JPH02237972A - Aromatic diamine compound and preparation thereof - Google Patents
Aromatic diamine compound and preparation thereofInfo
- Publication number
- JPH02237972A JPH02237972A JP1058027A JP5802789A JPH02237972A JP H02237972 A JPH02237972 A JP H02237972A JP 1058027 A JP1058027 A JP 1058027A JP 5802789 A JP5802789 A JP 5802789A JP H02237972 A JPH02237972 A JP H02237972A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- aromatic diamine
- bis
- diamine compound
- ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Aromatic diamine compound Chemical class 0.000 title claims abstract description 21
- 239000007858 starting material Substances 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 238000006210 cyclodehydration reaction Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003960 organic solvent Substances 0.000 abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 abstract description 4
- 229920006015 heat resistant resin Polymers 0.000 abstract description 4
- IEZVMRGFNUNABR-UHFFFAOYSA-N 2,3,4,5-tetraphenyl-1h-pyrrole Chemical group C1=CC=CC=C1C1=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 IEZVMRGFNUNABR-UHFFFAOYSA-N 0.000 abstract description 3
- OBMPNKMLPBVYRM-UHFFFAOYSA-N 2,3-bis(4-nitrophenyl)-1,4-diphenylbutane-1,4-dione Chemical compound C1=CC([N+](=O)[O-])=CC=C1C(C(=O)C=1C=CC=CC=1)C(C=1C=CC(=CC=1)[N+]([O-])=O)C(=O)C1=CC=CC=C1 OBMPNKMLPBVYRM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 2
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 4
- 239000005695 Ammonium acetate Substances 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 229940043376 ammonium acetate Drugs 0.000 description 4
- 235000019257 ammonium acetate Nutrition 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000001119 stannous chloride Substances 0.000 description 4
- 235000011150 stannous chloride Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- MVFJHAFRIJSPFI-UHFFFAOYSA-N 3-(3,4,5-triphenylthiophen-2-yl)benzene-1,2-diamine Chemical compound NC=1C(=C(C=CC=1)C=1SC(=C(C=1C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)N MVFJHAFRIJSPFI-UHFFFAOYSA-N 0.000 description 2
- ZUMJXLDDCLRIPJ-UHFFFAOYSA-N 4-[4-(4-aminophenyl)-2,5-diphenyl-1h-pyrrol-3-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=C(C=2C=CC=CC=2)NC(C=2C=CC=CC=2)=C1C1=CC=C(N)C=C1 ZUMJXLDDCLRIPJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BUNDFJLZZANTOM-UHFFFAOYSA-N NC=1C(=C(C=CC1)C=1OC(=C(C1C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)N Chemical compound NC=1C(=C(C=CC1)C=1OC(=C(C1C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)N BUNDFJLZZANTOM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- YYJGJCFVHFUOAM-UHFFFAOYSA-N 3,4-bis(4-nitrophenyl)-2,5-diphenyl-1H-pyrrole Chemical compound [O-][N+](=O)c1ccc(cc1)-c1c([nH]c(c1-c1ccc(cc1)[N+]([O-])=O)-c1ccccc1)-c1ccccc1 YYJGJCFVHFUOAM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 244000005894 Albizia lebbeck Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- NSSHZYXLDIXBFE-UHFFFAOYSA-N C1=CC=C(C=C1)C2=C(NC(=C2C3=CC=CC=C3)C4=C(C(=CC=C4)N)N)C5=CC=CC=C5 Chemical compound C1=CC=C(C=C1)C2=C(NC(=C2C3=CC=CC=C3)C4=C(C(=CC=C4)N)N)C5=CC=CC=C5 NSSHZYXLDIXBFE-UHFFFAOYSA-N 0.000 description 1
- ADJNFKVRNPEGHK-UHFFFAOYSA-N C1=CC=C(C=C1)C2=C(NC(=C2C3=CC=CC=C3[N+](=O)[O-])C4=CC=CC=C4[N+](=O)[O-])C5=CC=CC=C5 Chemical compound C1=CC=C(C=C1)C2=C(NC(=C2C3=CC=CC=C3[N+](=O)[O-])C4=CC=CC=C4[N+](=O)[O-])C5=CC=CC=C5 ADJNFKVRNPEGHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GURLNXRFQUUOMW-UHFFFAOYSA-K [Al](Cl)(Cl)Cl.[AlH3] Chemical compound [Al](Cl)(Cl)Cl.[AlH3] GURLNXRFQUUOMW-UHFFFAOYSA-K 0.000 description 1
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- MIIQUCFATSFCBP-UHFFFAOYSA-L azanium;magnesium;trioxido(oxo)-$l^{5}-arsane Chemical compound [NH4+].[Mg+2].[O-][As]([O-])([O-])=O MIIQUCFATSFCBP-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-N iron;hydrochloride Chemical compound Cl.[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- JWSMTBMIGYJJJM-UHFFFAOYSA-N magnesium;azane Chemical compound N.[Mg+2] JWSMTBMIGYJJJM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- JOQGJRQKCIJIDB-UHFFFAOYSA-N tin;hydrochloride Chemical compound Cl.[Sn] JOQGJRQKCIJIDB-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- ZJVTYKZWDWVIFD-UHFFFAOYSA-N zinc;hydrochloride Chemical compound Cl.[Zn] ZJVTYKZWDWVIFD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyrrole Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規な芳香族ジアミン化合物およびその製造方
法、特にテトラフエニルピロール構造を有する新規な芳
香族ジアミン化合物およびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel aromatic diamine compound and a method for producing the same, particularly a novel aromatic diamine compound having a tetraphenylpyrrole structure and a method for producing the same.
（従来の技術）
従来、全芳香族ポリイミドやボリアミドなどは優れた耐
熱性とともに優れた機械特性を存し、広く工業材料とし
て使用されてきたが、これらの多くは有機溶媒に不溶で
あり、その成形性に多くの問題があった。このような樹
脂の中でジアミノテトラフェニルチオフエンおよびジア
ミノテトラフェニルフランを原料として製造されるポリ
イミドやポリアミドは有機溶媒等に可溶であることが報
告されている，〔例えば、Ｙ．Ｉｍａｉ ｅｔ ａｌ．
， Ｊ．Ｐｏｌｙｍ．Ｓｃｉ．， Ｐｏｆｙａ＋， Ｃ
ｈｅｍ． Ｅｄ．． ２２＋ ２１８９ （１９８４）
， ｉｂｉｄ，２３． １７９７ （１９８５）． ［
ＵＰＡＣ ３２ｎｄ ＩｎｔｅｒｎａｔｉｏｎａｌＳｙ
ｍｐｏｓｉｕｍ ｏｎ Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ
， ｐｒｅｐｒ．＋ ５．７．１８（１９８Ｂ）．日化
第５７秋季年会講演豫稿集ＩＩ， ＩＥ５１２（１９８
Ｂ） ）。(Prior art) Fully aromatic polyimides and polyamides have excellent heat resistance and excellent mechanical properties, and have been widely used as industrial materials, but many of them are insoluble in organic solvents and their There were many problems with moldability. Among such resins, polyimides and polyamides produced using diaminotetraphenylthiophene and diaminotetraphenylfuran as raw materials are reported to be soluble in organic solvents [for example, Y. Imai et al.
, J. Polym. Sci. , Pofya+, C
hem. Ed. ．． 22+ 2189 (1984)
, ibid, 23. 1797 (1985). [
UPAC 32nd InternationalSy
Mposium on Macromolecules
, prepr. + 5.7.18 (198B). Proceedings of the 57th Autumn Annual Meeting of Nikka, IE512 (198
B) ).
したがって、前記ジアミノテトラフェニルチオフエンお
よびジアミノテトラフエニルフランの代りにジアミノテ
トラフェニルピロールを用いることにより有機溶媒に可
溶な成形性に優れた耐熱性樹脂が得られると思われるが
、このような芳香族ジアミンは現在知られていない。Therefore, it seems that by using diaminotetraphenylpyrrole in place of diaminotetraphenylthiophene and diaminotetraphenylfuran, a heat-resistant resin that is soluble in organic solvents and has excellent moldability can be obtained. Aromatic diamines are currently unknown.
（発明が解決しようとする課題）
本発明は上記のような工業的有用性の豫見される新規な
芳香族ジアミン、特にテトラフェニルビロール骨格を有
する新規な芳香族ジアミンを提供するものであり、また
その製造方法を提供するものである．
（課題を解決するための手段）
本発明者らはこのような新規な芳香族ジアミン化合物を
得る方法につき鋭意研究を重ねた結果、１．２−ビス（
４−ニトロフェニル）−１．２−ジベンゾイルエタンを
出発物質として、ビス（ニトロフエニル）ジフエニルピ
ロールヲ経由スル合成法によりこの目的に適合する新規
な芳香族ジアミン化合物が得られることを確かめ本発明
を完成するに至った。(Problems to be Solved by the Invention) The present invention provides a novel aromatic diamine that is highly regarded for its industrial utility as described above, particularly a novel aromatic diamine having a tetraphenylpyrrole skeleton. , and also provides a manufacturing method. (Means for Solving the Problems) As a result of extensive research into the method of obtaining such a novel aromatic diamine compound, the present inventors found that 1,2-bis(
It was confirmed that a novel aromatic diamine compound suitable for this purpose could be obtained by a synthesis method via bis(nitrophenyl)diphenylpyrrole using 4-nitrophenyl)-1,2-dibenzoylethane as a starting material, and the present invention I was able to complete it.
本発明の第一の発明は、化学構造式、 で表わされる芳香族ジアミン化合物である。The first invention of the present invention is a chemical structural formula, It is an aromatic diamine compound represented by
本発明の第二の発明は、１，２−ビス（４−ニトロフエ
ニル）−１．２−ジベンゾイルエタンを脱水環化反応に
より、ジニトロピロール化合物よし、これを還元するこ
とを特徴とする化学構造式、で表わされる芳香族ジアミ
ン化合物を製造する方法である。The second invention of the present invention is a chemical structure characterized in that 1,2-bis(4-nitrophenyl)-1,2-dibenzoylethane is reduced to a dinitropyrrole compound by a cyclodehydration reaction. This is a method for producing an aromatic diamine compound represented by the formula.
（作 用） 以下、本発明の構成を作用とともに詳述する。(for production) Hereinafter, the configuration of the present invention will be explained in detail together with its operation.
本発明における出発原料となる１．２−ビス（４−ニト
ロフェニル）−１．２−ジベンゾイルエタン（ＩＩ）
は、パラニト口ペンジルフエニルケトンを塩基で処理し
、ハロゲンで酸化カシプリングすることにより合成され
る。1,2-bis(4-nitrophenyl)-1,2-dibenzoylethane (II), which is the starting material in the present invention, can be obtained by treating paranitrate penzylphenyl ketone with a base and oxidizing it with a halogen. be synthesized.
で表わされるジニトロビロール化合物は、構造式（Ｉｆ
）で表わされるジケトン化合物にアンモニアを作用させ
て説水閉環反応することにより得られる．ここでアンモ
ニアは気体状態で反応溶液に直接に処理してもよいが、
加熱するとともに分解してアンモニアが住成できるアン
モニウム塩を使用するのが好ましい．ここで用いるアン
モニウム塩は酢酸アンモニウム、炭酸アンモニウム、炭
酸水素アンモニウム、リン酸アンモニウム、フフ化アン
モニウム、塩化アンモニウム、臭化アンモニウム、ヨウ
化アンモニウム、硫酸アンモニウム、硝酸アンモニウム
、チオシアン酸アンモニウム、ヒ酸マグネシウムアンモ
ニウム、リン酸マグネシウムアンモニウムなどが挙げら
れるが、特に酢酸アンモニウムが好ましい。実際には、
上記一般式（ｎ）で表わされるジケトン化合物を酢酸ア
ンモニウム存在下に加熱反応させることにより行なわれ
る．この反応の温度は、０〜２５０゜Ｃであるが、経済
的には５０−１８０℃の温度で行なうのが好ましい．こ
の反応に使用しうる溶媒としては、広範囲の有機溶媒が
使用でき、特に、酢酸が好ましい。The dinitrovirol compound represented by has the structural formula (If
) can be obtained by reacting the diketone compound represented by ammonia with aqueous ring closure reaction. Here, ammonia may be directly treated in the reaction solution in a gaseous state, but
It is preferable to use ammonium salts that decompose with heating to form ammonia. The ammonium salts used here are ammonium acetate, ammonium carbonate, ammonium hydrogen carbonate, ammonium phosphate, ammonium fufluoride, ammonium chloride, ammonium bromide, ammonium iodide, ammonium sulfate, ammonium nitrate, ammonium thiocyanate, magnesium ammonium arsenate, and phosphoric acid. Examples include magnesium ammonium, and ammonium acetate is particularly preferred. in fact,
This reaction is carried out by heating a diketone compound represented by the above general formula (n) in the presence of ammonium acetate. The temperature of this reaction is 0 to 250°C, but economically it is preferably carried out at a temperature of 50 to 180°C. As the solvent that can be used in this reaction, a wide range of organic solvents can be used, and acetic acid is particularly preferred.
反応時間は用いた試薬の量、溶媒の種類、反応温度など
に大きく左右されるが、数十分から数日間反応させるの
が好ましい。Although the reaction time largely depends on the amount of reagent used, the type of solvent, the reaction temperature, etc., it is preferable to allow the reaction to occur for several tens of minutes to several days.
構造式（１）で表わされる芳香族ジアミン化合物は、構
造式（ＩＩＩ）で表わされるジニトロ化合物を還元剤を
用いて還元することにより得られる．ここで用いる還元
剤は、水素、鉄一塩酸系、すず一塩酸系、塩化第一すず
一塩酸系、亜鉛一塩酸系、亜鉛一酢酸系、水素化アルミ
ニウムー塩化アルミニウム系、三塩化チタン、水硫化ナ
トリウム、硫化アンモニウムなどを挙げることができる
。特に、接触水素化法あるいは塩化第一すず一塩酸法が
この反応の還元法として好ましい。The aromatic diamine compound represented by the structural formula (1) can be obtained by reducing the dinitro compound represented by the structural formula (III) using a reducing agent. The reducing agents used here include hydrogen, iron monohydrochloride, tin monohydrochloride, stannous chloride monohydrochloride, zinc monohydrochloride, zinc monoacetic acid, aluminum hydride-aluminum chloride, titanium trichloride, and water. Examples include sodium sulfide and ammonium sulfide. In particular, a catalytic hydrogenation method or a stannous chloride monohydrochloric acid method is preferred as a reduction method for this reaction.
（実施例） 以下本発明を実施例によりさらに詳細に説明する。(Example) The present invention will be explained in more detail below using examples.
次Ｉｌ吐上
３．４−ビス（４−ニトロフエニル）−２．５−ジフェ
ニルピロール（ＩＩＩ）の合成１．２−ビス（４−ニト
ロフェニル）−１．２−ジベゾイルエタン（ ■） ４
８．０ ｇ （０．１ ｍｏｌ）と酢酸アンモニウム３
８．５ ｇ （０．５ ｍｏｌ）とに氷酢酸３５０一を
加え、還流下で撹拌しながら３時間反応を行なった。得
られた反応溶液を大量の蒸留水に投入し、赤黄色の析出
物をろ過し乾燥した．氷酢酸より再結晶して赤黄色の板
状晶を得た。収量は４０．２ｇ （収率８７％）であっ
た。3. Synthesis of 4-bis(4-nitrophenyl)-2,5-diphenylpyrrole (III) 1.2-bis(4-nitrophenyl)-1,2-dibezoylethane (■) 4
8.0 g (0.1 mol) and ammonium acetate 3
To 8.5 g (0.5 mol) was added 350 g of glacial acetic acid, and the reaction was carried out for 3 hours while stirring under reflux. The resulting reaction solution was poured into a large amount of distilled water, and the red-yellow precipitate was filtered and dried. Recrystallization from glacial acetic acid gave red-yellow plate crystals. The yield was 40.2 g (yield 87%).
融点 ３３２〜３３３゜Ｃ
赤外吸収スペクトル（ＫＢｒ） １６６０ｃｍ−Ｉ（
Ｃ＝０）の吸収が消失． ３３３０ｃｍ−’ （＞Ｎｌ
ｌ）’ＩＩ−ＮＭＲ （ジメチルスルホキシドーｃＬ
） ８．２〜７．８ （ｍ． ４Ｈ， Ｎ（ｈ基のオル
ト位の芳香族プロトン）， ７．５〜７．１ ｐｐｍ（
ｍ． １５８，外の芳香族プロトン）
元素分析値 炭素 水素 窒素計算値（％
） ７２．８７ ４．１４ ９．１０実測
値（％） ７２．５９ ４．２５ ９．３
８１星■又
３，４−ビス（４−アミノフエニル）−２．５−ジフェ
ニルビロール（１）の合成（塩化第一すず法）
３．４−ビス（４−ニトロフェニル）−２．５一ジフェ
ニルピロール（ ｍ ） ４０．２ ｇ （０．０８７
ｍｏｌ）を氷酢酸３００ ｄに分散し、これに、塩化第
一すず二水和物２１６ ｇ （０．９５７ｍｏｌ）を溶
かした濃塩酸１００ ｄを加え、還流下で４時間撹拌し
た。反応後、反応溶液を大量の蒸留水に投入し析出物を
ろ別した。Melting point 332-333°C Infrared absorption spectrum (KBr) 1660cm-I (
Absorption of C=0) disappears. 3330cm-'(>Nl
l)'II-NMR (dimethyl sulfoxide cL
) 8.2-7.8 (m. 4H, N (aromatic proton ortho position of h group), 7.5-7.1 ppm (
m. 158, outer aromatic proton) Elemental analysis value Carbon Hydrogen Nitrogen calculation value (%
) 72.87 4.14 9.10 Actual value (%) 72.59 4.25 9.3
81 stars ■ Synthesis of 3,4-bis(4-aminophenyl)-2,5-diphenylvirol (1) (stannous chloride method) 3.4-bis(4-nitrophenyl)-2.5- Diphenylpyrrole (m) 40.2 g (0.087
mol) was dispersed in 300 d of glacial acetic acid, 100 d of concentrated hydrochloric acid in which 216 g (0.957 mol) of stannous chloride dihydrate was dissolved was added, and the mixture was stirred under reflux for 4 hours. After the reaction, the reaction solution was poured into a large amount of distilled water, and the precipitate was filtered off.
これを４０％水酸化ナトリウム水溶液、次いで蒸留水で
十分に洗浄して乾燥した。トルエンで２回再結晶し、白
色の針状晶を得た。収量は２９．４ｇ （収率８４％
）であった。This was thoroughly washed with a 40% aqueous sodium hydroxide solution, then with distilled water, and dried. It was recrystallized twice from toluene to obtain white needle-like crystals. Yield: 29.4g (yield: 84%)
)Met.
融点 ２６５〜２６６゜Ｃ
赤外吸収スペクトル（ＫＢｒ） ３３２７ｃｍ−’
（＞ＮＨ），３２２５． ３４１０ｃｍ− ’ （
Ｎｌｌｚ）元素分析値 炭素 水素 窒素
計算値（％） ８３，７６ ５．７７ １０
．４６実測値（％） ８３．５８ ５．９３
１０．２３１益炎主
３．４−ビス（４−アミノフェニル）−２．５−ジフェ
ニルピロール（１）の合成（塩化第一すず法）
３．４−ビス（４−アミノフェニル）−２．５ージフェ
ニルピロール（Ｉ）の合成（水素添加法）３，４−ビス
（４−ニトロフエニル）−２．５−ジフェニルピロール
Ｃｍ ） ２３．１ ｇ （０．０５ ｍｏｌ）および
１０％パラジウムカーボン５，５ｇを取り１，４−ジオ
キサン２００ ｒｕ１を加えた。８０゜Ｃで撹拌しなが
ら水素を供給し、約１２時間後に水素の消費が終了した
ので反応を止めた。反応溶液から、活性炭と１．４−ジ
オキサンを除去し、得られた固体をトルエンで２回再結
晶し、白色の針状晶を得た。収量は１３．２ｇ （収
率６６％）であった。Melting point 265-266°C Infrared absorption spectrum (KBr) 3327cm-'
(>NH), 3225. 3410cm-' (
Nllz) Elemental analysis value Carbon Hydrogen Nitrogen calculation value (%) 83,76 5.77 10
．． 46 Actual value (%) 83.58 5.93
10.231 Synthesis of 3.4-bis(4-aminophenyl)-2.5-diphenylpyrrole (1) (stannous chloride method) 3.4-bis(4-aminophenyl)-2. Synthesis of 5-diphenylpyrrole (I) (hydrogenation method) 3,4-bis(4-nitrophenyl)-2,5-diphenylpyrrole Cm) 23.1 g (0.05 mol) and 10% palladium on carbon 5, 5g was taken and 200ru1 of 1,4-dioxane was added. Hydrogen was supplied while stirring at 80°C, and the reaction was stopped after about 12 hours when the consumption of hydrogen was completed. Activated carbon and 1,4-dioxane were removed from the reaction solution, and the resulting solid was recrystallized twice from toluene to obtain white needle-like crystals. The yield was 13.2 g (66% yield).
融点 ２６４〜２６５゜Ｃ
赤外吸収スペクトル（ＫＢｒ） ３３２６ｃｍ−’
（＞ＮＯ），３２２５．３４１０ｃｍ− ’ （ Ｎ
ｌｌｔ）元素分析値 炭素 水素 窒素計
算値（％） ８３．７６ ５．７７ １０．
４６実測値（％”） ８３，９３ ５．８２
１０．２４１監斑上
３，４−ビス（４−アミノフェニル）−１．２−ジベン
ゾイルエタン（Ｕ）の合成
パラニト口ペンジルフエニルケトン１０５ ｇ（０．４
３５ｍｏｌ）を脱水蒸留したエタノール３００ｄに分散
し、金属ナトリウム１０ ｇ （０．４３５ ｍｏｌ原
子）を少量ずつ室温で添加すると紫色の溶液となる。こ
れに脱水蒸留したエーテル２００戚を加えた。次に、よ
う素５５ ｇ （０．２１８ ｍｏｌ）を溶かしたエー
テル溶液５００ ｄを約２時間かけて０゜Ｃで撹拌しな
がら滴下した。Melting point 264-265°C Infrared absorption spectrum (KBr) 3326cm-'
(>NO), 3225.3410cm-' (N
llt) Elemental analysis value Carbon Hydrogen Nitrogen calculation value (%) 83.76 5.77 10.
46 Actual value (%”) 83,93 5.82
10.241 Synthesis of 3,4-bis(4-aminophenyl)-1,2-dibenzoylethane (U) 105 g (0.4
When 10 g (0.435 mol atoms) of metallic sodium is added little by little at room temperature, a purple solution is obtained. To this was added ether 200, which had been dehydrated and distilled. Next, 500 d of an ether solution containing 55 g (0.218 mol) of iodine was added dropwise over about 2 hours with stirring at 0°C.
その後、室温で２時間撹拌して反応させた。反応後、溶
媒を留去し、残留固体を蒸留水で洗浄し乾燥した。クロ
ロホルムで再結晶して白色の針状結晶を得た。収量は８
２ｇ （収率７８％）であった。Thereafter, the mixture was stirred at room temperature for 2 hours to react. After the reaction, the solvent was distilled off, and the remaining solid was washed with distilled water and dried. Recrystallization from chloroform gave white needle-like crystals. Yield is 8
2g (yield 78%).
融点 ２３２〜２３３ ’Ｃ
赤外吸収スペクトル（ＫＢｒ） １６６０ｃｍ−’（
Ｃ＝Ｏ）’Ｈ ＮＭＲ （ＣＤＣＩ３） ８．１ 〜
７．２（ｍ，１８Ｈ，芳香族プロトン）． ５．６ｐｐ
ｍ （ｓ， ２１１，脂肪族メチンプロトン）
元素分析値 炭素 水素 窒素計算値（％
） ６９，９０ ４．２０ ５．８０実測
値（％”） ６９．６０ ３，９１ ５．
７０皇考五又
３，４−ビス（４−アミノフェニル）−２．５一ジフエ
ニルピロール（ １ ） １．００４ ｇ （２．５ｍ
ｍｏｌ）を２．８ ｄのＮ−メチル−２−ピロリドンに
溶解し、ドライアイスーアセトン浴で凍結した。これに
０．５０８ ｇ （２．５ａ＋ｍｏｌ）のイソフタル酸
クロリドを固体のまま一度に加えた。ドライアイスーア
セトン浴から水浴にかえ、０゜Ｃで３時間撹拌後、粘ち
ょうな重合溶液を３００ ｄのメタノール中に投入する
ことにより３３５０ｃｍ−’にアミド結合のＮ−Ｈの吸
収、１６５０ｃｍ−’にカルボニルの吸収がそれぞれ観
察された。Melting point 232-233'C Infrared absorption spectrum (KBr) 1660cm-' (
C=O)'H NMR (CDCI3) 8.1 ~
7.2 (m, 18H, aromatic proton). 5.6pp
m (s, 211, aliphatic methine proton) Elemental analysis value Carbon Hydrogen Nitrogen calculation value (%
) 69,90 4.20 5.80 Actual value (%”) 69.60 3,91 5.
70 Koko five-pronged 3,4-bis(4-aminophenyl)-2.5-diphenylpyrrole (1) 1.004 g (2.5m
mol) in 2.8 d of N-methyl-2-pyrrolidone and frozen in a dry ice-acetone bath. To this was added 0.508 g (2.5a+mol) of isophthalic acid chloride in solid form all at once. The dry ice-acetone bath was changed to a water bath, and after stirring at 0°C for 3 hours, the viscous polymerization solution was poured into methanol at 300 d to absorb N-H of the amide bond at 3350 cm-', and at 1650 cm-'. Carbonyl absorption was observed in each case.
収率 ９８％
固有粘度 ０．５６ ｄｌ／ｇ ＣｔｌＡ硫酸中３０゜
Ｃ， ０．５ ｇ７ｄｌの濃度で測定）
元素分析値 炭素 水素 窒素計算値（％
） ８１．３４ ４．７４ ７．９０実測
値（％） ８１．０８ ４．９８ ７．６
２ガラス転移点（示差走査熱量測定）３１１゜Ｃ熱重量
測定による１０％重量減少温度は、空気中４７６゜Ｃ、
窒素中５１８゜Ｃであった。Yield: 98% Intrinsic viscosity: 0.56 dl/g Measured in CtlA sulfuric acid at 30°C, concentration of 0.5 g/7 dl) Elemental analysis: Carbon Hydrogen Nitrogen Calculated values (%)
) 81.34 4.74 7.90 Actual value (%) 81.08 4.98 7.6
2 Glass transition point (differential scanning calorimetry) 311°C 10% weight loss temperature by thermogravimetry is 476°C in air;
The temperature was 518°C in nitrogen.
このボリマは、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メ
チル−２−ビロリドン、ジメチルホルムアミド、ｍ−ク
レゾール、ピリジンに可溶で、アセトン、クロロホルム
、メチルアルコールに不溶であった。This volima was soluble in N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylformamide, m-cresol, and pyridine, and insoluble in acetone, chloroform, and methyl alcohol.
（発明の効果）
本発明は一般式（１）で表わされる芳香族ジアミン化合
物およびその有利な製造方法を提供する。(Effects of the Invention) The present invention provides an aromatic diamine compound represented by the general formula (1) and an advantageous method for producing the same.
従来の多くの芳香族ジアミン化合物を原料として製造さ
れた全芳香族ポリアミドなどの耐熱性樹脂が多くの有機
溶媒に対して低い溶解性を有するために成形が困難であ
ったのに対し、本発明のジアミン化合物を原料として製
造された耐熱性樹脂は有機溶媒に可溶で成形が容易であ
り、しかも優れた耐熱性、電気的特性、機械的特性を有
するので工業材料としての価値が大きい。Conventionally, heat-resistant resins such as fully aromatic polyamides manufactured using many aromatic diamine compounds as raw materials have low solubility in many organic solvents, making them difficult to mold. The heat-resistant resin produced using the diamine compound as a raw material is soluble in organic solvents and easy to mold, and has excellent heat resistance, electrical properties, and mechanical properties, so it has great value as an industrial material.
Claims (1)
ベンゾイルエタンを出発物質とし、これを脱水環化反応
により、ジニトロピロール化合物とし、これを還元する
ことを特徴とする化学構造式、 ▲数式、化学式、表等があります▼ で表わされる芳香族ジアミン化合物の製造方法。[Claims] 1. An aromatic diamine compound represented by the chemical structural formula ▲ Numerical formula, chemical formula, table, etc. ▼. A chemical structure characterized by using 2,1,2-bis(4-nitrophenyl)-1,2-dibenzoylethane as a starting material, converting this into a dinitropyrrole compound through a cyclodehydration reaction, and reducing this compound. A method for producing an aromatic diamine compound represented by the formula, ▲Mathematical formula, chemical formula, table, etc.▼.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1058027A JP2718981B2 (en) | 1989-03-13 | 1989-03-13 | Aromatic diamine compound and method for producing the same |
| KR1019890016707A KR0134880B1 (en) | 1989-03-13 | 1989-11-17 | Presses for the preparation diamin derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1058027A JP2718981B2 (en) | 1989-03-13 | 1989-03-13 | Aromatic diamine compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02237972A true JPH02237972A (en) | 1990-09-20 |
| JP2718981B2 JP2718981B2 (en) | 1998-02-25 |
Family
ID=13072466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1058027A Expired - Lifetime JP2718981B2 (en) | 1989-03-13 | 1989-03-13 | Aromatic diamine compound and method for producing the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2718981B2 (en) |
| KR (1) | KR0134880B1 (en) |
-
1989
- 1989-03-13 JP JP1058027A patent/JP2718981B2/en not_active Expired - Lifetime
- 1989-11-17 KR KR1019890016707A patent/KR0134880B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR900014316A (en) | 1990-10-23 |
| JP2718981B2 (en) | 1998-02-25 |
| KR0134880B1 (en) | 1998-04-22 |
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