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United States Patent (19) 11 Patent Number: 5,917,023 Hagemeyer Et Al

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United States Patent (19) 11 Patent Number: 5,917,023 Hagemeyer Et Al USOO5917023A United States Patent (19) 11 Patent Number: 5,917,023 Hagemeyer et al. (45) Date of Patent: Jun. 29, 1999 54 REDUCTIVE COUPLING OF 3,041,377 6/1962 Harast ................................. 534/585 X NITROBENZENE OR NITROBENZENES 3,578,720 5/1971 Dodman et al. ........................ 534/572 SUBSTITUTED ON THE NUCLEUS TO GIVE 3,700,605 10/1972 Dodman et al. ........................ 502/324 3,989,764 11/1976 Wooley ................................... 568/949 ESSESSENGE 4,265,834 5/1981 Birkenstock et al. .................. 564/421 REDOX CATALYSTS 5,689,005 11/1997 Hagemeyer et al. ................... 564/420 OTHER PUBLICATIONS 75 Inventors: Alfred Hagemeyer, Rheine; Daniel Heineke, Ludwigshafen; Guido Voit, Finholt et al., J. Am. Chem. Soc., vol. 77, p. 4163, 1955. Schriesheim; Tom Witzel, Meier et al., Chem. Ber, vol. 89, pp. 2301-2305, 1965. Ludwigshafen, all of Germany Ohe et al., J. Org. Chem., vol. 54, No. 17, pp. 41.69–4174, 1989. 73 Assignee: BASF Aktiengesellshcaft, Gellner et al., J. Chem. Soc., pp. 1145-1148, 1949. Ludwigshafen, Germany Kmiewcik, J. Org. Chem, vol. 30, pp. 2014-2020, 1965. Lin et al., J. of Xiamen University, vol. 25, No. 4, Jul. 1986, pp. 449–455. 21 Appl. No.: 08/869,760 Konishi et al., Chem. Lett., vol. 11, pp. 1351-1354, 1980. 22 Filed: Jun. 5, 1997 Primary Examiner Fiona T. Powers 30 Foreign Application Priority Data Attorney, Agent, or Firm-Keil & Weinkauf Jun. 5, 1996 DEI Germany ........................... 196 22 644 57 ABSTRACT Aug. 20, 1996 DEI Germany ........................... 19633 552 Nitrobenzene or a nitrobenzene Substituted on the nucleus is 51) Int. Cl. ........................ C07C 245/08; CO7C 291/08 Subjected to reductive coupling to give the corresponding 52 U.S. Cl. ............................................. 534/572; 534/585 aZobenzene and azoxybenzene under heterogeneous cataly 58 Field of Search ..................................... 534/585,572; sis with Substantial avoidance of overreduction to aniline 502/353 derivatives by means of a redox catalyst in its reduced or partly reduced form, the redox catalyst containing at least 56) References Cited one active metal component capable of a change of oxida tion State. U.S. PATENT DOCUMENTS 1,451,489 4/1923 Brown et al. ........................... 534/572 10 Claims, 2 Drawing Sheets U.S. Patent Jun. 29, 1999 Sheet 1 of 2 5,917,023 Se FIG.1 5,917,023 1 2 REDUCTIVE COUPLING OF carrier and the active metal in the form of a Lewis acid NITROBENZENE OR NITROBENZENES compound, many Secondary reactions occur and all that is SUBSTITUTED ON THE NUCLEUS TO GIVE obtained is a complex product mixture, the Selectivity for THE CORRESPONDINGAZOBENZENES aZobenzene being low. AND AZOXYBENZENES BY MEANS OF 5 Konishi et al., in Chem. Lett. 11 (1980), 1351–1354, REDOX CATALYSTS describe the deoxygenation of nitrobenzene to azobenzene by contact with a carbon catalyst which was impregnated The invention relates to a process for the reductive with KCO. This process has the disadvantage that the coupling of nitrobenzene or nitrobenzenes Substituted on the carbon is gradually consumed by Oxidation to oxides of nucleus under heterogeneous catalysis to give the corre carbon and the catalyst becomes leSS mechanically stable. In sponding azobenzenes and azoxybenzenes with Substantial this process, the carbon is thus a Stoichiometric reduction avoidance of overreduction to aniline derivatives by means reagent which cannot be regenerated. The reaction is there of a redox catalyst in its reduced or partly reduced form, the fore Strictly not a heterogeneous catalysis but a Stoichiomet redox catalyst containing at least one active metal compo ric fluid-Solid reaction. nent capable of a change of oxidation State. In one embodi 15 German Laid-Open Application DOS 1,810,828 (ICI, ment of the present invention, the above process is carried 1969) describes the continuous, steady-state reduction of out in the presence of water. In the description, the term nitrobenzene to predominantly nitroSobenzene, but also to nitrobenzene includes both nitrobenzene as Such and aZOxy- and azobenzene with CO in the gas phase over nitrobenzenes Substituted on the nucleus. The novel reduc catalysts which contain two or more of the heavy metals Ti, tive nitrobenzene coupling can be carried out by a steady V, Cr, Mn, Fe, Co, Ni, Cu, Ge, Zr, Mo, Ag, Sn, Sb, La, Ce, State as well as a non-Steady-state reaction. Nd, Ta, W, Re, Au, Hg, Tl, Pb, Bi and Thin the form of their AZobenzene and azoxybenzene are important intermedi oxides, hydroxides, carbonates or phosphates. Preferred ates in the chemical industry and are used, inter alia, in the heavy metal pairs are Pb-Mn for the preparation of nitroso Synthesis of antioxidants, dyes, active ingredients, polymer compounds, Co-Mn for the preparation of nitroSO com modifiers, adhesives and Sealing compounds, photoresists 25 pounds or azoxybenzene compounds and Cu-Ce for the and photosensitive Systems. preparation of azo compounds. Accordingly, the prior art also discloses the reduction of According to this Laid-Open Application, Ag-Mn-O on a nitrobenzene to azobenzene and/or azoxybenzene, azoben ceramic carrier (pumice) and a feed of nitrobenzene and CO Zene conventionally being prepared by diazotizing aniline give azobenzene and nitrobenzene in a ratio of 3:7 in the and reacting the diazonium Salt with benzene in the liquid condensate. phase (cf., among many references, Finholt, Jacobsen, With Co-Mn-O on pumice and a feed of nitrobenzene Ogard and Thomsen in J. Am. Chem. Soc. 77 (1955), 4163, and CO, azoxybenzene and nitrobenzene in a ratio of 3:7 are Meier and Bohler in Chem. Ber. 89 (1965), 2301, and Ohe, obtained in the condensate. Uemura, Sugita, Matsuda and Taga in J. Org. Chem. 54(17) With Ce-Fe-O on pumice, a mixture of azoxybenzene (1989), 4169–4174). 35 and azobenzene and unconverted nitrobenzene are obtained Disadvantages of these reactions are the very expensive with a nitrobenzene conversion of 20%. reduction reagents which cannot be regenerated and which With Ce-Cu-O on pumice and with different Ce/Cu have to be used in SuperStoichiometric amounts. In most of ratios, from 55 to 72% of azobenzene and from 6.5 to 14% these processes, moreover, large amounts of Salts are of azoxybenzene, based in each case on the nitrobenzene obtained, which is also disadvantageous. 40 introduced, were found in the condensate. The first reductions of the gas phase are described by When Ce-Bi-O was used, only very low activity with a Buckley et al. in J. Chem. Soc. (1949), 1146-46 and by conversion of only from 5 to 10% was found. Kmiecik in J. Org. Chem. 30 (1965), 2014-2020. Buckley et When Fe-Cu-O on pumice was used, a nitrobenzene al. describe the reduction of nitrobenzene to azobenzene conversion of 56% was achieved, many other products, eg. without a catalyst by heating nitrobenzene for 24 hours at 45 diphenylurea, being found in the condensate in addition to 250 C. under a CO pressure of 3000 atm, azobenzene being aZobenzene and azoxybenzene. obtained in a yield of 97.5%. At 200° C. or at below 2500 The use of Mn-Ni-Co-O on pumice gave a mixture of atm, Virtually no reduction took place. Kmiecik describes aZobenzene and azoxybenzene in the condensate at a con the reduction of nitrobenzene to azobenzene with CO in the version of almost 50%. presence of iron pentacarbonyl catalysts in dry benzene. At 50 On the other hand, with Mn-Co-O, Mn-O, Fe-Mn-O, about 200° C. and CO pressures of about 3000 psig (.207 Ce-Fe-O, Ce-Mn-O and Pb-Mn-O on C and Ag-Mn-O on bar) and with reaction times of about 3 hours, azobenzene pumice, nitroSobenzene was obtained as the main product. yields of up to 80% were obtained. With Cu-Ce-O on pumice, a mixture of nitrosobenzene However, these two processes have disadvantages in that and azobenzene was obtained in the fluidized bed at a they must be carried out at very high CO preSSures and for 55 nitrobenzene conversion of 20%. The use of Fe-Mn-O on long reaction times. pumice gave a mixture of azobenzene, azoxybenzene and Processes for the reduction of nitrobenzene under het nitroSobenzene at a nitrobenzene of about 25%. erogeneous catalysis to give azobenzene and/or azoxyben The disadvantage of the above German Laid-Open Zene in the gas phase are also known. Application 1,810,828 is the incomplete, generally very low For example, Lin et al. in Ziran Kexueban 25(4) (1986), 60 nitrobenzene conversion (from 5 to 56% according to the 449-455, describe the interaction of CO with nitrobenzene Examples) and the consequently poor yields of azobenzene over metal oxide catalysts Selected from the group consist and azoxybenzene, which entail expensive Separation of ing of CuO, MoC), VO and PdC), each on SiO carriers. Substances and recycling of nitrobenzene. Moreover, In these reactions, CO is oxidized to CO while nitrobenzene according to this German Laid-Open Application, only very is reduced to various N-containing compounds, phenazine 65 Small catalyst Space Velocities are used, resulting in corre and azobenzene also being formed. This reaction has in spondingly low Space-time yields (1 g of nitrobenzene/h particular the disadvantage that, owing to the acidic SiO2 with 12 g of catalyst material, which corresponds to a 5,917,023 3 4 WHSV (Weight Hourly Space Velocity) of 0.08 h"). cation DOS 1,810,828 which can be deduced simply from Furthermore, the active metal components of the catalysts the fact that, in the novel process, the Selectivity with respect used are present in reduced form only in a Small proportion to azobenzene and azoxybenzene is Substantially higher than at the Surface or were for the most part not Subjected to any in the process according to the above application.
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