Regio- and chemoselective catalytic transfer hydrogenation of aromatic nitro and carbonyl as well as reductive cleavage of azo compounds over novel mesoporous NiMCM-41 molecular sieves

Organic Letters

Volumn 4, Issue 24, 2002, Pages 4297-4300

  Mohapatra, Susanta K ^a   Sonavane, Sachin U ^b   Jayaram, Radha V ^b   Selvam, Parasuraman ^a,c  

^a INDIAN INSTITUTE OF TECHNOLOGY BOMBAY   (India)

^b INSTITUTE OF CHEMICAL TECHNOLOGY   (India)

^c TOHOKU UNIVERSITY   (Japan)

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ARTICLE;

EID: 0041736506     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol026936p     Document Type: Article

References (27)

1. Kabalka, G. W.; Verma, R. S. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, UK, 1991; Vol. 8, pp 363.
2. Larock, R. C. Comprehensive Organic Transformations: A Guide to Functional Group Preparation, 2nd ed; Wiley-VCH: New York, 1999; p 823.
3. Merlic, C. A.; Motamed, S.; Quinn, B. J. Org. Chem. 1995, 60, 3365.
4. Doxsee, K. M.; Fiegel, M.; Stewart, K. D.; Canary, J. W.; Knobler C. B.; Cram, D. J. J. Am. Chem. Soc. 1987, 109, 3089.
5. Smith, G. V.; Notheisz, F. Heterogeneous Catalysis in Organic Chemistry; Academic: New York, 1999; p 71.
6. For a monograph, see: Hudlicky, M. Reduction in Organic Chemistry, 2nd ed.; American Chemical Society: Washington, DC, 1996.
7. Pasto, D. J. J. Am. Chem. Soc. 1979, 101, 6852.
8. (a) Andrews, M. J.; Pillai, C. N. Indian J. Chem. B 1978, 16, 465.
9. (b) Ayyanger, N. R.; Lugade, A. G.; Nikrad, P. V.; Sharma, V. K. Synthesis 1981, 640.
10. Gilchrist, T. L. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 8, p 388.
11. (a) Upadhya, T. T.; Ramaswamy, V.; Sabade, D. P.; Katdure, D. P.; Sudalai, A. Chem. Commun. 1997, 1119.
12. (b) Sonavane, S. U.; Jayaram, R. V. Synth. Commun. In press.
13. Kresge, C. T.; Leonowicz, M. E.; Roth, W. T.; Vartuli, J. C.; Beck, J. S. Nature 1992, 359, 710.
14. Selvam, P.; Bhatia, S. K.; Sonwane C. G. Ind. Eng. Chem. Res. 2001, 40, 3237.
15. (a) Mahalingam, R. J.; Badamali, S. K.; Selvam, P. Chem. Lett. 1999, 1141.
16. (b) Badamali, S. K.; Sakthivel, A.; Selvam, P. Catal. Lett. 2000, 65, 153.
17. (c) Sakthivel, A.; Dapurkar, S. E.; Selvam, P. Catal. Lett. 2001, 77, 155.
18. (d) Sakthivel, A.; Selvam, P. J. Catal. 2002, 211, 134.
19. (e) Mohapatra, S. K.; Sahoo, B.; Keune, W.; Selvam, P. Chem. Commun. 2002, 1466.
20. 2, followed by 6 h in air. For further details, see: Sakthivel, A.; Badamali, S. K.; Selvam P. Micropor. Mesopor. Mater. 2000, 39, 457.
21. -1, and pore size = 30 Å) support the mesoporous nature of the sample. Inductively coupled plasma-atomic emission (ICP-AES) analysis shows 4.3 wt % Ni loading in the catalyst.
22. Thermogravimetric (TG) analysis of calcined NiMCM-41 shows a 20% weight loss indicating its acidic nature. This is well supported by the temperature-programmed desorption of ammonia studies. Differential thermal analysis (DTA) shows corresponding endothermic transition.
23. In a typical CTH reaction, KOH pellets (20 mmol) were dissolved in propan-2-ol (20 mL) to which substrate (20 mmol) was added along with 100 mg of catalyst. It was then refluxed at 356 K for a few hours depending upon the nature of the substrate. The products were analyzed using a gas chromatograph fitted with an OV-101 column. For recycling purposes the catalyst was recovered, after the first reaction, by simple filtration and washed three times with acetone followed by water, then it was dried at 373 K. This catalyst was reused for the subsequent cycles.
24. The effect of various hydrogen donors such as primary and secondary alcohols on the CTH of nitrobenzene was performed over NiMCM-41 The former gave lower yields (ethanol/15%; propan-1-ol/66%; butan-1-ol/59) while the latter (propan-2-ol/93%; butan-2-ol/81%) gave higher yields of aniline. In addition, the dehydrogenation product is ketone, which can easily be removed from the reaction system. In the case of tertiary alcohols, e.g., 2-methylpropan-1-ol, the reaction did not proceed as there is no α-hydrogen and hence they cannot act as hydrogen donors. Therefore, in this study, we used propan-2-ol as the hydrogen donor.
25. Ho, T. L.; Olah, G. A. Synthesis 1988, 91.
26. -1, and pore size = 30 Å).
27. 2 (7.85% Ni) under identical reaction conditions, which gives >95% yield in the 1st run, and 83% yield for the 6th run.