JP4531699B2 - 高品質3,3’,4,4’−テトラアミノビフェニルの調製方法 - Google Patents
高品質3,3’,4,4’−テトラアミノビフェニルの調製方法 Download PDFInfo
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- ammonolysis
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- dinitrobiphenyl
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- 238000000034 method Methods 0.000 title claims description 28
- 230000008569 process Effects 0.000 title claims description 15
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical group C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title description 7
- 238000005915 ammonolysis reaction Methods 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 11
- GPEWLWUJPTXWAQ-UHFFFAOYSA-N 2-chloro-4-(3-chloro-4-nitrophenyl)-1-nitrobenzene Chemical group C1=C(Cl)C([N+](=O)[O-])=CC=C1C1=CC=C([N+]([O-])=O)C(Cl)=C1 GPEWLWUJPTXWAQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- PPZNNDLMYHPBNY-UHFFFAOYSA-N 5-(3-amino-4-nitrophenyl)-2-nitroaniline Chemical group C1=C([N+]([O-])=O)C(N)=CC(C=2C=C(N)C(=CC=2)[N+]([O-])=O)=C1 PPZNNDLMYHPBNY-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 3
- 239000010949 copper Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004693 Polybenzimidazole Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920002480 polybenzimidazole Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 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 2
- OCEINMLGYDSKFW-UHFFFAOYSA-N 4-(4-amino-3-nitrophenyl)-2-nitroaniline Chemical compound C1=C([N+]([O-])=O)C(N)=CC=C1C1=CC=C(N)C([N+]([O-])=O)=C1 OCEINMLGYDSKFW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CZVHCFKUXGRABC-UHFFFAOYSA-N N,N'-Diacetylbenzidine Chemical compound C1=CC(NC(=O)C)=CC=C1C1=CC=C(NC(C)=O)C=C1 CZVHCFKUXGRABC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YSTSBXDVNKYPTR-UHFFFAOYSA-N 1-[4-(4-acetylphenyl)phenyl]ethanone Chemical group C1=CC(C(=O)C)=CC=C1C1=CC=C(C(C)=O)C=C1 YSTSBXDVNKYPTR-UHFFFAOYSA-N 0.000 description 1
- BDLNCFCZHNKBGI-UHFFFAOYSA-N 1-nitro-4-(4-nitrophenyl)benzene Chemical group C1=CC([N+](=O)[O-])=CC=C1C1=CC=C([N+]([O-])=O)C=C1 BDLNCFCZHNKBGI-UHFFFAOYSA-N 0.000 description 1
- MWWXARALRVYLAE-UHFFFAOYSA-N 2-acetyloxybut-3-enyl acetate Chemical compound CC(=O)OCC(C=C)OC(C)=O MWWXARALRVYLAE-UHFFFAOYSA-N 0.000 description 1
- SBKFTPXVDYDVFI-UHFFFAOYSA-N 3-nitro-6-(4-nitrophenyl)benzene-1,2-diamine Chemical group Nc1c(N)c(ccc1-c1ccc(cc1)[N+]([O-])=O)[N+]([O-])=O SBKFTPXVDYDVFI-UHFFFAOYSA-N 0.000 description 1
- UNKCJDGKXMGEEF-UHFFFAOYSA-N 4-(3,4-dinitrophenyl)-1,2-dinitrobenzene Chemical group C1=C([N+]([O-])=O)C([N+](=O)[O-])=CC=C1C1=CC=C([N+]([O-])=O)C([N+]([O-])=O)=C1 UNKCJDGKXMGEEF-UHFFFAOYSA-N 0.000 description 1
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 alkali metal sulfite Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940075933 dithionate Drugs 0.000 description 1
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NIQQIJXGUZVEBB-UHFFFAOYSA-N methanol;propan-2-one Chemical compound OC.CC(C)=O NIQQIJXGUZVEBB-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VGFDUXNDMUMYHD-UHFFFAOYSA-N n-[4-(4-acetamido-3-nitrophenyl)-2-nitrophenyl]acetamide Chemical compound C1=C([N+]([O-])=O)C(NC(=O)C)=CC=C1C1=CC=C(NC(C)=O)C([N+]([O-])=O)=C1 VGFDUXNDMUMYHD-UHFFFAOYSA-N 0.000 description 1
- NJHLEUDJQFLOPE-UHFFFAOYSA-N n-acetyl-n-[4-(4-amino-3-nitrophenyl)-2-nitrophenyl]acetamide Chemical compound C1=C([N+]([O-])=O)C(N(C(C)=O)C(=O)C)=CC=C1C1=CC=C(N)C([N+]([O-])=O)=C1 NJHLEUDJQFLOPE-UHFFFAOYSA-N 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000006146 oximation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 description 1
- 229940075931 sodium dithionate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
1.それらが、原材料のひとつとしてベンジジンを利用しており、これは、公知の発癌剤である。
2.銅塩類によって触媒されたDCBの直接アンモノリシスには、高温(200°−300℃)と圧力900−1000psigを必要とし、それは、安全という観点からこのプロセスを危険なものとしている。前記特許操作によりDCBの直接アンモノリシスについての我々独自の経験はTABを得るには非常に失望させるものであり、タール状物質が常にそれに付随してくるからである。
3.直接アンモノリシスにおいて、銅は、おそらくインサイチュでTABと安定な錯体を形成し、その結果、前記錯体からのTAB放出がゆっくりとなる。
4.直接アンモノリシスにおいて、銅は、おそらく対応するトリアミノビフェニルとおよび少量の銅と安定な錯体を形成し、その結果、これらの不純物をTABから分離するのがゆっくりとなる。
5.ジオキシム化方法において、多くの段階が高価なビフェニルから出発して必要となり、低収率である。
Ti−スーパーオキサイド触媒(1)の製造
添加漏斗、窒素入口および還流濃縮器を付属した2口丸底フラスコに入れた無水MeOH(50mL)中Ti(OiPr)4(5.0g、0.0175モル)の溶液に対して、50%H2O2(5.98g、0.175モル)をゆっくり40分かけて室温で攪拌しながら添加した。すぐに形成された黄色の沈殿物を焼結漏斗によりろ過し、無水メタノールで洗浄し室温(25℃)減圧下(3mmHg)で1時間乾燥した、収率:3.94g(98%)。EPRスペクトルは、9.76GHz、298Kで稼動するBruker EMXスペクトロメータに記録し、g値は、標準マーカー:α、α’−ジフェニル―β―ピクリルヒドラジル(DPPH,g=2.0036)を参考に、決定した。熱重力および差分熱分析(TG/DTA)は、30−400℃の範囲で温度プログラム10℃/分でTG/DTA22、TG/DTA32システム(Seiko Instruments Inc.)で行った。
3,3’−ジクロロ−4,4’−ジニトロビフェニル(DCDNB)の酸化操作による製造
窒素ガスバブラー、添加漏斗、水濃縮器および攪拌磁気棒を付属した2口丸底フラスコに、3,3’−ジクロロベンジジエン(5g、0.019モル)、Ti−スーパーオキサイド触媒(1)(2.5g、50wt%)および無水メタノール(30mL)を入れた。50%H2O2水(10.74g、0.158モル)をゆっくり攪拌しながら20分間、添加した。反応は発熱性で、黄色から赤茶色の変化が、H2O2添加時に観察された。この反応経過を、TLC〔酢酸エチル中〕によりモニタリングし、完了後、触媒1をろ過除去し、メタノールは、減圧下で蒸発させた。粗生成物の重量は、4.2g(66.28%)で、その純度をガスクロマトグラフィで分析した。
アンモノリシス操作による3,3’−ジアミノ−4,4’−ジニトロビフェニル(DADNB)の製造
メタノール(100mL)中3,3’−ジクロロ−4,4’−ジニトロビフェニル(5g、0.0197モル)および過剰のアンモニア溶液(100mL)の混合物を、オートクレーブに入れ、全混合物を100℃で3時間加熱した。反応完了後、メタノールを蒸留により除去し、アミノ生成物が沈殿した。次にそれをろ過し、H2Oで洗浄し、乾燥させた。収率3.82g(86.99%)融点226℃。
ニトロ基還元による3,3’−4,4’−テトラアミノビフェニル(TAB)の製造
3,3’−ジニトロベンジジン(2g、0.007モル)および塩化第一スズ(6.4g、0.034モル)の混合物を、エタノール(125mL)中0℃で攪拌し、濃HCl(30%)を30分かけて滴下した。この反応混合物を、10−12時間還流した。テトラミンの塩を沈殿させ、冷10%NaOH溶液により塩基性とし、固体をろ過し、水で洗浄し、真空中で乾燥させ、TABを収率80%(1.159g)で得た。
1.反応の全3段階において、生成物の単離が、簡便なろ過により行うことができる。
2.DCBのアンモノリシスは、いかなる金属触媒を使用することもなく、中等度の反応温度(100℃)でしかも内因性圧力(250psig)で行うことができる。
3.生成物TABは、銅やその塩類の夾雑もなく産生でき、従って、TAB純度が高まる。
4.副生物(銅塩類とTABのジアミン錯体類)はこの反応混合物中で全く産生されない。
5.酸化、アンモノリシスおよび還元の全3段階で定量的変換が得られる。
Claims (10)
- 式1の純粋で、高品質の3,3’,4,4’−テトラアミノビフェニル(TAB)
a.式2の3,3’ジクロロベンジジンをチタンスーパーオキサイド触媒と溶媒の存在下、酸化剤により酸化し、式3の3,3’ジクロロ4,4’ジニトロビフェニルを得るステップと;
d.生成した混合物をアルカリにより塩基性とし、式1の3,3’,4,4’テトラアミノビフェニルを得るステップと、
を含む方法。 - 前記使用したチタンスーパーオキサイドは、不均質触媒である請求項1記載の方法。
- 前記酸化剤は、30〜50%v/vの濃度を有するH2O2である請求項1記載の方法。
- 前記溶媒は、アセトニトリル、アセトン、メタノール、酢酸および水を含む有機溶媒である請求項1記載の方法。
- アンモノリシスを、50−200℃の範囲の温度で実施する請求項1記載の方法。
- アンモノリシスを、100℃で実施する請求項1記載の方法。
- アンモノリシスを、100−500psig(ゲージ圧として0.69〜3.45MPa)の範囲の圧力で実施する請求項1記載の方法。
- アンモノリシスを、100psig(ゲージ圧として0.69MPa)において実施する請求項1記載の方法。
- 還元剤が、SnCl2/濃HCl混合物を含む群から選択される請求項1記載の方法。
- 還元が、50−60℃の範囲の温度で実施される請求項1記載の方法。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/IN2003/000403 WO2005063679A1 (en) | 2003-12-29 | 2003-12-29 | Process for the preparation of high quality 3,3',4,4'-tetraminobiphenyl |
Publications (2)
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JP2007527848A JP2007527848A (ja) | 2007-10-04 |
JP4531699B2 true JP4531699B2 (ja) | 2010-08-25 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP2005512715A Expired - Fee Related JP4531699B2 (ja) | 2003-12-29 | 2003-12-29 | 高品質3,3’,4,4’−テトラアミノビフェニルの調製方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US6835854B1 (ja) |
EP (1) | EP1727781B1 (ja) |
JP (1) | JP4531699B2 (ja) |
AU (1) | AU2003290403A1 (ja) |
DE (1) | DE60327567D1 (ja) |
WO (1) | WO2005063679A1 (ja) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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UA94709C2 (ru) * | 2007-12-05 | 2011-06-10 | Шова Денко К.К. | Способ получения 3,3`,4,4` тетрааминобифенила |
CN105111092B (zh) * | 2015-10-15 | 2017-06-30 | 响水恒利达科技化工有限公司 | 一种3,3′,4,4′‑四氨基联苯的连续制备方法 |
CN115108918B (zh) * | 2021-03-23 | 2023-06-02 | 湖北汇达科技发展有限公司 | 一种3,3`,4,4`-四氨基联苯的制备方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2047933C3 (de) * | 1969-10-14 | 1974-01-17 | Kuraray Co., Ltd., Kurashiki, Okayama (Japan) | Verfahren zur Herstellung von aromatischen Polybenzimidazolen |
US3943175A (en) * | 1969-10-21 | 1976-03-09 | Celanese Corporation | Synthesis of pure 3,3'-diaminobenzidine |
US3865876A (en) * | 1969-10-21 | 1975-02-11 | Celanese Corp | Synthesis of 3,3{40 -diaminobenzidine from 3,3{40 -dichlorobenzidine |
JPS5441847B2 (ja) * | 1972-05-26 | 1979-12-11 | ||
JPS5548504B2 (ja) * | 1972-05-29 | 1980-12-06 | ||
DE3111470C2 (de) * | 1981-03-24 | 1983-03-17 | Hoechst Ag, 6000 Frankfurt | Verfahren zur Reinigung von rohem 3,4,3',4'-Tetraaminodiphenyl |
JPS60158146A (ja) * | 1984-01-27 | 1985-08-19 | Wakayama Seika Kogyo Kk | 3,3’,4,4’−ビフエニルテトラミンの精製方法 |
US5041666A (en) * | 1987-08-06 | 1991-08-20 | Hoechst Celanese Corporation | Method for the production of 3,3'4,4'-tetraaminobiphenyl |
US5235105A (en) * | 1991-07-12 | 1993-08-10 | Hoechst Aktiengesellschaft | Process for the production of pure 3,3',4,4'-tetraamino-biphenyl |
-
2003
- 2003-12-29 AU AU2003290403A patent/AU2003290403A1/en not_active Abandoned
- 2003-12-29 EP EP03782766A patent/EP1727781B1/en not_active Expired - Lifetime
- 2003-12-29 JP JP2005512715A patent/JP4531699B2/ja not_active Expired - Fee Related
- 2003-12-29 WO PCT/IN2003/000403 patent/WO2005063679A1/en not_active Application Discontinuation
- 2003-12-29 DE DE60327567T patent/DE60327567D1/de not_active Expired - Lifetime
-
2004
- 2004-03-19 US US10/804,886 patent/US6835854B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
AU2003290403A1 (en) | 2005-07-21 |
DE60327567D1 (de) | 2009-06-18 |
JP2007527848A (ja) | 2007-10-04 |
US6835854B1 (en) | 2004-12-28 |
WO2005063679A1 (en) | 2005-07-14 |
EP1727781B1 (en) | 2009-05-06 |
EP1727781A1 (en) | 2006-12-06 |
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