Hydrazines (R
2N−NR
2) are a class of chemical compounds with two
nitrogen atoms linked via a covalent bond and which carry from one up to four alkyl or aryl substituents. Hydrazines can be considered as derivatives of the inorganic
hydrazine
Hydrazine is an inorganic compound with the chemical formula . It is a simple pnictogen hydride, and is a colourless flammable liquid with an ammonia-like odour. Hydrazine is highly hazardous unless handled in solution as, for example, hydraz ...
(H
2N−NH
2), in which one or more hydrogen atoms have been replaced by hydrocarbon groups.
Production
*
1,1-Dimethylhydrazine
Unsymmetrical dimethylhydrazine (abbreviated as UDMH; also known as 1,1-dimethylhydrazine, heptyl or Geptil) is a chemical compound with the formula H2NN(CH3)2 that is primarily used as a rocket propellant. At room temperature, UDMH is a colorle ...
is produced by the reduction of
''N''-nitrosodimethylamine.
[ Siegfried Hauptmann: ''Organische Chemie'', 2. durchgesehene Auflage, VEB Deutscher Verlag für Grundstoffindustrie, Leipzig, 1985, S. 522–523, .]
* The reduction of
benzenediazonium chloride
Benzenediazonium tetrafluoroborate is an organic compound with the formula 6H5N2F4. It is a salt of a diazonium cation and tetrafluoroborate. It exists as a colourless solid that is soluble in polar solvents. It is the parent member of the ary ...
with
tin(II) chloride
Tin(II) chloride, also known as stannous chloride, is a white crystalline solid with the formula . It forms a stable dihydrate, but aqueous solutions tend to undergo hydrolysis, particularly if hot. SnCl2 is widely used as a reducing agent (in ac ...
and
hydrochloric acid
Hydrochloric acid, also known as muriatic acid or spirits of salt, is an aqueous solution of hydrogen chloride (HCl). It is a colorless solution with a distinctive pungency, pungent smell. It is classified as a acid strength, strong acid. It is ...
provides
phenylhydrazine
Phenylhydrazine is the chemical compound with the formula . It is often abbreviated as . It is also found in edible mushrooms.
Properties
Phenylhydrazine forms monoclinic prisms that melt to an oil around room temperature which may turn yellow ...
.
* 2,4-Dinitrophenylhydrazine is produced by the reaction of 1-chloro-2,4-dinitrobenzene with hydrazine.
* Tetraphenylhydrazine is formed by the oxidation of diphenylamine with
potassium permanganate
Potassium permanganate is an inorganic compound with the chemical formula KMnO4. It is a purplish-black crystalline salt, which dissolves in water as K+ and ions to give an intensely pink to purple solution.
Potassium permanganate is widely us ...
in acetone.
Classification
Hydrazines can be divided into three groups according to the degree of substitution. Hydrazines belonging to the same group behave similarly in their chemical properties. Monosubstituted hydrazines and so-called asymmetrically disubstituted hydrazines, where (only) two hydrocarbon groups are bonded to the same nitrogen atom are colorless liquids. Aliphatic monosubstituted and asymmetrically disubstituted hydrazines are very water soluble, strongly alkaline and good reducing agents. Aromatic monosubstituted and asymmetrically disubstituted hydrazines are poorly soluble in water, less basic and weaker reducing agents. For the preparation of aliphatic hydrazines, the reaction of hydrazine with alkylating compounds such as alkyl halides is used, or by reduction of nitroso derivatives. Aromatic hydrazines are prepared by reducing aromatic diazonium salts.
In symmetric disubstituted hydrazines, a hydrocarbon group is bonded to each of the hydrazine nitrogen atoms. Like asymmetrically disubstituted hydrazines, they are liquids, but their boiling points are typically higher. In particular, the aliphatic compounds are basic and reducing agents and are soluble in water. Aromatic symmetric disubstituted hydrazines are not soluble in water. Symmetrically disubstituted hydrazines are prepared by reducing nitro compounds under basic conditions or by reducing the azines.
Tri- or tetrasubstituted aliphatic hydrazines are water-insoluble weakly basic compounds. The corresponding arylhydrazines are solid colorless substances which are insoluble in water and substantially not basic. They react with concentrated
sulfuric acid
Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid (English in the Commonwealth of Nations, Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen, ...
to form violet or dark blue compounds.
History
Phenylhydrazine
Phenylhydrazine is the chemical compound with the formula . It is often abbreviated as . It is also found in edible mushrooms.
Properties
Phenylhydrazine forms monoclinic prisms that melt to an oil around room temperature which may turn yellow ...
and
2,4-dinitrophenylhydrazine had been used historically in analytical chemistry to detect and identify compounds with carbonyl groups. Phenylhydrazine was used to study the structure of
carbohydrate
A carbohydrate () is a biomolecule composed of carbon (C), hydrogen (H), and oxygen (O) atoms. The typical hydrogen-to-oxygen atomic ratio is 2:1, analogous to that of water, and is represented by the empirical formula (where ''m'' and ''n'' ...
s, because the reaction of the sugar's
aldehyde group
In organic chemistry, an aldehyde () (lat. ''al''cohol ''dehyd''rogenatum, dehydrogenated alcohol) is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred ...
s lead to well crystallizing
phenylhydrazone
Hydrazones are a class of organic compounds with the structure . They are related to ketones and aldehydes by the replacement of the oxygen =O with the = functional group. They are formed usually by the action of hydrazine on ketones or aldehydes. ...
s or
osazone
Osazone are a class of carbohydrate derivatives found in organic chemistry formed when reducing sugars are reacted with excess of phenylhydrazine at boiling temperatures.
Formation
Osazone formation was developed by Emil Fischer, who used t ...
s.
Examples
Organohydrazines and their derivatives are numerous, especially when
hydrazone
Hydrazones are a class of organic compounds with the structure . They are related to ketones and aldehydes by the replacement of the oxygen =O with the = functional group. They are formed usually by the action of hydrazine on ketones or aldehydes. ...
s are included.
*
monomethyl hydrazine
Monomethylhydrazine (MMH) is a highly toxic, volatile hydrazine derivative with the chemical formula . It is used as a rocket propellant in bipropellant rocket engines because it is hypergolic with various oxidizers such as nitrogen tetroxide () a ...
, where one of the hydrogen atoms on the hydrazine molecule has been replaced with a methyl group (CH
3). Due to the symmetry of the hydrazine molecule, it does not matter which hydrogen atom is replaced. It is sometimes used as a rocket fuel.
*
1,1-dimethylhydrazine
Unsymmetrical dimethylhydrazine (abbreviated as UDMH; also known as 1,1-dimethylhydrazine, heptyl or Geptil) is a chemical compound with the formula H2NN(CH3)2 that is primarily used as a rocket propellant. At room temperature, UDMH is a colorle ...
(unsymmetrical dimethylhydrazine, UDMH) and
1,2-dimethylhydrazine
Symmetrical dimethylhydrazine (SDMH), or 1,2-dimethylhydrazine, is the organic compound with the formula (CH3NH)2. It is one of the two isomers of dimethylhydrazine. Both isomers are colorless liquids at room temperature, with properties similar ...
(
symmetrical dimethylhydrazine
Symmetrical dimethylhydrazine (SDMH), or 1,2-dimethylhydrazine, is the organic compound with the formula (CH3NH)2. It is one of the two isomers of dimethylhydrazine. Both isomers are colorless liquids at room temperature, with properties similar ...
) are hydrazines where two hydrogen atoms are replaced by
methyl group
In organic chemistry, a methyl group is an alkyl derived from methane, containing one carbon atom bonded to three hydrogen atoms, having chemical formula (whereas normal methane has the formula ). In formulas, the group is often abbreviated a ...
s. UDMH is the easier of the two to manufacture and is a fairly common rocket fuel.
*
gyromitrin
Gyromitrin is a toxin and carcinogen present in several members of the fungal genus '' Gyromitra'', like '' G. esculenta''. Its formula is . It is unstable and is easily hydrolyzed to the toxic compound monomethylhydrazine . Monomethylhydraz ...
and
agaritine are hydrazine derivatives found in the commercially produced mushroom species ''
Agaricus bisporus
''Agaricus bisporus'', commonly known as the cultivated mushroom, is a basidiomycete mushroom native to grasslands in Eurasia and North America. It is cultivated in more than 70 countries and is one of the most commonly and widely consumed ...
''.
Gyromitrin
Gyromitrin is a toxin and carcinogen present in several members of the fungal genus '' Gyromitra'', like '' G. esculenta''. Its formula is . It is unstable and is easily hydrolyzed to the toxic compound monomethylhydrazine . Monomethylhydraz ...
is metabolized into monomethyl hydrazine.
*
Isoniazid
Isoniazid, also known as isonicotinic acid hydrazide (INH), is an antibiotic used for the treatment of tuberculosis. For active tuberculosis, it is often used together with rifampicin, pyrazinamide, and either streptomycin or ethambutol. F ...
,
iproniazid
Iproniazid (Marsilid, Rivivol, Euphozid, Iprazid, Ipronid, Ipronin) is a non-selective, irreversible inhibition, irreversible monoamine oxidase inhibitor (MAOI) of the hydrazine (antidepressant), hydrazine class. It is a xenobiotic that was origi ...
,
hydralazine
Hydralazine, sold under the brand name Apresoline among others, is a medication used to treat high blood pressure and heart failure. This includes high blood pressure in pregnancy and very high blood pressure resulting in symptoms. It has bee ...
, and
phenelzine
Phenelzine, sold under the brand name Nardil among others, is a non-selective and irreversible monoamine oxidase inhibitor (MAOI) of the hydrazine family which is primarily used as an antidepressant and anxiolytic to treat depression and a ...
are
medication
Medication (also called medicament, medicine, pharmaceutical drug, medicinal product, medicinal drug or simply drug) is a drug used to medical diagnosis, diagnose, cure, treat, or preventive medicine, prevent disease. Drug therapy (pharmaco ...
s whose molecules contain hydrazine-like structures.
*
2,4-dinitrophenylhydrazine (2,4-DNPH) is commonly used to test for
ketones
In organic chemistry, a ketone is an organic compound with the structure , where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group (a carbon-oxygen double bond C=O). The simplest ketone is acetone ( ...
and
aldehydes
In organic chemistry, an aldehyde () (lat. ''al''cohol ''dehyd''rogenatum, dehydrogenated alcohol) is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred ...
in
organic and
clinical chemistry.
*
phenylhydrazine
Phenylhydrazine is the chemical compound with the formula . It is often abbreviated as . It is also found in edible mushrooms.
Properties
Phenylhydrazine forms monoclinic prisms that melt to an oil around room temperature which may turn yellow ...
, C
6H
5NHNH
2, the first hydrazine to be discovered.
References
Further reading
*
{{Hydrazines
Functional groups
Organonitrogen compounds