Mercury(II) Acetate-Ethylenediaminetetraacetic Acid


[1600-27-7]  · C4H6HgO4  · Mercury(II) Acetate-Ethylenediaminetetraacetic Acid  · (MW 318.69) (EDTA)

[60-00-4]  · C10H16N2O8  · Mercury(II) Acetate-Ethylenediaminetetraacetic Acid  · (MW 292.28)

(dehydrogenation of tertiary amines,2 oxidation of tertiary amines to amides3)

Physical Data: Hg(OAc)2: mp 179-182 °C. EDTA: mp 250 °C (dec).

Solubility: sol CH2Cl2, AcOH; slightly sol alcohols; insol benzene, hexane, etc.

Preparative Method: by simply mixing the two commercially available reagents in an appropriate solvent.

Handling, Storage, and Precautions: acute poison. Hg(OAc)2 is easily absorbed through the skin and is corrosive. Exposure to all mercury compounds is to be strictly avoided. Releases toxic Hg fumes when heated to decomposition. Protect from light.

The addition of EDTA to HgII salts has a beneficial effect on the selectivity of dehydrogenation of tertiary amines (see also Mercury(II) Acetate).1 Thus papaverin has been reported to produce a mixture of two dehydrogenated products (eq 1) when treated with equal amounts of (AcO)2Hg and EDTA. By contrast, in the absence of EDTA, papaverin is cleaved at the methylene bridge.2 Amine oxidation has also been employed in the construction of ajmalicine (eq 2)3 and yohimbine.4 In this case, only 2 equiv of HgII are required as opposed to 5 equiv if (AcO)2Hg is used alone.4

The mixture of (AcO)2Hg and EDTA can also convert oxidizable tertiary amines into lactams (eq 3).5

Related Reagents.

Mercury(II) Acetate; Mercury(II) Trifluoroacetate.

1. (a) Larock, R. C. AG(E) 1978, 17, 27. (b) Larock, R. C. T 1982, 38, 1713. (c) Larock, R. C. Organomercury Compounds in Organic Synthesis; Springer: Berlin, 1985. (d) Larock, R. C. Solvomercuration/Demercuration Reactions in Organic Synthesis; Springer: Berlin, 1986.
2. (a) Knabe, J. AP 1959, 292, 416. (b) Knabe, J. AP 1960, 293, 121. (c) Knabe, J.; Grund, G. AP 1963, 296, 854. (d) Knabe, J.; Roloff, H. CB 1964, 97, 3452.
3. Gutzwiller, J.; Pizzolato, G.; Uskoković, M. JACS 1971, 93, 5907.
4. Stork, G.; Guthikonda, R. N. JACS 1972, 94, 5109.
5. (a) Möhrle, H. AP 1964, 297, 474. (b) Fujii, T.; Yoshifuji, S. CPB 1972, 20, 1451. (c) Fujii, T.; Yoshifuji, S.; Michishita, K.; Mitsukuchi, M.; Yoshida, K. CPB 1973, 21, 2695. (d) Wenkert, E.; Angell, E. C. SC 1988, 18, 1331.

Pavel Ko&cbreve;ovský

University of Leicester, UK

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