JP4406550B2 - Method for producing arylamine - Google Patents
Method for producing arylamine Download PDFInfo
- Publication number
- JP4406550B2 JP4406550B2 JP2003337868A JP2003337868A JP4406550B2 JP 4406550 B2 JP4406550 B2 JP 4406550B2 JP 2003337868 A JP2003337868 A JP 2003337868A JP 2003337868 A JP2003337868 A JP 2003337868A JP 4406550 B2 JP4406550 B2 JP 4406550B2
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- JP
- Japan
- Prior art keywords
- group
- atom
- ring
- compound
- aromatic
- 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 - Fee Related
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- 150000004982 aromatic amines Chemical class 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- -1 aromatic amine compound Chemical class 0.000 claims description 131
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 125000003118 aryl group Chemical group 0.000 claims description 41
- 125000003545 alkoxy group Chemical group 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 27
- 125000004104 aryloxy group Chemical group 0.000 claims description 25
- 125000000623 heterocyclic group Chemical group 0.000 claims description 24
- 125000003342 alkenyl group Chemical group 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 125000000732 arylene group Chemical group 0.000 claims description 18
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 18
- 125000005843 halogen group Chemical group 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- 125000005551 pyridylene group Chemical group 0.000 claims description 12
- 125000005556 thienylene group Chemical group 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 125000002950 monocyclic group Chemical group 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- 125000002619 bicyclic group Chemical group 0.000 claims description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 6
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 5
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 4
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 4
- 229960004643 cupric oxide Drugs 0.000 claims description 4
- 229940045803 cuprous chloride Drugs 0.000 claims description 4
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 4
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 claims description 4
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- 229960000355 copper sulfate Drugs 0.000 claims description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- 229960003280 cupric chloride Drugs 0.000 claims description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 3
- 229940112669 cuprous oxide Drugs 0.000 claims description 3
- 125000005184 naphthylamino group Chemical group C1(=CC=CC2=CC=CC=C12)N* 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 125000003277 amino group Chemical group 0.000 description 20
- 239000012535 impurity Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000000304 alkynyl group Chemical group 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 150000001491 aromatic compounds Chemical class 0.000 description 8
- 125000005647 linker group Chemical group 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006471 dimerization reaction Methods 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical group C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 6
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 6
- 239000007810 chemical reaction solvent Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 239000012776 electronic material Substances 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 125000005259 triarylamine group Chemical group 0.000 description 5
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010751 Ullmann type reaction Methods 0.000 description 4
- 150000007824 aliphatic compounds Chemical class 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical group C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 4
- 125000003493 decenyl group Chemical group [H]C([*])=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 4
- 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 4
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 125000002541 furyl group Chemical group 0.000 description 4
- 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 4
- 125000006038 hexenyl group Chemical group 0.000 description 4
- 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 4
- 125000005980 hexynyl group Chemical group 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 4
- 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 4
- 125000005071 nonynyl group Chemical group C(#CCCCCCCC)* 0.000 description 4
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 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
- 125000005069 octynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 4
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 125000005981 pentynyl group Chemical group 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004076 pyridyl group Chemical group 0.000 description 4
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 4
- 125000001544 thienyl group Chemical group 0.000 description 4
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 4
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 description 4
- YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-UHFFFAOYSA-N 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- NGEDUOQBIJQWQK-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)-4-phenylcyclohexa-1,5-dien-1-yl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(CC=2)(N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC=CC=2)=C1 NGEDUOQBIJQWQK-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 125000005266 diarylamine group Chemical group 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- NDVASEGYNIMXJL-NXEZZACHSA-N (+)-sabinene Chemical compound C=C1CC[C@@]2(C(C)C)[C@@H]1C2 NDVASEGYNIMXJL-NXEZZACHSA-N 0.000 description 2
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- HGEMCUOAMCILCP-UHFFFAOYSA-N 2-methyldodecane Chemical compound CCCCCCCCCCC(C)C HGEMCUOAMCILCP-UHFFFAOYSA-N 0.000 description 2
- XXPBFNVKTVJZKF-UHFFFAOYSA-N 9,10-dihydrophenanthrene Chemical compound C1=CC=C2CCC3=CC=CC=C3C2=C1 XXPBFNVKTVJZKF-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 2
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical compound C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 description 2
- 238000006887 Ullmann reaction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001334 alicyclic compounds Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000004653 anthracenylene group Chemical group 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 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 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- 229930006974 beta-terpinene Natural products 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
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- 150000002941 palladium compounds Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- USDOQCCMRDNVAH-UHFFFAOYSA-N sigma-cadinene Natural products C1C=C(C)CC2C(C(C)C)CC=C(C)C21 USDOQCCMRDNVAH-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229940031439 squalene Drugs 0.000 description 1
- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- BRNULMACUQOKMR-UHFFFAOYSA-N thiomorpholine Chemical compound C1CSCCN1 BRNULMACUQOKMR-UHFFFAOYSA-N 0.000 description 1
- XJPBRODHZKDRCB-UHFFFAOYSA-N trans-alpha-ocimene Natural products CC(=C)CCC=C(C)C=C XJPBRODHZKDRCB-UHFFFAOYSA-N 0.000 description 1
- GZEDKDBFUBPZNG-UHFFFAOYSA-N tridec-1-yne Chemical compound CCCCCCCCCCCC#C GZEDKDBFUBPZNG-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- USDOQCCMRDNVAH-KKUMJFAQSA-N β-cadinene Chemical compound C1C=C(C)C[C@H]2[C@H](C(C)C)CC=C(C)[C@@H]21 USDOQCCMRDNVAH-KKUMJFAQSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Indole Compounds (AREA)
Description
本発明は有機半導体素子における正電荷輸送材料、又はその中間体として有用なアリールアミン、特にトリアリールアミン又はジアリールアミンを高純度且つ低コストで製造する方法を提供するものである。 The present invention provides a method for producing an arylamine, particularly a triarylamine or diarylamine, useful as a positive charge transport material in an organic semiconductor element, or an intermediate thereof, with high purity and low cost.
本発明はアリールアミン化合物を合成する際のウルマン縮合反応として分類される反応の範疇に含まれる。
ウルマン縮合反応は芳香族アミンを芳香族ハロゲン化合物、好ましくは芳香族ヨウ化化合物とを塩基及び銅触媒の存在下に反応させてアリールアミンを合成する方法であり、Ｆ．Ｕｌｌｍａｎｎによって発見された（非特許文献１参照）。この反応は一般的に反応時間が長く、しかも実用的なアリール化速度を達成するためには通常２００℃以上の高温を必要とするため、原料の分解や生成物の酸化、不均化、二量化反応等によって副生成物が多く生成する。
The present invention falls within the category of reactions classified as Ullmann condensation reactions when synthesizing arylamine compounds.
The Ullmann condensation reaction is a method of synthesizing an arylamine by reacting an aromatic amine with an aromatic halogen compound, preferably an aromatic iodide compound, in the presence of a base and a copper catalyst. Discovered by Ullmann (see Non-Patent Document 1). This reaction generally takes a long reaction time, and usually requires a high temperature of 200 ° C. or higher to achieve a practical arylation rate. Therefore, decomposition of the raw material, oxidation of the product, disproportionation, A large amount of by-products are generated by the quantification reaction or the like.
これらの副生成物は目的化合物とイオン化電位やフロンティア軌道の電子密度分布が異なり、有機半導体素子における電気特性の低下を招くため、使用されるアリールアミン化合物は極めて高純度のものが要求される。例えば、正孔輸送材料の移動度に対する不純物の影響について、イオン化電位の小さな不純物の添加によりその正孔移動度が低下することが報告されている（非特許文献２〜４参照）。これは不純物が正孔トラップを形成することが原因と指摘されており、少なくとも生成物の酸化や２量化によって副生するイオン化電位の小さな不純物は可能な限り含まないことが高移動度を得るための条件となる。また、アリールアミン誘導体について中性ならびにカチオンラジカル状態でのフロンティア軌道の電子密度分布に偏りが小さい場合に高い移動度を示すという報告がされており（非特許文献５参照）、酸化によって生成した極性基を有する着色性不純物の存在は電気特性低下の原因となる。そのため電子材料用素材中のこれらの副生成物は出来るだけ排除する必要があるが、その分離精製が非常に困難であり、再結晶やカラムクロマト法で繰り返し精製しなければならずコスト高となる課題があった。 These by-products are different from the target compound in ionization potential and electron density distribution in the frontier orbitals, leading to a decrease in the electrical characteristics of the organic semiconductor device, so that the arylamine compound used is required to have a very high purity. For example, regarding the influence of impurities on the mobility of a hole transport material, it has been reported that the hole mobility is lowered by the addition of an impurity having a small ionization potential (see Non-Patent Documents 2 to 4). In order to obtain high mobility, it is pointed out that impurities form hole traps, and at least impurities with a small ionization potential by-produced by oxidation or dimerization of the product are not included as much as possible. It becomes the condition of. In addition, it has been reported that arylamine derivatives exhibit high mobility when the electron density distribution of the frontier orbitals in neutral and cation radical states is small (see Non-Patent Document 5), and the polarity generated by oxidation The presence of a coloring impurity having a group causes a decrease in electrical characteristics. For this reason, it is necessary to eliminate these by-products in the materials for electronic materials as much as possible, but their separation and purification is very difficult, and they must be repeatedly purified by recrystallization or column chromatography, resulting in high costs. There was a problem.
ウルマン反応において、電気特性に悪影響を及ぼす副生成物を抑制する方法は従来報告されている。例えば、ハロゲン化芳香族化合物と大過剰の芳香族アミン化合物とを反応させてスチリル化合物、アリールアミン化合物を合成する方法（特許文献１，特許文献２参照）、ハロゲン化芳香族化合物と芳香族アミン化合物とを反応させてフルオレン骨格を有するアリールアミン化合物を合成する際に、銅触媒の使用量を減量して副生成物を抑制する方法（特許文献３参照）、ハロゲン化芳香族化合物と芳香族アミン化合物とを銅紛触媒及び塩基の存在下で反応させてトリアリールアミン誘導体を合成する際に、不活性気体雰囲気と無機亜硫酸塩の併用により副生成物を抑制する方法（特許文献４参照）などが提案されているが、いずれの場合も副生成物は抑制されるものの依然として着色性不純物や酸化物、分解物などが生成し、電子材料用素材又はその中間体として使用するには高度に精製する必要があった。 In the Ullmann reaction, a method for suppressing a by-product that adversely affects electrical characteristics has been reported. For example, a method of synthesizing a styryl compound and an arylamine compound by reacting a halogenated aromatic compound with a large excess of an aromatic amine compound (see Patent Document 1 and Patent Document 2), a halogenated aromatic compound and an aromatic amine When synthesizing an arylamine compound having a fluorene skeleton by reacting with a compound, a method of reducing the amount of copper catalyst used to suppress by-products (see Patent Document 3), halogenated aromatic compounds and aromatics A method of suppressing a by-product by using an inert gas atmosphere and an inorganic sulfite together when a triarylamine derivative is synthesized by reacting an amine compound with a copper powder catalyst and a base (see Patent Document 4) In each case, by-products are suppressed, but coloring impurities, oxides, decomposition products, etc. are still produced, and the materials for electronic materials are used. Or had to be highly purified for use as intermediates.
高純度のアリールアミン化合物を製造するためには、より低温で反応させることが好ましく、芳香族アミン化合物とヨウ素化芳香族化合物とを芳香族溶媒中、銅触媒と水酸化カリウムと第三級アミン化合物の共存下に１２０〜１５０℃で反応するトリアリールアミン化合物の製造方法が提案されている（特許文献６〜９参照）。しかし、これらの方法は低温においても反応は効率よく進行するが、収率と純度共に満足のいくものではなく、上記の課題は解決できない。 In order to produce a high purity arylamine compound, it is preferable to react at a lower temperature. An aromatic amine compound and an iodinated aromatic compound are mixed in an aromatic solvent, a copper catalyst, potassium hydroxide, and a tertiary amine. A method for producing a triarylamine compound that reacts at 120 to 150 ° C. in the presence of the compound has been proposed (see Patent Documents 6 to 9). However, in these methods, the reaction proceeds efficiently even at low temperatures, but the yield and purity are not satisfactory, and the above problems cannot be solved.
また、低温でアリールアミン化合物を合成する別法としてはパラジウム触媒、ホスフィン化合物、塩基の共存下に塩素化芳香族化合物や臭素化芳香族化合物と、芳香族アミン化合物とを芳香族溶媒中、２０〜１４０℃で反応させる方法（特許文献１１〜１５、非特許文献５〜１０参照）が提案されているが、パラジウム化合物は非常に高価であり、反応後の分離回収にも難点があるため工業的に有利な製造方法とは言えず、また収率や純度も満足のいくものではなかった。 As another method for synthesizing an arylamine compound at a low temperature, a chlorinated aromatic compound or a brominated aromatic compound and an aromatic amine compound in an aromatic solvent in the presence of a palladium catalyst, a phosphine compound, and a base, Although a method of reacting at ~ 140 ° C (see Patent Documents 11 to 15 and Non-Patent Documents 5 to 10) has been proposed, a palladium compound is very expensive and is difficult to separate and recover after the reaction. The production method is not particularly advantageous, and the yield and purity are not satisfactory.
本発明はウルマン反応においてアリールアミン化合物を合成する際に電気特性に悪影響を及ぼす不純物を抑制することで、極めて高純度のアリールアミン、特にトリアリールアミン又はジアリールアミンを合成することができ、電子材料用又はその中間体としての使用に適する素材を低コストに製造する方法を提供するものである。 The present invention can synthesize very high purity arylamines, particularly triarylamines or diarylamines, by suppressing impurities that adversely affect electrical properties when synthesizing arylamine compounds in the Ullmann reaction. The present invention provides a method for producing a material suitable for use as an intermediate or an intermediate thereof at low cost.
すなわち、上記の目的は、下記構成により達成される。
（１）
銅触媒および塩基存在下、芳香族アミン化合物と芳香族ハロゲン化合物とを、８０ｋＰａ以下の減圧下で反応させることを特徴とするアリールアミンの製造方法であって、
前記銅触媒が、銅粉、塩化第一銅、塩化第二銅、臭化第一銅、臭化第二銅、沃化銅、酸化第一銅、酸化第二銅、硫酸銅、硝酸銅、炭酸銅または水酸化第二銅から選択される少なくとも１種であり、
前記塩基が、アルカリ金属水酸化物、アルカリ金属炭酸化物、アルカリ金属燐酸化物またはアルカリ金属アルコキシドから選択される少なくとも１種であり、
前記芳香族ハロゲン化合物が下記一般式（Ｉ）または（ＩＩ）で表わされる化合物であり、
前記芳香族アミン化合物が下記一般式（ＩＩＩ）または（ＩＶ）で表わされる化合物である、アリールアミンの製造方法。
式（Ｉ）および（ＩＩ）中、
Ｑは塩素原子、臭素原子またはヨウ素原子を表す。
Ｘは−Ｃ（Ｒ１５）（Ｒ１６）−、酸素原子、硫黄原子、−Ｎ（Ｒ１７）−、シクロアルキレン基、アリーレン基、フリレン基、チエニレン基、ピリジレン基、−Ｎ＝Ｎ−、または−Ｃ（Ｒ１５）＝Ｃ（Ｒ１６）−を表す。ｎ２は０〜３の整数を表し、ｎ２が０の場合には単結合を表す。ｎ２が２以上の場合にはＸは同じでも異なっていてもよい。
Ｒ１〜Ｒ１６は各々独立して水素原子、アルキル基、アルケニル基、アリール基、アルコキシ基、アリールオキシ基、ジメチルアミノ基、Ｎ−エチル−Ｎ−フェニルアミノ基、ジフェニルアミノ基、Ｎ−フェニル−Ｎ−ナフチルアミノ基、ニトロ基、またはハロゲン原子を表す。
Ｒ１７はアルキル基、アルケニル基、アリール基、アルコキシ基、アリールオキシ基、ジメチルアミノ基、Ｎ−エチル−Ｎ−フェニルアミノ基、ジフェニルアミノ基、Ｎ−フェニル−Ｎ−ナフチルアミノ基、ニトロ基、またはハロゲン原子を表す。
Ｒ１〜Ｒ５もしくはＲ６〜Ｒ１７における２つの基によって更に飽和環、シクロペンテン環、シクロヘキセン環、シクロオクテン環、または、芳香環を形成してもよい。
Ｒ６〜Ｒ１７において、炭素数１〜１０のアルキレン基、３〜１０員のシクロアルキレ
ン基、６〜１０員のアリーレン基、フリレン基、チエニレン基、またはピリジレン基を介
して式（ＩＩ）で表わされる構造をもう１つ有していてもよい。
Ｒ１〜Ｒ１７におけるアルキル基、アルケニル基、アリール基、アルコキシ基、アリールオキシ基、ジメチルアミノ基、Ｎ−エチル−Ｎ−フェニルアミノ基、ジフェニルアミノ基、およびＮ−フェニル−Ｎ−ナフチルアミノ基は、更にアルキル基、単環式または二〜四環式アリール基、アルコキシ基、アリールオキシ基、ニトロ基、またはハロゲン原子から選択される置換基を有していてもよい。
式（ＩＩＩ）および（ＩＶ）中、
Ｙは−Ｃ（Ｒ３４）（Ｒ３５）−、酸素原子、硫黄原子、シクロアルキレン基、アリーレン基、フリレン基、チエニレン基、ピリジレン基、−Ｎ＝Ｎ−、または−Ｃ（Ｒ３４）＝Ｃ（Ｒ３５）−を表す。
ｎ４は０〜３の整数を表し、ｎ４が０の場合は単結合を表す。ｎ４が２以上の場合はＹは同じでも異なっても良い。
Ｒ１８〜Ｒ３５は水素原子、アルキル基、アルケニル基、アリール基、アルコキシ基、アリールオキシ基、またはニトロ基を表す。
また、Ｒ１８〜Ｒ２３もしくはＲ２４〜Ｒ３５において２つの基によって飽和環、シクロペンテン環、シクロヘキセン環、シクロオクテン環、または、芳香環、または複素環を形成してもよい。
Ｒ２４〜Ｒ３５において、炭素数１〜１０のアルキレン基、３〜１０員のシクロアルキ
レン基、６〜１０員のアリーレン基、フリレン基、チエニレン基、またはピリジレン基を
介して式（ＩＶ）で表される構造をもう１つ有していてもよい。
Ｒ１８〜Ｒ３５におけるアルキル基、アルケニル基、アリール基、アルコキシ基、およびアリールオキシ基は、更にアルキル基、アルケニル基、単環式または二〜四環式アリール基、アルコキシ基、アリールオキシ基、ニトロ基、から選択される置換基を有していてもよい。
（２）
前記の減圧度が７０〜１０ｋＰａであることを特徴とする上記（１）に記載のアリールアミンの製造方法。
（３）
不活性ガスを導入しながら反応させることを特徴とする上記（１）または（２）に記載のアリールアミンの製造方法。
That is, the above object is achieved by the following configuration.
(1)
A process for producing an arylamine, comprising reacting an aromatic amine compound and an aromatic halogen compound under reduced pressure of 80 kPa or less in the presence of a copper catalyst and a base,
The copper catalyst is copper powder, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, copper iodide, cuprous oxide, cupric oxide, copper sulfate, copper nitrate, At least one selected from copper carbonate or cupric hydroxide,
The base is at least one selected from alkali metal hydroxides, alkali metal carbonates, alkali metal phosphates or alkali metal alkoxides;
The aromatic halogen compound is a compound represented by the following general formula (I) or (II):
A method for producing an arylamine, wherein the aromatic amine compound is a compound represented by the following general formula (III) or (IV).
In formulas (I) and (II)
Q represents a chlorine atom, a bromine atom or an iodine atom.
X is -C (R15) (R16)-, oxygen atom, sulfur atom, -N (R17)-, cycloalkylene group, arylene group, furylene group, thienylene group, pyridylene group, -N = N-, or -C. (R15) = C (R16)-is represented. n2 represents an integer of 0 to 3, and when n2 is 0, it represents a single bond. When n2 is 2 or more, X may be the same or different.
R1 to R16 are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, dimethylamino group, N-ethyl-N-phenylamino group, diphenylamino group, N-phenyl-N. -Represents a naphthylamino group , a nitro group, or a halogen atom.
R17 is an alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, dimethylamino group, N-ethyl-N-phenylamino group, diphenylamino group, N-phenyl-N-naphthylamino group , nitro group, or Represents a halogen atom.
A saturated ring, a cyclopentene ring, a cyclohexene ring, a cyclooctene ring, or an aromatic ring may be further formed by two groups in R1 to R5 or R6 to R17 .
R6 to R17 are represented by the formula (II) via an alkylene group having 1 to 10 carbon atoms, a 3 to 10 membered cycloalkylene group, a 6 to 10 membered arylene group, a furylene group, a thienylene group, or a pyridylene group. You may have another structure .
The alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, dimethylamino group, N-ethyl-N-phenylamino group, diphenylamino group, and N-phenyl-N-naphthylamino group in R1 to R17 are: Further, it may have a substituent selected from an alkyl group, a monocyclic or bicyclic to tetracyclic aryl group, an alkoxy group, an aryloxy group, a nitro group, or a halogen atom.
In formulas (III) and (IV),
Y is -C (R34) (R35)-, oxygen atom, sulfur atom, cycloalkylene group, arylene group, furylene group, thienylene group, pyridylene group, -N = N-, or -C (R34) = C (R35 )-.
n4 represents an integer of 0 to 3, and when n4 is 0, it represents a single bond. When n4 is 2 or more, Y may be the same or different.
R18 to R35 each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, or a nitro group.
In addition, a saturated ring, a cyclopentene ring, a cyclohexene ring, a cyclooctene ring, an aromatic ring, or a heterocyclic ring may be formed by two groups in R18 to R23 or R24 to R35 .
R24 to R35 are represented by the formula (IV) via an alkylene group having 1 to 10 carbon atoms, a 3 to 10 membered cycloalkylene group, a 6 to 10 membered arylene group, a furylene group, a thienylene group, or a pyridylene group. Another structure may be included .
The alkyl group, alkenyl group, aryl group, alkoxy group and aryloxy group in R18 to R35 are further an alkyl group, alkenyl group, monocyclic or bicyclic to tetracyclic aryl group, alkoxy group, aryloxy group, nitro group And may have a substituent selected from
(2)
Said pressure reduction degree is 70-10kPa, The manufacturing method of the arylamine as described in said (1) characterized by the above-mentioned.
(3)
The method for producing an arylamine according to the above (1) or (2), wherein the reaction is carried out while introducing an inert gas.
本発明により、電子材料用素材、又はその中間体として有用なアリールアミン、特にトリアリールアミン又はジアリールアミン化合物を極めて容易な操作で低コストで製造することができ、高い実用性を有するものである。 According to the present invention, an arylamine, particularly a triarylamine or diarylamine compound useful as an electronic material or an intermediate thereof can be produced at a low cost by an extremely easy operation, and has high practicality. .
本発明を更に詳細に説明する。
尚、本発明は特許請求の範囲に記載の構成を有するものであるが、以下、その他についても参考のため記載した。
本発明はアリールアミン、特に電子材料用素材又はその中間体として有用な一群のトリアリールアミンもしくはジアリールアミンを銅触媒と塩基の共存下でウルマン縮合反応を用いて製造する際に、反応器内の圧力が１気圧未満の減圧下で反応を行う製造方法である。本発明の製造方法では従来提案されているアリールアミン合成法と比較して着色性の酸化生成物、分解物、二量化生成物などの副生成物を極めて高度に抑制することができ、高純度なアリールアミン化合物を製造することができる。ここで合成されたアリールアミン化合物は着色がなく、電気特性の低下を招く極性基を有する不純物やイオン化電位の低い不純物をほとんど含まないので、極めて容易な精製で電子材料用素材またはその中間体として使用することが出来る。
The present invention will be described in further detail.
In addition, although this invention has a structure as described in a claim, it described below also for reference below.
The present invention provides an arylamine, particularly a group of triarylamines or diarylamines useful as a material for electronic materials or intermediates thereof, in the presence of a copper catalyst and a base using an Ullmann condensation reaction. In this production method, the reaction is carried out under a reduced pressure of less than 1 atm. In the production method of the present invention, by-products such as coloring oxidation products, decomposition products, and dimerization products can be suppressed to a very high degree as compared with the conventionally proposed arylamine synthesis methods, and high purity. Arylamine compounds can be prepared. The arylamine compound synthesized here is not colored and contains almost no impurities having polar groups or low ionization potentials that cause a decrease in electrical properties, so it can be used as a material for electronic materials or an intermediate thereof with extremely easy purification. Can be used.
本発明における反応中の減圧度は微減圧でも不純物抑制効果は得られるが、通常８０ｋＰａ以下で行われる。より高い不純物抑制効果を得るために、減圧度は高い方が好ましく、使用原料により適切な減圧状態が選択される。無溶媒反応の場合は通常、使用原料が反応温度において反応系より除去されない減圧度が選択されるが、高い減圧度で反応系より留去された使用原料を反応系内に戻しながら反応させることも可能である。反応溶媒を用いる場合には反応溶媒が留去しない減圧度が選択されるか、または溶媒を還流させながら反応がおこなわれる減圧度が選択される。 In the present invention, the degree of reduced pressure during the reaction is usually 80 kPa or less, although an impurity suppressing effect can be obtained even if the pressure is reduced slightly. In order to obtain a higher impurity suppressing effect, the degree of reduced pressure is preferably higher, and an appropriate reduced pressure state is selected depending on the raw materials used. In the case of solventless reaction, the degree of vacuum is usually selected so that the raw materials used are not removed from the reaction system at the reaction temperature, but the reaction is carried out while returning the raw materials distilled from the reaction system at a high degree of vacuum. Is also possible. When a reaction solvent is used, the degree of vacuum at which the reaction solvent is not distilled off is selected, or the degree of vacuum at which the reaction is performed while refluxing the solvent is selected.
減圧度が過度に高くないことが反応中に留出してくる使用原料を捕捉する上で好ましく、反応中の減圧度は５ｋＰａ以上あることが好ましい。反応中の減圧度の好ましい範囲は７０〜１０ｋＰａであり、更に好ましくは６０〜１０ｋＰａである。減圧度を上記範囲とすることは、比較的容易な設備や安価なコストで充分な不純物抑制効果を得て、かつ反応中に留出してくる使用原料の捕捉が容易であることからも好ましい。 It is preferable that the degree of vacuum is not excessively high in order to capture raw materials distilled during the reaction, and the degree of vacuum during the reaction is preferably 5 kPa or more. A preferable range of the degree of vacuum during the reaction is 70 to 10 kPa, and more preferably 60 to 10 kPa. It is preferable that the degree of vacuum is in the above range because a sufficient impurity suppression effect can be obtained with relatively easy equipment and low cost, and the used raw material distilled during the reaction can be easily captured.
また本発明では、反応時に不活性ガスを導入することが、副生成物の生成を防止するので好ましい。不活性ガスは例えば、窒素、ヘリウム、ネオン、アルゴン、クリプトン、キセノン等を用いることが出来るが、この中でも安価な窒素ガスが好ましい。不活性ガスを導入する際には常温において反応系内を不活性ガスで十分に置換した後、不活性ガスを導入しながら減圧下で反応を行うことが好ましい。反応系内の不活性ガスによる置換は、通常反応系内を８ｋＰａ以下、より好ましくは４ｋＰａ以下、更に好ましくは２ｋＰａ以下に減圧した後、不活性ガスで常圧まで戻す操作を繰り返して行われる。不活性ガスは反応器の下部より導入しながら反応させることがより好ましい。
反応器内の残留酸素は５％以下、好ましくは１％以下、更に好ましくは０．１％以下で反応させることが好ましい。
Further, in the present invention, it is preferable to introduce an inert gas during the reaction, because the formation of by-products is prevented. For example, nitrogen, helium, neon, argon, krypton, xenon, or the like can be used as the inert gas, but among these, inexpensive nitrogen gas is preferable. When introducing the inert gas, it is preferable to perform the reaction under reduced pressure while introducing the inert gas after sufficiently replacing the inside of the reaction system with the inert gas at room temperature. Substitution with an inert gas in the reaction system is usually performed by repeatedly reducing the pressure in the reaction system to 8 kPa or less, more preferably 4 kPa or less, and even more preferably 2 kPa or less, and then returning to normal pressure with an inert gas. It is more preferable to react while introducing the inert gas from the lower part of the reactor.
It is preferable to carry out the reaction at a residual oxygen in the reactor of 5% or less, preferably 1% or less, more preferably 0.1% or less.
本発明で使用する芳香族ハロゲン化合物は好ましくは下記一般式(A)で表わされる化合物である。 The aromatic halogen compound used in the present invention is preferably a compound represented by the following general formula (A).
式（A）中、
Ｑは塩素原子、臭素原子またはヨウ素原子を表わす。
ｎ１は０〜５の整数を表す。
Ｒａは複数ある場合は各々独立して水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリールオキシ基、ジ置換アミノ基、ニトロ基、ヘテロ環残基、ハロゲン原子または−Ｌ１−Ｒｂで表される基を表わす。Ｌ１は二価の連結基を表わす。Ｒｂはアルキル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリールオキシ基、ジ置換アミノ基、ニトロ基、ヘテロ環残基、またはハロゲン原子を表す。
Ｒａ、Ｒｂ、Ｌ１で表される基は各々置換基を有していてもよい。
複数のＲａによって更に環を形成してもよい。
In formula (A),
Q represents a chlorine atom, a bromine atom or an iodine atom.
n1 represents the integer of 0-5.
When there are a plurality of Ras, each is independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, disubstituted amino group, nitro group, heterocyclic residue, halogen atom or -L1. Represents a group represented by -Rb. L1 represents a divalent linking group. Rb represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a disubstituted amino group, a nitro group, a heterocyclic residue, or a halogen atom.
The groups represented by Ra, Rb and L1 may each have a substituent.
A plurality of Ras may form a ring.
式（A）で表される芳香族ハロゲン化合物は、より好ましくは下記一般式（I）または（II）で表わされる化合物である。 The aromatic halogen compound represented by the formula (A) is more preferably a compound represented by the following general formula (I) or (II).
式（I）および（II）中、
Ｑは塩素原子、臭素原子またはヨウ素原子を表わす。
Ｘは二価の連結基を表わし、ｎ２が２以上の場合にはＸは同じでも異なっていてもよい。Ｘは好ましくは−Ｃ（Ｒ１５）（Ｒ１６）−、酸素原子、硫黄原子、−Ｎ（Ｒ１７）−、シクロアルキレン基、アリーレン基、二価のヘテロ環残基、−Ｎ＝Ｎ−、または−Ｃ（Ｒ１５）＝Ｃ（Ｒ１６）−であり、更に好ましくは３〜１０員のシクロアルキレン基、６〜１０員の単環式または二環式のアリーレン基、フリレン基、チエニレン基、ピリジレン基である。
ｎ２は０〜３の整数を表わし、ｎ２が０の場合には単結合を表す。
Ｒ１〜Ｒ１７は各々独立して水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリールオキシ基、ジ置換アミノ基、ニトロ基、ヘテロ環残基、またはハロゲン原子を表わす。
Ｒ１〜Ｒ５もしくはＲ６〜Ｒ１７における２つの基によって更に環を形成してもよい。
In formulas (I) and (II),
Q represents a chlorine atom, a bromine atom or an iodine atom.
X represents a divalent linking group, and when n2 is 2 or more, X may be the same or different. X is preferably -C (R15) (R16)-, an oxygen atom, a sulfur atom, -N (R17)-, a cycloalkylene group, an arylene group, a divalent heterocyclic residue, -N = N-, or- C (R15) = C (R16)-, more preferably a 3-10 membered cycloalkylene group, a 6-10 membered monocyclic or bicyclic arylene group, a furylene group, a thienylene group, a pyridylene group. is there.
n2 represents an integer of 0 to 3, and when n2 is 0, it represents a single bond.
R1 to R17 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a disubstituted amino group, a nitro group, a heterocyclic residue, or a halogen atom.
A ring may be further formed by two groups in R1 to R5 or R6 to R17.
Ｒ６〜Ｒ１７において、二価の連結基を介して式（II）で表わされる構造をもう１つ有していてもよい。この場合、複数の式（II）で表わされる構造において、両者の連結部位は同一でも異なっても良い。 R6 to R17 may have another structure represented by the formula (II) through a divalent linking group. In this case, in the structure represented by a plurality of formulas (II), the connecting sites may be the same or different.
一般式（I）、（II）において、Ｒ１〜Ｒ１７は具体的には水素原子；メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル、ノナデシル、イコシル、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル、シクロノニル、シクロデシルなどの直鎖、分岐または環状の炭素数１〜２０のアルキル基；ビニル、アリル、プロペニル、ブテニル、ペンテニル、ヘキセニル、ヘプテニル、オクテニル、ノネニル、デセニル、ウンデセニル、ドデセニル、トリデセニル、テトラデセニル、ペンタデセニル、ヘキサデセニル、ヘプタデセニル、オクタデセニル、ノナデセニル、イコセニル、ヘキサジエニル、ドデカトリエニル等の直鎖、分岐、または環状の炭素数２〜２０のアルケニル基；エチニル、ブチニル、ペンチニル、ヘキシニル、ヘプチニル、オクチニル、ノニニル、シクロオクチニル、シクロノニニル、シクロデシニル等の直鎖、分岐または環状の炭素数２〜２０のアルキニル基；フェニル、ナフチル、フェナントリル、アントリル等の単環式またはニ〜四環式アリール基；メトキシ、エトキシ、プロポキシ、ブトキシ、ペンチルオキシ、ヘキシルオキシ、ヘプチルオキシ、オクチルオキシ、ノニルオキシ、デシルオキシ、ドデシルオキシ、オクタデシルオキシ等の炭素数１〜２０のアルコキシ基；フェノキシ、ナフチルオキシ等のアリールオキシ基；ジメチルアミノ、Ｎ−エチル−Ｎ−フェニルアミノ、ジフェニルアミノ、Ｎ−フェニル−Ｎ−ナフチルアミノ等のジ置換アミノ基；ニトロ基；フリル、チエニル、ピリジル等のヘテロ環残基；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子を表わす。好ましくは水素原子、アルキル基、アルコキシ基、アリール基、ジ置換アミノ基、ニトロ基、ヘテロ環残基、ハロゲン原子であり、より好ましくは水素原子、アルキル基、アルコキシ基、アリール基、ニトロ基である。また、二価の連結基としては、アルキレン基（好ましくは炭素数１〜１０）、シクロアルキレン基（好ましくは３〜１０員）、アリーレン基（好ましくは６〜１０員）、二価のヘテロ環残基が好ましく挙げられ、この中でもシクロアルキレン基、アリーレン基、フリレン基、チエニレン基、ピリジレン基が特に好ましい。 In the general formulas (I) and (II), R1 to R17 are specifically hydrogen atoms; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms such as pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl; vinyl, Allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, o Linear, branched, or cyclic C2-C20 alkenyl groups such as tadecenyl, nonadecenyl, icocenyl, hexadienyl, dodecatrienyl, etc .; ethynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, cyclooctynyl, cyclononynyl, cyclodecynyl, etc. A linear, branched or cyclic alkynyl group having 2 to 20 carbon atoms; a monocyclic or di- to tetracyclic aryl group such as phenyl, naphthyl, phenanthryl, anthryl; methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyl C1-C20 alkoxy groups such as oxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, octadecyloxy; aryloxy groups such as phenoxy, naphthyloxy; dimethylamino, N- Di-substituted amino groups such as til-N-phenylamino, diphenylamino, N-phenyl-N-naphthylamino; nitro groups; heterocyclic residues such as furyl, thienyl, pyridyl; fluorine atoms, chlorine atoms, bromine atoms, iodine Represents a halogen atom such as an atom. Preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a disubstituted amino group, a nitro group, a heterocyclic residue, and a halogen atom, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, and a nitro group. is there. Examples of the divalent linking group include an alkylene group (preferably having 1 to 10 carbon atoms), a cycloalkylene group (preferably 3 to 10 members), an arylene group (preferably 6 to 10 members), and a divalent heterocycle. A residue is mentioned preferably, Among these, a cycloalkylene group, an arylene group, a furylene group, a thienylene group, and a pyridylene group are particularly preferable.
一般式（Ａ）、（I）、（II）において、Ｒａ、Ｒｂ、Ｌ１、Ｒ１〜Ｒ１７は更に置換基を有してもよく、反応に関与しないものであれば特に制限されない。具体的にはメチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル等のアルキル基；ビニル、アリル、プロペニル、ブテニル、ペンテニル、ヘキセニル、ヘプテニル、オクテニル、ノネニル、デセニル、ウンデセニル、ドデセニル、トリデセニル、テトラデセニル、ペンタデセニル、ヘキサデセニル、ヘプタデセニル、オクタデセニル、ノナデセニル、イコセニル、ヘキサジエニル、ドデカトリエニル等のアルケニル基；エチニル、ブチニル、ペンチニル、ヘキシニル、ヘプチニル、オクチニル、ノニニル、シクロオクチニル、シクロノニニル、シクロデシニル等のアルキニル基；フェニル、ナフチル、フェナントリル、アントリル等の単環式またはニ〜四環式アリール基；メトキシ、エトキシ、プロポキシ、ブトキシ、ペンチルオキシ、ヘキシルオキシ、ヘプチルオキシ、オクチルオキシ、ノニルオキシ、デシルオキシ等のアルコキシ基；フェノキシ、ナフチルオキシ等のアリールオキシ基；ジメチルアミノ、Ｎ−エチル−Ｎ−フェニルアミノ、ジフェニルアミノ、Ｎ−フェニル−Ｎ−ナフチルアミノ等のジ置換アミノ基；ニトロ基；フリル、チエニル、ピリジル等のヘテロ環残基；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子等が挙げられる。好ましくは水素原子、アルキル基、アルコキシ基、アリール基、ジ置換アミノ基、ニトロ基、ヘテロ環残基、ハロゲン原子であり、より好ましくは水素原子、アルキル基、アルコキシ基、アリール基、ニトロ基である。 In the general formulas (A), (I), and (II), Ra, Rb, L1, R1 to R17 may further have a substituent and are not particularly limited as long as they do not participate in the reaction. Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl; vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, Alkenyl groups such as dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icocenyl, hexadienyl, dodecatrienyl, etc .; ethynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, cyclooctyl, cyclodecyl Groups: monocyclic or di- to tetracyclic aryl groups such as phenyl, naphthyl, phenanthryl, anthryl, etc .; methoxy, ethoxy, Alkoxy groups such as poxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy; aryloxy groups such as phenoxy, naphthyloxy; dimethylamino, N-ethyl-N-phenylamino, diphenylamino, N -Disubstituted amino groups such as phenyl-N-naphthylamino; nitro groups; heterocyclic residues such as furyl, thienyl, pyridyl; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom and the like. Preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a disubstituted amino group, a nitro group, a heterocyclic residue, and a halogen atom, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, and a nitro group. is there.
また、複数のＲａ、Ｒ１〜Ｒ５もしくはＲ６〜Ｒ１７における２つの基によって更に環を形成してもよい。具体的にはシクロブタン、シクロペンタン、シクロヘキサンなどの飽和環；シクロペンテン、シクロヘキセン、シクロオクテンなどの部分飽和環；ベンゼン、ナフタレンなどの芳香環；ピロリジン、ピリジン、ピラン、オキソラン、チオラン、オキサン、チアンなどのヘテロ環が挙げられる。好ましくは飽和環、芳香環が挙げられる。 Moreover, you may form a ring further by two groups in several Ra, R1-R5, or R6-R17. Specifically, saturated rings such as cyclobutane, cyclopentane, and cyclohexane; partially saturated rings such as cyclopentene, cyclohexene, and cyclooctene; aromatic rings such as benzene and naphthalene; pyrrolidine, pyridine, pyran, oxolane, thiolane, oxane, thiane, and the like A heterocycle is mentioned. A saturated ring and an aromatic ring are preferable.
一般式（II）のＸにおけるシクロアルキレン基とは具体的にはシクロペンチレン、シクロヘキシレン、シクロヘプチレン等を表わす。またアリーレン基とは具体的にはフェニレン、ナフチレン、アントリレン、フェナントリレン、ピレニレン等を表わす。 The cycloalkylene group in X of the general formula (II) specifically represents cyclopentylene, cyclohexylene, cycloheptylene and the like. The arylene group specifically represents phenylene, naphthylene, anthrylene, phenanthrylene, pyrenylene and the like.
Ｑは塩素原子、臭素原子またはヨウ素原子を表わし、好ましくは臭素原子、ヨウ素原子である。 Q represents a chlorine atom, a bromine atom or an iodine atom, preferably a bromine atom or an iodine atom.
本発明で使用する芳香族アミン化合物は好ましくは下記一般式(B)で表わされる化合物である。 The aromatic amine compound used in the present invention is preferably a compound represented by the following general formula (B).
式（B）中、
ｎ３は０〜５の整数を表す。
Ｒｃは複数ある場合は各々独立して水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリールオキシ基、ジ置換アミノ基、ニトロ基、ヘテロ環残基、ハロゲン原子または−Ｌ２−Ｒｅで表される基を表わす。Ｒｄは水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリールオキシ基、ジ置換アミノ基、ニトロ基、ヘテロ環残基、ハロゲン原子または−Ｌ２−Ｒｅで表される基を表わす。Ｌ２は二価の連結基を表わす。Ｒｅはアルキル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリールオキシ基、ジ置換アミノ基、ニトロ基、ヘテロ環残基、ハロゲン原子を表す。
Ｒｃ、Ｒｄ、Ｒｅ、Ｌ２で表される基は各々置換基を有していてもよい。
複数のＲｃによって更に環を形成してもよい。
In formula (B),
n3 represents an integer of 0 to 5.
When there are a plurality of Rc, each independently represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, disubstituted amino group, nitro group, heterocyclic residue, halogen atom or -L2. Represents a group represented by -Re; Rd represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a disubstituted amino group, a nitro group, a heterocyclic residue, a halogen atom or a group represented by -L2-Re. Represent. L2 represents a divalent linking group. Re represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a disubstituted amino group, a nitro group, a heterocyclic residue, or a halogen atom.
The groups represented by Rc, Rd, Re, and L2 may each have a substituent.
A plurality of Rc may further form a ring.
本発明において使用される芳香族アミン化合物は、より好ましくは下記一般式（III）もしくは（IV）で表わされる化合物である。 The aromatic amine compound used in the present invention is more preferably a compound represented by the following general formula (III) or (IV).
式（III）および（IV）中、
Ｙは二価の連結基を表わし、ｎ４が２以上の場合はＹは同じでも異なっても良い。Ｙは好ましくは−Ｃ（Ｒ３４）（Ｒ３５）−、酸素原子、硫黄原子、シクロアルキレン基、アリーレン基、二価のヘテロ環残基、−Ｎ＝Ｎ−、または−Ｃ（Ｒ３４）＝Ｃ（Ｒ３５）−であり、更に好ましくは３〜１０員のシクロアルキレン基、６〜１０員の単環式または二環式のアリーレン基、フリレン基、チエニレン基、ピリジレン基である。
ｎ４は０〜３の整数を表わし、ｎ４が０の場合は単結合を表わす。
Ｒ１８〜Ｒ３５は水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリールオキシ基、アミノ基、ニトロ基、ヘテロ環残基、またはハロゲン原子を表わす。
また、Ｒ１８〜Ｒ２３もしくはＲ２４〜Ｒ３５において２つの基によって飽和環、不飽和環、複素環を形成してもよい。
Ｒ２４〜Ｒ３５において、二価の連結基を介して式（IV）で表わされる構造をもう１つ有していてもよい。この場合、複数の式（IV）で表わされる構造において、両者の連結部位は同一でも異なっても良い。
In formulas (III) and (IV),
Y represents a divalent linking group. When n4 is 2 or more, Y may be the same or different. Y is preferably -C (R34) (R35)-, oxygen atom, sulfur atom , cycloalkylene group, arylene group, divalent heterocyclic residue, -N = N-, or -C (R34) = C ( R35)-, more preferably a 3 to 10-membered cycloalkylene group, a 6 to 10-membered monocyclic or bicyclic arylene group, a furylene group, a thienylene group, and a pyridylene group.
n4 represents an integer of 0 to 3, and when n4 is 0, it represents a single bond.
R18 to R35 each represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a nitro group, a heterocyclic residue, or a halogen atom.
Moreover, you may form a saturated ring, an unsaturated ring, and a heterocyclic ring by two groups in R18-R23 or R24- R35 .
R24 to R35 may have another structure represented by the formula (IV) through a divalent linking group. In this case, in the structure represented by a plurality of formulas (IV), both of the connecting sites may be the same or different.
一般式（III）、（IV）において、Ｒ１８〜Ｒ３５は具体的には水素原子；メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル、ノナデシル、イコシル、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル、シクロノニル、シクロデシルなどの直鎖、分岐または環状の炭素数１〜２０のアルキル基；ビニル、アリル、プロペニル、ブテニル、ペンテニル、ヘキセニル、ヘプテニル、オクテニル、ノネニル、デセニル、ウンデセニル、ドデセニル、トリデセニル、テトラデセニル、ペンタデセニル、ヘキサデセニル、ヘプタデセニル、オクタデセニル、ノナデセニル、イコセニル、ヘキサジエニル、ドデカトリエニル等の直鎖、分岐、または環状の炭素数２〜２０のアルケニル基；エチニル、ブチニル、ペンチニル、ヘキシニル、ヘプチニル、オクチニル、ノニニル、シクロオクチニル、シクロノニニル、シクロデシニル等の直鎖、分岐または環状の炭素数２〜２０のアルキニル基；フェニル、ナフチル等の単環式またはニ環式アリール基；メトキシ、エトキシ、プロポキシ、ブトキシ、ペンチルオキシ、ヘキシルオキシ、ヘプチルオキシ、オクチルオキシ、ノニルオキシ、デシルオキシ、ドデシルオキシ、オクタデシルオキシ等の炭素数１〜２０のアルコキシ基；フェノキシ、ナフチルオキシ等のアリールオキシ基；アミノ基；メチルアミノ、ｎ−ヘキシルアミノ、フェニルアミノ、ジメチルアミノ、Ｎ−エチル−Ｎ−フェニルアミノ、ジフェニルアミノ、Ｎ−フェニル−Ｎ−ナフチルアミノ等の置換アミノ基；ニトロ基；フリル、チエニル、ピリジル等のヘテロ環残基を表わす。好ましくは水素原子、アルキル基、アルコキシ基、アリール基、アミノ基、置換アミノ基、ニトロ基、ヘテロ環残基、ハロゲン原子であり、より好ましくは水素原子、アルキル基、アルコキシ基、アリール基、アミノ基、置換アミノ基である。 In the general formulas (III) and (IV), R18 to R35 are specifically hydrogen atoms; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms such as pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl; vinyl, Allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl Linear, branched, or cyclic C2-C20 alkenyl groups such as octadecenyl, nonadecenyl, icocenyl, hexadienyl, dodecatrienyl, etc .; ethynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, cyclooctynyl, cyclononynyl, cyclodecynyl, etc. A linear, branched or cyclic alkynyl group having 2 to 20 carbon atoms; a monocyclic or bicyclic aryl group such as phenyl or naphthyl; methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyl C1-C20 alkoxy groups such as oxy, nonyloxy, decyloxy, dodecyloxy, octadecyloxy; aryloxy groups such as phenoxy, naphthyloxy; amino groups; methylamino, n-hexylamino, phenoxy It represents furyl, thienyl, a heterocyclic residue such as pyridyl; arylamino, dimethylamino, N- ethyl -N- phenylamino, diphenylamino, N- phenyl--N--substituted amino groups such naphthylamino; nitro group. Preferred are a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an amino group, a substituted amino group, a nitro group, a heterocyclic residue, and a halogen atom, and more preferred are a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, amino Group, a substituted amino group.
一般式（Ｂ）、（III）、（IV）において、Ｒｃ、Ｒｄ、Ｒｅ、Ｌ２、Ｒ１８〜Ｒ３５は更に置換基を有してもよく、反応に関与しないものであれば特に制限されない。具体的にはメチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル等のアルキル基；ビニル、アリル、プロペニル、ブテニル、ペンテニル、ヘキセニル、ヘプテニル、オクテニル、ノネニル、デセニル、ウンデセニル、ドデセニル、トリデセニル、テトラデセニル、ペンタデセニル、ヘキサデセニル、ヘプタデセニル、オクタデセニル、ノナデセニル、イコセニル、ヘキサジエニル、ドデカトリエニル等のアルケニル基；エチニル、ブチニル、ペンチニル、ヘキシニル、ヘプチニル、オクチニル、ノニニル、シクロオクチニル、シクロノニニル、シクロデシニル等のアルキニル基；フェニル、ナフチル、フェナントレン、アントラセン等の単環式またはニ〜四環式アリール基；メトキシ、エトキシ、プロポキシ、ブトキシ、ペンチルオキシ、ヘキシルオキシ、ヘプチルオキシ、オクチルオキシ、ノニルオキシ、デシルオキシ等のアルコキシ基；フェノキシ、ナフチルオキシ等のアリールオキシ基；アミノ基；メチルアミノ、ｎ−ヘキシルアミノ、フェニルアミノ、ジメチルアミノ、Ｎ−エチル−Ｎ−フェニルアミノ、ジフェニルアミノ、Ｎ−フェニル−Ｎ−ナフチルアミノ等の置換アミノ基；ニトロ基；フリル、チエニル、ピリジル等のヘテロ環残基が挙げられる。好ましくは水素原子、アルキル基、アルコキシ基、アリール基、アミノ基、置換アミノ基、ニトロ基、ヘテロ環残基であり、より好ましくは水素原子、アルキル基、アルコキシ基、アリール基、アミノ基、置換アミノ基である。また、二価の連結基としては、アルキレン基（好ましくは炭素数１〜１０）、シクロアルキレン基（好ましくは３〜１０員）、アリーレン基（好ましくは６〜１０員）、二価のヘテロ環残基が好ましく挙げられ、この中でもシクロアルキレン基、アリーレン基、フリレン基、チエニレン基、ピリジレン基が特に好ましい。 In the general formulas (B), (III), and (IV), Rc, Rd, Re, L2, and R18 to R35 may further have a substituent and are not particularly limited as long as they do not participate in the reaction. Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl; vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, Alkenyl groups such as dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icocenyl, hexadienyl, dodecatrienyl, etc .; ethynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, cyclooctyl, cyclodecyl Groups; monocyclic or di- to tetracyclic aryl groups such as phenyl, naphthyl, phenanthrene and anthracene; methoxy, ethoxy, Roxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy and other alkoxy groups; phenoxy, naphthyloxy and other aryloxy groups; amino groups; methylamino, n-hexylamino, phenylamino, dimethylamino N-ethyl-N-phenylamino, diphenylamino, substituted amino groups such as N-phenyl-N-naphthylamino; nitro groups; heterocyclic residues such as furyl, thienyl, pyridyl and the like. Preferred are a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an amino group, a substituted amino group, a nitro group, and a heterocyclic residue, and more preferred are a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an amino group, and a substituent. It is an amino group. Examples of the divalent linking group include an alkylene group (preferably having 1 to 10 carbon atoms), a cycloalkylene group (preferably 3 to 10 members), an arylene group (preferably 6 to 10 members), and a divalent heterocycle. Residues are preferred, and among them, a cycloalkylene group, an arylene group, a furylene group, a thienylene group, and a pyridylene group are particularly preferred.
また、複数のＲｃ、Ｒ１８〜Ｒ２３もしくはＲ２４〜Ｒ３５における２つの基によって更に環を形成してもよい。具体的にはシクロブタン、シクロペンタン、シクロヘキサンなどの飽和環；シクロペンテン、シクロヘキセン、シクロオクテンなどの部分飽和環；ベンゼン、ナフタレンなどの芳香環；ピロリジン、ピロール、ピペリジン、ピリジン、モルホリン、チオモルホリン、ピペラジン、アザシクロヘプタン、アザシクロヘプテン、アザシクロヘプタトリエン等、オキソラン、チオラン、オキサン、チアンなどのヘテロ環が挙げられる。好ましくは飽和環、芳香環が挙げられる。 Moreover, you may form a ring further by two groups in several Rc, R18-R23, or R24- R35 . Specifically, saturated rings such as cyclobutane, cyclopentane and cyclohexane; partially saturated rings such as cyclopentene, cyclohexene and cyclooctene; aromatic rings such as benzene and naphthalene; pyrrolidine, pyrrole, piperidine, pyridine, morpholine, thiomorpholine, piperazine, Examples include heterocycles such as azacycloheptane, azacycloheptene, azacycloheptatriene, oxolane, thiolane, oxane, thiane. A saturated ring and an aromatic ring are preferable.
一般式（IV）のＹにおけるシクロアルキレン基とは具体的にはシクロペンチレン、シクロヘキシレン、シクロヘプチレン等を表わす。またアリーレン基とは具体的にはフェニレン、ナフチレン、アントリレン、フェナントリレン、ピレニレン等を表わす。
芳香族アミン化合物の使用量は、芳香族アミン化合物および芳香族ハロゲン化合物の反応部位の数、反応温度、また芳香族ハロゲン化合物を基質兼溶媒として用いる場合等、個々の反応によって異なる。ハロゲン化合物１モルに対し、通常０．１〜２０倍モル、好ましくは０．３〜１０倍モルである。
Specific examples of the cycloalkylene group represented by Y in the general formula (IV) include cyclopentylene, cyclohexylene, cycloheptylene and the like. The arylene group specifically represents phenylene, naphthylene, anthrylene, phenanthrylene, pyrenylene and the like.
The amount of the aromatic amine compound used varies depending on the individual reaction, such as the number of reaction sites of the aromatic amine compound and the aromatic halogen compound, the reaction temperature, and when the aromatic halogen compound is used as a substrate and solvent. It is 0.1-20 times mole normally with respect to 1 mol of halogen compounds, Preferably it is 0.3-10 times mole.
本発明で使用される銅触媒としては、特に制限されるものではなく、ウルマン縮合反応で通常使用される触媒を用いることができる。例えば銅粉、塩化第一銅、塩化第二銅、臭化第一銅、臭化第二銅、沃化銅、酸化第一銅、酸化第二銅、硫酸銅、硝酸銅、炭酸銅、水酸化第二銅等が挙げられ、好ましくは塩化銅、臭化銅、沃化銅である。これらの銅触媒の使用量は芳香族ハロゲン化合物１モルに対して通常０．００１〜０．４モル、好ましくは０．００５〜０．３モル、更に好ましくは０．０１〜０．２モルである。 The copper catalyst used in the present invention is not particularly limited, and a catalyst usually used in the Ullmann condensation reaction can be used. For example, copper powder, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, copper iodide, cuprous oxide, cupric oxide, copper sulfate, copper nitrate, copper carbonate, water Examples include cupric oxide, and copper chloride, copper bromide, and copper iodide are preferable. The amount of these copper catalysts used is usually 0.001 to 0.4 mol, preferably 0.005 to 0.3 mol, more preferably 0.01 to 0.2 mol, per mol of the aromatic halogen compound. is there.
また必要に応じてヨウ化リチウム、ヨウ化ナトリウム、ヨウ化カリウム、ヨウ化ルビジウム、ヨウ化セシウム等の助触媒を添加することもできる。これらの助触媒を添加する場合、その使用量は芳香族ハロゲン化合物１モルに対して０．００１〜０．４モル、好ましくは０．００５〜０．３モル、更に好ましくは０．０１〜０．２モルである。 If necessary, a promoter such as lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide or the like can be added. When these promoters are added, the amount used is 0.001 to 0.4 mol, preferably 0.005 to 0.3 mol, more preferably 0.01 to 0 mol, per mol of the aromatic halogen compound. .2 moles.
本発明において使用される塩基としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム等のアルカリ金属水酸化物、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸ルビジウム、炭酸セシウム等のアルカリ金属炭酸化物、燐酸三リチウム、燐酸三ナトリウム、燐酸三カリウム等のアルカリ金属燐酸化物、ナトリウムメトキシド、ナトリウムエトキシド、カリウムメトキシド、カリウムエトキシド、リチウム−ｔｅｒｔ−ブトキシド、ナトリウム−ｔｅｒｔ−ブトキシド、カリウム−ｔｅｒｔ−ブトキシド等のアルカリ金属アルコキシドが挙げられる。上記中アルカリ金属アルコキシドは反応系にそのまま添加するか、またはアルカリ金属、水素化アルカリ金属、水酸化アルカリ金属等とアルコールから調製して使用してもよい。これらの塩基のなかで好ましくはアルカリ金属炭酸化物、アルカリ金属水酸化物である。
これらの塩基は芳香族アミン化合物に対して１．０〜４．０等量、好ましくは１．１〜３．０等量、更に好ましくは１．２〜２．０等量使用される。
Examples of the base used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and other alkali metal hydroxides, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, carbonate Alkali metal carbonates such as cesium, alkali metal phosphates such as trilithium phosphate, trisodium phosphate, tripotassium phosphate, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium-tert-butoxide, sodium- Examples thereof include alkali metal alkoxides such as tert-butoxide and potassium-tert-butoxide. Among the above, the alkali metal alkoxide may be added to the reaction system as it is, or prepared from an alkali metal, an alkali metal hydride, an alkali metal hydroxide, etc. and an alcohol. Of these bases, alkali metal carbonates and alkali metal hydroxides are preferred.
These bases are used in an amount of 1.0 to 4.0 equivalents, preferably 1.1 to 3.0 equivalents, more preferably 1.2 to 2.0 equivalents, relative to the aromatic amine compound.
本発明の製造方法においては、反応溶媒を使用しなくても良いが、必要に応じて芳香族化合物もしくは脂肪族化合物を反応溶媒として用いることができる。具体的には１気圧において１００℃以上の沸点を有する以下の溶媒が挙げられる。
（i）ハロゲン化されてもよい芳香族炭化水素化合物：トルエン、キシレン、メシチレン、デュレン、エチルベンゼン、ジエチルベンゼン、イソプロピルベンゼン、ジイソプロピルベンゼン、ジフェニルメタン、クロロベンゼン、１，２−ジクロロベンゼン、１，２，４−トリクロロベンゼン等。
（ii）環骨格がジヒドロ化、テトラヒドロ化、ヘキサヒドロ化、オクタヒドロ化、デカヒドロ化等、部分的に水素添加された水素化芳香族炭化水素化合物：１，４−ジヒドロナフタレン、１，２，３，４−テトラヒドロナフタレン、９，１０−ジヒドロアントラセン、９，１０−ジヒドロフェナントレン、４，５，９，１０−テトラヒドロピレン、１，２，３，６，７，８−ヘキサヒドロピレン、ドデカヒドロトリフェニレン等。
（iii）飽和脂肪族化合物：オクタン、ノナン、デカン、ウンデカン、ドデカン、トリデカン、２−メチルドデカン、４−エチルウンデカン、テトラデカン、ペンタデカン、３，３−ジメチルトリデカン、ヘキサデカン、ヘプタデカン、２−メチル−４−エチルテトラデカン等。
（iv）不飽和脂肪族化合物：２−ヘプチン、３−ヘプチン、２−オクテン、３−ノネン、１−デシン、１−ウンデセン、４−ドデセン、３，３−ジメチル−１−デセン、１，３，５−ドデカトリエン、５−トリデセン、３−メチル−４−エチル−２−デセン、１−ドデシン、３−ドデセン−１−イン、１−トリデシン、５，５−ジメチル−３−ウンデセン−１−イン、５−エチニル−１，３−ドデカジエン等や、オシメン、ミルセン、スクアレン等。
（v）飽和脂環式化合物：ジシクロヘキシル、デカヒドロナフタレン、ドデカヒドロフルオレン等。
（vi）不飽和脂環式化合物：α−テルピネン、β−テルピネン、γ−テルピネン、テルピノレン、（＋）−α−フェランドレン、（−）−β−フェランドレン、（−）−1−p−メンテン、（＋）−３−メンテン、ジペンテン、（＋）−リモネン、（＋）−サビネン、（＋）−α−ピネン、（＋）−β−ピネン、（−）−β−カジネン、（−）−β−カリオフィレン、（−）−β−サンタレン、（−）−α−セドレン、（＋）−β−セリネン、（−）−β−ビサボレン、α−フムレン等。
In the production method of the present invention, a reaction solvent may not be used, but an aromatic compound or an aliphatic compound can be used as a reaction solvent as necessary. Specific examples include the following solvents having a boiling point of 100 ° C. or higher at 1 atmosphere.
(I) Aromatic hydrocarbon compounds that may be halogenated: toluene, xylene, mesitylene, durene, ethylbenzene, diethylbenzene, isopropylbenzene, diisopropylbenzene, diphenylmethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4- Trichlorobenzene and the like.
(Ii) Hydrogenated aromatic hydrocarbon compounds in which the ring skeleton is partially hydrogenated, such as dihydro, tetrahydro, hexahydro, octahydro, decahydro, etc .: 1,4-dihydronaphthalene, 1,2,3, 4-tetrahydronaphthalene, 9,10-dihydroanthracene, 9,10-dihydrophenanthrene, 4,5,9,10-tetrahydropyrene, 1,2,3,6,7,8-hexahydropyrene, dodecahydrotriphenylene, etc. .
(Iii) saturated aliphatic compounds: octane, nonane, decane, undecane, dodecane, tridecane, 2-methyldodecane, 4-ethylundecane, tetradecane, pentadecane, 3,3-dimethyltridecane, hexadecane, heptadecane, 2-methyl- 4-ethyltetradecane and the like.
(Iv) Unsaturated aliphatic compounds: 2-heptin, 3-heptin, 2-octene, 3-nonene, 1-decyne, 1-undecene, 4-dodecene, 3,3-dimethyl-1-decene, 1,3 , 5-dodecatriene, 5-tridecene, 3-methyl-4-ethyl-2-decene, 1-dodecyne, 3-dodecene-1-yne, 1-tridecyne, 5,5-dimethyl-3-undecene-1- In, 5-ethynyl-1,3-dodecadiene and the like, ocimene, myrcene, squalene and the like.
(V) Saturated alicyclic compounds: dicyclohexyl, decahydronaphthalene, dodecahydrofluorene and the like.
(Vi) Unsaturated alicyclic compound: α-terpinene, β-terpinene, γ-terpinene, terpinolene, (+)-α-ferrandolene, (−)-β-ferrandolene, (−)-1-p- Menten, (+)-3-Mentene, Dipentene, (+)-Limonene, (+)-Sabinene, (+)-α-Pinene, (+)-β-Pinene, (-)-β-Cadinene, (- )-[Beta] -caryophyllene, (-)-[beta] -santalene, (-)-[alpha] -cedrene, (+)-[beta] -selinene, (-)-[beta] -bisabolene, [alpha] -humulene and the like.
上記の溶媒のなかでも、トルエン、キシレン、ジエチルベンゼン、ジイソプロピルベンゼン等のアルキルベンゼンや、α−テルピネン、β−テルピネン、γ−テルピネン、フェランドレン、テルピノレン等のテルペンが好ましい。これらの溶媒を用いた場合は不純物生成の抑制効果が向上し、高収率で高純度なアリールアミンを製造することができる。
これら芳香族化合物及び脂肪族化合物は、１種単独で又は２種以上を組み合わせて溶媒として使用することができる。これらの反応溶媒を使用する場合は、通常原料の芳香族ハロゲン化合物１モルに対して１００〜１０００ｍｌの割合で使用される。
Among the above solvents, alkylbenzenes such as toluene, xylene, diethylbenzene, and diisopropylbenzene, and terpenes such as α-terpinene, β-terpinene, γ-terpinene, ferrandrene, and terpinolene are preferable. When these solvents are used, the effect of suppressing the generation of impurities is improved, and a high yield and high purity arylamine can be produced.
These aromatic compounds and aliphatic compounds can be used as a solvent singly or in combination of two or more. When these reaction solvents are used, they are usually used in a proportion of 100 to 1000 ml with respect to 1 mol of the aromatic halogen compound as a raw material.
本発明における反応温度は８０〜２８０℃の範囲である。使用する芳香族ハロゲン化物が塩素化合物、臭素化合物の場合には、反応時間は反応条件より異なるが、通常１〜１２時間程度である。使用する芳香族ハロゲン化物がヨウ素化合物の場合には、８０〜１３０℃の反応温度で非常に効率良く反応が進行し、その場合の反応時間は使用する原料と添加する有機塩により異なるが、通常１〜３時間程度である。 The reaction temperature in this invention is the range of 80-280 degreeC. When the aromatic halide to be used is a chlorine compound or a bromine compound, the reaction time varies depending on the reaction conditions, but is usually about 1 to 12 hours. When the aromatic halide used is an iodine compound, the reaction proceeds very efficiently at a reaction temperature of 80 to 130 ° C., and the reaction time in this case varies depending on the raw material used and the organic salt to be added. About 1 to 3 hours.
本発明で合成され得るアリールアミン類の具体例を下記に示すが、本発明はこれに限定されない。 Specific examples of arylamines that can be synthesized in the present invention are shown below, but the present invention is not limited thereto.
次に本発明を実施例により更に具体的に説明するが、本発明はこれらに限定されるものではない。なお純度の評価は高速液体クロマトグラフィー（以下、ＨＰＬＣと略記する）によった。 EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to these. The purity was evaluated by high performance liquid chromatography (hereinafter abbreviated as HPLC).
実施例１
Ｎ，Ｎ’−ジフェニル− Ｎ，Ｎ’ −ビス（３−メチルフェニル）−（ｐ−ターフェニル）−４，４’−ジアミン（I−１３）の合成
Ｎ−（３−メチルフェニル）−Ｎ−フェニルアミン１３．５４ｇ（７３．８９ｍｍｏｌ）、４，４’’−ジヨード−１，１’：４’，１’’−ターフェニル１１．８７ｇ（２４．６３ｍｍｏｌ）、炭酸カリウム２７．２３g（１９７．０ｍｍｏｌ）、硫酸銅５水和物１．００g（４．０ｍｍｏｌ）を混合し反応系内を窒素置換した。その後、窒素を導入しながら５０ｋＰａの減圧下において２３０〜２４０℃で２時間反応した。反応後、トルエン２５ｍｌと水５０ｍｌを添加し分液後、水洗して有機層を無水硫酸ナトリウムで乾燥した。乾燥剤を濾別後、トルエンを減圧濃縮して酢酸エチル２８ｍｌ添加し冷却晶析後濾別して、白色粗結晶として目的化合物（I−１３）を１３．７g（収率９４．０％）得た。融点１８９〜１９０℃。ＨＰＬＣ含量(カラム：ＧＬ Ｓｃｉｅｎｃｅ Ｉｎｅｒｔｓｉｌ ＯＤＳ−３)、溶離液：アセトニトリル／水（Ｖ／Ｖ＝８０／２０）、検出ＵＶ：３００ｎｍ、流量：１．０ｍｌ／ｍｉｎ）は９９．２％であった。また不純物は、極性基を有する酸化生成物Ａが０．０１１％、及び酸化生成物Ｂが０％、イオン化電位の小さな酸化生成物Ｃが０．００４％、イオン化電位の小さな二量化生成物Ｄが０．０１６％、及び二量化生成物Ｅが０．００９％であった。
Example 1
Synthesis of N, N′-diphenyl-N, N′-bis (3-methylphenyl)-(p-terphenyl) -4,4′-diamine (I-13) N- (3-methylphenyl) -N -Phenylamine 13.54 g (73.89 mmol), 4,4 ″ -diiodo-1,1 ′: 4 ′, 1 ″ -terphenyl 11.87 g (24.63 mmol), potassium carbonate 27.23 g (197 0.0 mmol) and copper sulfate pentahydrate 1.00 g (4.0 mmol) were mixed, and the reaction system was purged with nitrogen. Then, it reacted at 230-240 degreeC under reduced pressure of 50 kPa, introducing nitrogen, for 2 hours. After the reaction, 25 ml of toluene and 50 ml of water were added and separated, washed with water, and the organic layer was dried over anhydrous sodium sulfate. After the desiccant was filtered off, toluene was concentrated under reduced pressure and 28 ml of ethyl acetate was added. After cooling and crystallization, it was filtered off to obtain 13.7 g (yield 94.0%) of the target compound (I-13) as white crude crystals. . Mp 189-190 ° C. HPLC content (column: GL Science Inertsil ODS-3), eluent: acetonitrile / water (V / V = 80/20), detection UV: 300 nm, flow rate: 1.0 ml / min) was 99.2%. . The impurities are 0.011% oxidation product A having a polar group, 0% oxidation product B, 0.004% oxidation product C having a small ionization potential, and dimerization product D having a small ionization potential. Was 0.016% and dimerized product E was 0.009%.
実施例２〜５
実施例１の反応系内の圧力を変えた以外は実施例１と同様の方法で合成を行った。その結果を表１に示す。
Examples 2-5
The synthesis was performed in the same manner as in Example 1 except that the pressure in the reaction system of Example 1 was changed. The results are shown in Table 1.
実施例６
実施例１において、減圧度を６６．６ｋＰａ、および窒素導入を行わなかった以外は実施例１と同様の方法で合成を行った。その結果を表１に示す。
Example 6
In Example 1, the synthesis was performed in the same manner as in Example 1 except that the degree of vacuum was 66.6 kPa and nitrogen was not introduced. The results are shown in Table 1.
比較例１
実施例１において反応中の減圧操作を行わない以外は実施例１と同様の方法で合成を行った。その結果を表１に示す。
Comparative Example 1
The synthesis was performed in the same manner as in Example 1 except that the decompression operation during the reaction was not performed in Example 1. The results are shown in Table 1.
実施例７
Ｎ，Ｎ，Ｎ’,Ｎ’−テトラ（３−メチルフェニル）−９，１０−ジアミノフェナントレン（例示化合物I−３２）の合成
９，１０−ビス（３−メチルアニリノ）フェナントレン６．６ｇ（１７．０ｍｍｏｌ）、ｍ−ヨードトルエン１４．８ｇ（６８．０ｍｍｏｌ）、水酸化カリウム３．８２ｇ（６８ｍｍｏｌ）、臭化第一銅０．９８ｇ（６．８ｍｍｏｌ）、テルピノレン１０ｍｌを混合し窒素気流下、８０ｋＰａの減圧下において１１５〜１２５℃で２時間反応させた。反応後、減圧濃縮にて反応溶媒を留去しトルエン５ｍｌ、酢酸エチル６７ｍｌ、水２２ｍｌ添加して分液した。有機層にメタノール７１ｍｌを添加して冷却晶析し、淡黄色粗結晶として目的化合物（I−３２）を９．０ｇ（収率９３．０％）得た。融点２２３〜２２４℃。ＨＰＬＣ含量(カラム：ＹＭＣ−Ａ−３１２、溶離液：メタノール／テトラヒドロフラン（Ｖ／Ｖ＝９９／１）、検出ＵＶ：２５４ｎｍ、流量：１．０ｍｌ／ｍｉｎ)は９９．６％であった。また不純物は、極性基を有する酸化生成物Ｆが０．００６％、及び酸化生成物Ｇが０．００１％、イオン化電位の小さな二量化生成物Ｈが０．０２０％、及び二量化生成物Iが０．００５％であった。
Example 7
Synthesis of N, N, N ′, N′-tetra (3-methylphenyl) -9,10-diaminophenanthrene (Exemplary Compound I-32) 9,10-bis (3-methylanilino) phenanthrene 6.6 g (17. 0 mmol), 14.8 g (68.0 mmol) of m-iodotoluene, 3.82 g (68 mmol) of potassium hydroxide, 0.98 g (6.8 mmol) of cuprous bromide and 10 ml of terpinolene, and 80 kPa under a nitrogen stream. For 2 hours at 115 to 125 ° C. After the reaction, the reaction solvent was distilled off by concentration under reduced pressure, and 5 ml of toluene, 67 ml of ethyl acetate and 22 ml of water were added for liquid separation. 71 ml of methanol was added to the organic layer and cooled and crystallized to obtain 9.0 g (yield 93.0%) of the target compound (I-32) as pale yellow crude crystals. 223-224 ° C. The HPLC content (column: YMC-A-312, eluent: methanol / tetrahydrofuran (V / V = 99/1), detection UV: 254 nm, flow rate: 1.0 ml / min) was 99.6%. Further, the impurities include 0.006% oxidation product F having a polar group, 0.001% oxidation product G, 0.020% dimerization product H having a small ionization potential, and dimerization product I. Was 0.005%.
比較例２
実施例７において減圧操作を行わない以外は実施例７と同様の方法で合成を行った。その結果を表２に示す。
Comparative Example 2
The synthesis was performed in the same manner as in Example 7 except that the decompression operation was not performed in Example 7. The results are shown in Table 2.
実施例８
９−フェニルカルバゾール（例示化合物II−１）の合成
カルバゾール１６．４７g（９８．５２ｍｍｏｌ）、ブロモベンゼン３１．０g（１９７．０４ｍｍｏｌ）、水酸化カリウム５．５３g（９８．５２ｍｍｏｌ）、塩化第一銅０．４g（８．０ｍｍｏｌ）を混合し、窒素気流下、３３ｋＰａの減圧下において１１５〜１２５℃で留出してくるブロモベンゼンを反応系内に戻しながら４時間反応した。反応後、トルエン５０ｍｌと水１００ｍｌを添加し分液後、水洗して有機層を無水硫酸ナトリウムで乾燥した。乾燥剤を濾別後、トルエンを減圧濃縮してメタノール３５２ｍｌ添加し晶析し、白色粗結晶として目的化合物（II−１）を２２．７g（収率９４．８％）得た。融点９６〜９７℃。ＨＰＬＣ含量（カラム：ＯＤＳ−８０ＴＭ、溶離液：アセトニトリル／水（Ｖ／Ｖ＝６５／３５）、緩衝剤：トリエチルアミン、酢酸各０．１％、検出ＵＶ：２５４ｎｍ、流量：１．０ｍｌ／ｍｉｎ）は９９．８％であった。また含有する不純物は、イオン化電位の小さな二量化生成物Ｊが０．００８％、及び二量化生成物Ｋが０％であった。
Example 8
Synthesis of 9-phenylcarbazole (Exemplary Compound II-1) 16.47 g (98.52 mmol) of carbazole, 31.0 g (197.04 mmol) of bromobenzene, 5.53 g (98.52 mmol) of potassium hydroxide, cuprous chloride 0.4 g (8.0 mmol) was mixed and reacted for 4 hours while returning bromobenzene distilled off at 115 to 125 ° C. under a reduced pressure of 33 kPa under a nitrogen stream. After the reaction, toluene (50 ml) and water (100 ml) were added, followed by liquid separation, washing with water, and drying the organic layer over anhydrous sodium sulfate. After the desiccant was filtered off, toluene was concentrated under reduced pressure and 352 ml of methanol was added and crystallized to obtain 22.7 g (yield 94.8%) of the desired compound (II-1) as white crude crystals. Melting point 96-97 ° C. HPLC content (column: ODS-80TM, eluent: acetonitrile / water (V / V = 65/35), buffer: triethylamine, acetic acid 0.1% each, detection UV: 254 nm, flow rate: 1.0 ml / min) Was 99.8%. The impurities contained were 0.008% for the dimerization product J having a small ionization potential and 0% for the dimerization product K.
比較例３
実施例８において減圧操作を行わない以外は実施例８と同様の方法で合成を行った。その結果を表３に示す。
Comparative Example 3
The synthesis was performed in the same manner as in Example 8 except that the decompression operation was not performed in Example 8. The results are shown in Table 3.
表１〜表３の結果より、減圧下で反応を行った場合には電気特性の低下を招く電子密度分布の異なる副生成物やイオン化電位の小さな副生成物が高度に抑制され、極めて高純度なアリールアミンを合成できることが判る。また、表１から反応系内の減圧度が高いほど不純物の抑制効果は高く、不純物抑制効果は反応系内の減圧度と密接に関係していることが判る。 From the results of Tables 1 to 3, when the reaction is carried out under reduced pressure, by-products with different electron density distributions and by-products with small ionization potentials that cause deterioration of electrical properties are highly suppressed, and extremely high purity. It can be seen that a novel arylamine can be synthesized. Moreover, it can be seen from Table 1 that the higher the degree of vacuum in the reaction system, the higher the effect of suppressing impurities, and the impurity suppression effect is closely related to the degree of vacuum in the reaction system.
Claims (3)
前記銅触媒が、銅粉、塩化第一銅、塩化第二銅、臭化第一銅、臭化第二銅、沃化銅、酸化第一銅、酸化第二銅、硫酸銅、硝酸銅、炭酸銅または水酸化第二銅から選択される少なくとも１種であり、
前記塩基が、アルカリ金属水酸化物、アルカリ金属炭酸化物、アルカリ金属燐酸化物またはアルカリ金属アルコキシドから選択される少なくとも１種であり、
前記芳香族ハロゲン化合物が下記一般式（Ｉ）または（ＩＩ）で表わされる化合物であり、
前記芳香族アミン化合物が下記一般式（ＩＩＩ）または（ＩＶ）で表わされる化合物である、アリールアミンの製造方法。
式（Ｉ）および（ＩＩ）中、
Ｑは塩素原子、臭素原子またはヨウ素原子を表す。
Ｘは−Ｃ（Ｒ１５）（Ｒ１６）−、酸素原子、硫黄原子、−Ｎ（Ｒ１７）−、シクロアルキレン基、アリーレン基、フリレン基、チエニレン基、ピリジレン基、−Ｎ＝Ｎ−、または−Ｃ（Ｒ１５）＝Ｃ（Ｒ１６）−を表す。ｎ２は０〜３の整数を表し、ｎ２が０の場合には単結合を表す。ｎ２が２以上の場合にはＸは同じでも異なっていてもよい。
Ｒ１〜Ｒ１６は各々独立して水素原子、アルキル基、アルケニル基、アリール基、アルコキシ基、アリールオキシ基、ジメチルアミノ基、Ｎ−エチル−Ｎ−フェニルアミノ基、ジフェニルアミノ基、Ｎ−フェニル−Ｎ−ナフチルアミノ基、ニトロ基、またはハロゲン原子を表す。
Ｒ１７はアルキル基、アルケニル基、アリール基、アルコキシ基、アリールオキシ基、ジメチルアミノ基、Ｎ−エチル−Ｎ−フェニルアミノ基、ジフェニルアミノ基、Ｎ−フェニル−Ｎ−ナフチルアミノ基、ニトロ基、またはハロゲン原子を表す。
Ｒ１〜Ｒ５もしくはＲ６〜Ｒ１７における２つの基によって更に飽和環、シクロペンテン環、シクロヘキセン環、シクロオクテン環、または、芳香環を形成してもよい。
Ｒ６〜Ｒ１７において、炭素数１〜１０のアルキレン基、３〜１０員のシクロアルキレ
ン基、６〜１０員のアリーレン基、フリレン基、チエニレン基、またはピリジレン基を介
して式（ＩＩ）で表わされる構造をもう１つ有していてもよい。
Ｒ１〜Ｒ１７におけるアルキル基、アルケニル基、アリール基、アルコキシ基、アリールオキシ基、ジメチルアミノ基、Ｎ−エチル−Ｎ−フェニルアミノ基、ジフェニルアミノ基、およびＮ−フェニル−Ｎ−ナフチルアミノ基は、更にアルキル基、単環式または二〜四環式アリール基、アルコキシ基、アリールオキシ基、ニトロ基、またはハロゲン原子から選択される置換基を有していてもよい。
式（ＩＩＩ）および（ＩＶ）中、
Ｙは−Ｃ（Ｒ３４）（Ｒ３５）−、酸素原子、硫黄原子、シクロアルキレン基、アリーレン基、フリレン基、チエニレン基、ピリジレン基、−Ｎ＝Ｎ−、または−Ｃ（Ｒ３４）＝Ｃ（Ｒ３５）−を表す。
ｎ４は０〜３の整数を表し、ｎ４が０の場合は単結合を表す。ｎ４が２以上の場合はＹは同じでも異なっても良い。
Ｒ１８〜Ｒ３５は水素原子、アルキル基、アルケニル基、アリール基、アルコキシ基、アリールオキシ基、またはニトロ基を表す。
また、Ｒ１８〜Ｒ２３もしくはＲ２４〜Ｒ３５において２つの基によって飽和環、シクロペンテン環、シクロヘキセン環、シクロオクテン環、または、芳香環、または複素環を形成してもよい。
Ｒ２４〜Ｒ３５において、炭素数１〜１０のアルキレン基、３〜１０員のシクロアルキ
レン基、６〜１０員のアリーレン基、フリレン基、チエニレン基、またはピリジレン基を
介して式（ＩＶ）で表される構造をもう１つ有していてもよい。
Ｒ１８〜Ｒ３５におけるアルキル基、アルケニル基、アリール基、アルコキシ基、およびアリールオキシ基は、更にアルキル基、アルケニル基、単環式または二〜四環式アリール基、アルコキシ基、アリールオキシ基、ニトロ基、から選択される置換基を有していてもよい。 A process for producing an arylamine, comprising reacting an aromatic amine compound and an aromatic halogen compound under reduced pressure of 80 kPa or less in the presence of a copper catalyst and a base,
The copper catalyst is copper powder, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, copper iodide, cuprous oxide, cupric oxide, copper sulfate, copper nitrate, At least one selected from copper carbonate or cupric hydroxide,
The base is at least one selected from alkali metal hydroxides, alkali metal carbonates, alkali metal phosphates or alkali metal alkoxides;
The aromatic halogen compound is a compound represented by the following general formula (I) or (II):
A method for producing an arylamine, wherein the aromatic amine compound is a compound represented by the following general formula (III) or (IV).
In formulas (I) and (II)
Q represents a chlorine atom, a bromine atom or an iodine atom.
X is -C (R15) (R16)-, oxygen atom, sulfur atom, -N (R17)-, cycloalkylene group, arylene group, furylene group, thienylene group, pyridylene group, -N = N-, or -C. (R15) = C (R16)-is represented. n2 represents an integer of 0 to 3, and when n2 is 0, it represents a single bond. When n2 is 2 or more, X may be the same or different.
R1 to R16 are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, dimethylamino group, N-ethyl-N-phenylamino group, diphenylamino group, N-phenyl-N. -Represents a naphthylamino group , a nitro group, or a halogen atom.
R17 is an alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, dimethylamino group, N-ethyl-N-phenylamino group, diphenylamino group, N-phenyl-N-naphthylamino group , nitro group, or Represents a halogen atom.
A saturated ring, a cyclopentene ring, a cyclohexene ring, a cyclooctene ring, or an aromatic ring may be further formed by two groups in R1 to R5 or R6 to R17 .
R6 to R17 are represented by the formula (II) via an alkylene group having 1 to 10 carbon atoms, a 3 to 10 membered cycloalkylene group, a 6 to 10 membered arylene group, a furylene group, a thienylene group, or a pyridylene group. You may have another structure .
The alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, dimethylamino group, N-ethyl-N-phenylamino group, diphenylamino group, and N-phenyl-N-naphthylamino group in R1 to R17 are: Further, it may have a substituent selected from an alkyl group, a monocyclic or bicyclic to tetracyclic aryl group, an alkoxy group, an aryloxy group, a nitro group, or a halogen atom.
In formulas (III) and (IV),
Y is -C (R34) (R35)-, oxygen atom, sulfur atom, cycloalkylene group, arylene group, furylene group, thienylene group, pyridylene group, -N = N-, or -C (R34) = C (R35 )-.
n4 represents an integer of 0 to 3, and when n4 is 0, it represents a single bond. When n4 is 2 or more, Y may be the same or different.
R18 to R35 each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, or a nitro group.
In addition, a saturated ring, a cyclopentene ring, a cyclohexene ring, a cyclooctene ring, an aromatic ring, or a heterocyclic ring may be formed by two groups in R18 to R23 or R24 to R35 .
R24 to R35 are represented by the formula (IV) via an alkylene group having 1 to 10 carbon atoms, a 3 to 10 membered cycloalkylene group, a 6 to 10 membered arylene group, a furylene group, a thienylene group, or a pyridylene group. Another structure may be included .
The alkyl group, alkenyl group, aryl group, alkoxy group and aryloxy group in R18 to R35 are further an alkyl group, alkenyl group, monocyclic or bicyclic to tetracyclic aryl group, alkoxy group, aryloxy group, nitro group And may have a substituent selected from
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