formula (94.8% yield). ) Got.
[0068]
Embedded image
The elemental analysis value, mass analysis value and melting point of this crystal were as follows. FIG. 1 shows the infrared absorption spectrum of this compound.
Example 2 Production of 1,3-diimino-4,11-di (2-ethoxyethoxy) pyrrolidino [3,4-b] phenothiazine (Compound of Specific Example I- (75)) Same as Example 1 except that instead of 63.3 parts of 1,4-diisopentoxy-2,3-dicyanophenothiazine, 7.23 parts of 1,4-di (2-ethoxyethoxy) -2,3-dicyanophenothiazine were used. 6.61 parts (yield: 87.9%) of brown crystals of the following structural formula 1,3-diimino-4,11-di (2-ethoxyethoxy) pyrrolidino [3,4-b] phenothiazine Got.
[0071]
Embedded image
The elemental analysis value, mass analysis value and melting point of this crystal were as follows. FIG. 2 shows the infrared absorption spectrum of this compound.
Example 3 Production of 1,3-diimino-4,11-diisopentoxy-10-ethylpyrrolidino [3,4-b] phenothiazine (Compound of Specific Example I- (30)) The same operation as in Example 1 was carried out except that 15.7 parts of 1,4-diisopentoxy-2,3-dicyano-10-ethylphenothiazine was used instead of 63.3 parts of 4-diisopentoxy-2,3-dicyanophenothiazine. As a result, 17.5 parts (yield: 84.5%) of yellow crystals of the following structural formula 1,3-diimino-4,11-diisopentoxy-10-ethylpyrrolidino [3,4-b] phenothiazine were obtained.
[0074]
Embedded image
The elemental analysis value, mass analysis value and melting point of this crystal were as follows. FIG. 3 shows the infrared absorption spectrum of this compound.
(Example 4) Production of phthalocyanine compound (compound of specific example IV- (34)) 15 parts of 2-n-butoxyethanol and 1,3-diimino-4,11-diisopentoxypyrroli produced in Example 1 After heating a mixture of 4.39 parts of dino [3,4-b] phenothiazine to 130 ° C., 0.76 parts of DBU and 0.47 parts of vanadium chloride were added. Next, after stirring at 155 to 160 ° C for 2 hours, the mixture was cooled to 60 to 70 ° C and 150 parts of methanol was added. After cooling to room temperature, the crystals were collected by filtration and dried to obtain 4.18 parts (yield 95.5%) of a phthalocyanine compound having the following structural formula.
[0077]
The gram extinction coefficient (εg) and maximum absorption wavelength (λmax) of this reaction product in toluene were as follows.
[0078]
εg: 9.3 × 10 4 ml / g. cm
λmax: 830 nm
The reaction product was purified by column chromatography to obtain 2.72 parts (εg: 1.30 × 10 5 ml / g.cm, λmax: 830 nm) of high-purity blue-green black powder.
[0079]
Embedded image
(Example 5) Production of phthalocyanine compound (compound of specific example IV- (27)) In Example 4, 0.30 parts of cuprous chloride was used instead of 0.47 parts of vanadium chloride, and the reaction time was 5 hours. The same operation as in Example 4 was carried out except that the above formula was used to obtain 4.28 parts (yield 97.9%) of a phthalocyanine compound having the following structural formula.
[0081]
The gram extinction coefficient (εg) and maximum absorption wavelength (λmax) of this reaction product in toluene were as follows.
[0082]
εg: 9.1 × 10 4 ml / g. cm
λmax: 789 nm
By purifying the reaction product by column chromatography, a highly pure product could be easily obtained.
[0083]
Embedded image
(Example 6) Production of phthalocyanine compound (compound of specific example IV- (93)) In Example 4, 4.39 parts of 1,3-diimino-4,11-diisopentoxy-pyrrolidino [3,4-b] phenothiazine. In the same manner as in Example 4 except that 4.15 parts of 1,3-diimino-4,11-di (2-ethoxyethoxy) pyrrolidino [3,4-b] phenothiazine prepared in Example 2 was used instead of By performing the operation, 3.65 parts (yield: 88.1%) of a phthalocyanine compound having the following structural formula were obtained.
[0085]
The gram extinction coefficient (εg) and maximum absorption wavelength (λmax) of the crystals in toluene were as follows.
[0086]
εg: 8.2 × 10 4 ml / g. cm
λmax: 830 nm
By purifying the reaction product by column chromatography, a highly pure product could be easily obtained.
[0087]
Embedded image
(Example 7) Production of phthalocyanine compound (compound of specific example IV- (36)) In Example 4, 1,39-diimino-4,11-diisopentoxy-pyrrolidino [3,4-b] phenothiazine 4.39 parts Instead of 0.47 parts of vanadium chloride, 4.67 parts of 1,3-diimino-4,11-diisopentoxy-10-ethylpyrrolidino [3,4-b] phenothiazine prepared in Example 3, respectively, The same operation as in Example 4 was carried out except that 0.30 parts of copper was used and the reaction time was changed to 5 hours to obtain 3.12 parts of a crude phthalocyanine compound having the following structural formula (yield: 75.3%). Got.
[0089]
The gram extinction coefficient (εg) and maximum absorption wavelength (λmax) of this reaction product in toluene were as follows.
[0090]
εg: 1.1 × 10 5 ml / g. cm
λmax: 774 nm
By purifying this reaction product by column chromatography, a highly purified product could be easily obtained.
[0091]
Embedded image
【The invention's effect】
By using the novel pyrrolidinophenothiazine compound as an intermediate, a phthalocyanine compound having excellent near-infrared absorption ability can be produced in a high yield in a short time. In addition, since the purity of the reaction product is high, a high-purity product can be easily obtained.
[Brief description of the drawings]
FIG. 1 is an infrared absorption spectrum of 1,3-diimino-4,11-diisopentoxypyrrolidino [3,4-b] phenothiazine produced in Example 1.
FIG. 2 is an infrared absorption spectrum of 1,3-diimino-4,11-di (2-ethoxyethoxy) pyrrolidino [3,4-b] phenothiazine produced in Example 2.
FIG. 3 is an infrared absorption spectrum of 1,3-diimino-4,11-diisopentoxy-10-ethylpyrrolidino [3,4-b] phenothiazine produced in Example 3.
Claims (3)
【化４】
Ｒ４Ｏ−Ｘ （ＩＩＩ）
（式中、Ｒ４はアルキル基またはアルコキシアルキル基を示し、Ｘはナトリウム原子またはカリウム原子を示す。）A process for producing a pyrrolidinophenothiazine compound of the general formula (I), comprising reacting a dinitrile compound represented by the general formula (II) with ammonia in the presence of a metal alkoxide represented by the general formula (III). .
Embedded image
R 4 O-X (III)
(In the formula, R 4 represents an alkyl group or an alkoxyalkyl group, and X represents a sodium atom or a potassium atom.)
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| KR20210144775A (en) * | 2019-04-26 | 2021-11-30 | 미쓰이 가가쿠 가부시키가이샤 | Optical materials, polymerizable compositions for optical materials, plastic lenses, eyewear, infrared sensors and infrared cameras |
| KR102684824B1 (en) | 2019-04-26 | 2024-07-15 | 미쓰이 가가쿠 가부시키가이샤 | Optical materials, polymerizable compositions for optical materials, plastic lenses, eyewear, infrared sensors and infrared cameras |
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| Publication number | Publication date |
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| JPH1160579A (en) | 1999-03-02 |
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