MERCURY(II) CHLORIDE SILVER(I) NITRITE 1
Mercury(II) Chloride Silver(I) Nitrite general route to nitroalkenes4 and has been employed in the
synthesis of 3-nitrocycloalkenones5 and (E)-2-nitrovinyltri-
methylsilane.6 However, better yields are usually obtained if
HgCl2 AgNO2
AgNO2/I2 is used instead.7
(HgCl2)
R R R
[7487-94-7] Cl2Hg (MW 271.49)
HgNO2 NaOH
HgCl2
InChI = 1/2ClH.Hg/h2*1H;/q;;+2/p-2/f2Cl.Hg/h2*1h;/q2*-1;m
(1)
InChIKey = LWJROJCJINYWOX-ZZJRNXLTCY AgNO2 H2O
NO2 NO2
(AgNO2)
[7783-99-5] AgNO2 (MW 153.88)
Bu
InChI = 1/Ag.HNO2/c;2-1-3/h;(H,2,3)/q+1;/p-1/fAg.NO2/qm;-1
NO2
InChIKey = KKKDGYXNGYJJRX-QGMACRPXCX
NO2 O2N
77% 80% 71%
(nitromercuration1 4 and synthesis of nitroalkenes from
alkenes4,5)
Form Supplied in: white, odorless needles or powder (both
1. (a) Larock, R. C., Angew. Chem., Int. Ed. Engl. 1978, 17, 27. (b) Larock,
reagents).
R. C., Tetrahedron 1982, 38, 1713. (c) Larock, R. C. Organomercury
Handling, Storage, and Precautions: acute poison. Exposure to
Compounds in Organic Synthesis; Springer: Berlin, 1985. (d) Larock,
R. C. Solvomercuration/Demercuration Reactions in Organic Synthesis;
all mercury compounds is to be strictly avoided. Releases toxic
Springer: Berlin, 1986.
Hg fumes when heated to decomposition. Protect from light.
2. Bachman, G. B.; Whitehouse, M. L., J. Org. Chem. 1967, 32, 2303.
3. Bloodworth, A. J.; Griffin, I. M., J. Chem. Soc., Perkin Trans. 1 1975,
695.
Mixing Mercury(II) Chloride and Silver(I) Nitrite generates
4. Corey, E. J.; Estreicher, H., J. Am. Chem. Soc. 1978, 100, 6294.
Hg(NO2)2 in situ, which reacts with alkenes to give nitromercu-
ration products with high regio- and stereoselectivity (eq 1).1 3 5. Vankar, Y. D.; Bawa, A., Synth. Commun. 1985, 15, 1253.
6. Ali, S. M.; Matsuda, Y.; Tanimoto, S., Synthesis 1988, 805.
The reaction with norbornene occurs without rearrangement,
7. Sy, W.-W.; By, A. W., Tetrahedron Lett. 1985, 26, 1193.
indicating that carbocationic character in the transition state is
little developed. On treatment with a base (NaOH or R3N), the
Ø
Pavel Kocovskż
primary adducts undergo an elimination reaction to afford
University of Leicester, Leicester, UK
nitroalkenes (eq 1).4 This two-step transformation represents a
Avoid Skin Contact with All Reagents