Abstract: The syntheses of the unprotected, (Z)-configurated hexon- and pentonhydroximo-lactones 2a–12a by oxidation of D-glucose, cellobiose, D-galactose, D-mannose, 2-acetamido-2-deoxy-D-glucose, D-ribose, and D-arabinose oxime with MnO2, Hg(OAc)2, or O2 in the presence of Cu2Cl2/pyridine are described. An (E/Z)-pair of protected hydroximo-lactones 14 and 15 was obtained by oxidation of the diisopropylidene-D-mannose oxime 13 with MnO2. In CH2Cl2 solution, the minor (E)-isomer 15 was slowly transformed into the major (Z)-isomer 14. The structure assignments for 2a–12a are based upon IR and NMR data, the Beckmann rearrangement of 1 and 14, and the X-ray structure analysis of 7a and 47. From the selectively deprotected hydroximo-lactones 2c, 8c, and 9c, the urethanes 2d, 2f, 8d, and 9d were prepared. (E/Z)-mixtures of the amino phosphates 27/28, 29/30, and 31/32 were obtained from the bromonitroso ethers 16, 19, and 17 and NaPO(OEt)2. The configuration of the bromonitroso ethers 18 and 19 were assigned on the basis of their CD spectra and of their correlation with the corresponding bromonitro ethers 24 and 25. Factors influencing the configuration of the hydroximo-lactones are briefly discussed.

Abstract: The polymer-supported chiral amino alcohol (3) has been prepared by the reaction of chloromethylated polystyrene resin and (S)-(–)-2-amino-3-(p-hydroxy)phenyl-1,1-diphenylpropan-1-ol (2); the chiral polymeric reagent has been prepared from (3) and borane. The asymmetric reductions of ketones and oxime ethers with the polymeric reagent have been shown to give optically active alcohols (up to 97% optical purity) and amines (up to 67% optical purity), respectively. The results are compared with those obtained with (S)-(–)-2-amino-1,1,3-triphenylpropan-1-ol (4) or (S)-(–)-2-amino-3-(p-benzyl-oxyphenyl)-1,1 -diphenylpropan-1-ol (5) which are soluble model reagents.

Abstract: The successive cyclopalladation–oxidation of E-pinacolone, E-2,2-dimethylcyclohexanone, 2,2,6,6-tetramethylcyclohexanone, and E-lupanone oxime led to the corresponding β-acetoxy derivatives; the second palladation in the case of the acetoxy compounds (2) and (8) takes place in one of the remaining methyl groups, being a regiospecific process, and in the case of the cyclic oximes the palladation occurs in the equatorial methyl group

Abstract: Several di- and trihydroxamate analogues of natural microbial iron chelators have been prepared. The syntheses involved linkage of core structural units, including pyridinedicarboxylic acid, benzenetricarboxylic acid, nitrilotriacetic acid, and tricarballylic acid, by amide bonds to 1-amino-omega-(hydroxyamino)alkanes to provide the polyhydroxamates 1-5. The required protected (hydroxyamino)alkanes 8, 16, and 21 were prepared by different routes. 1-Amino-3-[(benzyloxy)amino]propane di-p-toluenesulfonate (8) was prepared from the N-protected aminopropanol 6 by oxidation to the aldehyde, formation of the substituted oxime, and reduction with NaBH3CN followed by deprotection of the Boc group. The pentyl derivatives 16 and 21 were made by direct alkylation with either benzyl acetohydroxamate or N-carbobenzoxy-O-benzylhydroxylamine. In Escherichia coli RW193 most of the analogues behaved nutritionally as ferrichrome. However, in E. coli AN193, a mutant lacking the ferrichrome receptor, capacity to use other natural siderophores was retained while response to all analogues was lost.

Abstract: Dicyanoethylated polystyrene, poly{1-[4-(2,2-dicyanoethyl)phenyl]ethylene} (2), which was obtained from the reaction of chloromethylated polystyrene, poly[1-(4-chloromethylphenyl)-ethylene] (1) with malononitrile under phase transfer reaction conditions, was treated with hydroxylamine in methanol to afford a polystyrene resin 3 with two amide oxime functions in the repeating unit. Resins 3 exhibit a higher adsorptivity of uranium in seawater than a corresponding resin 5 with one amide oxime function in the repeating unit. The effective adsorption of uranyl ions by resins 3 is attributed to the close proximity of the two amide oxime functions in the styrene monomeric unit, which can effectively coordinate to a uranyl ion.

Abstract: Reaction of the oxime of lanost-8-en-3-one with Na2PdCl4 carbopalladates a 4-methyl group which can be converted into monodeuteriomethyl and iodomethyl compounds.

Abstract: The synthesis of R-(+) and S-(-) isomers of O-[3-tert-butylamino)-2-hydroxypropyl] cyclopropyl methyl ketone oxime (falintolol) is described. The syn and anti isomers of falintolol were obtained in two different ways from cyclopropyl methyl ketoxime or from falintolol. For comparison purposes, the enantiomers of the dicyclopropyl ketone oxime derivatives were also prepared. Structure-activity relationships are described.

Abstract: Trimethylsilyl azide (TMSA) was reacted with an oxime ester or a Reissert salt in the presence of trimethylsilyl trifluoromethanesulfonate to give tetrazole derivative. The details of these reactions are examined.

Abstract: 2,3-O-Isopropylidene-D-ribose(7) reacted with p-methoxybenzylmagnesium chloride in tetrahydrofuran to give the D-allotriol (6a)(77%). Periodate oxidation of compound (6a) followed by reaction with hydroxylamine hydrochloride in pyridine gave (E,Z)-5-deoxy-2,3-O-isopropylidene-5-(p-methoxy-phenyl)-L-ribose oxime (18a) which was converted into the nitrile methanesulphonate (19a) with methanesulphonyl chloride in pyridine. Reduction of the nitrile (19a) with lithium aluminium hydride gave (2R,3S,4R)-3,4-isopropylidenedioxy-2-(p-methoxybenzyl)pyrrolidine (2a)[45% from (6a)], which was converted into the epoxide (24a)(68%)via the bromo acetates (28a) and (29a). Regioselective opening of the epoxide ring in compound (24a) with acidic allyl alcohol gave the allyl ether (30a)(63%) which was converted into the N-benzyl 3-acetoxy compound (31a)(77%). Removal of the allyl and benzyl groups, by treatment with palladium-charcoal under acidic conditions followed by hydrogenolysis, gave (–)-anisomycin (1a)(86%).A similar series of reactions afforded demethoxyanisomycin (1b) which showed antibiotic activity against Trichomonas vaginalis[about one sixth the activity of anisomycin (1a)].

Abstract: Oxime blocked polyisocyanate cross-linking agents for use with amine epoxy resin adducts in cathodic electrodeposition processes. The oxime blocking agents are the reaction products of acyclic aliphatic carbonyl-containing compounds having at least 7 carbon atoms and hydroxylamine. The oxime blocked polyisocyanates produce cathodic electrodeposited coatings which are smoother than coatings produced by oxime blocked polyisocyanates known in the art.

Abstract: The successive cyclopalladation–oxidation of E-pinacolone, E-2,2-dimethylcyclohexanone, 2,2,6,6-tetramethylcyclohexanone, and E-lupanone oxime led to the corresponding β-acetoxy derivatives; the second palladation in the case of the acetoxy compounds (2) and (8) takes place in one of the remaining methyl groups, being a regiospecific process, and in the case of the cyclic oximes the palladation occurs in the equatorial methyl group.

Abstract: The structure of the title compound obtained from 2(1H)-quinoxalinone oxime by the template effect of Co(II) and Ni(II) ion has been determined by three dimensional X-ray analysis

Abstract: A new reducing agent was prepared from borane and amino alcohols. The reagent is very effective for chemoselective reduction of ketones in the presence of esters, oxime ethers, tertiary amides, nitriles, halides, and acyl chlorides. The polymeric reagent prepared from borane and polymer-supported amino alcohol was also prepared easily. Aldehydes are highly selectively reduced to primary alcohols in the presence of ketone with the polymeric reagent. Simple filtration separated cleanly the unchanged ketone from the polymeric reagent which gave, after hydrolysis, only primary alcohol as the product. The polymeric reagent was regenerated by treatment with borane and could be reused.

Abstract: Ketoximes, when treated with KO2 (1 equiv) in the presence of di-μ-chlorobis(2-methylallyl)dipalladium(II) (01 equiv per Pd) in dichloromethane, give methylene dioximes in moderate yields This alkylation of ketoximes with CH2Cl2 is also promoted by the use of potassium carbonate in the presence of phase-transfer catalysts such as 18-crown-6 Study on the reactivity of a series of ketoximes in these reactions shows that proton abstraction by base is a crucial step in the latter reaction By contrast, in the former system the reactivity is supposed to be controlled by nucleophilicity of the oximate anion coordinated to palladium(II) Application of the present reaction to (E,E)-1,2-diketone dioxime such as dimethylglyoxime leads to the formation of novel 21-membered ring heteromacrocyclic compounds in which oxime units are sequentially linked by methylene bridge

Abstract: α,β-Unsaturated nitroalkenes are readily reduced by SnCl2·2H2O in alcoholic media to the α-alkoxy oxime derivatives in high yields. In the presence of ethanethiol, the corresponding α-alkylthio oximes are formed.

Abstract: Cinetique de l'equilibre Ni(IV)+Ni(II)⇄2Ni(III) a ete etudiee en fonction du pH (de 4 a 10). Le coordinat associe est le dimethyl-3,14 tetraaza-4,7,10,13 hexadecadiene-3,13 dione-2,15 dioxime

Abstract: Methods for introducing various pharmacophoric amine-containing substituents into the adamantane system have been investigated. These include β-and α-aminoalkyloxyimino, β-aminoalkylidene, β-hydroxyethylamino, and β-phenylethylamino. Aminoalkyloxyimines were prepared by alkylation of the anion of adamantanone oxime with the corresponding aminoalkyl chloride, and a 2-aminoethylidene derivative was prepared by Wittig reaction of 2-dimethylaminoethyltriphenylphosphonium bromide with adamantanone. The reaction of 6-hydroxy-7-methyl-6-phenyladamantane-2,4-dione with aqueous sodium cyanide has been shown to be both regio- and stereo-selective, only the C-2 carbonyl group reacting from the most hindered direction. This is possibly due to stabilisation of the cyanohydrin by hydrogen bonding between the hydroxy and C-4 carbonyl groups. When trimethylsilyl cyanide was used in place of sodium cyanide, the reaction remained regioselective but, in the absence of hydrogen bond stabilisation, the stereoselectivity was lost and two trimethylsilyloxy cyanides were isolated, epimeric at C-2. The stereochemistry of one epimer has been determined by X-ray crystallography, details of which are reported here. Hydrogenation of the trimethylsilyloxy cyanides then gave the corresponding β-hydroxyamine, isolated as the hydrochloride. Finally 5,7-diphenyl-1,3-diaza-adamantan-6-one was prepared by a literature method and converted, with difficulty, into the oxime which was reduced by RedAl to the corresponding amine.

Abstract: The polarity index, retention index, coefficient ϱ and partial Gibbs function of one mole of a solute methylene group and the Sevcik A criterion were determined at different temperatures for some aromatic hydroxyoximes and intermediate ketones by means of gas-liquid chromatography using n-alkanes as nonpolar agents and n-alcohols as polar agents. The relations between these parameters and the relations between the polarity and the compound structure were discussed. In the oxime and ketone molecules the polarity of the hydrophilic groups changes in the following order: OH>NOH>O;and OH>CO>O, respectively. The ketones have less polarity than the oximes. The phenolic hydroxyl group has twice the polarity of the oxime and the carbonyl groups. The chlorine atom at the ortho position in relation to the hydroxyl group sharply increases the polarity.

Abstract: The oxime ester compound [(isopropylideneamino)oxy]-ethyl-2-[[(6-chloroquinoxalinyl)oxy]phenoxy]propionate, processes for the preparation thereof, herbicidal compositions containing said compound and methods of use of the composition.

Abstract: Several oximes, acetohydroxamic acid, and 3-nitropropionic acid were examined to determine if they could serve as substrates for heterotrophic nitrification by an Alcaligenes sp., previously isolated from soil and shown to actively nitrify pyruvic oxime. Neither acetohydroxamic acid, the aldoximes of acetaldehyde or butyraldehyde, or the alkyl oxime, acetone oxime, were used as nitrification substrates or as sole sources of carbon or nitrogen. α-Ketobutyric oxime, α-ketoglutaric oxime, and 3-nitropropionic acid, however, were nitrified and growth occurred when these compounds served as sole sources of carbon and nitrogen. Experiments with resting cells and cell-free extracts of the Alcaligenes sp. grown on α-ketobutyric oxime and α-ketoglutaric oxime indicate that these substrates are nitrified via an organic pathway as the rates of hydroxylamine (the nitrogen hydrolysis product) conversion are kinetically insufficient. 3-Nitropropionic acid metabolism by resting cells of the Alcaligenes sp. grown in 3-ni...

Abstract: A novel process for the production of 0-substituted oximes is disclosed. The process involves reacting an oxime with an alkali-metal hydroxide optionally in a solvent which forms an azeotrope with water to form a mixture of the alkali metal salt of the oxime and water, removing all or a portion of the water by distilling the mixture azeotropically and reacting the distilled mixture with an organohalide compound.

Abstract: Oxime ethers containing a 4-phenoxyphenoxy group in the molecules were synthesized and their insect growth regulating (IGR) activities were studied. Of these new IGR’s, propionaldehyde oxime O-2-(4-phenoxyphenoxy)ethyl ether and propionaldehyde oxime O-2-(4-phenoxy-phenoxy)propyl ether were found to be most effective, having much higher activities than metho-prene against larvae of Culex pipiens pallens and Musca domestica by the immersion method and medium method, respectively. In addition, the effects of steric isomerism of these compounds were examined; their IGR activities were found to have a close relationship to the juvenile hor-mone activity by the Galleria wax test.