Hydrazine
Product Manager
Sandra Forbes
Name Reactions
Wolff-Kishner Reduction
The conversion of aldehydes and ketones into alkanes involves a reduction process. When a carbonyl compound undergoes condensation with hydrazine, it forms a hydrazone. Subsequent treatment with a base triggers the reduction of the carbon atom, accompanied by the oxidation of the hydrazine into gaseous nitrogen, ultimately yielding the corresponding alkane.
Recent Literature
Neutral catalysts derived from flavin, specifically a vitamin B2 derivative, can quantitatively hydrogenate various olefins in the presence of hydrazine and under atmospheric pressure of oxygen. This environmentally friendly process is highly efficient and robust, producing only water and nitrogen gas as waste products.
Y. Imada, T. Kitagawa, T. Ohno, H. Iida, T. Naota, Org. Lett., 2010, 12, 32-35.
DOI: 10.1021/ol902393p
In the presence of a 5-ethyl-3-methyllumiflavinium perchlorate catalyst and under an oxygen atmosphere, olefins can undergo hydrogenation when treated with hydrazine. This process results in excellent yields of the corresponding hydrogenated products, with environmentally benign water and molecular nitrogen being the sole waste products.
Y. Imada, H. Iida, T. Naota, J. Am. Chem. Soc., 2005, 127, 14544-14545.
DOI: 10.1021/ja053976q
While Ir-catalyzed alcohol deoxygenation via dehydrogenation/Wolff-Kishner reduction is primarily efficient with activated alcohols under harsh conditions, Ru-catalyzed aliphatic primary alcohol deoxygenation demonstrates good functional group tolerance and exceptional efficiency under practical reaction conditions. This method's synthetic utility is further highlighted by its complete chemo- and regio-selectivity in complex molecular environments.
X.-J. Dai, C.-J. Li, J. Am. Chem. Soc., 2016, 138, 5344-5440.
DOI: 10.1021/jacs.6b02344
Using V2O5/TiO2 as a heterogeneous and recyclable catalyst, the hydrogenation of nitro compounds to their corresponding amines can be mediated under blue LED irradiation at ambient temperature. In this process, hydrazine hydrate serves as the reductant, and ethanol acts as the solvent, enabling a green, sustainable, and low-cost production method.
S. Kumar, S. K. Maurya, J. Org. Chem., 2023, 88, 8690-8702.
In the presence of Pd/C, several bromo, chloro, iodo, and multihalogenated nitroarenes can be selectively reduced with hydrazine hydrate to yield the corresponding halogenated anilines in good yields. By applying microwave irradiation at elevated temperatures and pressures, dehalogenated products can be successfully isolated.
F. Li, B. Frett, H.-y Li, Synlett, 2014, 25, 1403-1408.
A scalable and operationally straightforward method for the chemoselective deoxygenation of a broad spectrum of N-heterocyclic N-oxides at room temperature is mediated by visible light, utilizing solely commercially available reagents. This protocol achieves an unprecedented chemoselective removal of the oxygen atom in a quinoline N-oxide, even in the presence of a pyridine N-oxide, through the careful choice of the photocatalyst.
K. D. Kim, J. H. Lee, Org. Lett., 2018, 20, 7712-7716.
DOI: 10.1021/acs.orglett.8b03446
Employing hydrazine under basic conditions facilitates an efficient and versatile synthesis of quinoline N-oxides from ortho-nitro chalcones through carbonyl umpolung. This transition-metal-free approach exhibits excellent functional group tolerance, environmental benignity, and gentle reaction conditions, with nitrogen gas as the sole byproduct.
G. Zhang, K. Yang, S. Wang, Q. Feng, Q. Song, Org. Lett., 2021, 23, 595-600.
DOI: 10.1021/acs.orglett.0c04162
Related
A selective photoinduced reduction of nitroarenes to N-arylhydroxylamines occurs with a wide substrate scope, remarkable functional-group tolerance, and high yields, without the need for a catalyst or additives. This process solely relies on light and methylhydrazine.
M. G. Kallitsaki, D. I. Ioannou, M. A. Terzidis, G. E. Kostakis, J. N. Lykakis, Org. Lett., 2020, 22, 4339-4343.
DOI: 10.1021/acs.orglett.0c01367
A straightforward method for reducing aromatic ketones and aldehydes to their corresponding methylene units involves synthesizing a carbomethoxyhydrazone intermediate, which readily decomposes to the reduced product. This reaction circumvents the use of hazardous hydrazine.
P. B. Cranwell, A. T. Russell, C. D. Smith, Synlett, 2016, 27, 131-135.
Quoted from: https://www.organic-chemistry.org/chemicals/reductions/hydrazine.shtm
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