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Sabatier-Senderens Reduction

Published Online: 15 SEP 2010

DOI: 10.1002/9780470638859.conrr554

Comprehensive Organic Name Reactions and Reagents

Comprehensive Organic Name Reactions and Reagents

How to Cite

2010. Sabatier-Senderens Reduction. Comprehensive Organic Name Reactions and Reagents. 554:2454–2457.

Publication History

  1. Published Online: 15 SEP 2010

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Abstract

  1. Top of page
  2. General Description of the Reaction
  3. General Reaction Scheme
  4. Proposed Mechanisms
  5. Modification
  6. Applications
  7. Related Reactions
  8. Cited Experimental Examples
  9. References

Sabatier and Senderens established nickel-based hydrogenation and converted the unsaturated organic molecules into corresponding saturated compounds by passing the vapor of organic molecules and hydrogen over hot, finely divided nickel and is know as Sabatier–Senderens reduction. Purity of nickel and reaction temperature are the most critical parameters for this reaction. This reaction is different from reductions using nascent hydrogen as the reducing agent, such as amalgam of sodium in alcohol (alkaline condition) and or zinc or tin with hydrochloric acid (acidic medium). Further the study finds the successful conversion of oleic acid into stearic acid, acetone to isopropanol, carbon monoxide into methane or a gaseous mixture rich in methane, phenol and p-cresol into cyclohexanol and p-methylcyclohexanol, etc. It is also found that the reduced cobalt, iron, copper, and powdered platinum have catalytic activities similar to nickel and reduce the naphthalene into tetralin.

1 General Description of the Reaction

  1. Top of page
  2. General Description of the Reaction
  3. General Reaction Scheme
  4. Proposed Mechanisms
  5. Modification
  6. Applications
  7. Related Reactions
  8. Cited Experimental Examples
  9. References

This reaction can be traced back to Debus's transformation of hydrocyanic acid into methylamine over platinum in 1863, De Wilde's hydrogenation of acetylene into ethylene and ethane in 1874, 1 and Mond's extensive work from 1890 to 1895. 2 However, it was in 1899 that Sabatier and Senderens established nickel-based hydrogenation 3 and converted the unsaturated organic molecules (e.g., ketones, aldehydes, alkenes and aromatics) into corresponding saturated compounds (i.e., alcohols, hydrocarbons) by passing the vapor of organic molecules and hydrogen over hot, finely divided nickel.

This nickel-based vapor phase hydrogenation became one of the most practically useful reactions and won Sabatier the Nobel Prize in 1912. 1 It is generally known as the Sabatier-Senderens reduction. 4

This reaction is different from reductions using nascent hydrogen as the reducing agent, such as amalgam of sodium in alcohol (alkaline condition) and or zinc or tin with hydrochloric acid (acidic medium). In this reaction, the purity of nickel and reaction temperature are found to be critical for successful hydrogenation. 1 For example, trace amounts of sulfur, bromine, or iodine will deactivate the nickel catalyst; in addition, it has been found that each hydrogenation process takes place only within a well-defined temperature range, 1 as evidenced by the hydrogenation of benzene to cyclohexane at temperatures ranging from 70° to 190°C, with an optimal temperature between 170° and 190°C, and the further reduction of benzene to methane accompanied by the deposited carbon on nickel at temperatures > 300°C. 5 Under the correct hydrogenation conditions, Sabatier et al. successfully converted oleic acid into stearic acid, acetone to isopropanol, carbon monoxide into methane or a gaseous mixture rich in methane, phenol and p-cresol into cyclohexanol and p-methylcyclohexanol, benzene to cyclohexane, and naphthalene to tetralin, etc. 1 All these reductions afford the expected products, except for the hydrogenation of naphthalene; other reducing methods may lead to the unexpected products, as demonstrated by the reduction of benzene with hydroiodic acid at 250°C to afford methyl cyclopentane, 1 and the hydrogenation of only one phenyl group of triphenylcarbinol over the Adam's platinum oxide catalyst. 6 At the same time, Sabatier et al. also found that the reduced cobalt, iron, copper, and powdered platinum have catalytic activities similar to nickel. Copper in particular is known to be superior to nickel during the hydrogenation of nitrobenzene to aniline, due to its insensitivity to accidental impurities. 1 It is interesting that Sabatier was able to reduce naphthalene into only tetralin, 7, 8 other researchers have successfully converted naphthalene into decalin over nickel. 9

3 Proposed Mechanisms

  1. Top of page
  2. General Description of the Reaction
  3. General Reaction Scheme
  4. Proposed Mechanisms
  5. Modification
  6. Applications
  7. Related Reactions
  8. Cited Experimental Examples
  9. References

Although Sabatier proposed that the hydrogenation occurs via nickel perhydride (NiH2) from the well-prepared and pure nickel, via a poorer hydride from nickel with impurities, or at a very high temperature, 1 it is clear that nickel can absorb a great deal of hydrogen, as indicated by the current use of the nickel hydrogen (Ni/H2) battery cell. 10 On the other hand, the hydrogenation of carbon monoxide into methane is assumed to involve the formation of an intermediate complex, CHxO, on the nickel surface 11 or an active carbon intermediate from the dissociation of carbon monoxide, 11 which is hydrogenated into methane. In addition, it has been proposed that hydrogen or non-hydrogen gas assists the dissociation of carbon monoxide. (11a) Alternatively, the Sabatier-Senderens reduction may proceed in another route, in which nickel inserts into hydrogen via oxidative addition, and the resulting intermediate forms a coordination complex with carbon monoxide; then a series of transformations, including acyl transfer and reductive elimination, take place until the formation of methane. In addition, the deposited carbon on nickel might be caused by dehydrogenation occurring at an elevated temperature. Displayed here is a tentative mechanism (next page) to illustrate the formation of methane from carbon monoxide.

original image

4 Modification

  1. Top of page
  2. General Description of the Reaction
  3. General Reaction Scheme
  4. Proposed Mechanisms
  5. Modification
  6. Applications
  7. Related Reactions
  8. Cited Experimental Examples
  9. References

In terms of hydrogenation, the Sabatier-Senderens reduction has been extensively modified, as shown by the Fischer-Tropsch Synthesis (or process), the Adkins Catalyst, and Raney-Nickel Catalyst. In addition, the silica black-supported nickel catalyst, 12 and nickel-based complex reducing agents (Nic, e.g. NaH-RONa-Ni(OAc)2), 13 have also been developed, the latter is a heterogeneous hydrogenation catalyst that works at atmospheric pressure.

5 Applications

  1. Top of page
  2. General Description of the Reaction
  3. General Reaction Scheme
  4. Proposed Mechanisms
  5. Modification
  6. Applications
  7. Related Reactions
  8. Cited Experimental Examples
  9. References

This reaction has an important application in organic synthesis, especially in the transformation of carbon monoxide or carbon dioxide into organic compounds.

7 Cited Experimental Examples

  1. Top of page
  2. General Description of the Reaction
  3. General Reaction Scheme
  4. Proposed Mechanisms
  5. Modification
  6. Applications
  7. Related Reactions
  8. Cited Experimental Examples
  9. References
original image

To a reaction flask were added 50 mL cotton seed oil and 2.5 g silica black-supported nickel catalyst, and the mixture was agitated until complete suspension was attained. Then the mixture was stirred with a mechanical stirrer for 10 min, and the flask was placed in a furnace and connected with a hydrogen tube that reached to the bottom of the flask. The flask was maintained at 180°C for different time intervals, while hydrogen was bubbled through at the rate of 400--450 bubbles/min at ordinary atmospheric pressure. At the end of hydrogenation period, the experiment was stopped, and the product was filtered through asbestos at 140°C. The degree of unsaturation for the oil was verified by iodine numbers.

Other references related to the Sabatier-Senderens reduction are cited in the literature. 14

References

  1. Top of page
  2. General Description of the Reaction
  3. General Reaction Scheme
  4. Proposed Mechanisms
  5. Modification
  6. Applications
  7. Related Reactions
  8. Cited Experimental Examples
  9. References
  • 1
    Sabatier, P., in Nobel Lectures, Chemistry 1901–1921, Elsevier Publishing, Amsterdam, 1966.
  • 2
    (a) Mond, L.; Langer, C. and Quincke, F., J. Chem. Soc., 1890, 57, 749. (b) Mond, L.; Langer, C. and Quincke, F., Chem. News, 1890, 62, 97. (c) Mond, L. and Langer, C., J. Soc. Chem., Trans., 1891, 59, 1090. (d) Mond, L. and Quincke, F., J. Chem. Soc., Trans., 1891, 59, 604. (e) Mond, L., J. Soc. Chem. Ind., 1895, 14, 945.
  • 3
    Sabatier, P. and Senderens, J. B., Compt. Rend., 1899, 128, 1173.
  • 4
    Sabatier, P. and Mailhe, A., Ann. Chim. Phys., 1908, 10, 527.
  • 5
    Bancroft, W. D. and George, A. B., J. Phys. Chem., 1931, 35, 2219.
  • 6
    Levene, P. A. and Stevens, P. G., J. Biol. Chem., 1930, 89, 471.
  • 7
    Sabatier, P. and Senderens, J. B., Compt. Rend., 1901, 132, 1254.
  • 8
    (a) Lush, E. I., Brit. Pat., Jan. 24, 1929, 304, 403. (b) Lush, E. I., J. Soc. Chem. Ind., 1927, 46, 454.
  • 9
    (a) Cerveny, W. J. and Corson, B. B., J. Am. Chem. Soc., 1944, 66, 2123. (b) Smith, H. M.; Rall, H. T. and Grandone, P., U. S. Bureau of Mines. Tech. Paper, 1938, 587 (c) Leroux, H., Compt. Rend., 1904, 139, 672.
  • 10
    (a) Button, R.; Pease, G.; Birchenough, A. and Petrik, J., Ni/H Cell Short Circuit Test, Electrical Systems Division, NASA LeRC, Preliminary Test Report 14, Apr. 20, 1992. (b) Sobornitskii, V. I. and Krapivnyi, N. G., Material Science, 1992, 27, 239. (c) Visscher, W. and Barendrecht, E., J. Appl. Electrochem., 1980, 10, 269.
  • 11
    (a) Sehested, J.; Dahl, S.; Jacobsen, J. and Rostrup-Nielsen, J. R., J. Phys. Chem. B, 2005, 109, 2432. (b) Lee, P.-I. and Schwarz, J. A., Ind. Eng. Chem. Proc. Des. Dev., 1986, 25, 76.
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    Williams, L. R. and Jacobson, C. A., Ind. Eng. Chem., 1934, 26, 800.
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    Brunet, J.-J.; Gallois, P. and Caubere, P., J. Org. Chem., 1980, 45, 1937.
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    (a) Samuel, P., Bull. Catal. Soc. India, 2003, 2, 82. (b) Grabke, H. J., Mater. Corr., 1998, 49, 317. (c) Alstrup, I., J. Catal., 1995, 151, 216. (d) Coenen, J. W. E.; van Nisselroy, P. F. M. T.; de Croon, M. H. J. M.; van Dooren, P. F. H. A. and van Meerten, R. Z. C., Appl. Catal., 1986, 25, 1. (e) McNaughton, N. J.; Abell, P. I.; Wright, I. P.; Fallick, A. E. and Pillinger, C. T., J. Phys. E.: Sci. Instrum., 1983, 16, 505. (f) Spencer, N. D. and Somorjai, G. A., Rep. Prog. Phys., 1983, 46, 1. (g) Harms, A.; Höhlein, B.; Jørn, E. and Skov, A., Oil Gas J., 1980, 78, 120. (h) Goodmann, D. W.; Kelley, R. D.; Madey, T. E. and White, J. M., J. Catal., 1980, 64, 479. (i) Rostrup-Nielsen, J. R. and Pedersen, K., J. Catal., 1979, 59, 395. (j) Bresler, S. A. and Ireland, J. D., Chem. Eng., 1972, 1, 94. (k) Gueron, J. and Magat, M., Ann. Rev. Phys. Chem., 1971, 22, 1. (l) Shuikin, N. I. and Erivanskaya, L. A., Russ. Chem. Rev., 1960, 29, 309. (m) Bailey, A. E., Ind. Eng. Chem., 1952, 44, 990. (n) Litkenhous, E. E., Ind. Eng. Chem., 1939, 31, 1059. (o) Litkenhous, E. E. and Mann, C. A., Ind. Eng. Chem., 1937, 29, 934. (p) Adkins, H.; Cramer, H. I. and Connor, R., J. Am. Chem. Soc., 1931, 53, 1402. (q) Adkins, H. and Cramer, H. I., J. Am. Chem. Soc., 1930, 52, 4349. (r) Adkins, H.; Connor, R. and Cramer, H., J. Am. Chem. Soc., 1930, 52, 5192. (s) Sabatier, P., Ind. Eng. Chem., 1926, 1005. (t) Gauger, A. W., J. Am. Chem. Soc., 1924, 46, 674. (u) Sabatier, P. and Senderens, J. B., Bull. Soc. Chim., 1907, [4] 1, 107. (v) Sabatier, P. and Senderens, J. B., Ann. Chim. Phys., 1905, [8] 4, 368. (w) Sabatier, P. and Mailhe, A., Compt. Rend., 1904, 139, 345. (x) Sabatier, P. and Senderens, J. B., Compt. Rend., 1902, 134, 514. (y) Sabatier, P. and Senderens, J. B., Compt. Rend., 1901, 132, 1255. (z) Sabatier, P. and Senderens, J. B., Compt. Rend., 1901, 132, 210.