WO1997037965A1 - Preparation of substituted aromatic amines - Google Patents
Preparation of substituted aromatic amines Download PDFInfo
- Publication number
- WO1997037965A1 WO1997037965A1 PCT/US1997/003966 US9703966W WO9737965A1 WO 1997037965 A1 WO1997037965 A1 WO 1997037965A1 US 9703966 W US9703966 W US 9703966W WO 9737965 A1 WO9737965 A1 WO 9737965A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- complex
- ferrate
- hydrogen
- aniline
- phenyl
- Prior art date
Links
- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001301 oxygen Substances 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001868 water Inorganic materials 0.000 claims abstract description 24
- 239000003446 ligand Substances 0.000 claims abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims abstract description 16
- UPHDFMNLYLLXDF-UHFFFAOYSA-N iron(2+);pentacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UPHDFMNLYLLXDF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 13
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 claims abstract description 12
- 150000001412 amines Chemical group 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 6
- 125000005270 trialkylamine group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- 239000011734 sodium Substances 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 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 claims description 16
- 239000007800 oxidant agent Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 9
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- HJMZMZRCABDKKV-UHFFFAOYSA-N carbonocyanidic acid Chemical class OC(=O)C#N HJMZMZRCABDKKV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- 229940072049 amyl acetate Drugs 0.000 claims description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001448 anilines Chemical class 0.000 claims 1
- 239000012736 aqueous medium Substances 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 abstract description 5
- 150000003973 alkyl amines Chemical class 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 125000005265 dialkylamine group Chemical group 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 19
- 238000007254 oxidation reaction Methods 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 9
- -1 alkali metal ferricyanide Chemical class 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000002638 heterogeneous catalyst Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 3
- 229940011051 isopropyl acetate Drugs 0.000 description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 3
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000006025 oxidative dimerization reaction Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- FKHKSWSHWLYDOI-UHFFFAOYSA-N 2-phenylbenzene-1,4-diamine Chemical compound NC1=CC=C(N)C(C=2C=CC=CC=2)=C1 FKHKSWSHWLYDOI-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229940039407 aniline Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000007630 basic procedure Methods 0.000 description 1
- 150000003940 butylamines Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical class [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000005932 reductive alkylation reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004007 reversed phase HPLC Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- JOKPITBUODAHEN-UHFFFAOYSA-N sulfanylideneplatinum Chemical compound [Pt]=S JOKPITBUODAHEN-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000010626 work up procedure Methods 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
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
- C01C3/12—Simple or complex iron cyanides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/04—Sodium compounds
Definitions
- the present invention relates to methods for the production phenyl-p-phenylenediamine (PPDA) and higher amines of structural formula (I) below from the starting material of structural formula(ll) below. More particularly it relates to a method for preparing PPDA wherein aniline is oxidized in the presence of trisodium pentacyano ferrate(ll)complexes containing various water soluble ligands, such as ammonia, mono alkyl amine, dialkyi amines, and trialkyl amines, and utilizing oxygen or hydrogen peroxide as the oxidizing agents. The complex is then reduced by hydrogenation using suitable heterogeneous metal catalysts.
- PPDA phenyl-p-phenylenediamine
- I structural formula
- n 2 to 5
- R, and R 2 are as set forth below
- R, and R 2 may be the same or different, must be ortho or meta to the amino group, and may be hydrogen, C r C 4 alkyl, C C 4 alkoxy, halogen, cyano, carboxylate salts and amides of carboxylic acids or mixtures thereof.
- the invention relates to the production of PPDA with the ability to recycle the transition-metal complex, high selectivity and yield.
- the conversion of aniline to N-phenyl-p-phenylenediamine is in the range of 40-85% .
- the yield of PPDA ranges from 91 to 97%.
- the method of this invention is also cost effective and produces no environmentally undesirable byproducts.
- the present invention is directed to an improved method for preparation of substituted aromatic amines of formula (I) comprising the steps of: a) oxidizing an aromatic amine of formula (II) in the presence of a metal pentacyano ferrate (II) complex to form an arylenediaminopentacyanoferrate complex, said metal being selected from the group consisting of potassium and sodium; and b) catalytically reducing said arylenediamino-pentacyanoferrate complex with hydrogen using a heterogeneous metal catalyst, producing the corresponding substituted aromatic amine of formula (I) .
- n 2 to 5
- R, and R 2 are as set forth below
- R T and R 2 may be the same or different, must be ortho or meta to the amino group, and may be hydrogen, C r C 4 alkyl, C r C 4 alkoxy, halogen, cyano, carboxylate salts and amides of carboxylic acids or mixtures thereof.
- the most preferred embodiment is directed to a process which oxidizes aniline in the presence of trisodium pentacyano ferrate (II) complexes containing various water soluble ligands, such as ammonia, mono alkyl amine, dialkyi amines, trialkyl amines and the like.
- Oxidizing agents may be oxygen or hydrogen peroxide.
- the N-phenyl-p- phenylenediamino pentacyano ferrate complex is then reduced with hydrogen using a heterogeneous metal catalyst, which may be supported or not supported. Suitable supports could include those known to the art such as, for example, carbon or alumina.
- the mixture of aniline and N- phenyl-p-phenylenediamine is then extracted with a suitable solvent after filtration of the heterogenous catalyst.
- Preferred solvents are environmentally friendly, water-immiscible, and easily recyclable.
- the aqueous layer containing the pentacyano ferrate (II) complex is then recycled.
- a preferred method of the present invention for producing N- phenyl-p-phenylenediamine involves the steps of a) the oxidation of aniline in the presence of trisodium pentacyano ferrate (II) complexes with the optional use of a heterogeneous metal catalyst; followed by b) reduction of the N-phenyl-p-phenyienediamino-pentacyano ferrate complex with hydrogen using a heterogeneous metal catalyst. In most cases, both steps (a) and (b) will use the same heterogeneous catalyst.
- any suitable oxidant including either oxygen or hydrogen peroxide may be used as the oxidizing agent. Oxygen is the preferred oxidizing agent. Still more preferred is the use of oxygen under pressure and at elevated temperatures which will increase the rate of oxidation and facilitate the completion of step a.
- the metal pentacyano ferrate (II) complexes useful in this invention must be of a water soluble type having water soluble ligands as a part of the complex.
- Preferred metals are the alkali metals such as sodium or potassium.
- the most preferred, trisodium pentacyano ferrate (II) complex containing various water soluble ligands, is illustrative of the class of complexes useful. These ligands may be ammonia, monoalkyl amines, dialkyi amines, or trialkyl amines.
- a preferred structure for this preferred complex is Na 3 [Fe(CN) 5 NH 3 -xH 2 0], or its dimer.
- the N-phenyl-p- phenylenediamino-pentacyano ferrate complex is reduced with hydrogen using a heterogeneous metal catalyst.
- This catalyst is selected from the heterogeneous metals of Group VIII such as palladium, platinum, ruthenium, rhodium, or nickel.
- the catalyst may or may not be supported. If supported, the supports may be carbon, alumina, and the like, many of which are known to those familiar with the art.
- the mixture of aniline and PPDA that is the product of the reaction is extracted with a suitable solvent. Then the heterogeneous catalyst is filtered off. Suitable solvents include those that are water-immiscible and easily recyclable. The aqueous layer containing the pentacyano ferrate (II) complex is then recycled.
- the compounds of this invention can be synthesized advantageously by the following general method.
- the preferred method for the preparation of PPDA is contained in the examples that follow.
- the first step of a preferred process of this invention involves dissolving sodium pentacyanoammino ferrate (II) in water.
- the synthesis of sodium pentacyanoammino ferrate (II) is known. It was prepared according to the method of G. Brauer "Handbook of Preparative Inorganic Chemistry", 2nd ed. Vol II, academic Press, New York, N.Y. 1 965 p 1 51 1 .
- Trisodium pentacyano ammino ferrate (ID) An alternate method for preparation of trisodium pentacyano ammino ferrate(ll) is the concurrent addition of aqueous solution of ferrous chloride tetrahydrate, stabilized with hypophosphorous acid, and sodium cyanide in the ratio of 1 to 5 equivalents to an aqueous solution of ammonium hydroxide.
- the aqueous solution of ammonium hydroxide may contain anywhere from one equivalent based on the ferrous chloride to a large excess. The preferred range is two to ten equivalents and the most preferred is three to six equivalents of ammonium hydroxide.
- the concurrent additions are done over one to three hours and the solution is then filtered if necessary to remove small amounts of iron hydroxides and the complex is precipitated by adding isopropanol or any convenient water soluble organic solvent.
- the complex may be dried or redissolved in water without drying and used directly. The excess ammonia and isopropanol are recovered.
- aniline a water miscible organic solvent may be added to help solubilize the aniline.
- this reaction may be run without organic solvent.
- solvents are ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol.
- Oxygen or hydrogen peroxide are two possible oxidizing agents that can be used.
- a heterogeneous metal catalyst may be added prior to the oxidation.
- the oxidized complex containing the N-phenyl-p-phenylenediamino ligand is subjected to hydrogenation in the presence of a heterogeneous metal catalyst.
- a heterogeneous metal catalyst This may be carried out without added solvent, or in the presence of a suitable water immiscible solvent.
- Possible solvents in this category include butyl acetate, hexanol, 2-ethyl- 1 -butanol, hexyl acetate, ethyl butyl acetate, amyl acetate, methyl isobutyl ketone or aniline and the like.
- the heterogeneous catalyst is removed by filtration and the organic layer separated.
- the solvent, aniline, and N-phenyl-p- phenylenediamine are recovered by distillation.
- the sodium pentacyanoammino ferrate(ll) is then recycled.
- the reaction is best carried out at a pH equivalent to the pH of the solution containing the dissolved complex in water.
- the pH is adjusted, when necessary, after each recycle of the complex by adding ammonia to the solution in order to maintain a pH equivalent to the initial pH of the solution at the start of the process.
- This adjustment of pH is achieved by the addition of an appropriate base, for example, ammonium hydroxide or ammonia, the ligand used in the complex.
- a more preferred range of pH is from 10 to 1 2.
- a pH equivalent to the pH of the dissolved complex, which is dependant on concentration of the solution is preferred.
- Oxygen and hydrogen pressures may be in the range of from about I atmosphere to 100 atmospheres. A preferred range of these pressures would be from about 2 to about 75 atmospheres. A preferred range of these pressures would be from about 50 to about 75 atmospheres, or about 5.0 x 1 0 6 to about 7.5 x 1 0 6 Nm 2 . Similar pressures are used for the reduction reaction with hydrogen..
- Temperatures may range up to the point where the complex looses stability which currently is believed to be from about 5°C to about 65°C in a closed system.
- the reaction can be carried out at lower temperatures, the rate of reaction of the oxidation step is significatnly lower.
- the preferred operation temperature for the oxidation reaction is between 30°C and 55°C, and most preferred range is between 45°C and 55°C.
- the temperature used will require a balance of factors to maximize the reaction rate and yeild of the process. Higher temperatures than specified here will slowly degrade the complex. Low temperatures reduce the solubility of the complex and decrease the rate of reaction.
- a number of ligands can be used instead of ammonia in the sodium pentacyano ferrate (II) complex.
- Ligands may be mono alkyl amines such as methyl, ethyl, propyl, or butyl amines, dialkyi amines such as dimethyl or diethyl amine and trialkyl amines such as trimethyl amine or triethyl amine.
- Other amines that can be used are N,N-dimethylaminoethanol,
- N,N,N',N'-tetramethylethylenediamine and substituted or unsubstituted pyridine.
- a variety of other ligands can be used, limited only by their solubility, and their ability to be displaced by aniline and by their stability.
- sodium pentacyano ferrates (II) containing ligands other than ammonia were prepared by substitution of the ammonia complex with an excess of the appropriate ligand.
- heterogeneous metal catalysts that may be used are palladium-on-carbon, platinum on-carbon, ruthenium-on-carbon, rhodium- on-carbon, and Raney nickel.
- Supports other than carbon such as alumina, Kieselguhr, silica, and the like can be used as well.
- Preferred among the catalysts that may be used are the noble metals. Still more preferred are supported noble metal catalysts. An even more preferred catalyst is platinum or palladium supported on carbon.
- the recyclability of the pentacyanoammino ferrate complex is demonstrated in various examples of this invention.
- the recycling procedure may be carried out at temperatures ranging from 25 Q C to 60°C, and most preferably between 45°C and 55°C.
- the recyclability is useful with ligands other than ammonia in the pentacyano ferrate (II) complex, such as pentacyanotrimethylamino ferrate (II) or pentacyanoisopropylamino ferrate (II) complexes.
- Experimental details of the recyclability, including conversion and yield data, are presented in the examples.
- Reductive alkylation of PPDA to produce antidegradants can be conducted by any one of various known methods known to those skilled in the art. See, for example, U.S. Patent No. 3,336,386, which is herein incorporated by reference.
- PPDA and a suitable ketone or aldehyde are reacted in the presence of hydrogen and a catalyst such as platinum sulfide with or without a support.
- Suitable ketones include methylisobutyl ketone, acetone, methylisoamyl ketone, and 2-octanone.
- Example 1 The Oxidation of Aniline using Hydrogen Peroxide as the Oxidizing Agent(step a); and Hydrogen (with 5% Palladium/Carbon) as the Reducing Agent (step b) in the Preparation of PPDA
- step a The reaction of step a was run using 3.0 g of aniline, 6.0 g sodium pentacyanoammino ferrate (II), 300 ml of distilled water and I.O g of 5% palladium on charcoal(Pd/C) (50% wet) in a three-neck flask equipped with mechanical stirrer and addition funnel. Eight ml of 30% hydrogen peroxide (oxidizing agent) was added in 0.5 hours.
- the heterogeneous catalyst was removed by filtration and the reaction mixture was transferred to a l-l Magne-drive autoclave. 1 .0 g of fresh Pd/C catalyst (50% water) was then added . The vessel was sealed, purged first with nitrogen and then with hydrogen and pressurized with hydrogen to about 1000 psig [69 atm or 6.9 x 1 0 6 Nm 2 ] . The vessel was agitated at room temperature for 2.0 hours. Isopropyl acetate was added to the reaction mixture after venting and purging with nitrogen. The catalyst was removed by filtration and the organic solution was analyzed by gas chromatography using a Varian 3400 instrument equipped with a DB-I capillary column. The product N-phenyl-p- phenylenediamine (PPDA)was found in 74.3% conversion, and aniline was measured at 1 8.4% . The yield based on conversion of aniline was 91 %.
- PPDA N-phenyl-p- phenylenediamine
- EXAMPLES 2 - 6 The Oxidation of Aniline using Oxygen as the Oxidizing Agent(step a) ; and Hydrogen with Several Metal Catalysts as the Reducing Agent (step b) in the Preparation of PPDA
- Example 2-6 Using the basic procedure depicted in Example 1 , several reactions were run in a l-liter Magne-Drive autoclave using 38.0 g. sodium pentacyanoammino ferrate (II), 1 8.6 g aniline, 2.0 g. metal catalyst 50.0 g. ethylene glycol and 1 50 g distilled water.
- the metal catalysts used in Examples 2-6 are supported Pd, Ru, Pt, Rh and Ni, respectively.
- the heterogeneous catalysts are present at 5% by weight on carbon and they are used at 4.0 g and 50% water.
- the nickel is used as 50% Ni/Kieselguhr 2.0 grams dry.
- the vessel was sealed, purged first with oxygen and pressurized to 400 psig [28 atm or 2.8 x 10 6 Nm "2 ].
- the vessel was agitated at room temperature for 2.5 hrs. After this agitation, the vessel was purged with nitrogen and then I00 ml of butyl acetate was pumped into the autoclave.
- the vessel was purged with hydrogen and then pressurized with hydrogen to 400 psig [28 atm or 2.8 x 10 6 Nm 2 ].
- the vessel was then agitated at room temperature for O hr.
- the ester solution was isolated and analyzed by HPLC.
- the nickel catalyst on Kieselguhr Example 6)was found to be inactive. Results of these Examples are presented in Table 1 .
- Example 7 Oxidation of Aniline using Oxygen and no Metal Catalyst (step a) ; and Reduction with Hydrazine (step b) in the preparation of PPDA.
- step (a) of the reaction was run in a l-l ⁇ ter Magne-Drive autoclave using 24 g of sodium pentacyanoammino ferrate (II), 1 2.8 g of aniline, 100 ml of ethylene glycol and 300 ml of distilled water.
- the vessel was sealed, purged with nitrogen, then oxygen and pressurized with oxygen to 400 psig [28 atm or 2.8 x 1 0 6 Nm 2 ].
- the vessel was agitated at 1 5-20°C with cooling to control the temperature for six hours.
- step (b) Following oxidation, a one ml sample was removed from the autoclave. Isopropyl acetate was then added to the sample, and the synthesis of PPDA was continued with the reduction, step (b), with hydrazine. The remaining mixture in the autoclave was purged with nitrogen, then hydrogen and pressurized with hydrogen to 400 psig [28 atm or 2.8 x 10 6 Nm 2 ] . The reaction was agitated at 1 5-25°C for one hour. The reaction was vented, purged with nitrogen and isopropyl acetate added.
- EXAMPLES 8 - 10 The Performance of the Oxidation (step a) and Reduction (step b) Reactions to Yield PPDA Under a Range of Pressures
- the reactions of these Examples were run in a similar fashion to those previously described.
- a I liter Magne-Drive autoclave using 76.0 g of three different batches of sodium pentacyanoammino ferrate (II), 37.2 g aniline, 4.0 g 5% Pd/C catalyst, 100 g ethylene glycol and 300 g distilled water were combined.
- the vessel was sealed, purged first with oxygen, then pressurized with oxygen to the desired pressure.
- the vessel was agitated at room temperature for 2.5 hours.
- EXAMPLES 1 1 and 12 Demonstration of the ability to recycle the sodium pentacyanoammino ferrate (II) complex
- the reaction was run in a l-liter Magne-Drive autoclave using 76.0 g sodium pentacyanoammino ferrate (II), 37.2 g aniline, 8.0 g. 5% Pd/C catalyst, 1 00 g ethylene glycol and 300 g distilled water.
- the vessel was sealed, purged first with oxygen and pressurized to 400 psig [28 atm or 2.8 x 1 0 6 Nm "2 ] with oxygen.
- the vessel was then agitated at room temperature for 2.5 hours.
- the vessel was purged first with nitrogen followed by the addition of 200 ml of butyl acetate pumped into the autoclave. Then the autoclave was pressurized with hydrogen to 400 psig [28 atm or 2.8 x 10 6 Nm "2 ] . The autoclave was agitated at room temperature for I.O hour. The clave was opened, the solution filtered to remove the metal catalyst, and the layers were separated.
- the ester layer was analyzed by gas chromatography, and the aqueous layer was returned to the autoclave. At this point, 37.2 g of aniline, and 8.0 g 5% Pd/C catalyst were added.
- the vessel was then sealed, purged first with oxygen and pressurized with oxygen to 400 psig [28 atm or 2.8 x 10 6 Nm 2 ].
- the mixture was agitated at room temperature for 2.5 hours, then purged with nitrogen. This was followed by the pumping of 200 ml butyl acetate into the autoclave.
- the vessel was then purged with hydrogen and pressurized with hydrogen to 400 psig [28 atm or 2.8 x 10 6 Nm 2 ].
- the mixture was agitated at room temperature for I.O hour.
- EXAMPLES 13 -15 The Use of Ligands other than Ammonia for Pentacyano Ferrate (II) Complex and Recycle
- the reaction was run in a l-liter Magne-Drive autoclave using 42.8g sodium pentacyanotrimethylamino ferrate (II), or the same amount of sodium pentacyanoisopropylamino ferrate (II), 1 8.6 g aniline, 4.0 g. 5% Pd/C catalyst, and 200.0 g distilled water.
- the vessel was sealed, purged first with oxygen and pressurized to 250 psig [18 atm or 1 .8 x 1 0 6 Nm "2 ] with oxygen.
- the vessel was then agitated at room temperature for 0.5 hours. Following the oxidation, The vessel was purged first with nitrogen followed by the addition of 200 ml of butyl acetate pumped into the autoclave. Then the autoclave was pressurized with hydrogen to 400 psig [28 atm or 2.8 x 10 6 Nm 2 ] . The autoclave was agitated at room temperature for I.O hour.
- the autoclave was opened and its contents removed. The mixture was then filtered and the aqueous and organic layers separated. The ester solution, contained in the organic layer, was analyzed by gas chromatography using a Perkin-Elmer Model 8310 Gas Chromatograph with a one meter SP21 00 column, and the aqueous layer was returned to the autoclave.
- the reaction was run in a 1 -liter Magna-Drive autoclave using 57 grams of sodium pentacyanotrimethylamino ferrate (II) , 27.9 g aniline, and 250 ml of distilled water.
- the vessel was sealed, purged first with oxygen and pressurized to 250 psig [1 8 atm or 1 .8 x 10 6 Nm 2 ] with oxygen.
- the vessel was then agitated at room temperature for three hours.
- the vessel was purged first with nitrogen, then opened and the catalysts added. Then butyl acetate (200 ml) was added. The vessel was sealed, then with pressurized with hydrogen to the desired pressure of 400 psig [28 atm or 2.8 x 10 6 Nm 2 ].
- the catalysts used for the reduction, step b were as shown in Table 5. The vessel was agitated at room temperature for I.O hr.
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Priority Applications (14)
Application Number | Priority Date | Filing Date | Title |
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CA002250850A CA2250850C (en) | 1996-04-04 | 1997-03-13 | Preparation of substituted aromatic amines |
JP53620497A JP3200441B2 (en) | 1996-04-04 | 1997-03-13 | Production of substituted aromatic amines |
PL97329158A PL188156B1 (en) | 1996-04-04 | 1997-03-13 | Method of obtaining substituted aromatic amines |
SK1374-98A SK283812B6 (en) | 1996-04-04 | 1997-03-13 | Preparation of substituted aromatic amines |
SK186-2003A SK283813B6 (en) | 1996-04-04 | 1997-03-13 | Preparation of trisodium pentacyano ferrate(II) complex |
IL12629497A IL126294A0 (en) | 1996-04-04 | 1997-03-13 | A method for preparing substituted aromatic amines |
PL97361695A PL188191B1 (en) | 1996-04-04 | 1997-03-13 | Method for manufacturing (ii) trisodium ferrate panta cyanoamine |
KR10-2004-7016795A KR100497955B1 (en) | 1996-04-04 | 1997-03-13 | Novel Method for Preparation of Trisodium Pentacyano Amino Ferrate(Ⅱ) |
EA199800890A EA001708B1 (en) | 1996-04-04 | 1997-03-13 | Preparation of substituted aromatic amines |
EP97909033A EP1021393A1 (en) | 1996-04-04 | 1997-03-13 | Preparation of substituted aromatic amines |
AU20785/97A AU712906B2 (en) | 1996-04-04 | 1997-03-13 | Preparation of substituted aromatic amines |
BR9708481A BR9708481A (en) | 1996-04-04 | 1997-03-13 | Preparation of substituted aromatic amines |
NO19984614A NO311758B1 (en) | 1996-04-04 | 1998-10-02 | Process for the preparation of substituted aromatic amines |
NO20013219A NO20013219D0 (en) | 1996-04-04 | 2001-06-27 | Process for the preparation of trisodium pentacyanoaminoferrate (II) |
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US08/628,181 | 1996-04-04 | ||
US08/628,181 US5728882A (en) | 1996-04-04 | 1996-04-04 | Preparation of substituted aromatic amines |
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US5925790A (en) * | 1997-03-13 | 1999-07-20 | Uniroyal Chemical Company, Inc. | Preparation of substituted aromatic amines |
US6069279A (en) * | 1999-06-14 | 2000-05-30 | Simon; Mark W. | Preparation of substituted aromatic amines |
US6229035B1 (en) | 1999-06-16 | 2001-05-08 | Uniroyal Chemical Company, Inc. | Preparation of substituted aromatic amines |
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EP0261096A2 (en) * | 1986-09-15 | 1988-03-23 | Monsanto Company | Preparation of substituted aromatic amines |
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GB1440767A (en) * | 1972-11-24 | 1976-06-23 | Ici Ltd | Oxidation process for the manufacture of 4-aminodiphenylamine and related higher amines |
US5117063A (en) * | 1991-06-21 | 1992-05-26 | Monsanto Company | Method of preparing 4-aminodiphenylamine |
US5728882A (en) * | 1996-04-04 | 1998-03-17 | Uniroyal Chemical Company, Inc. | Preparation of substituted aromatic amines |
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EP0261096A2 (en) * | 1986-09-15 | 1988-03-23 | Monsanto Company | Preparation of substituted aromatic amines |
EP0272238A2 (en) * | 1986-12-17 | 1988-06-22 | Monsanto Company | Preparation of substituted aromatic amines |
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CHEMICAL ABSTRACTS, vol. 112, no. 22, 28 May 1990, Columbus, Ohio, US; abstract no. 210156n, NICKEL ULRICH ET AL.: "Determination of hexacyanoferrate based on its catalytic influence on the oxidation of p-phenylenediamines by iron" page 803; column 1; XP002033144 * |
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