Mercury(II) Chloride-Silver(I) Nitrite


[7487-94-7]  · Cl2Hg  · Mercury(II) Chloride-Silver(I) Nitrite  · (MW 271.49) (AgNO2)

[7783-99-5]  · AgNO2  · Mercury(II) Chloride-Silver(I) Nitrite  · (MW 153.88)

(nitromercuration1-4 and synthesis of nitroalkenes from alkenes4,5)

Form Supplied in: white, odorless needles or powder (both reagents).

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.

Mixing Mercury(II) Chloride and Silver(I) Nitrite generates Hg(NO2)2 in situ, which reacts with alkenes to give nitromercuration products with high regio- and stereoselectivity (eq 1).1 -3 The reaction with norbornene occurs without rearrangement, indicating that carbocationic character in the transition state is little developed. On treatment with a base (NaOH or R3N), the primary adducts undergo an elimination reaction to afford nitroalkenes (eq 1).4 This two-step transformation represents a general route to nitroalkenes4 and has been employed in the synthesis of 3-nitrocycloalkenones5 and (E)-2-nitrovinyltrimethylsilane.6 However, better yields are usually obtained if AgNO2/I2 is used instead.7

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. Bachman, G. B.; Whitehouse, M. L. JOC 1967, 32, 2303.
3. Bloodworth, A. J.; Griffin, I. M. JCS(P1) 1975, 695.
4. Corey, E. J.; Estreicher, H. JACS 1978, 100, 6294.
5. Vankar, Y. D.; Bawa, A. SC 1985, 15, 1253.
6. Ali, S. M.; Matsuda, Y.; Tanimoto, S. S 1988, 805.
7. Sy, W.-W.; By, A. W. TL 1985, 26, 1193.

Pavel Ko&cbreve;ovský

University of Leicester, UK

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