Aliphatic hydrazine

Among the oxidative procedures for preparing azo compounds are oxidation of aromatic amines with activated manganese dioxide oxidation of fluorinated aromatic amines with sodium hypochlorite oxidation of aromatic amines with peracids in the presence of cupric ions oxidation of hindered aliphatic amines with iodine pentafluoride oxidation of both aromatic and aliphatic hydrazine derivatives with a variety of reagents such as hydrogen peroxide, halogens or hypochlorites, mercuric oxide, A-bromosuccinimide, nitric acid, and oxides of nitrogen. 

Description Flammable, hygroscopic liquid. Fumes in air and gradually turns yellow. Characteristic ammonia-like fishy odour of aliphatic hydrazines (Budavari, 1996)... 

Aliphatic hydrazines of the type RiC(CN)NHNHC(CN)Rj are prepared by the interaction of ketone cyanohydrins and hydrazine. These compounds can be oxidized to azonitriles with hypobromous acid in methanol. In a similar manner, ethyl azodicarboxylate, CjH50jCN=NC0jCiHj, is synthesized by the action of hypochlorous acid on ethyl hydrazodicar-boxylate (83%)- ... 

Aliphatic hydrazines react with cyclopropanone or cyclopropanone hemiacetals, providing good access to carbinol-type adducts which are versatile sources for the synthesis of cyclo-propylidenehydrazines. Upon reacting hemiacetal 10 with A,A-dimethylhydrazine, without solvent, the distillable but sensitive hemiaminal 39 was formed in 64% yield. ... 

Flammable, hygroscopic, mobile liq. Fumes in air and gradually turns yellow. Corrosive to skint Characteristic ammoniaca odor of aliphatic hydrazines. d 0.791 dH 0.782. mp —58. bp Q 63.9 . njf1 1.40753. Miscible with water with evolution of heat. Also miscible with alcohol, ether, dimethylformamide, hydrocarbons. LDn in mice, rats (mg/kg) 265, 122 orally 250, 119 I.v. (Witkin). 

Zheng et al. developed a variation of the Fischer indole synthesis whereby quinone 136 and aliphatic hydrazine 137 were combined to furnish fused indole 138. The newly disclosed reaction has much to recommend it the conditions are mild, the quinones are easily accessed by oxidation of commercially available phenols, and the hydrazines can be cyclic or acyclic (13AG(I)1753). 

The modified procedure involves refluxing the N-substituted phthaUmide in alcohol with an equivalent quantity of hydrazine hydrate, followed by removal of the alcohol and heating the residue with hydrochloric acid on a steam bath the phthalyl hydtazide produced is filtered off, leaving the amine hydrochloride in solution. The Gabriel synthesis has been employed in the preparation of a wide variety of amino compounds, including aliphatic amines and amino acids it provides an unequivocal synthesis of a pure primary amine. 

Carvone, menthone, acetophenone etc Apply an aadic solution of 2,4-dinitrophenyl-hydrazine, 4-nitrophenylhydrazine or 2,4-dinitro-phenylsemicarbazide onto the previously applied sample solution Aliphatic and aromatic hydra-zones and carbazones can be differentiated by their colors [82]... 

Hydrazine, EtOH, 85% yield. Note that the cleavage of an anilide and a benzoylpyrrole is much more facile than that of a typical aliphatic benzamide. 

The interaction between l,5-diphenylpentadiyn-2,4-one-l and its aliphatic analog, 1,5-dimethylpentadiyn-2,4-one, with substituted hydrazines gives rise to a linear adduct, vinylacetylenylketone, which then cyclizes into 5-phenylethynylpyra-zoles and 5-methyl-3-propynylpyrazoles in 70-90% yields, respectively (73S47) (Scheme 21). 

It is interesting that the cyclization of the 2,4-dinitrophenylhydrazone of the aliphatic analog, l,5-dimethylpentadione-3, can also be performed in alkaline conditions. Heating hydrazine in boiling methanol in the presence of sodium methoxide results in l-(2,4-dinitrophenyl)-3-propynyl-5-methylpyrazole (84%) (74JOC843). 

Similarly, dipropynylketone behaves as an aliphatic analog which forms the corresponding 5-methyl-3-(l-propynyl)pyrazoles (70-90% yield) with hydrazine or monosubstituted hydrazines in methyl alcohol at room temperature (74ZOR136) (Scheme 23). 

Although the addition of hydrazine and its derivatives to acetylenic ketones has been studied in considerable detail, their interaction with hydrazones and mono-alkylhydrazones is less well known. Yandovskii and Klindukhova (74ZOR730) have studied the reaction between hydrazones and alkylhydrazones of aliphatic ketones with dipropynylketones and showed that hydrazones of acetone, methyl-ethylketone, and cyclohexane easily add to one of the triple bonds of dipropynylketone to form 4-methyl-1,1,3-trialkyl-2,3-diaza-l,4-nonadien-7-yn-6-ones (yields... 

In a recent review of heterocyclic compounds no further mention is made of the three-membered ring structures for the condensation products from hydrazine and carbonyl compounds. However, the products obtained from azodicarbonyl derivatives with aliphatic diazo compounds were formulated as diaziridines [Eq. (1)]. Recent investi-... 

Herbert and Hay reported a bisphenolic monomer, 3,8-bis(4-hydroxyphenyl)-A-phenyl-1,2-naphthalimide (Table 6.1), as well as its corresponding polyf V-phenyl imido aryl ether sulfone) via transimidization reactions with hydrazine monohydrate, aliphatic amines, and an amino acid.193 These polysulfones with... 

Hydrazides (RCONHNH2) are highly useful starting materials and intermediates in the synthesis of heterocyclic molecules.2 They can be synthesized by hydrazinolysis of amides, esters and thioesters.3 The reaction of hydrazine with acyl chlorides or anhydrides is also well known,4 but it is complicated by the formation of 1,2-diacylhydrazines, and often requires the use of anhydrous hydrazine which presents a high thermal hazard. Diacylation products predominate when hydrazine reacts with low molecular weight aliphatic acyl chlorides, which makes the reaction impractical for preparatory purposes.5... 

Dinitrophenyl-hydrazine has been successfully employed in the analysis of simple aldehydes, substituted aldehydes, glyoxal and gluteraldehyde (43-45), all the isomers of the C3 to C7 aliphatic ketones (44,45) and in the determination of formaldehyde in tobacco smoke (46). 

Monosubstituted hydrazines treated with nitrous acid give azides in a reaction exactly analogous to the formation of aliphatic diazo compounds mentioned in 12-47. Among other reagents used for this conversion have been N204 ° and nitrosyl tetrafluoroborate (NOBp4). ... 

A variety of cleavage conditions have been reported for the release of amines from a solid support. Triazene linker 52 prepared from Merrifield resin in three steps was used for the solid-phase synthesis of aliphatic amines (Scheme 22) [61]. The triazenes were stable to basic conditions and the amino products were released in high yields upon treatment with mild acids. Alternatively, base labile linker 53 synthesized from a-bromo-p-toluic acid in two steps was used to anchor amino functions (Scheme 23) [62]. Cleavage was accomplished by oxidation of the thioether to the sulfone with m-chloroperbenzoic acid followed by 13-elimination with a 10% solution of NH4OH in 2,2,2-trifluoroethanol. A linker based on l-(4,4 -dimethyl-2,6-dioxocyclohexylidene)ethyl (Dde) primary amine protecting group was developed for attaching amino functions (Scheme 24) [65]. Linker 54 was stable to both acidic and basic conditions and the final products were cleaved from the resin by treatment with hydrazine or transamination with ra-propylamine. 

Tricyclic antihistamines as a rule carry aliphatic nitrogen as a substituent on a side chain attached to the central ring the side chain nitrogen may be part of a heteroaromatic ring. Conjugate addition of p-chloroaniline (49) to the substituted vinylpyridine 50 gives the alkylated aniline 51. Treatment of that intermediate with nitrous acid leads to N-nitroso intermediate 52 which is then reduced to the hydrazine (53). Reaction of 53 with N-methyl-4-piperidone... 

Hydrazines and compounds that can be hydrogenated to hydrazines undergo N-N bond rupture on noble metal catalysts. Pd seems to be the best catalyst for the hydrogenolysis of the N-N bonds in aromatic hydrazines, whereas Rh seems best for the aliphatic ones. Ni is also useful for the hydrogenolysis of N-N bonds in hydrazines. 

A reagent of nickel boride/hydrazine hydrate reduces both aromatic and aliphatic nitro compounds. For example, it has been used for synthesis of 4-(benzyloxy)indole and -alky ltryp-... 

Related (diisopropoxyphosphoryl)- and (diisobutoxyphosphoryl)formonitrile oxides (114), generated in basic media from the corresponding oximes react in situ with alcohols, phenols, alkanethiols, thiophenols, aliphatic and aromatic primary amines, hydrazines and hydrazides as well as 4-aminoantipyryne to give hydroxymates, thiohydroxymates, and amidoximes, respectively. It is important to note that the addition is stereoselective and gives E-adducts with the exception of (i-Pr0)2P(0)C( N0H)0Me, which is formed as a 1 1 mixture of E and Z isomers. 

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