Amines phenylhydrazine

It was reported only recently that A-methyl transfer from an oxaziridine to an amine occurs with formation of an N—N bond (79JA6671). N—N bond forming reactions with A-unsubstituted oxaziridines had been found immediately after discovery of this class of compound (64CB2521) and have led to simple hydrazine syntheses (79AHC(24)63). Secondary amines like diethylamine or morpholine are A-aminated by (52) in the course of some minutes at room temperature with yields exceeding 90% (77JPR195). Further examples are the amination of aniline to phenylhydrazine, and of the Schiff base (96) to the diaziridine (97). 

If there is no phenyl substituent in the 3-position the amination ability decreases. The acyloxaziridine (104) yields only 11% of a semicarbazide derivative with piperidine. In the presence of strong bases an intramolecular amination competes. Compound (104) reacts with methoxide within a couple of seconds to give phenylhydrazine carboxylic ester (106), and with cyclohexylamine to give the substituted semicarbazide (107). A diaziridinone (105) is assumed to be the common intermediate, formed by an intramolecular reaction from deprotonated (104) (67CB2600). 

Kojic acid — see also Pyran-4-one, 5-hydroxy-2-hydroxymethyl-, 3, 611 acylation, 3, 697 application, 3, 880 occurrence, 3, 692 reactions, 3, 714, 715 with amines, 3, 700 with phenylhydrazine, 3, 700 synthesis, 3, 810 Kokusagine occurrence, 4, 989 Kokusaginine occurrence, 4, 989 synthesis, 4, 990 Koopmans theorem, 2, 135 Kostanecki-Robinson reaction chromone and coumarin formation in, 3, 819-821 mechanism, 3, 820 flavones, 3, 819... 

The Bucherer carbazole synthesis " involves the treatment of a naphthyl alcohol (1 or 4) or a naphthyl amine (2 or 5) with a phenylhydrazine 3 in the presence of aqueous sodium bisulfite to afford, after acidic work-up, either a benzo[a]carbazole 4 or benzo[c]carbazole 6. 

The pseudo-ionone has a peculiar but not very pronounced odour it docs not oombine with bisulphite of sodium as most of the ketones of the higher series, but, in other respects, it possesses the ordinary characteristic properties of the ketones, forming, in particular, products of condensation with phenylhydrazine, hydroxyl-amine and other substituted ammonias. 

Likewise, l-[4-methylbenzyl]-4,7-dihydroxy-l,2,3-triazolo[4,5-d]pyridazine 275 reacts with phenylhydrazine, HMDS 2, and (NH4)2S04 to give the monoamino product 276 in 60% yield [83]. Reaction of l-benzyl-3-n.-butyl-4-hydroxy-l,2,3-triazo-lo[4,5-d]-pyrimidine 277 for 8 h at 120°C with cyclopentylamine, HMDS 2, and (NH4)2S04 affords the aminated product 278 in 49% yield [84] (Scheme 4.33). 

Divalent Co substitution in copper amine oxidase revealed 19% of the native specific activity (for MeNH2) and 75% of the native reactivity toward phenylhydrazine. The major cause of this was a 68-fold increase in Km for 02. These investigations support the idea that electrons flow directly to bound 02 without the need for a prior metal reduction and that the Cu does not redox cycle but simply provides electrostatic stabilization during reduction of 02 to 02-. 1211... 

Interaction, in presence of diluent below 0°C, with isopropylamine or isobuty-lamine caused separation of explosive liquids, and with aniline, phenylhydrazine and 1,2-diphenylhydrazine, explosive solids [1], In absence of diluents, contact with most aliphatic or non-aromatic heterocyclic amines often leads to uncontrolled oxidation and/or explosions [2], During oxidation of two steroidal dienes in dry pyridine at —35 to —40°C, on one occasion each of the reactions was accompanied by violent explosions [3],... 

Symmetrically disubstituted thioureas have been synthesized by heating thiourea with aromatic amines or phenylhydrazine under environmentally benign conditions without solvent in a conventional microwave oven (Scheme 54).136... 

Filter, wash toluene with water, NaHC03, water and dry, evaporate in vacuum to get 100 g gamma-Cl-butyraldehyde (I) (can distill 28/2). 10 g (I), 20 g 3-nitro-phenylhydrazine dissolve in the minimum volume of hot ethanol containing 10% glacial acetic acid. Heat on steam bath one hour cool and add water until dark oil separates. Evaporate in vacuum the ethanol and decant the water to get the oily gamma-Cl-butyraldehyde-3-intro-phenylhydrazone(II). 29 g (11), 300 ml concentrated HC1, ZOO ml benzene stir three hours, replace benzene with fresh benzene and stir four hours. Combine the two benzene portions, wash with water and dry, evaporate in vacuum to get 4 g 3-(beta-Cl-ethyl)-4 and 6-nitroindole (m). 3.56 g (III), 200 ml ethanol, 200 ml 34% aqueous DMA (or other amine) and let stand at room temperature for one week. Evaporate in vacuum the ethanol, filter, dissolve the precipitate in dilute HC1 and filter. Basify the filtrate with dilute NaOH to precipitate 3 g 4 and 6-nitro-DMT (IV). 5.2 g (IV), 350 ml ethanol, 100 ml IN NaOH heat to 50° and add a solution of 3 g Na dithionite in 15 ml 0.2N NaOH. filter hot and evaporate in vacuum to get 2 g 4 and 6 amino-DMT (can purity by dissolving in HC1, filter, basify, extract with ether and dry and evaporate in vacuum the extract). 

The reason for the rate increase in the presence of phenylhydrazine remains unclear. The authors note that phenylhydrazone also accelerates the reaction and that the formation of the hydrazone from the solvent (acetone) cannot be ignored. Phenylhydrazine is known to reduce Cu(II) to Cu(I) (115), and the authors observed that the hydrazone is also capable of this reduction. It is interesting that the same rate acceleration could not be induced by other amine bases such as pyridine, l,5-diazabicyclo[4.3.0]non-5-ene (DBN), or DBU. While it is likely that phenyl-hydrazine-phenylhydrazone accelerates the slow step of the catalytic cycle through some sort of interaction with the metal, the exact nature of this involvement remains unclear. Elucidation of its role in the reaction may greatly aid the development of this transformation, and it is expected that it will impact the ultimate solution to this problem. 

The condensation of nitrosobenzene with phenylhydroxylamine which is described below is an example of this similarity. Hydroxyl-amine and phenylhydrazine also react with nitrosobenzene, but the details of these reactions cannot be given here. 

Kitaoka und Onodera 103) postulieren die intermolekulare Oxido-reduktion zwischen 103 und einem Mol Phenylhydrazin aufgrund des starken Reduktionsvermogens von N-Benzyl-(l-desoxy-l-p-toluidino-D-fructosyl)amin, das z.B. in essigsaurer Losung dutch Sauerstoff in N-Benzyl-D-arabonamid und p-Tolylformamid gespalten wird. 

The reactivity of the keto group is not influenced by the substitution the reaction of 3-(trifluoromethylmercapto)-2-butanone with hydroxyl-amine hydrochloride gives the corresponding oxime in good yield. Cyclization of diketones and keto esters to pyrazole derivatives succeeds by the well-known method using phenylhydrazine ... 

When the zwitterionic 1,3-oxazine iminium salt 113, which is a 1 1 mixture of ( )- and (Z)-isomers A and B, was treated with phenylhydrazine, pyrazolo[3,4-, [l,3]oxazine derivatives 114 were formed in moderate yields (Equation 7). Surprisingly, the products of the cyclizations 114 existed only as the ( )-isomers. Products with an ( )-double-bond were also formed exclusively on nucleophilic replacement of the 4-chloro substituents of 113A and 113B by various amines or a-amino esters <1999H(51)2893>. 

Fischer, E. Hber einige Reactionen des Phenylhydrazins und Hydroxyl-amins. Ber. 22, 1930 (1889). 

As lactams of 4-amino-3-oxobutanoic acids, tetramic acids react with amines (87JPJ858) and with phenylhydrazine. The latter reaction is catalyzed with para-toluenesulfonic acid. Thus, for example, l/2b give phenyl-hydrazone 65 in 80% yield that, in turn, under the conditions of the Fischer indole synthesis, may give rise to pyrrolo[4,3-b]indolene 66 (90TH1). (See Fig. 31.)... 

Phenylhydrazine Hydrochloride Phenylhydrazinium Chloride Phenyl Hydroxide Phenylmethanol Phenylmethyl Alcohol Phenylmethyl Amine Phenylphosphine Dichloride Phenylphosphine Thiodichloride Phenylphosphonothioic Dichloride Phenyl Phosphonous Dichloride Phenylpropylene 1 -Phenyltetradecane 1-Phenylundecane Phosgene Phosphoric Acid Phosphoric Sulfide... 

P-Phenylethyl alcohol, 812,816 Phenylethylene, 1015,1024 a-Phenylethylamine, 560, 566 P-Phenylethy,amine, 560, 567,569 Phenylethylbarbituric acid, 1003,1005 P-Phenylethyl bromide, 283 P-Phenylethyl iodide, 288 Phenylglycine-o-carboxylic acid, 980 Phenylglyoxal, 866 Phenylhydrazine, 635, 636 hydrochloride, 636, 637 Phenylhydrazine acetate reagent, 343, 721 ... 

Pyrylium cations form pyridines with ammonia and pyridinium salts with primary amines (B-82MI 505-02). For example, 2,4,6-triphenylpyrylium cation (261 Z=0) yields 2,4,6-triphenylpyridine with ammonia, the corresponding 1-methylpyridinium salt with methylamine, and pyridine 1-arylimines with phenylhydrazine. Xanthylium ions (210), where ring opening cannot readily occur, form adducts (262) with ammonia, amines, amides, ureas, sulfonamides and imides. Similar adducts (e.g. 263) are formed by benzo[( ]pyrylium ions. 

A large variety of aromatic amines react with isatins to give anils (132).169,232,269,305,312,411 413 The imine from isatin and o-hydroxy-aniline forms complexes with copper acetate and zinc iodide.413 Reaction of these anils (132) with phenylhydrazine gives the isatin-3-phenylhydrazone.411 The imine 132 (R = 5-Me, R = H, Ar = p-tolyl)... 

C-alkylation of secondary and tertiary aromatic amines by hexafluoroacetone or methyl trifluoropyruvate is performed under mild conditions [772] (equation 147) The reaction of phenylhydrazine with hexafluoroacetone leads selectively to the product of the C-hydroxyalkylation at the ortho position of the aromatic ring The change from the para orientation characteristic for anilines is apparently a consequence of a cyclic transition state arising from the initial N hydroxy alkylation at the primary amino group [173] (equation 148)... 

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