Hydrazine Hydrate (NH₂NH₂·H₂O)

Biographical Sketches

Asheesh Kumar Jain was born in Khandwa, MadhyaPradesh, India. He completed his B.Sc. (1996) and M.Sc. (1998) degrees in organic chemistry at S.N.P.G. college (D.A.V.V. University, Indore) Khandwa, India. He joined the Defence Research and Development Establishment in 2002 as a Junior Research Fellow and is currently pursuing a Ph.D. under the tutelage of Dr. R. C. Malhotra. His present research focus is on incapacitating agents.

Introduction

The synthetic utilities of hydrazine hydrate have been extensively investigated in organic chemistry. Among reducing agents, hydrazine hydrate stands out for its application to a broad variety of reductive transformations. It is easy to use and reduces many functional groups, such as carbonyl compounds, alkenes, alkynes and nitro groups under mild reaction conditions. Hydrazine hydrate is commercially available. It is a liquid (mp -52 °C, bp 120-121 °C, d = 1.027 g/mL), and is ­soluble in water, ethanol, methanol, propanol and iso­butanol.

Abstracts

(A) Hydrazine hydrate is used in the reduction of carbonyl ­compounds to their corresponding methylene group via the Wolf-Kishner reduction [1] and the Huang-Minlon modification. [2]
(B) Hydrazine hydrate is often used as the hydrogen donor for the transfer reduction of many organic compounds. It is used in combination with many different catalysts, including Raney Nickel, [3] platinum, [4] ruthenium, [5] palladium on carbon, iron(III) oxide, graphite, and iron(III) chloride with activated carbon. Recently, hydrazine hydrate was used with zinc [6] and magnesium [7] as a low-cost and selective reducing agent for nitro compounds to amines.
(C) A very useful reagent for simple hydrazone synthesis, hydrazine hydrate reacts with carbonyl groups. [8] [9] Hydrazones are useful synthetic intermediates and have been converted to vinyl iodides [10] and vinyl selenides. [11]
(D) Carbazates are obtained simply by reacting alkyl or aryl chloroformates with hydrazine hydrate, or with alkyl or aryl hydrazine derivatives. [12]
(E) The most widely used method to prepare hydrazides is hydrazinolysis of the corresponding esters with hydrazine monohydrate. [13] Recently, Toda et al. reported the use of hydroquinone and hydrazine as an alternative to hydrazine monohydrate in the solid state hydrazinolysis of esters. [14] Peng and Song reported the hydrazinolysis of esters under simultaneous microwave and ultrasound irradiation. [15]
(F) An extended application of hydrazine hydrate is in the preparation of o-nitrobenzenesulfonylhydrazide (NBSH). This reagent has been shown to be valuable in the synthesis of allenes from pro­pargylic alcohols, [16] and for the reductive transposition of allylic ­alcohols. [17]

References

• 1a Todd D. Org. React.  1948,  4:  378 
• 1b Szmant HH. Angew. Chem., Int. Ed. Engl.  1968,  7:  120 
• 1c Reusch W. Reduction   Dekker; New York: 1968.  p.171-185 
• 1d Clark C. Hydrazine   Mathieson Chemical Corp.; Baltimore: 1953. 
• 2a Huang-Minlon . J. Am. Chem. Soc.  1946,  68:  2487 
• 2b Huang-Minlon . J. Am. Chem. Soc.  1949,  71:  3301 
• 2c Durham LJ. Mcleod DJ. Cason J. Org. Synth. Coll. Vol. IV  1963,  510 
• 2d Hunig S. Lucke E. Brenningesr W. Org. Synth.  1963,  43:  34 
• 3a Furst A. Berlo RC. Hooton S. Chem. Rev.  1965,  65:  51 
• 3b Ayynger NR. Lugade AC. Nikrad PV. Sharma VK. Synthesis  1981,  640 
• 4a Pietra S. Ann. Chim. (Rome)  1955,  45:  850 
• 4b Rondestvedt Jr. CS. Johnson TA. Chem. Eng. News  1977,  55 (27):  38 
• 4c Bavin PMG. Org. Synth.  1960,  40:  5 
• 5 Weiser HB. Milligan WO. Cook EL. Inorg. Synth.  1946,  215 
• 6 Gowda S. Gowda DC. Indian J. Chem., Sect. B  2003,  42:  180 
• 7 Srinivasa GR. Abiraj K. Gowda DC. Indian J. Chem., Sect. B  2003,  42:  2885 
• 8 Schonberg A. Fateen AEK. Sammour AEMA. J. Am. Chem. Soc.  1957,  79:  6020 
• 9 Baltzly R. Mehta NB. Russell PB. Brooks RE. Grivsky EM. Steinberg AM. J. Org. Chem.  1961,  26:  3669 
• 10 Barton DHR. Basiardes G. Fourrey J.-L. Tetrahedron Lett.  1983,  24:  1605 
• 11 Barton DHR. Basiardes G. Fourrey J.-L. Tetrahedron Lett.  1984,  25:  1287 
• 12a Dupont V. Lecoq A. Mangeot JP. Aubry A. Boussard G. Marraud M. J. Am. Chem. Soc.  1993,  115:  8898 
• 12b Allcock SJ. Gilchrist TL. Shuttleworth SJ. King FD. Tetrahedron  1991,  47:  10053 
• 13a Yale HL. Losee K. Martins J. Holsing M. Perry FM. Bernstein J. J. Am. Chem. Soc.  1953,  75:  1933 
• 13b Bruice TC. Benkovic SJ. J. Am. Chem. Soc.  1964,  86:  418 
• 14 Toda F. Hyoda S. Okada K. Hirotsu K. J. Chem. Soc., Chem. Commun.  1995,  1531 
• 15 Peng Y. Song G. Green Chem.  2001,  3:  302 
• 16 Myers AG. Zheng B. J. Am. Chem. Soc.  1996,  118:  4492 
• 17 Myers AG. Zheng B. Tetrahedron Lett.  1996,  37:  4841