Hydrazine Adducts Research Articles

Aluminium Hydrazides: Dimeric Bis(tert-butyl)aluminium Hydrazides withSix-Membered Al2N4 and Five-Membered Al2N3 Heterocycles

Treatment of the hydrazine adduct (Me3C)2AlCl·NH2NHSiMe3 (2) with n-butyllithium afforded the colorless dialkylaluminium hydrazide (Me3C)2AlN(SiMe3)NH2 (3) by the release of butane and the precipitation of LiCl. Hydrazide 3 gave a dimer in solution and in the solid state. As shown by a crystal structure determination, a six-membered Al2N4 heterocycle with two intact endocyclic N−N bonds was formed by a head-to-tail dimerization. Upon sublimation of 3 in vacuum, a rearrangement was observed which gave an isomeric compound 4 after the migration of a hydrogen atom of a hydrazido ligand. The molecular core of 4 comprises a five-membered Al2N3 heterocycle, in which the Al atoms are bridged by one hydrazido ligand similar to 3. The second ligand, however, has only one nitrogen atom in a bridging position with an exocyclic N−N bond. A similar compound (5) was obtained by the reaction of bis(tert-butyl)aluminium chloride with phenylhydrazine and n-butyllithium.

High Lateral Resolution Imaging by Secondary Ion Mass Spectrometry of Photopatterned Self-Assembled Monolayers Containing Aryl Azide

Imaging secondary ion mass spectrometry (SIMS) is used to map the distribution of molecular and elemental species in a patterned self-assembled monolayer (SAM) with 1 μm lateral resolution. The patterned SAMs are made by exposing polycrystalline Au to a solution of bis(11-(4-azido(benzoyloxy))-1-undecyl) disulfide, I, which forms a photosensitive SAM (Au-I) on the Au. Subsequent UV irradiation (λ>260 nm) of Au-I SAMs through a mask and a thin film of a secondary amine results in attachment of the amine to the Au-I SAM only in the irradiated regions. The Au-I SAM is photosensitive by virtue of a pendant aryl azide group which reacts with secondary amines under UV irradiation to form hydrazine or azepine photoadducts. A large molecular fragment ion corresponding to vinyl ferrocene (m/z 212) was mapped with 1 μm lateral resolution on a Au-I SAM that had been irradiated through a mask and a thin film of (2-ferrocenylethyl)(2',2',2'-trifluoroethyl)amine. SIMS can also detect intact molecular ions M + corresponding to the 3H-azepine and hydrazine photoadducts obtained upon irradiation of Au-I SAMs in the presence of diethyl- and dibutylamines. Smaller fragment ions characteristic of the 3H-azepine and hydrazine adducts were also observed. The mass assignments were verified by a series ofisotopic labeling experiments in which the observed ions displayed the expected isotopic shifts.

Dicarboxylates of 3‐Methylidene‐β‐lactams: Addition Reactions to the Exocyclic Double Bond, Formation of Spiro‐β‐lactams, and Reductive Ring Opening by Hydrazines

AbstractO‐, S‐, and N‐Nucleophiles are added to the exocyclic double bond of the title compounds 1. The addition of O‐ or S‐nucleophiles yields stable products (Scheme 1), while addition of N‐nucleophiles results in thermally labile compounds (Scheme 2). The reaction is studied by spectroscopic methods. From hydrazine adducts, a spiro[azetidine‐3,3′‐pyrazolidine] 7 is obtained, and the addition products of methyl‐ and benzylhydrazine rearrange to pyrazol‐4‐carboxylates 6. Furthermore, the exocyclic double bond is used for the formation of spiro‐β‐lactams either by cyclopropane formation or by Diels‐Alder reactions (Scheme 4). The steric course of all reactions is studied, and it is shown that all reactions with the double bond occur from the side opposite to the bulkier substitutent at C(4) of the β‐lactam ring.

Benzylhydrazine as a pseudo-substrate of bovine serum amine oxidase

Bovine serum amine oxidase is inhibited by benzylhydrazine (BHy), but recovers full activity after a few hours incubation [Hucko-Haas & Reed (1970) Biochem. Biophys. Res. Commun. 38, 396-400]. The first phase of the process, requiring about 15 min, was found to consist of a mechanism-based hydrazine-transfer reaction leading to formation of the hydrazine-bound enzyme, benzaldehyde and H2O2. At variance with the enzymic process, the reaction with O2 preceded the benzaldehyde release. Two reaction intermediates could be characterized by optical spectroscopy and were assigned as the azo derivative and the benzaldehyde hydrazone, the latter one probably being involved in the reaction with O2. No reduction of Cu was detected at any stage. The hydrazine adduct could also be obtained by stoichiometric reaction of hydrazine with the native enzyme. The decay of this species occurred in about 8 h and was not studied in detail. The Cu-binding inhibitor NN-diethyldithiocarbamate affected the BHy reaction by stabilizing the benzaldehyde hydrazone form as against the azo derivative and the reaction with O2. However, under these same conditions the initial spectroscopic properties of the diethyldithiocarbamate adduct were recovered if the oxidase was left overnight. The reaction with O2 was abolished only upon removal of at least one Cu atom from the enzyme. On the basis of the failure to detect any change of Cu redox state and the enzyme behaviour in the presence of inhibitors, a reaction mechanism involving the formation of a hydroperoxy intermediate, as in the FAD-containing enzymes, is tentatively proposed.

ChemInform Abstract: RING TRANSFORMATION OF 4‐AMINO‐1H‐1,5‐BENZODIAZEPINE‐3‐CARBONITRILE. II. FORMATION OF RING‐OPENED HYDRAZINE ADDUCTS

AbstractDas Benzodiazepin (I) reagiert mit Hydrazinen zu den Hydrazonen (III).

Ring transformation of 4-amino-1H-1,5-benzodiazepine-3-carbonitrile. II. Formation of ring-opened hydrazine adducts.

Hydrazines readily reacted with 4-amino-1H-1, 5-benzodiazepine-3-carbonitrile (1) to afford ring-opened hydrazine adducts (2) which were recyclized to compounds 3, 4 and 9 by treatment with aqueous sodium hydroxide solution. Compound 4 was converted to 5 by loss of ammonia in good yield. All the reactions described here were carried out in water.

Synthesis of 3,5-bis( m- or m,m′-di-substituted- p-aminophenyl)- n-amino-1,2,4-triazole and its application to benzidine yellow type pigment

3,5- Bis(m- or m,m′- di-substituted-p- aminophenyl)-N- amino-1,2,4- triazoles ( 4) were synthesized by the oxidative dimerization of the hydrazine adduct of m- or m,m′- di-substituted-p- aminobenzonitriles ( 3) followed by acid-catalysed rearrangement. They were used to prepare Benzidine Yellow type pigments ( 8), the thermal stability of which was definitely superior to that of Benzidine Yellow ( 7) while a slight blue shift of absorption maximum was observed.

Thermal decomposition of hydrazinium aluminium sulfate hydrate and hydrazinate

As a part of our research programme on hydrazine derivatives [I-4]. we have prepared a number of hydrazinium metal sulfates [ 1.S] (N2 H5), M(SO4)2, where M = Mn, Fe, Co, Ni, Cu. Zn, Cd and Mg and their hydrazine adducts [2] of the type (N2H5)2M(SO4)2 . 3 N2H4. where M = Fe, Co and Ni, as well as N2H5AI(SO4)2 . 6N2H4. Recently, we reported [5.6] the thermal analysis of these compounds. Our .literature survey on the thermal analysis of alums [7] and aluminium salts [8] indicated that, although the preparation of hydrazinium aluminium sulfate dodecahydrate, N2H5Al(SO4)2 . 12 H2O, has been reported [9], there appears to be no report on its thermal analysis. Here, we report the results df the thermal analysis of N2H5Al(SO4)2 . 12 H2O and N2H5Al(SO4)2 . 2N2H4.

The chemistry of cyclopentadienyl nitrosyl compounds of molybdenum. Part 13. Hydrazine, hydrazido(1–)-, and hydrazido(2–)-complexes

Reaction of [{Mo(η-C5H5)(NO)X2}2](X = Cl, Br, or I), [Mo(η-C5H5)I(NO)(O2CMe)], or [Mo(C5H5)2I(NO)] with alkyl- or aryl-hydrazines, NHRNR′R″(R = R′= H, R″= Me, Ph, C6H4NO2-p, C6H4Me-p, or C6F5; R = H, R′= R″= Me or Et or R′= Me, R″= Ph; R = R′= R″= Me), affords (i) simple hydrazine adducts. [Mo(η-C5H5)(NHRNR′R″)(NO)X2](1), (ii) hydrazido(1–)-complexes, [Mo(η-C5H5)(NRNR′R″)l(NO)](2), and (iii) hydrazido(2–) complexes, [{Mo(η-C5H5)(NO)X}2NNR′R″](4). Protonation of (2) or (4) with HBF4 gives the hydrazine adducts [Mo(η-C5H5)I(NHRNR′R″)(NO)][BF4](3). The species (1), on the basis of spectral data, may contain either a unidentate or a chelating hydrazine, the latter forming a three- membered ring with the metal. Species (2) may also contain a three-membered MoNN chelate ring which on protonation affords (3), whose structure is known to involve a bidentate hydrazine bound to only one metal atom. The binuclear species (4) contain the hydrazido(2–)-ligand asymmetrically bridging the two Mo atoms, one N atom being bound to one Mo atom by a σ- and a (pπ→dπ)-donor bond, and the other Mo atom being attached to both N atoms viaσ bonds in a three-membered ring. The chemical and structural relationships between (1), (2), (3), and (4) are discussed.

Reaction of stannic chloride with hydrazine

Dilute chloroform solutions of stannic chloride and anhydrous hydrazine react to form products of empirical compositions, SnCl 3·N 2H 3 (I), SnCl 4·2N 2H 4 (II), SnCl 4·3N 2H 4 (III) and SnCl 4·4N 2H 4 (IV). Of these products only I is a pure compound, the others being mixtures of trichloromonohydrazino—stannane or its hydrazine adducts with hydrazine hydrochloride. Repeated extraction of these with anhydrous hydrazine yields a dark polymeric solid, SnN 4H 4 (V). On refluxing I with chloroform solutions of hydrazine, pyridine or α-picoline, adducts SnCl 3· N 2H 3·2N 2H 4 (VI), SnCl 3·N 2H 3·2C 5H 5N (VII) and SnCl 3·N 2H 3·C 5H 4(CH 3)N (VIII) respectively are produced. Interconversion and thermal decomposition of some of these compounds have been studied and their infra-red spectra measured. Possible mechanisms of their formation are given.