Dimethylhydrazines

Dimeihylamine, C2H7N, (CH3)2NH. Colourless, inflammable liquid with an ammoniacal odour, mp -96" C, b.p. 7°C. Occurs naturally in herring brine. Prepared in the laboratory by treating nitrosodimetbyl-aniline with a hot solution of sodium hydroxide. Dimethylamine is largely used in the manufacture of other chemicals. These include the solvents dimethylacetamide and dimethyl-formamide, the rocket propellant unsym-metrical dimethylhydrazine, surface-active agents, herbicides, fungicides and rubber accelerators. 

Dimethylhydrazine Air, hydrogen peroxide, nitric acid, nitrous oxide... 

MMHa.nd UDMH. MonomethyUiydrazine and yyz -dimethylhydrazine are manufactured by Olin Corp. using the same Raschig process and equipment employed for anhydrous hydrazine. Chloramine, prepared as described above, reacts with methylamine or dimethylamine instead of with... 

Hydraziae is toxic and readily absorbed by oral, dermal, or inhalation routes of exposure. Contact with hydraziae irritates the skin, eyes, and respiratory tract. Liquid splashed iato the eyes may cause permanent damage to the cornea. At high doses it can cause convulsions, but even low doses may result ia ceatral aervous system depressioa. Death from acute exposure results from coavulsioas, respiratory arrest, and cardiovascular coUapse. Repeated exposure may affect the lungs, Hver, and kidneys. Of the hydraziae derivatives studied, 1,1-dimethylhydrazine (UDMH) appears to be the least hepatotoxic monomethyl-hydrazine (MMH) seems to be more toxic to the kidneys. Evidence is limited as to the effect of hydraziae oa reproductioa and/or development however, animal studies demonstrate that only doses that produce toxicity ia pregaant rats result ia embryotoxicity (164). 

U/ .f-dimethylhydrazine is employed as a fuel in space appHcations. /V,/V-r)ichloroalkylamines can be converted to nitriles in basic media or by treatment with CsF in acetonitrile (69). 

The determination of organic compounds by their direct catalytic effect on indicator reaction rates is a relatively unexplored ai ea promising valuable analytical chai acteristics, as we have recently shown in the determination of traces of unsymmetrical dimethylhydrazine (UDMH) by the oxidation of 3,3, 5,5 -tetramethylbenzidine (TMB) by atmospheric oxygen initiated with persulfate [1]. 

A. 0-Methyl-ls -2-octalone id,lA-Dimethylhydra2one. A 250-ml., round-bottomed flask equipped with a magnetic stirring bar and a Dean-Stark water separator is maintained under a dry nitrogen atmosphere (Note 1) and eharged with 7.4 g. (0.045 mole) of 10-methyl-A -2-oetalone [2(3 f)-Naphthalenone, 4,4a,5,6,7,8-hexahydro-4a-methyl-] (Note 2), 9.0 g. (0.15 mole) of N,N-dimethylhydrazine, 150 ml. of dry benzene, and 0.02 g. of p-toluenesulfonie aeid. This mixture is refluxed for 10-14 hours, after whieh time no further water separates. Benzene and excess N,A -dimethylhydrazine are then removed by simple distillation, and the residue is distilled under reduced pressure to give 8.1 g. (87%) of the dimethylhydrazone as a pale-yellow liquid, b.p. 94-98 (0.2 mm.) (Notes 3, 4). 

Dimethylhydrazine Dimethyl nitrosamine bis (Dimethylthiocarbamoyl) disulphide Dinitrobenzene (all isomers)... 

The thionitrosyl group may be stabilized either by a dimethylamino substituent or by the use of a highly bulky ort/io-substituted aryl groups. Ai,A -Dimethylthionitrosoamine M2NNS is obtained as a low melting, deep purple solid from the reaction of 1,1-dimethylhydrazine with sulfur (Eq. 10.1) or by the reduction of Mc2NNSO with LiAlH4. This thermally unstable derivative is monomeric in solution. 

Diphenylisoinclole (29) can be prepared by a modified Leuckart reaction of o-dibenzoylbenzene (46), using an ammonium salt of formic acid the process is essentially a reductive alkylation of ammonia, accompanied by cyclization, and leads to 29 in 44% yield with ammonium formate, and 47 in 28% yield with methylammonium formate. 1,3-Diphenylisoindole. (29) can also be obtained in good yield by the reaction of 46 with 1,1-dimethylhydrazine. ... 

The reaction of 1-heterobut- l-en-3-ynes with nonsymmetric dimethylhydrazine furnished 1,5-dimethylpyrazole (111) (72ZOR651). 

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