MERCURY(II) NITRATE 1
Mercury(II) Nitrate1
HO
Hg(NO3)2
Hg(NO3)2·H2O
NaCl
AcO
[7783-34-8] H2HgN2O7 (MW 342.63)
O
InChI = 1/Hg.2NO3.H2O/c;2*2-1(3)4;/h;;;1H2/q+2;2*-1;
CuCl
AcO
O (2)
InChIKey = KVICROHOONHSRH-UHFFFAOYAE
AcO
HgNO3
HgCl
(oxymercuration;4 9 amidomercuration;12,15 cyclopropane
cleavage;17,19 glycosylation23)
In a close analogy to alkenic alcohols, unsaturated hydroperox-
Alternate Name: mercuric nitrate.
ides react with Hg(NO3)2 to give cyclic peroxides which can be
ć%
Physical Data: mp 79 C; bp (dec); d 4.3 g cm-3.
further elaborated.8,11
Solubility: insol alcohol; very sol H2O (in dilute solutions forms
an insol basic salt); sol acetone, THF, DME, dioxane, NH3,
Amidomercuration.12 The mercuration of terminal or cyclic
HNO3, and other dilute acids.
alkenes with Hg(NO3)2 in MeCN12,13,14 affords amides via the
Form Supplied in: transparent, hygroscopic crystals with slight
Ritter reaction (eq 3).13 In contrast to the original, strong acid-
odor of HNO3.
mediated reaction, this modification is less prone to rearrange-
ć%
Drying: heating of the monohydrate to 55 60 C/10-2 mmHg.2,3
ments as it proceeds via a mercuronium ion.13,14 The reaction
Handling, Storage, and Precautions: acute poison. Exposure to
works with mono- and disubstituted double bonds but fails with
all mercury compounds is to be strictly avoided. Releases toxic
trisubstituted alkenes.14 Other HgII salts, namely (AcO)2Hg and
Hg fumes when heated to decomposition. Protect from light.
(CF3CO2)2Hg, are not satisfactory,13 apparently owing to their
lower electrophilicity.
Oxymercuration. The reactivity of Hg(NO3)2 is similar to
R
that of other HgII salts (acetate and trifluoroacetate)1 so that this
1. Hg(NO3)2
R
+ (3)
MeCN
reagent can be employed to achieve similar goals such as elec-
2. NaBH4 HN
trophilic additions. The nitrate is often superior to its relatives
COMe
(due to its higher electrophilicity) and may exhibit some vari-
ations in reactivity.4 Thus, for instance, conjugated dienes af-
Primary amides and TsNH2 similarly add across alkenic double
ford products of both 1,4- and 1,2-addition (eq 1).5,6 By contrast,
bonds to give the corresponding tosylamides.15 Asymmetric, in-
with Hg(OAc)2, only the 1,2-adduct is formed.5 In the absence of
tramolecular amidomercuration employing chiral carbamates has
stronger nucleophiles (in a nonnucleophilic solvent), nitratomer-
also been described (eq 4).16
curation has been observed.7 In the presence of Cl2 or Br2, the
HgX group in the original adduct is replaced by halogen.7
CCl3
O CCl3
O
Hg(NO3)2
1. Hg(NO3)2, MeOH *
N O
R*O N O MeCN
*
R*O
(4)
*
H
1 h
2. KCl
HgX
ClHg + ClHg (1)
OMe OMe
2:1
Cyclopropane Ring Opening.17 19 Mercury(II) nitrate ap-
pears to be the reagent of choice to accomplish stereospecific cor-
In the presence of Hydrogen Peroxide, alkenes are peroxymer-
ner opening19 of cyclopropyl derivatives (eqs 5 and 6);19,20 other
curated8 on reaction with Hg(NO3)2 as a result of H2O2 being a
HgII salts are less reactive.19,21 The reaction is also regioselective:
stronger nucleophile than NO3-.
the cleavage occurs between the most and the least substituted
Like other HgII salts, mercury(II) nitrate effects intramolecu-
carbon.19 The resulting organomercurials can be transmetalated
lar alkoxymercuration of unsaturated alcohols to produce oxy-
by transition metals (Pd, Mo, Cu) to accomplish a variety of in-
gen heterocycles (eq 2).9 Similar to other electrophilic additions,
teresting transformations.19
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
1. Hg(NO3)2
sources of hard halogen anion (NaCl, KBr, CuCl2, etc.). By con-
(5)
2. KBr
trast, quenching with soft reagents (e.g. CuCl) reliably affords the
stable chloromercurio compound. Excess of strong acids should OH
BrHg
O
Hg2+
be avoided as H+ catalyzes reversion.9,10
Avoid Skin Contact with All Reagents
2 MERCURY(II) NITRATE
Hg2+ Org. Chem. 1978, 43, 4048. (d) Porter, N. A.; Cudd, M. A.; Miller, R.
BrHg
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.;
1. Hg(NO3)2
Courtneidge, J. L.; Curtis, R. J.; Spencer, M. D., J. Chem. Soc., Perkin
(6)
2. KBr
Trans. 1 1990, 2951. (g) Bloodworth, A. J.; Spencer, M. D., Tetrahedron
O O
Lett. 1990, 31, 5513.
9. Ko%0ńovskż, P., Organometallics 1993, 12, 1969.
Glycosylation. Thioglycosides can be utilized as glyco- 10. For further discussion, see: Lilikarntakul, S.; Hirama, M.; Itô, S.,
Tetrahedron Lett. 1987, 28, 1207.
sylating agents in conjunction with anhydrous Hg(NO3)2 (or
11. Bloodworth, A. J.; Curtis, R. J.; Mistry N., J. Chem. Soc., Chem.
AgNO3).22 Although the reaction normally affords mixtures of
Commun. 1989, 954.
Ä…- and ²-glycosides,22 neighboring group participation can render
12. (a) Fry, A. J.; Simon, J. A., J. Org. Chem. 1982, 47, 5032. (b) Barluenga,
it stereoselective (for discussion and examples, see Mercury(II)
J.; Jimenez, C.; Najera, C.; Yus, M., J. Chem. Soc., Perkin Trans. 1 1983,
Chloride Cadmium Carbonate).23
591. (c) Barluenga, J.; Ferrera, L.; Najera, C.; Yus, M., Synthesis 1984,
831.
Miscellaneous. ²-Pinene undergoes a Ritter-type transforma-
13. Brown, H. C.; Kurek, J. T., J. Am. Chem. Soc. 1969, 91, 5647.
tion on reaction with Hg(NO3)2/MeCN24 to give the starting ma-
14. (a) Chow, D.; Robson, J. H.; Wright, G. F., Can. J. Chem. 1965, 43, 312.
terial for the synthesis of aristoteline25 and other indole alkaloids
(b) Geger, J.; Vogel, D., J. Prakt. Chem. 1969, 311, 737. (c) Kozikowski,
(eq 7);25 the reaction is not enantioselective and gives racemic
A. P.; Scripko, J., Tetrahedron Lett. 1983, 24, 2051. (d) Henning, R.;
products.24,25 Mercuration of enolizable ketones has little syn- Urbach, H., Tetrahedron Lett. 1983, 24, 5343.
thetic value: thus, for instance, acetone has been found to produce
15. Barluenga, J.; Jiménez, C.; Nájera, C.; Yus, M., J. Chem. Soc., Chem.
Commun. 1981, 670 and 1178.
a mixture of nine compounds.26
16. Harding, K. E.; Hollingsworth, D. R.; Reibenspies, J., Tetrahedron Lett.
1989, 30, 4775.
N
17. (a) Collum, D. B.; Mohamadi, F.; Hallock, J. S., J. Am. Chem. Soc. 1983,
Hg(NO3)2
(7) 105, 6882. (b) Collum, D. B.; Still, W. C.; Mohamadi, F., J. Am. Chem.
MeCN
Soc. 1986, 108, 2094.
O
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.;
Related Reagents. Mercury(II) Acetate; Mercury(II) Trifluo-
Eshnazarov, Yu. Kh.; Mochalov, S. S.; Shabarov, Yu. S.; Zefirov, N. S.,
roacetate; Mercury(II) Perchlorate.
Metalloorg. Khim. 1992, 5, 690 (Chem. Abstr. 1992, 117, 251 458j).
19. (a) Ko%0ńovskż, P.; `
rogl, J., J. Org. Chem. 1992, 57, 4565. (b) Ko%0ńovskż,
P.; `
rogl, J.; Gogoll, A.; Hanua
, V.; Poláa
ek, M., J. Chem. Soc., Chem.
Commun. 1992, 1086. (c) `
rogl, J.; Ko%0ńovskż, P., Tetrahedron Lett. 1992,
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rogl, J.; Pour, M.; Gogoll, A., J. Am. Chem.
R. C., Tetrahedron 1982, 38, 1713. (c) Larock, R. C. Organomercury
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Springer: Berlin, 1986.
42, 937.
2. Sokolov, V. I.; Reutov, O. A., Izv. Akad. Nauk SSSR, Ser. Khim. 1968,
21. Similar reactivity has been observed for isoelectronic TlIII: Ko%0Å„ovsky,
225.
P.; Pour, M.; Gogoll, A.; Hanua
, V.; Smr%0Å„ina, M., J. Am. Chem. Soc.
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A list of General Abbreviations appears on the front Endpapers