Abstract: The oxime of isopropyl phenyl ketone (Z-isomer) with NaOAc–Na2PdCl4 gives [Pd3(ONCPriPh)6] and whereas pinacolone oxime carbopalladates regiospecifically on the t-butyl group, the dimethylhydrazone carbopalladates only on the methyl group: acetone oxime O-allyl ether palladates on the central carbon atom of the allyl group with nucleophilic attack (e.g. by OMe–) on the terminal carbon atom.

Abstract: The carbon-13 chemical shifts for a number of relatively rigid ketoximes are presented. It is shown that the chemical shift difference, A6 (sj~rr-onri), for the carbons a to the oxime carbon depends on the dihedral angle between the C=N and C.-H bonds. This stereochernical dependence is then used to determine the preferred conforn~ation of substituted cyclohexanone oximes.

Abstract: New carbene complexes of (acetophenone oxime, 2-C,N)chloro(1,3-diphenylimidazolidin-2-ylidene)palladium(II) (1), (benzophenone oxime, 2-C,N)chloro(1,3-diphenylimidazolidin-2-ylidene)palladium(II) (2), and chloro(N,N-dimethylbenzylamine, 2-C,N)(1,3-diphenylimidazolidin-2-ylidene)palladium(II) (3) have been prepared by reactions between dimeric cyclopalladated complexes and 1,1′,3,3′-tetraphenyl-2,2′-biimidazolidinylidene. Chlorine atoms were shown to be situated at the trans position to the aryl-palladium σ bond on the basis of IR spectra. These carbene complexes underwent halogen metathesis with LiBr to yield the corresponding bromo derivatives. Triphenylphosphine displaced the chlorine atom in 1, 2, and 3, converting each to a cationic carbene complex, in which the nitrogen donor of cyclopalladation moiety remained coordinated to palladium.

Abstract: 15N chemical shifts of the Z and E isomers of twenty-two ketoximes and fourteen aldoximes have been determined at the natural-abundance level of 15N, using Fourier transform methods. The influences of π delocalization, methyl substituents and solute concentration on the oxime nitrogen shielding have been determined. The 15N shifts for oximes of several cycloalkanones have been measured and the influence of ring size on the chemical shifts is discussed.

Abstract: 4-(2-Oxo- or hydroxyimino-cycloalkan-1-ylmethyl)phenylacetic acid derivative and nontoxic pharmaceutically acceptable salt thereof are useful as an anti-inflammatory agent. The above 2-oxo-compound may be prepared by (a) hydrolyzing and decarboxylating 4-(1-alkoxycarbonyl-2-oxocycloalkan-1-ylmethyl)phenylacetic acid ester derivative or (b) reacting p-halomethylphenylacetic acid ester derivative with an enamine of cycloalkanone and hydrolyzing the resulting product. And further, the above 2-hydroxyimino-compound may be prepared by (c) reacting 4-(2-oxocycloalkan-1-ylmethyl)phenylacetic acid derivative (the product of process (a) or (b)) with hydroxylamine or (d) reacting a dilithium salt of cycloalkanone oxime with p-halomethyl- or p-sulfonyloxymethyl-phenylacetic acid ester derivative and hydrolyzing the resulting product.

Abstract: Chemical syntheses of [UL- 14C]-labelled N-hydroxytyrosine, p-hydroxyphenylpyruvic acid oxime, p-hydroxyphenylacetaldoxime, and p-hydroxyphenylacetonitrile in high yields from L-[UL-14 C]-tyrosine are described. These syntheses involve initial conversion of L-tyrosine to p-hydroxyphenylpyruvic acid, which then is allowed to react with hydroxylamine to form p-hydroxypheny lpyruvic acid oxime. N-Hydroxytyrosine is obtained from the latter by reduction with sodium cyanoborohydride, and is oxidatively decar-boxylated to p-hydroxyphenylacetaldoxime by treatment with ammonia. Finally, p-hydroxyphenylacetonitrile is obtained by dehydration of the aldoxime with thionylchloride. All synthesized compounds were identified by combined GLC/MS of their trimethylsilyl derivatives. The commercial availability of several specifically labelled 14C, 2H, and 3H tyrosines and of 2H and 3H sodium cyanoborohydride makes the method equally useful for synthesis of various specifically labelled compounds.

Abstract: The carbon-13 chemical shifts for a number of relatively rigid ketoximes are presented. It is shown that the chemical shift difference, A6 (sj~rr-onri), for the carbons a to the oxime carbon depends on the dihedral angle between the C=N and C.-H bonds. This stereochernical dependence is then used to determine the preferred conforn~ation of substituted cyclohexanone oximes.

Abstract: New carbene complexes of (acetophenone oxime, 2-C,N)chloro(1,3-diphenylimidazolidin-2-ylidene)palladium(II) (1), (benzophenone oxime, 2-C,N)chloro(1,3-diphenylimidazolidin-2-ylidene)palladium(II) (2), and chloro(N,N-dimethylbenzylamine, 2-C,N)(1,3-diphenylimidazolidin-2-ylidene)palladium(II) (3) have been prepared by reactions between dimeric cyclopalladated complexes and 1,1′,3,3′-tetraphenyl-2,2′-biimidazolidinylidene. Chlorine atoms were shown to be situated at the trans position to the aryl-palladium σ bond on the basis of IR spectra. These carbene complexes underwent halogen metathesis with LiBr to yield the corresponding bromo derivatives. Triphenylphosphine displaced the chlorine atom in 1, 2, and 3, converting each to a cationic carbene complex, in which the nitrogen donor of cyclopalladation moiety remained coordinated to palladium.

Abstract: The electrochemical oxidation of titanium metal in the presence of an essentially non-aqueous electrolyte phase yields titanium(III) species in solution. It has been shown that this method of generating TiX3 (X = balancing anion) forms the basis of a convenient way of reducing insitu certain organic functional groups (sulfoxide, oxime, haloketone, vinyl dicarboxylic acid, and nitro aromatics). The stoichiometry of the reaction has been established in each case, and corresponds to the oxidation of TiX3 and the formation of the appropriate organic compound. The yields are comparable to those reported in experiments using aqueous titanous chloride.

Abstract: Sodium acyloxyborohydrides, [NaBH3 (OCOR)], prepared from an equivalent mol sodium borohydride and various carboxylic acids in tetrahydrofuran reduced oxime ethers to the corresponding amines. Particularly sodium trifluoroacetoxyborohydride gave best results.

Abstract: Solanascone (1), a new tetracyclic sesquiterpene ketone, has been isolated from Nicotiana tabacum cv. Burley; its structure was confirmed by X-ray analysis of its corresponding oxime (2).

Abstract: Electron impact studies on eight α,β-unsaturated carbonyl oximes revealed many interesting hydrogen and skeletal rearrangements which were substantiated by deuterium labelling, exact mass measurements and metastable studies. Loss of H· and OH· as well as formation of the indenyl and fluorenyl cations and the [C9H6N]+ fragment proceed through cyclic intermediates. All the ionized oximes undergo a Beckmann rearrangement in the gaseous phase leading to intense aroyl cation peaks. Formation of the styrene radical ions and cleavage of the bond α to the oxime function have also been noticed.

Abstract: In the presence of sodium acetate, the reaction of 4-chromanone oxime with lithium tetrachloropalladate(II) affords an ortho-palladated binuclear complex. The reaction of the complex with carbon monoxide in methanol was also examined.

Abstract: Die Oxime der 1,5,6,7-Tetrahydro-4H-indol-4-one 1a–c bilden bei der Beckmann-Umlagerung mit Polyphosphorsaure unter Alkylwanderung die Lactame 5, 8 und 10. Die Schmidt-Reaktion von 1a und 1b sowie die Beckmann-Umlagerung uber die Oximtosylate von 1b und 1c geben unter Arylwanderung die isomeren Lactame 3,6 und 11. Der Unterschied im Verhalten zu den entsprechenden Tetrahydro-4H-indazol-4-onen wird diskutiert. Enehydrazines, 22: Lactams from 1,5,6,7-Tetrahydro-4H-indol-4-ones The oximes of the 1,5,6,7-tetrahydro-4H-indol-4-ones la–c form the lactams 5, 8. and 10 with alkyl migration in the Beckmann rearrangement with polyphosphoric acid. The Schmidt reactions of 1a and 1b and the Beckmann rearrangements via the oxime tosylates of 1b and 1c give the isomeric lactams 3, 6, and 11 with aryl migration. The difference in behaviour compared to the corresponding tetrahydro-4H-indazol-4-ones is discussed.

Abstract: N-Nitroso compounds can be determined using a chemiluminescence analyzer by means of the nitric oxide liberated as a volatile product of their denitrosation using hydrogen bromide [1, 2]. Much of the nitrite present in or added to a food matrix can be lost even during storage in a refrigerated condition and thus the possibility arises of its conversion into compounds other than nitrosamines and nitrosamides which could also give rise to nitric oxide under, for instance, thermal degradation. Among compounds potentially formed from nitrite that have been studied in relation to their breakdown to nitric oxide have been included an alkyl nitrate, an alkyl nitrite, an amine oxide, an azoxy compound, a nitramine, a nitro guanidine, a nitrolic acid, a nitrone, an oxime, a pseudonitrole, a pseudonitrosite, a thionitrite, a thionitrate as well as C-nitro and C-nitroso compounds. Only in the case of the nitrolic acid and the thionitrate was it likely that interference with the determination of N-nitroso compounds could occur to any considerable extent.

Abstract: Ammonia, oxygen e.g., as air, and a ketone react in contact with a catalyst such as porous, amorphous silica or alumina which may or may not have a coating to form an oxime, at temperatures such as 50°-500° C. The oximes have known utilities, including uses as oxidation inhibitors and as intermediates for production of amides. In particular, when the ketone is cyclohexanone, the cyclohexanone oxime in the reaction product can further be converted to the cyclic amide, caprolactam, e.g. by contacting the product with an aluminosilicate catalyst having average pore diameter of at least 7 angstroms, especially a molecular sieve, suitably downstream in the same reaction vessel. Caprolactam is the monomer starting material for nylon 6.

Abstract: Ultraviolet irradiation of hydrocarbon solutions of 2,4,6-tri-tert-butylnitrosobenzene (1) formed The initial products were 2-methyl-1-nitroso-2-(3,5-di-tert-butyl)-phenylpropane (Ar—C(CH3)2CH2NO)2 (3) and a mixed dimer (4). Secondary and minor photoproducts isolated included 2-methyl-2-(3,5-di-tert-butyl)phenylpropanal oxime (5), 2-methyl-2-(3,5-di-tert-butyl)phenylpropanal (6) derived from 5, and 1,3,5-tri-tert-butylbenzene (7). The initial products are explained by formation of a tri-tert-butylphenyl radical (15), rearrangement of a hydrogen atom from an orthotert-butyl to the ring in 15, and rapid recombination of the neophyl radical with nitric oxide. Photolysis of 2,5-di-tert-butylnitrosobenzene (2) initially gave (10). Product analysis indicated a comparatively complex mixture including 1,4-di-tert-butylbenzene (11), 2,5-di-tert-butylphenol (12), and 2,5-di-tert-butylanilino-p-(2,5-di-tert-butyl)quinone (13). Evidence indicates that 12 and 13 form from free radical reactions involving 10 and the 2,...

Abstract: A hydrocarbon fuel, especially a copper-sweetened aviation jet fuel, contains a metal deactivator which is an oxime of either an orthohydroxy aromatic ketone or α-hydroxy aliphatic ketone, or an imine of a diamine with an ortho hydroxy aromatic ketone, an alkyl substituted ortho hydroxy aromatic aldehyde or a -diketone Preferred materials include oximes of 2-hydroxy-5-t-butyl benzophenone and 2-hydroxy-5-nonyl acetophenene and di-imines of ethylene and propylene diamines with benzoyl acetone, 5-t-octylsalicylaldehye or 2-hydoroxy-5-methyl butyrophenone The metal de-activator is added in conventional proportions, typically about 5 to 10 ppm (by weight) to the fuel which may contain either conventional additives such as anti-static, anti-icing and corrosion inhibiting additives

Abstract: Crystals of trans-azido bis(dimethylglyoximato)pyridinecobalt(III) are monoclinic, space group P21/c The unit cell constants are a = 8731(3), b = 13982(3), c = 17961(5) A,β = 12680(1), V = 17557 A3, and Z = 4 The structure was determined from three dimensional X-ray data (2152 independent reflections) obtained by the θ-2θ scan method using a CAD–4 automated four-circle diffractometer Structure solution was effected by Patterson and Fourier methods and refined by block diagonal least squares method to a conventional R value of 0041 The two dimethyl glyoximato monoanions occupy the equatorial plane with pyridine and azide groups in the axial positions Azide N–N bond distances were found to be 1155(6) and 1126(7) A with the longer bond adjacent to the cobalt atom Cobalt–nitrogen bonds in the axial positions are significantly longer than those in the equatorial plane Although the O–O interatomic distances between the separate oxime anions are close to 25 A the hydrogen bonding is deci