WO2010029208A1 - Preparación de azo compuestos con catalizadores sólidos - Google Patents
Preparación de azo compuestos con catalizadores sólidos Download PDFInfo
- Publication number
- WO2010029208A1 WO2010029208A1 PCT/ES2009/070378 ES2009070378W WO2010029208A1 WO 2010029208 A1 WO2010029208 A1 WO 2010029208A1 ES 2009070378 W ES2009070378 W ES 2009070378W WO 2010029208 A1 WO2010029208 A1 WO 2010029208A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- process according
- catalyst
- metal oxide
- amine
- support
- Prior art date
Links
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000011949 solid catalyst Substances 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052737 gold Inorganic materials 0.000 claims abstract description 54
- 239000010931 gold Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 48
- 150000001412 amines Chemical class 0.000 claims abstract description 31
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 29
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000768 polyamine Polymers 0.000 claims abstract description 10
- 229920000620 organic polymer Polymers 0.000 claims abstract description 8
- 125000000129 anionic group Chemical group 0.000 claims abstract description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 5
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 5
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 5
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 35
- 230000008569 process Effects 0.000 claims description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- -1 Azo compound Chemical class 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000412 dendrimer Substances 0.000 claims description 6
- 229920000736 dendritic polymer Polymers 0.000 claims description 6
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 claims description 4
- JQULXIOYDDCNGR-UHFFFAOYSA-N 2-amino-2-methylpropanenitrile Chemical compound CC(C)(N)C#N JQULXIOYDDCNGR-UHFFFAOYSA-N 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- 235000014121 butter Nutrition 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 4
- 229940012189 methyl orange Drugs 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 4
- ASAYZKXYWACRGR-UHFFFAOYSA-N 1-N,1-N'-dimethylcyclohexa-2,4-diene-1,1,4-triamine Chemical group CNC1(NC)CC=C(N)C=C1 ASAYZKXYWACRGR-UHFFFAOYSA-N 0.000 claims description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000002019 doping agent Substances 0.000 claims description 3
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 2
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 claims description 2
- JTIHSSVKTWPPHI-UHFFFAOYSA-N 2-amino-2-phenylacetonitrile Chemical compound N#CC(N)C1=CC=CC=C1 JTIHSSVKTWPPHI-UHFFFAOYSA-N 0.000 claims description 2
- ZXIXBPGNGUZOBB-UHFFFAOYSA-N 2-amino-2-phenylpropanenitrile Chemical compound N#CC(N)(C)C1=CC=CC=C1 ZXIXBPGNGUZOBB-UHFFFAOYSA-N 0.000 claims description 2
- HJXPGCTYMKCLTR-UHFFFAOYSA-N 2-bromo-9,9-diethylfluorene Chemical compound C1=C(Br)C=C2C(CC)(CC)C3=CC=CC=C3C2=C1 HJXPGCTYMKCLTR-UHFFFAOYSA-N 0.000 claims description 2
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 claims description 2
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- LHNICELDCMPPDE-UHFFFAOYSA-N anthracen-9-amine Chemical compound C1=CC=C2C(N)=C(C=CC=C3)C3=CC2=C1 LHNICELDCMPPDE-UHFFFAOYSA-N 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 2
- HSOHBWMXECKEKV-UHFFFAOYSA-N cyclooctanamine Chemical compound NC1CCCCCCC1 HSOHBWMXECKEKV-UHFFFAOYSA-N 0.000 claims description 2
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 claims description 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N mono-n-propyl amine Natural products CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004888 n-propyl amino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 claims description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 claims description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 37
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 26
- 229910052760 oxygen Inorganic materials 0.000 description 26
- 239000001301 oxygen Substances 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 238000007254 oxidation reaction Methods 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- 239000012188 paraffin wax Substances 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 150000002828 nitro derivatives Chemical class 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- TVUARPCSZQNJJZ-UHFFFAOYSA-N 2-(4-ethenylphenyl)ethanol Chemical group OCCC1=CC=C(C=C)C=C1 TVUARPCSZQNJJZ-UHFFFAOYSA-N 0.000 description 3
- CRQSAKXMWFFXJG-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methyl]oxirane Chemical compound C1=CC(C=C)=CC=C1CC1OC1 CRQSAKXMWFFXJG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- PBTOMDGEYFDLSV-UHFFFAOYSA-N n,n-bis(methylamino)aniline Chemical compound CNN(NC)C1=CC=CC=C1 PBTOMDGEYFDLSV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- QWLSHZKQRSNZKL-UHFFFAOYSA-N phenyl(pyridin-2-yl)diazene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=N1 QWLSHZKQRSNZKL-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002123 temporal effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-M 4-aminobenzenesulfonate Chemical compound NC1=CC=C(S([O-])(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 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
- 239000012917 MOF crystal Substances 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
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- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
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- 150000002826 nitrites Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 229920002401 polyacrylamide Polymers 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Definitions
- the present invention relates to heterogeneous solid catalysts based on nanoparticulate metal oxides containing or not gold and on different supports containing or not gold nanoparticles capable of promoting the formation of azo compounds and especially azo symmetric or asymmetric aromatic compounds by reaction of pure amines , mixtures of amines or polyamines with atmospheric oxygen as oxidizing agent.
- These catalysts can operate in continuous processes or in load processes, being able in this case to recover the solid by filtration and be reused in a new reaction without reducing its catalytic activity.
- these catalysts contain gold in the form of nanoparticles, it is possible to couple the oxidation process of the amines with a previous process consisting in the formation of these amines by hydrogenation of nitro compounds. In this way, a single catalyst can effect the transformation of nitro compounds into azo compounds.
- azo compounds can be classified as symmetrical and asymmetric depending on whether the substituents of each of the nitrogens are identical or different.
- R 2 symmetric: R 1 R 2
- N N 'asymmetric R 1 different from R 2
- R 1 aromatic R 1 and / or R 2 aryl azo compounds Scheme 1. Functional group and azo structure compouestos
- Azo compounds are used as carbon free radical generators, as pigments, dyes, food additives, as pharmaceutical compounds and as metal ligands.
- the azo compounds represent an intermediate oxidation state between the nitro compounds and the amines and, therefore, can be obtained from compounds of any of these families (Scheme 2).
- the reactions are carried out using stoichiometric amounts of oxidizing or reducing agents, which often contain transition metals or annoying reagents for the environment. To date, no process using heterogeneous catalysis has been described in the state of the art, which has a high conversion, and which has a high selectivity. R2 oxidation reduction
- N N ⁇ [H 2 NR 1
- the azo compounds can be prepared from amines by reaction with oxidizing agents such as lead tetraacetate. Azo compounds can also be obtained by reducing nitro compounds with metals such as lead.
- the azo aromatic asymmetric compounds can be prepared by a coupling reaction of a diazonium salt with an aromatic compound activated against the electrophilic substitution reaction. In this case, the usual way to prepare the diazonium salt is by reaction with nitrites in acidic medium. Also in this case, stoichiometric amounts of nitrite that acts as a moderate oxidant are required.
- heterogeneous and reusable catalysts are used to carry out the formation of azo compounds from amines by aerobic oxidation.
- the process of the invention allows obtaining azo aliphatic and aromatic compounds of amines and polyamines with a high yield and high purity while the heterogeneous nature of the solid catalyst facilitates its separation, recovery and reuse.
- the present invention relates to a process for preparing azo compounds comprising the reaction between at least:
- Azo compounds are currently obtained by non-catalytic reactions that use stoichiometric amounts of metals or metal compounds or other reagents. The azo formation procedures compounds described so far do not comply with the principles of "Green Chemistry" which aims to develop chemical processes that do not produce negative by-products for the environment.
- the starting substrate of the synthesis could be a nitro compound which is first subjected to a selective catalytic hydrogenation of the nitro group and, subsequently, in the same or different reactor and with the same or different gold catalyst it could suffer a subsequent oxidation to compound azo.
- Scheme 3 summarizes the synthesis sequence.
- the catalyst support used is a metal oxide of any of the elements of the groups, 3, 4, 5, 6, 8, 9, 11 and 13.
- said metal oxide is selected from T ⁇ O2, Ce x Oy, AI2O3, MgO, CaO, Cu x Oy,
- the metal oxide is titanium oxide. According to another preferred embodiment the metal oxide is cerium oxide. According to another preferred embodiment the metal oxide is ytrium oxide. According to another preferred embodiment the metal oxide is iron oxide.
- the metal oxide is zirconium oxide.
- the particle size of the oxide may preferably be between 1 and 50 nm.
- the metal oxides mentioned above may also contain a small percentage of other / other elements (metallic or not) that can act as doping agents. These elements are preferably selected from elements of groups 9, 10, 11 and 12. Some non-limiting examples of these elements may be Pt, Pd, Fe, Cu, La, Pr, Au, N, C, S and combinations thereof.
- nanoparticulate titanium oxide (average particle size of 25 nm) predominantly in anatase phase (80%) catalyzes the formation of aniline in azobenzene with a conversion of 97% and a selectivity of 99% .
- nanoparticulate cerium oxide (average particle size 5 nm) is capable of producing a 90% conversion and 59% azobenzene selectivity.
- the catalyst support can be at least one microporous material, preferably a zeolitic material. Also, in particular, the support can be at least one structured mesoporous material.
- the support is silica.
- the support is at least one anionic laminar compound of the hydrotalcite type or its derivatives.
- the support is activated carbon.
- the support is at least one organic polymer.
- This support may be a copolymer that may be selected from styrene copolymer, 4-hydroxyethylstyrene copolymer and 4-glycidylstyrene copolymer.
- the support is a dendrimer type polymer that can be selected from dendrimer type
- the catalyst can also comprise at least one metal of the groups
- said metal is gold.
- the size of these gold nanoparticles is of vital importance in the catalytic activity, since the activity of the catalyst decreases strongly when the gold particles exceed a size of 20 nm.
- An appropriate particle size to observe the catalysis of the oxidation reaction with amines oxygen would preferably be between 1 and
- gold is approximately in a percentage between 0.01 and 10%, more preferably between 0.05 and 6% by weight in reference to the catalyst.
- the metal oxide may contain gold nanoparticles.
- the nature of the support has an influence on the activity and final selectivity of the catalyst.
- These gold nanoparticles are preferably supported on an insoluble material that can be an organic polymer or activated carbon or even an organic-inorganic support such as for example a metal-organic lattice material (MOF).
- MOF metal-organic lattice material
- the catalytic activity that the metal oxide can present is markedly increased by these gold nanoparticles.
- These metal oxides themselves can, in turn, have some catalytic activity in the oxidation reaction of aromatic amines by oxygen to form azobenzenes. But as we have said, the activity measured as a reaction rate increases significantly towards the compound azo when the nanoparticulate oxide is modified by adsorption of gold nanoparticles on its surface. They can also be supports suitable zeolites and structured mesoporous oxides with or without subsequent treatments, or combinations thereof among others.
- a preferred catalyst is one in which three co-monomers (styrene, p-glycidylstyrene and p-2-hydroxyethylstyrene) form a polymeric support.
- the proportions of the monomers can be varied over a wide range with a preferred ratio of styrene / p-glycidylstyrene / p-2-hydroxyethylstyrene 90/7/3.
- Polystyrenes containing other neutral or positively or negatively charged co-monomers, polyacrylates and polyacrylamides are other polymers that can be used as support.
- soluble polymers of the dendrimer type can serve as supports of the nanoparticles of gold.
- supports are active carbons of different origin and chemical composition. These supports improve their efficiency by increasing the area.
- other insoluble supports where the gold nanoparticles are deposited are the organic-inorganic hybrid materials and in particular the metal-organic reticular materials (MOF). In these latter, micro- / mesosporous crystalline materials formed by interactions between a metal or subanometric metal aggregates with organic spacers, gold nanoparticles can occupy exterior or interior positions relative to the MOF crystal.
- MOF metal-organic reticular materials
- other supports of gold nanoparticles are metal oxides, both amorphous and crystalline and structured, both laminar and porosity in the range 0.7 to 100 nm.
- These oxides that are used as support can contain two or more metals.
- the crystallographic phase in any of the metal oxides can be pure or mixture of several in any proportion.
- the particle size of the support can be between several manometers up to several microns.
- the oxide may be stoichiometric or the ratio between the metal and the oxygen differ from that expected based on the valences of the elements.
- a preferred embodiment of the present invention consists of 0.1-4% by weight of gold with crystal size between 2 and 10 nm on titanium oxide of 25 nanometers of average particle size and in its anatase phase.
- metal oxides with or without gold nanoparticles may contain small proportions of other metals and nonmetallic elements that act as doping agents.
- the predominantly anatase phase titanium oxide is doped with a
- the supports can also be amorphous, but they can also have some kind of structure.
- the supports can be laminar, such as hydrotalcite-type materials (mixed oxides of a divalent and a trivalent metal) or derived from mixed oxides.
- the process of the present invention comprises an amine or polyamine as the starting compound for obtaining the corresponding azo compound.
- the amines usable within the framework of the present invention are aliphatic or aromatic amines and polyamines. Especially suitable are those amines that have substituents that increase the electron density in nitrogen. Thus, in the case of aromatic amines, those that have electron donor groups attached to the aromatic ring are the ones that react with the highest speed.
- the amine or polyamine may be an amine of the formula
- R (NH 2 ) n
- R is selected from the group consisting of alkyl substituted or unsubstituted with 1 to 20 carbon atoms, aryl substituted or unsubstituted with 6 to 15 carbon atoms, arylalkyl substituted or unsubstituted with 7 to 15 carbon atoms, alkenyl substituted or unsubstituted with 2 to 20 carbon atoms, alkynyl substituted or unsubstituted with 2 to 20 carbon atoms, cycloalkyl substituted or unsubstituted with 3 to 20 carbon atoms, cycloalkenyl substituted or unsubstituted with 4 at 20 carbon atoms and cycloalkynyl substituted or unsubstituted with 5 to 20 carbon atoms; and n is 1, 2, 3, 4, 5 or 6.
- the amine or polyamone is selected from n-propylamine, isopropylamine, ⁇ -cyano isopropylamine, n-butylamine, n-hexylamine, n-octylamine, laurylamine, cyclopentylamine, cyclohexylamine, cyclooctylamine, 1,2-diaminoethane, 1, 12-diaminododecane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, hydrogenated 2,4-diaminodiphenylmethane, hydrogenated toluylenediamine, aniline, benzylamine, ⁇ -cyanobenzylamine, ⁇ -cyano- ⁇ -phenylethanamine, 2- aminotoluene, 4-aminotoluene ,
- the mixture of two amines in suitable proportions allows asymmetric compounds to form azo where the groups R 1 and R 2 of scheme 1 are different.
- An especially important case is when the two groups R 1 and R 2 are different aromatic groups.
- These azo asymmetric compounds can be obtained with high selectivity by treating a mixture of the amines with oxygen in the presence of the catalysts of the present invention (see examples 6 and 7).
- the selectivity with respect to the formation of the asymmetric compound azo is particularly high when one of the amines is rich in electrons and the other is poor. In aromatic amines derived from benzene, this difference in the electron density of the nitrogen atoms can be determined based on the electroder or electroceptor nature of the substituents present in the aromatic ring.
- azo compounds of the present invention can be transformed into other compounds with a greater or lesser oxidation state, for example, among other azoxy and nitro compounds and hydrazines and amines.
- the starting amine can be aniline and this is oxidized to azobenzene.
- the starting amine can be (4,4-dimethylamino) aniline and is oxidized to obtain butter yellow.
- the starting product is a mixture of sodium (4,4-dimethylamino) aniline and 4-aminobenzenesulfonate and what is obtained is methyl orange.
- starting from Dcianoisopropylamine is oxidized to obtain azo bis (isobutyronitrile).
- the catalyst used in this example refers to a copolymer of three monomers, styrene / p-glycidylstyrene / p-2-hydroxyethylstyrene in proportion 90/7/3 containing gold nanoparticles (1.5% by weight, 5 nm average size).
- This catalyst is prepared by forming the polymer via radicals, synthesizing the gold nanoparticles by reduction of AuCI 4 " and subsequent cross-linking of the epoxy and alcohol groups according to the procedure described in the literature and known in the state of the art (Miyamura, H .; Matsubara, R .; Miyazaki, Y .; Kobayashi, S. Angew. Chem. Int. Ed. 2007, 46, 4151) 2 g are introduced into a reinforced glass reactor equipped with a pressure and temperature controller. of aniline and the amount of gold catalyst supported in polymer matrix to achieve a gold / aniline molar ratio of 1 mol%.
- the reactor is purged 3 times with 5 bar of oxygen and then sealed and pressurized with oxygen at the final pressure of 5 bar.
- the reactor is completely submerged in a paraffin bath preheated to 100 0 C and is magnetically stirred. During the experiment, the pressure of O 2 is maintained around 5 bar providing more oxygen when appropriate.
- the course of the reaction and the temporal evolution of the products is determined by analyzing aliquots at different times.
- the reactor samples are diluted with acetonitrile, centrifuged to remove catalyst particles and the supernatant is analyzed with GC-MS. After 6 days the conversion is 50%.
- the process takes place using a single catalyst in two stages consisting of the first in the transformation of nitrobenzene into aniline and the second in the oxidation of the aniline to azobenzene.
- a titanium oxide catalyst (Degusa P25) containing 1.5% by weight of gold nanoparticles (5 nm average size).
- This catalyst is prepared by precipitation-deposition on P25 from aqueous solutions HAuCI 4 where the pH is increased to a value greater than 5 (typically 7) according to the procedure described in the literature (Abad, A .; Corma, A .; Garda, H. Chem. Eur. J.
- the bath temperature is lowered to 100 0 C and all hydrogen is removed from the reactor, the system being purged 3 times with 5 bar of oxygen.
- the reactor is charged with molecular oxygen at the pressure of 5 bar and in the same way as the inner stage, the pressure of O 2 is maintained at a value greater than 3 bar, providing more oxygen when appropriate.
- the course of the reaction is determined by analyzing aliquot at different times. The samples are centrifuged to remove catalyst particles and the supernatant is analyzed with GC-MS. After 9 hours, the yield of azobenzene is 92%.
- the reactor is completely submerged in a paraffin bath preheated to 100 0 C and is magnetically stirred. During the experiment, the O2 pressure is maintained at a value greater than 3 bar, supplying more oxygen when appropriate.
- the course of the reaction is determined by analyzing aliquots of the reaction crude at different times. The samples are centrifuged to remove catalyst particles and the supernatant is analyzed by GC-MS. After 16 hours, a yield of 99% of the yellow butter [(4,4'-bis (N, N-dimethylamino) azobenzene] is obtained.
- the O2 pressure is maintained at a value greater than 3 bar, supplying more oxygen when appropriate.
- the crude is centrifuged to remove the catalyst and the supernatant is taken to dryness.
- the solid residue is recrystallized from a small volume of hot toluene. The crystals They are filtered, washed with cold ether and dried under reduced pressure overnight. A yield of 92% of methyl orange is obtained, which proves to be pure based on its spectroscopic properties of 1 H NMR, 13 C NMR, UV and elemental analysis.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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US13/063,551 US20110313142A1 (en) | 2008-09-15 | 2009-09-10 | Preparation of azo compounds with solid catalysts |
JP2011526521A JP2012502891A (ja) | 2008-09-15 | 2009-09-10 | 固体触媒を用いたアゾ化合物の調製 |
EP09812735.0A EP2327688A4 (en) | 2008-09-15 | 2009-09-10 | PREPARATION OF AZOIC COMPOUNDS WITH SOLID CATALYSTS |
CN2009801361517A CN102159536A (zh) | 2008-09-15 | 2009-09-10 | 用固体催化剂制备偶氮化合物 |
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ES200802659A ES2334877B1 (es) | 2008-09-15 | 2008-09-15 | Preparacion de azo compuestos con catalizadores solidos. |
ESP200802659 | 2008-09-15 |
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WO2010029208A1 true WO2010029208A1 (es) | 2010-03-18 |
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US (1) | US20110313142A1 (es) |
EP (1) | EP2327688A4 (es) |
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CN102875412B (zh) * | 2012-10-22 | 2014-12-10 | 浙江万丰化工有限公司 | 一种由含氨基化合物氧化制备偶氮化合物的方法 |
CN103319913A (zh) * | 2013-06-18 | 2013-09-25 | 安科智慧城市技术(中国)有限公司 | 一种染料插层类水滑石纳米复合材料的制备方法 |
CN105085329B (zh) * | 2014-05-04 | 2017-07-07 | 中国科学院大连化学物理研究所 | 一种芳香胺氧化制备芳香氧化偶氮苯的方法 |
CN104193647B (zh) * | 2014-08-30 | 2016-03-30 | 大庆市华兴化工有限责任公司 | 双氮庚酰胺的制备方法 |
JP6172693B1 (ja) * | 2016-09-06 | 2017-08-02 | 小西化学工業株式会社 | アゾ化合物の製造方法 |
US11999097B2 (en) * | 2018-05-21 | 2024-06-04 | Virginia Tech Intellectual Properties, Inc. | Selective deposition of materials for composite structures via additive manufacturing |
CN115337919B (zh) * | 2021-05-14 | 2023-11-28 | 兰州大学 | 氢氧化锆作为催化剂催化苯胺或其衍生物制备二苯基二氮烯或其衍生物的应用 |
CN116393127B (zh) * | 2023-03-03 | 2024-05-24 | 安徽大学 | 用于偶氮苯类化合物合成的缺陷铜基催化剂及其制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5350121A (en) * | 1976-10-19 | 1978-05-08 | Teijin Ltd | Preparation of azobenzene |
US5917023A (en) * | 1996-06-05 | 1999-06-29 | Basf Aktiengesellshcaft | Reductive coupling of nitrobenzene or nitrobenzenes substituted on the nucleus to give the corresponding azobenzenes and azoxybenzenes by means of redox catalysts |
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JP4522672B2 (ja) * | 2003-06-26 | 2010-08-11 | 旭化成ケミカルズ株式会社 | 環状脂肪族オキシムの製造法 |
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2009
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- 2009-09-10 JP JP2011526521A patent/JP2012502891A/ja active Pending
- 2009-09-10 US US13/063,551 patent/US20110313142A1/en not_active Abandoned
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See also references of EP2327688A4 |
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Also Published As
Publication number | Publication date |
---|---|
JP2012502891A (ja) | 2012-02-02 |
EP2327688A1 (en) | 2011-06-01 |
ES2334877A1 (es) | 2010-03-16 |
ES2334877B1 (es) | 2011-01-04 |
EP2327688A4 (en) | 2014-03-05 |
US20110313142A1 (en) | 2011-12-22 |
CN102159536A (zh) | 2011-08-17 |
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