MERCURY(II) NITRATE

1

Mercury(II) Nitrate

1

Hg(NO

3

)

2

·H

2

O

[7783-34-8]

H

2

HgN

2

O

7

(MW 342.63)

InChI = 1/Hg.2NO3.H2O/c;2*2-1(3)4;/h;;;1H2/q+2;2*-1;
InChIKey = KVICROHOONHSRH-UHFFFAOYAE

(oxymercuration;

4

–

9

amidomercuration;

12,15

cyclopropane

cleavage;

17,19

glycosylation

23

)

Alternate Name:

mercuric nitrate.

Physical Data:

mp 79

◦

C; bp (dec); d 4.3 g cm

−

3

.

Solubility:

insol alcohol; very sol H

2

O (in dilute solutions forms

an insol basic salt); sol acetone, THF, DME, dioxane, NH

3

,

HNO

3

, and other dilute acids.

Form Supplied in:

transparent, hygroscopic crystals with slight

odor of HNO

3

.

Drying:

heating of the monohydrate to 55–60

◦

C/10

−

2

mmHg.

2,3

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.

Oxymercuration. The reactivity of Hg(NO

3

)

2

is similar to

that of other Hg

II

salts (acetate and trifluoroacetate)

1

so that this

reagent can be employed to achieve similar goals such as elec-
trophilic additions. The nitrate is often superior to its relatives
(due to its higher electrophilicity) and may exhibit some vari-
ations in reactivity.

4

Thus, for instance, conjugated dienes af-

ford products of both 1,4- and 1,2-addition (eq 1).

5,6

By contrast,

with Hg(OAc)

2

, only the 1,2-adduct is formed.

5

In the absence of

stronger nucleophiles (in a nonnucleophilic solvent), nitratomer-
curation has been observed.

7

In the presence of Cl

2

or Br

2

, the

HgX group in the original adduct is replaced by halogen.

7

ClHg

OMe

ClHg

1. Hg(NO

3

)

2

, MeOH

OMe

(1)

+

2:1

2. KCl

In the presence of Hydrogen Peroxide, alkenes are peroxymer-

curated

8

on reaction with Hg(NO

3

)

2

as a result of H

2

O

2

being a

stronger nucleophile than NO

3

−

.

Like other Hg

II

salts, mercury(II) nitrate effects intramolecu-

lar alkoxymercuration of unsaturated alcohols to produce oxy-
gen heterocycles (eq 2).

9

Similar to other electrophilic additions,

oxymercuration is a priori a reversible reaction. It has been shown
that selecting the method of quenching is crucial to minimize the
reversion. Thus, oxymercuration products with rigid, antiperipla-
nar arrangement of the C–HgX and C–O bonds (eq 2) imme-
diately revert back to the starting material upon treatment with
sources of hard halogen anion (NaCl, KBr, CuCl

2

, etc.). By con-

trast, quenching with soft reagents (e.g. CuCl) reliably affords the
stable chloromercurio compound. Excess of strong acids should
be avoided as H

+

catalyzes reversion.

9,10

HO

AcO

AcO

HgCl

O

O

HgNO

3

AcO

(2)

Hg(NO

3

)

2

CuCl

NaCl

In a close analogy to alkenic alcohols, unsaturated hydroperox-

ides react with Hg(NO

3

)

2

to give cyclic peroxides which can be

further elaborated.

8,11

Amidomercuration.

12

The mercuration of terminal or cyclic

alkenes with Hg(NO

3

)

2

in MeCN

12,13,14

affords amides via the

Ritter reaction (eq 3).

13

In contrast to the original, strong acid-

mediated reaction, this modification is less prone to rearrange-
ments as it proceeds via a mercuronium ion.

13,14

The reaction

works with mono- and disubstituted double bonds but fails with
trisubstituted alkenes.

14

Other Hg

II

salts, namely (AcO)

2

Hg and

(CF

3

CO

2

)

2

Hg, are not satisfactory,

13

apparently owing to their

lower electrophilicity.

1. Hg(NO

3

)

2

R

HN

R

COMe

+

(3)

MeCN

2. NaBH

4

Primary amides and TsNH

2

similarly add across alkenic double

bonds to give the corresponding tosylamides.

15

Asymmetric, in-

tramolecular amidomercuration employing chiral carbamates has
also been described (eq 4).

16

R*O

N
H

O

O

CCl

3

O

N

R*O

O

CCl

3

HgX

(4)

*

*

*

1 h

Hg(NO

3

)

2

MeCN

Cyclopropane Ring Opening.

17

–

19

Mercury(II) nitrate ap-

pears to be the reagent of choice to accomplish stereospecific cor-
ner opening

19

of cyclopropyl derivatives (eqs 5 and 6);

19,20

other

Hg

II

salts are less reactive.

19,21

The reaction is also regioselective:

the cleavage occurs between the most and the least substituted
carbon.

19

The resulting organomercurials can be transmetalated

by transition metals (Pd, Mo, Cu) to accomplish a variety of in-
teresting transformations.

19

(5)

OH

BrHg

1. Hg(NO

3

)

2

O

Hg

2+

2. KBr

Avoid Skin Contact with All Reagents

2

MERCURY(II) NITRATE

(6)

O

O

1. Hg(NO

3

)

2

BrHg

Hg

2+

2. KBr

Glycosylation.

Thioglycosides can be utilized as glyco-

sylating agents in conjunction with anhydrous Hg(NO

3

)

2

(or

AgNO

3

).

22

Although the reaction normally affords mixtures of

α

- and β-glycosides,

22

neighboring group participation can render

it stereoselective (for discussion and examples, see Mercury(II)
Chloride–Cadmium Carbonate).

23

Miscellaneous. β-Pinene undergoes a Ritter-type transforma-

tion on reaction with Hg(NO

3

)

2

/MeCN

24

to give the starting ma-

terial for the synthesis of aristoteline

25

and other indole alkaloids

(eq 7);

25

the reaction is not enantioselective and gives racemic

products.

24,25

Mercuration of enolizable ketones has little syn-

thetic value: thus, for instance, acetone has been found to produce
a mixture of nine compounds.

26

(7)

O

N

Hg(NO

3

)

2

MeCN

Related Reagents. Mercury(II) Acetate; Mercury(II) Trifluo-

roacetate; Mercury(II) Perchlorate.

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.

Sokolov, V. I.; Reutov, O. A., Izv. Akad. Nauk SSSR, Ser. Khim. 1968,
225.

3.

Fieser & Fieser 1982

, 10, 254.

4.

(a) Brown, H. C.; Kurek, J. T.; Rei, M. H.; Thompson, K. L., J. Org.
Chem. 1984

, 49, 2551. (b) Kartashov, V. R.; Sokolova, T. N.; Vasil’eva,

O. V.; Timofeev, I. V.; Grishin, Yu. K.; Bazhenok, D. V.; Zefirov, N. S.,
Zh. Org. Khim. 1990

, 26, 1800.

5.

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Chem. Commun. 1976

, 578.

6.

Nikanorov, V. A.; Rozenberg, V. I.; Svitan’ko, Z. P.; Reutov, O. A., Dokl.
Akad. Nauk SSSR 1987

, 293, 634.

7.

(a) Bloodworth, A. J.; Cooper, P., J. Chem. Soc., Chem. Commun. 1986,
709. (b) Barluenga, J.; Martinez-Gallo, J. M.; Nájera, C.; Yus, M., J.
Chem. Soc., Chem. Commun. 1985

, 1422 and J. Chem. Res. (S) 1986,

274.

8.

(a) Bloodworth, A. J.; Loevitt, M. E., J. Chem. Soc., Chem. Commun.
1976, 94. (b) Bloodworth, A. J.; Griffin, I. M., J. Chem. Soc., Perkin
Trans. 1 1975

, 195. (c) Nixon, J. R.; Cudd, M. A.; Porter, N. A., J.

Org. Chem. 1978

, 43, 4048. (d) Porter, N. A.; Cudd, M. A.; Miller, R.

W.; McPhail, A. T., J. Am. Chem. Soc. 1980, 102, 414. (e) Porter, N.
A.; Zuraw, P. J., J. Org. Chem. 1984, 49, 1345. (f) Bloodworth, A. J.;
Courtneidge, J. L.; Curtis, R. J.; Spencer, M. D., J. Chem. Soc., Perkin
Trans. 1 1990

, 2951. (g) Bloodworth, A. J.; Spencer, M. D., Tetrahedron

Lett. 1990

, 31, 5513.

9.

Koˇcovský, P., Organometallics 1993, 12, 1969.

10.

For further discussion, see: Lilikarntakul, S.; Hirama, M.; Itô, S.,
Tetrahedron Lett. 1987

, 28, 1207.

11.

Bloodworth, A. J.; Curtis, R. J.; Mistry N., J. Chem. Soc., Chem.
Commun. 1989

, 954.

12.

(a) Fry, A. J.; Simon, J. A., J. Org. Chem. 1982, 47, 5032. (b) Barluenga,
J.; Jimenez, C.; Najera, C.; Yus, M., J. Chem. Soc., Perkin Trans. 1 1983,
591. (c) Barluenga, J.; Ferrera, L.; Najera, C.; Yus, M., Synthesis 1984,
831.

13.

Brown, H. C.; Kurek, J. T., J. Am. Chem. Soc. 1969, 91, 5647.

14.

(a) Chow, D.; Robson, J. H.; Wright, G. F., Can. J. Chem. 1965, 43, 312.
(b) Geger, J.; Vogel, D., J. Prakt. Chem. 1969, 311, 737. (c) Kozikowski,
A. P.; Scripko, J., Tetrahedron Lett. 1983, 24, 2051. (d) Henning, R.;
Urbach, H., Tetrahedron Lett. 1983, 24, 5343.

15.

Barluenga, J.; Jiménez, C.; Nájera, C.; Yus, M., J. Chem. Soc., Chem.
Commun. 1981

, 670 and 1178.

16.

Harding, K. E.; Hollingsworth, D. R.; Reibenspies, J., Tetrahedron Lett.
1989, 30, 4775.

17.

(a) Collum, D. B.; Mohamadi, F.; Hallock, J. S., J. Am. Chem. Soc. 1983,
105

, 6882. (b) Collum, D. B.; Still, W. C.; Mohamadi, F., J. Am. Chem.

Soc. 1986

, 108, 2094.

18.

(a) Bandaev, S. G.; Eshnazarov, Yu. Kh.; Nasyrov, I. M.; Mochalov, S.
S.; Shabarov, Yu. S., Zh. Org. Khim. 1988, 24, 733. (b) Bandaev, S. G.;
Eshnazarov, Yu. Kh.; Mochalov, S. S.; Shabarov, Yu. S.; Zefirov, N. S.,
Metalloorg. Khim. 1992

, 5, 690 (Chem. Abstr. 1992, 117, 251 458j).

19.

(a) Koˇcovský, P.; Šrogl, J., J. Org. Chem. 1992, 57, 4565. (b) Koˇcovský,
P.; Šrogl, J.; Gogoll, A.; Hanuš, V.; Polášek, M., J. Chem. Soc., Chem.
Commun. 1992

, 1086. (c) Šrogl, J.; Koˇcovský, P., Tetrahedron Lett. 1992,

33

, 5991. (d) Koˇcovský, P.; Šrogl, J.; Pour, M.; Gogoll, A., J. Am. Chem.

Soc. 1994

, 116, 186. (e) Koˇcovský, P., Grech, J. M.; Mitchell, W. L., J.

Org. Chem. 1995

, 60, 482.

20.

Langbein, G.; Siemann, H.-J.; Gruner, I.; Müller, C., Tetrahedron 1986,
42

, 937.

21.

Similar reactivity has been observed for isoelectronic Tl

III

: Koˇcovsky,

P.; Pour, M.; Gogoll, A.; Hanuš, V.; Smrˇcina, M., J. Am. Chem. Soc.
1990, 112, 6735.

22.

Hanessian, S.; Bacquet, C.; Lehong, N., Carbohydr. Res. 1980, 80, C17.

23.

(a) Wiesner, K.; Tsai, T. Y. R.; Jin, H., Helv. Chim. Acta 1985, 68, 300.
(b) Wiesner, K.; Tsai, T. Y. R., Pure Appl. Chem. 1986, 58, 799.

24.

(a) Delpech, B.; Khuong-Huu, Q., Tetrahedron Lett. 1973, 1533.
(b) Delpech, B.; Khuong-Huu, Q., J. Org. Chem. 1978, 43, 4898.
(c) Rappoport, Z.; Winstein, S.; Young, W. G., J. Am. Chem. Soc. 1972,
94

, 2320.

25.

(a) Mirand, C.; Massiot, G.; Lévy, J., J. Org. Chem. 1982, 47, 4169.
(b) Stevens, R. V.; Kenney, P. M., J. Chem. Soc., Chem. Commun. 1983,
384.

26.

Johnson, F. A.; Perry, W. D., Organometallics 1989, 8, 2646.

Pavel Koˇcovský

University of Leicester, Leicester, UK

A list of General Abbreviations appears on the front Endpapers