4589-97-3

Usage

Preparation

To a solution of 50 gm (0.34 mole) of ω-oximinoacetophenone (ω-isonitrosoacetophenone) in 150 ml of ethanol is added to a solution of 48 gm (0.595 mole) of sodium acetate and 24 gm (0.345 mole) of hydrox-ylamine hydrochloride in 75 ml of water. The mixture is heated at reflux for 4 hr. After cooling, a large portion of the Solvent is evaporated off under reduced pressure. The mixed crude product, which precipitates, is filtered off, washed with water, and air-dried to afford 51 gm (92%), m.p. 150-158°C. The separation of the three isomers by fractional crystallization pro-cedures depends on the relative ratio of the components in the mixture, the concentration of the components in the solvent, the length of time the solvent-product mixture is heated, etc. It is therefore important that the progress of the crystallization be followed by thin-layer chromatography using freshly prepared tic plates [Merck (Darmstadt) silica gel G is recom-mended as the coating]. The suggested tic solvent is benzene-ethyl acetate (7:3), detection by iodine vapor; 0.45 Rf for phenyl-amphi-glyoxime (I), 0.40 Rf for phenyl-anti-glyoxime (II), and 0.35 Rf for phenyl-syn-glyoxime(III). Anti-glyoxime (II), and 0.35 Rf for phenyl-syn-glyoxime(III). Anti-phenyl-amphi-glyoxime (I) is separated from the mixed product by repeated recrystallization from acetone-chloroform (or alcohol-water), m.p. 178-180°C; UV, λmax (95% ethanol) 230 mμ (ε 14,800). Phenyl-anti-glyoxime (II) is isolated from the mother liquor of the first crystallization in the separation of (I). The residue from the evaporation of this mother liquor is crystallized repeatedly from acetone-chloroform. After sublimation, the properties of the material are as follows: sublima-tion temperature, 90°C (0.2 mm Hg); m.p. 166-168°C; UV, λmax (95% ethanol) 228 mμ (ε 14,380). Only about 1% of pure isomer is isolated from the starting product. Phenyl-syn-glyoxime (III) is isolated by crystallizing the starting product from a dilute solution of ethyl acetate, m.p. 168-170°C; UV, λmax (95% ethanol) 252 mμ (ε 12,200).

InChI:InChI=1/C8H8N2O2/c11-9-6-8(10-12)7-4-2-1-3-5-7/h1-6,10,12H/b8-6+

Upstream product

• 532-54-7 E-isonitrosoacetophenone 
• 70-11-1 α-bromoacetophenone 
• 67-56-1 methanol 
• 100-75-4 N-nitrosopiperidine 
• 536-74-3 phenylacetylene 
• 64-17-5 ethanol 
• 2648-61-5 2,2-dichloroacetophenone 
• 532-54-7 oxo-phenyl-acetaldehyde oxime 
• 614-27-7 methyl 3-oxo-3-phenylpropionate 
• 1074-12-0 phenylglyoxal hydrate 
• 78113-09-4 α,α’-dichloromethylacetophenone 
• 98-86-2 acetophenone 

Downstream Products

• 20034-83-7 phenyl-glyoxal-bis-(4-bromo-phenylhydrazone) 
• 10349-06-1 3-phenylfurazan 
• 7707-64-4 3-phenyl-furazan 5-oxide 
• 825-52-5 2-(hydroxyimino)-2-phenylacetonitrile 
• 5700-56-1 1,2-diaminophenylethane 
• 53641-61-5 1-phenyl-1-acetylamino-2-acetylaminoethane 
• 10242-38-3 2-hydroxyimino-2-phenyl-acetohydroximoyl chloride 
• 10242-38-3 syn-2-Chlor-2-hydroxyimino-acetophenonoxim 
• 25327-36-0 (Z)-2-(hydroxyimino)-2-phenylacetic acid 
• 68272-44-6 acetoxyimino-phenyl-acetonitrile 
• 62779-70-8 (1S)-1-phenylethylene-1,2-diamine 
• 62779-69-5 (R)-1,2-Diamino-1-phenylethane 
• 170242-71-4 (1R)-[N,N'-bis(2'-hydroxybenzylidene)]-1-phenyl-1,2-diaminoethane 
• 41013-31-4 HOC₆H₄CHNCH(C₆H₅)CH₂NCHC₆H₄OH 

Relevant academic research and scientific papers

IMPROVED METHOD FOR PRODUCING SPECIFIC OXIMES AND OXIMETHERS

Method for preparing certain oximes and oxime O-methyl ethers by reacting poorly water-soluble carbonyl compounds with salts of hydroxylamine or hydroxylamine O-methyl ether or the free base of hydroxylamine in the presence of certain phosphoric esters or salts thereof of the formula (I) wherein R1, R2 and X are defined as specified in the description.

Green and highly selective protocol for the synthesis of oximes

A green and efficient protocol has been developed for the synthesis of either exclusively a monoxime or exclusively a dioxime from a host of 1,2-dicarbonyl compounds on silica.

Synthesis and characterization of a new dioxime: Thermal and magnetic behavior of its heterotrinuclear BF+2-capped complexes

New heterotrinuclear complexes have been obtained from dinuclear Fe(III) oxygen-bridged N,N'-bis(salicylidene)ethylenediamine (salenH2) and bis(salicylidene)-o-phenylenediamine (salophH2) and Co(II), Ni(II), Cu(II) salts. Then, heterotrinuclear vic-dioxime complexes containing [image omitted] caps have been synthesized. The complexes have been characterized as low-spin distorted octahedral Fe(III) bridged by COO- groups. The structure of dioxime and its complexes were identified by using elemental analysis, magnetic susceptibility, thermal analysis, ICP-AES, 1H-NMR, and IR spectral data.

One-pot synthesis of 3-amino-4-aryl- and 3-amino-4-hetarylfurazans

A "one pot" method for the synthesis of 3-amino-4-aryl- and 3-amino-4-hetarylfurazans from β-aryl- and 4-β-hetaryl-β-oxo acid esters was developed.

Electrical conductivity of chloro(phenyl)glyoxime and its Co(II), Ni(II) and Cu(II) complexes

Chloro(phenyl)glyoxime, a vicinal dioxime, and its Ni(II), Cu(II) and Co(II) complexes were prepared. XRD patterns of the complexes point to similar crystal structures. IR and elemental analysis data revealed the 1:2 metal-ligand ratio in the complexes. The Co(II) complex is a dihydrate. Temperature dependence of electrical conductivity of the solid ligand and its complexes was measured in the temperature range 25-250°C; it ranged between 10-14-10-6 Ω-1 cm-1 and increased with rising temperature. The activation energies were between 0.61-0.80 eV. The Co(II) complex has lower electric conductivity than the Ni(II) and Cu(II) complexes. This difference in the conductivity has been attributed to differences in the stability of the complexes.

Nitrosamine Photolysis as a Synthetic Method: The Addition of Aminium Radicals to Unsaturated Carbon-Carbon Bonds

Acid complexed nitrosamines decompose from their lowest singlet excited state to gine aminium radicals and nitric oxide radical transients.Aminium radicals initiate addition of various unsaturated groups to give 1-amino-2-nitroso compounds under an inert atmosphere, or 1-amino-2-nitrates under oxygen.In this report, photoaddition of nitroamines to olefins, acetylenes and fused aromatic hydrocarbons, and the subsequent transformations of the intermediates are described.Aminium radical initiated intramolecular cyclization to prepare tetracyclic aza compounds is also described.While photoaddition of nitrosamines to 4-propenylanisole or 3-butenol wes efficient, that to 3-butenyl benzoates under oxidative conditions was only fair, obviously due to the presence of a benzene ring.The oxidative photoaddition to 3-butenyl halide was followed by spontaneous cyclization to an azaspiro compound.The photoaddition to phenyl-substituted acetylenes gave β-nitroso enamines which hydrolyzed to diketomonoximes under neitral conditions but decomposed extensively under acidic conditions.Certain fused aromatic hydrocarbons acted as singlet sensitizers as well as substrates to induce similar addition giving amino nitroso adducts.These adducts took different courses of conversion dependent on reaction conditions, and on steric and electronic factors.