Error message

  • Deprecated function: Unparenthesized `a ? b : c ? d : e` is deprecated. Use either `(a ? b : c) ? d : e` or `a ? b : (c ? d : e)` in include_once() (line 1439 of /home/science2016/public_html/includes/bootstrap.inc).
  • Deprecated function: Array and string offset access syntax with curly braces is deprecated in include_once() (line 3557 of /home/science2016/public_html/includes/bootstrap.inc).

Catalytic Oxidation of Ethylene Glycol by Dioxygen in Alkaline Medium. The New Example of One-stage Oxidative Cleavage of C–C Bond

Andrei Sakharov, Pavel Sakharov and Gennady Zaikov
Affiliation: 
N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences 4, Kosygin str., 119334 Moscow, Russia
DOI: 
https://doi.org/10.23939/chcht06.01.019
AttachmentSize
PDF icon full_text.pdf128.78 KB

Keywords:

Abstract: 
Reaction of low temperature oxidations of ethylene glycol (EG) by molecular oxygen in the presence of salts of bivalent copper and alkali both in water and in waterless solutions was investigated. It was found that at low (close to room) temperatures and in waterless solutions the basic product of EG oxidation is formic acid. Rise in the temperature from 290–315 K to 350–360 K or reaction flow in water-containing solutions leads to sharp change of reaction direction. EG in these conditions is oxidized with primary formation of glycolic acids salts. The change in the reaction direction is connected, apparently, with decrease in the stability of chelate complexes of Cu2+ ions with dianionic form of EG. The mechanism of glycolic acids formation includes, possibly, a stage of two-electronic reduction of О2 in the reaction of dioxygen with monoanionic forms of EG, coordinated on Cu2+ centers.
References: 

[1] Sakharov A., Mazaletskaya L. and Skibida I.: Kinetika i Kataliz, 2001, 42, 730.

[2] Skibida I. and Sakharov A.: Ross. Khim. Zh., 1995, 39, 14.

[3] Sakharov A. and Skibida I.: Kinetika i Kataliz, 1988, 29, 118.

[4] Sakharov A., Silakhtaryan N. and Skibida I.: Kinetika i Kataliz, 1996, 37, 393.

[5] Sakharov A. and Skibida I.: Khim. Fizika, 2001, 20, 101.

[6] Skibida I. and Sakharov A.: Catalysis Today, 1996, 27, 187.
https://doi.org/10.1016/0920-5861(95)00186-7

[7] Sakharov A. and Skibida I.: Dokl. Phys. Khim., 2000, 372, 785.

[8] Emanuel N., Denisov E. and Maizus Z.: Liquid-Phase Oxidation of Hydrocarbons. Plenum Press, New York 1967.

[9] Habermann N., Jung G., Klaassen M. and Klufers P.: Chem. Ber., 1992, 125, 809.
https://doi.org/10.1002/cber.19921250409

[10] Demmin T., Swerdloff M. and Rogic M.: J. Amer. Chem. Soc., 1981, 103, 5795.
https://doi.org/10.1021/ja00409a030

[11] Russell G., Bemis A., Geels E. et al.: Adv. Chem. Ser., 1965, 51, 112.
https://doi.org/10.1021/ba-1965-0051.ch010

[12] Skibida I. and Sakharov A.: [in:] Centi G. and Trifiro F. (Eds). New Developments in Selective Oxidation. Elsevier Science Publishers, Amsterdam 1990.

[13] Jones R., Summervile D. and Basolo F.: Chem. Rev., 1975, 79, 139.
https://doi.org/10.1021/cr60318a002