MERCURY(II) SULFATE

1

Mercury(II) Sulfate

HgSO

4

[7783-35-9]

HgO

4

S

(MW 296.66)

InChI = 1/Hg.H2O4S/c;1-5(2,3)4/h;(H2,1,2,3,4)/q+2;/p-

2/fHg.O4S/qm;-2

InChIKey = DOBUSJIVSSJEDA-KQKOKJCMCA

(converts alkynes and vinyl halides into ketones;

1

–

5

,

9

facilitates

conversion of glucals into furan derivatives

7

)

Alternate Name:

mercuric sulfate.

Physical Data:

mp dec; d 6.470 or 7.56 g cm

−3

.

Solubility:

insol H

2

O (dec into a yellow, basic sulfate); sol HCl,

hot dil H

2

SO

4

, HNO

3

, and conc solution of NaCl.

Form Supplied in:

white, odorless, monoclinic crystals, granules,

or powder.

Handling, Storage, and Precautions:

acute poison; exposure to

all mercury compounds is to be strictly avoided. Releases toxic
Hg fumes when heated to decomposition. Protect from light.

In combination with strong acids

1

–

4

or Dowex 50,

4

,

5

HgSO

4

is often employed as a catalyst for effecting hydration of alkynes,
which results in the formation of the corresponding ketones
(eq 1). This strategy has been used in the synthesis of 19-norpro-
gesterone

6

and histamine.

3b

(1)

HO

HO

O

1% HgSO

4

Dowex 50

MeOH, H

2

O

84%

D-Glucal has been found to produce (2R)-(1,2-dihydroxyethyl)-

furan when treated with HgSO

4

/H

2

SO

4

(eq 2).

7

Other glycals

undergo hydration or elimination.

8

HgSO

4

, H

2

SO

4

HO

HO

OH

O

OH

OH

(2)

H

2

O

95%

Similarly to other mercury(II) salts, HgSO

4

effects hydroly-

sis of vinyl halides to ketones

9

and allylic oxidation (Deigès

reaction).

10

Related Reagents. Mercury(II) Acetate.

1.

(a) Larock, R. C., Angew. Chem., Int. Ed. Engl. 1978, 17, 27. (b) Larock,
R. C., Tetrahedron 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.

Reicherst, J. S.; Nieuwland, J. A., Org. Synth., Coll. Vol. 1941, 1,
229.

3.

(a) Mondon, A., Justus Liebigs Ann. Chem. 1954, 585, 43. (b) Fraser, M.
M.; Raphael, R. A., J. Chem. Soc 1952, 226.

4.

Hajos, Z. G.; Doebel, K. J.; Goldberg, M. W., J. Org. Chem. 1964, 29,
2527.

5.

(a) Newman, M. S., J. Am. Chem. Soc. 1953, 75, 4740. (b) Billimoria, J.
D.; MacLagan, N. F., J. Chem. Soc 1954, 3257.

6.

Bucourt, R.; Tessier, J.; Nominé, G., Bull. Soc. Chem. Fr., Part 2 1963,
1923.

7.

Hauser, F. M.; Ellenberger, S. R.; Ellenberger, W. P., Tetrahedron Lett.
1988, 29, 4939.

8.

Gonzalez, F.; Lesage, S.; Perlin, A. S., Carbohydr. Res. 1975, 42,
267.

9.

Arzoumanian, H.; Metzger, J., J. Organomet. Chem. 1973, 57, C1.

10.

For a review, see: Arzoumanian, H.; Metzger, J., Synthesis 1971,
527.

Pavel Ko˘covský

University of Leicester, Leicester, UK

Avoid Skin Contact with All Reagents