Organic hydrazine derivatives

B. V. Yoffe, M. A. Kuznetsov, and A. A. Potekhin, The Chemistry of Organic Hydrazine Derivatives (in Russian). Khimiya, Leningrad, 1979. 

The further fate is not explicitly known, but molecule rearrangements and/or the addition of O2, NO c and NO3 is possible. From secondary amines, azo compounds or organic hydrazines (derived from hydrazine N2H4) can be given ... 

Uses Reducing agent corrosion inhibitor wastewater treatment electrolytic plating redox reactions polymerization catalyst organic hydrazine derivs. rocket propellant corrosion inhibitor, oxygen scavenger in boiler... 

Low-valent nitrogen and phosphorus compounds are used to remove hetero atoms from organic compounds. Important examples are the Wolff-Kishner type reduction of ketones to hydrocarbons (R.L. Augustine, 1968 D. Todd, 1948 R.O. Hutchins, 1973B) and Barton s olefin synthesis (p. 35) both using hydrazine derivatives. 

Cyclic ADC compounds are similarly prepared by oxidation of the corresponding cyclic hydrazine derivatives. The most commonly encountered compounds are the 3//-l,2,4-triazole-3,5(4//)-diones (5), and in particular the 4-phenyl derivative (5, R = Ph), usually abbreviated as PTAD. Similarly, the abbreviation MTAD is used for the 4-methyl derivative. First prepared by Thiele,18 PTAD remained unused in organic synthesis until Cookson reported its powerful dienophilic properties some 70 years later.19 PTAD is an isolable, red, crystalline compound, prepared by r-butyl hypochlorite oxidation of 4-phenylurazole.20 Other oxidants which have been successfully... 

R.S. Atkinson, in S.D. Barton u. W.D. Oilis, in J.O. Sutherland, Comprehensive Organic Chemistry, Derivatives of Hydrazine and Related Compounds, Bd.2, S. 219 ff. Pergamon Press, Oxford - New York Toronto Sydney Paris Frankfurt 1979. 

Alkyl halides would not react with [CrCl2(MeCN)2], but the alkyl derivatives [RCr(salen)(H20)] and [RCr(salphen)(H20)] (R = Me, Ph) are said to form on reaction of the organic hydrazines with the Crm-Schiffs base complexes in MeCN under nitrogen followed by oxidation with oxygen and hydrolysis.1128... 

Organic hydrazines or diazanes are substitution products of NH2—NH2 and have many properties similar to those of amines in being basic and forming acyl derivatives as well as undergoing alkylation and condensations with carbonyl compounds (Section 16-4C). Unsymmetrical hydrazines can be prepared by careful reduction of /V-nitrosamines. l,l-Dimethyldiazane is prepared in this way for use as a rocket fuel ... 

Dimethyl azodicarboxylate (manufactured by Tokyo Kasel Kogyo Co., Japan) was purchased from CTC Organic, 792 Windsor Street, Atlanta, GA 30315. Overheating of dimethyl azodicarboxylate should be avoided because of the danger of explosion. Distillation should be conducted from a temperature-controlled bath in the hood behind a safety shield. The material used distilled at 71-72°C (2 mm), at a bath temperature of 84-86°C. It is important that the addition of this compound to the reaction mixture be carried out at a constant rats without Interruption because it tends to freeze in the syringe needle. The checkers explored the use of diethyl azodicarboxylate because of its lower cost and wider availability. However, the corresponding hydrazine derivative Is more difficult to separate from the -lactone product of this step. 

The mechanism of action of rifamycins involves primarily a strong, but noncovalent, interaction with DNA-dependent RNA polymerase enzyme in sensitive bacterial cells. The mammalian enzyme is not affected, which explains the selective toxicity neither is it mutated to resistant organisms. RNA polymerase has two components. The core enzyme contains polypeptide subunits a, J3, and i and a c factor, which are needed for recognition of RNA synthesis initiation sites. The drug binds to the J subunit of the complete enzyme only. The result is effective inhibition of RNA synthesis. It is of interest that many rifampinlike hydrazine derivatives were also found to be potent inhibitors of reverse transcriptase and shown to have antiviral properties. 

Reaction of the hydrazine derivatives 133 with 5-nitro-2-furaldehyde 134 afforded the corresponding 4,6-disub-stituted-2-(5-nitrofurfurylidenehydrazino)-l,3,5-triazines 135 (Equation 20). The products had low solubility in most organic solvents, except DMSO. However, purification was achieved by recrystallization from methanolic and ethanolic water solutions. 

The stabilizer systems for polyacetals are invariably composed of a hindered phenol with a costabilizer. The hindered phenols in use are 2,2 -methylenebis-(4-methyl-6-tert-butyl-phenol), 1,6-hexamethyle-nebis-3-(3,5-di-rert-butyl-4-hydroxyphenyl)-propionate, and pentaerythrityl-tetrakis-3-(3,5-di-fert-butyl-4-hydroxyphenyl)-propionate. A large number of nitrogen-containing organic compounds have been described as costabiKzers for polyacetals, e.g., dicyandiamide, melamine, terpolyamides, urea, and hydrazine derivatives. The effectiveness of these compounds is based on their ability to react with formaldehyde and to neutralize acids, especially formic acid, formed by oxidation. In addition to nitrogen compounds, salts of long-chain fatty acids (e.g., calcium stearate, calcium ricinoleate, or calcium citrate) are also used as acid acceptors. The practical concentrations are 0.1-0.5% for the phenolic antioxidant and 0.1-1.0% for the costabilizer. 

The most common inorganic chemical blowing agent is sodium bicarbonate. The most popular organics are shown in Table B. 1. Chemical blowing agents are mainly hydrazine derivatives. 

The possibility of using the polyurethane ionomeric resins as water dispersions, free of organic solvents and surface-active agents, simplifies the development of environmentally friendly production facilities [6-8]. Hydrazine-containing polyurethanes having ionic groups in their macrochains combine the properties of ionomeric resins with those of polyurethanes based on hydrazine derivatives [6,9]. 

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