Benzoylhydrazine

Recently (82CC450) the conversion of aromatic hydrazides into indazolones in good yield when treated with three equivalents of n-butyllithium has been described. For example, benzoylhydrazine afforded indazolone in an 80% yield (Scheme 51). 

The parent heterocycle of pyrido[2,3-e][l,2,4]triazine and its phenyl derivative 39 were prepared (89JHC475) by cyclization with polyphos-phoric acid of 3-acyIhydrazino-2-aminopyridines 36, obtained by reduction of the corresponding 3-acylhydrazino-2-nitropyridines 35. Compounds 35 were obtained from 3-fluoro-2-nitropyridine 34 either by reaction with benzoylhydrazine or by reaction with hydrazine and subsequent for-mylation of the initially formed 3-hydrazino-2-nitropyridine 38. Attempts to prepare 38 from 3-chloro-2-nitropyridine gave 2-hydrazino-3-chloropyridine 37. These results could be explained by semiempirical calculations (CNDO and MNDO calculations). 

The reaction between benzoylhydrazine and ethyl or phenyl phosphorodichloridate yields 5-(2-benzoylhydrazino)-5,6-dihydro-2,8-diphenyl-4i7-l,3,4,6,7,5-oxatetra-azaphosphocine 5-oxide (32).87... 

Benzophenone, 46, 36 N-(2-Benzothiazolyl)urea, 46, 72 Benzoyl chloride, reaction with hydrogen fluoride, 46, 4 Benzoyl fluoride, 46, 3 Benzoylhydrazine, 46, 8S Benzoyl peroxide, reaction with diethyl ethylmalonate, 45, 37 2-Benzyl-2-carbomethoxycyclopenta-none, 45, 7... 

A facile one-pot synthesis for the synthesis of the dicarbonylrhenium(I) complex [Re(CO)2Cl(N2)(PPh3)2] has been developed which gives this compound in good yields. It starts from a mixture of perrhenate, HCl, PPhs, and benzoylhydrazine in CH2Cl2/methanol. When CO gas is bubbled into this mixture, the known pale-yellow complex [Re(CO)2Cl(N2)(PPh3)2] precipitates from the solution. This compound represents a useful precursor for the synthesis of a number of rhenium(II) and (surprisingly) rhenium(V) complexes. ... 

Aroylhydrazines are readily oxidised in protic solvents. Benzoylhydrazine and 2-benzoylphenylhydrazine show anodic waves in an acetate buffer at +0.08 and +0.02 V vs. see respectively [147], The most studied member of this group, because of its importance as the photographic developer phenidone, is 1-phenyl-pyrazolin-3-one 33. Phenidone shows a one-electron oxidation wave at a rotating... 

This new class of meso-ionic compounds have been recently synthesized. -Methyl-iV-benzoylhydrazine (147, R = Me, R = Ph) and aryl isocyanide dichlorides (ArN=CCl2) yield 1,3,4-oxadiazolium chlorides (154, R = Me, R = Ph, R = Ar), which with diazomethane give the meso-ionic l,3,4-oxadiazol-2-imines (153) as yellow crystalline compounds. Subsequently this synthetic method has been extended by the use of acylisocyanide dichlorides. These reagents yield the 1,3,4-oxadiazol-2-imines 153, R = SO,R, and 153, R = COR. "... 

Sultones react easily with amines and anilines <1989PHA294, 1989EJC259, 1987LA481> 1,2-oxathiin 2,2-dioxide derivatives 104 condensed to give the corresponding sultams 105 but 1,2-oxathiane 2,2-oxides 16 were cleaved by aniline or benzoylhydrazine derivatives to provide the corresponding sulfonic acids 106 (Scheme 25) <1993AFF256>. 

The synthesis and characterization of V02+ complexes of hydrazones (94) and (95) derived from benzoylhydrazine and o-hydroxy aromatic aldehydes and ketones were also reported772 and molecular weight determinations, IR, electronic spectra and magnetic properties were explained assuming a dimeric structure (96) with each unit having a five-coordinate square pyramidal geometry. 

Condensations involving a two-carbon 1,2-dielectrophile, such as an a-halocarbonyl compound or a 1,2-dihaloalkane, are fairly common. Thus reaction of dichloroacetyl chloride with N-phenyl-N -benzoylhydrazine gives the 1,3,4-oxadiazine (168) (78JPR452). Condensation of a-halo ketones with thiohydrazides (Scheme 15) is a useful general route to 1,3,4-thiadiazines and many examples are known (69ZC111,70LA(74l)45,76JPR971). 

N-Acetyl-lV -benzoylhydrazine forms Cu(L — 2H) (157) which are planar, but differ in structure from the nickel and cobalt analogues.178... 

No hydrolysis is observed when 2,5-diphenyl-1,3,4-oxadiazole, which has a solubility in water of 0.03%, is treated with mineral acids. Neither concentrated HN03 nor treatment with fuming H2S04 at 100° for 4 hours attacks the oxadiazole ring. Similar stability is shown by 2-(o>-styryl)-5-aryl-l, 3,4-oxadiazole.19 On the other hand, the attempt to obtain the free acid by treatment of 2-phenyl-5-p-car-bethoxyphenyl-1,3,4-oxadiazole with caustic soda produces 1 -p-carboxybenzoyl-2-benzoylhydrazine.23 Other aryl-substituted compounds as well as 1,3,4-oxadiazoles substituted in the 2,5-position by various heterocyclic groups are hydrolyzed by mineral acids.26... 

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