Mercury(I) Nitrate1


[7782-86-7]  · Hg2N2O6  · Mercury(I) Nitrate  · (MW 561.24)

(synthesis of alkyl nitrates from alkyl halides3)

Alternate Name: mercurous nitrate.

Physical Data: mp about 70 °C (dec); bp explodes; d 4.785 g cm-3

Solubility: insol alcohol, ether; sol H2O containing 1% HNO3 (with H2O alone, basic salt is formed).

Form Supplied in: dihydrate (usual form); colorless monoclinic crystals, usually with slight odor of HNO3. Drying: dehydration in vacuum; however, heating above 100 °C causes decomposition.2

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.

While nitrates are frequently prepared from alkyl halides on reaction with Silver(I) Nitrate in MeCN, mercury(I) nitrate offers a cheaper alternative (eq 1). Yields are high for primary, allylic, and benzylic bromides and satisfactory for secondary bromides. Tertiary bromides react slowly, whereas a-bromo carbonyl compounds are virtually inert.3

Benzyl nitrates (ArCH2ONO2) synthesized in this way give the corresponding aldehydes (ArCH=O) upon reflux with NaOH in aq MeOH.4

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. Potts, R. A.; Allred, A. L. IC 1966, 5, 1066.
3. McKillop, A.; Ford, M. E. T 1974, 30, 2467.
4. McKillop, A.; Ford, M. E. SC 1974, 4, 45.

Pavel Ko&cbreve;ovský

University of Leicester, UK

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