Abstract: Oxidation by rat liver microsomes of 13 compounds involving a CN(OH) function (including N-hydroxyguanidines, amidoximes, ketoximes, and aldoximes) was found to occur with the release of nitrogen oxides such as NO, NO2-, and NO3-. The greatest activities were observed with liver microsomes from dexamethasone-treated rats (up to 8 nmol of NO2- nmol of P450-1 min-1). A detailed study of the microsomal oxidation of some of these compounds was performed. Oxidation of N-(4-chlorophenyl)-N‘-hydroxy-guanidine led to the formation of the corresponding urea and cyanamide in addition to NO, NO2-, and NO3-. Formation of all these products was dependent on NADPH, O2, and cytochromes P450. Oxidation of two arylamidoximes was found to occur with formation of the corresponding amides and nitriles in addition to nitrogen oxides. Oxidation of 4-(chlorophenyl)methyl ketone oxime gave the corresponding ketone and nitroalkane as well as NO, NO2-, and NO3-. These reactions were also dependent on cytochromes P450 and required ...

Abstract: New oximsulfonate compounds of formulae (I) or (II), wherein m is 0 or 1; x is 1 or 2; R1 is, for example phenyl, which is unsubstituted or substituted or R1 is a heteroaryl radical that is unsubstituted or substituted, or, if m is 0, R1 additionally is C2-C6alkoxycarbonyl, phenoxycarbonyl or CN; R'1 is for example C2-C12alkylene, phenylene; R2 has for example one of the meanings of R1; n is 1 or 2; R3 is for example C1-C18alkyl, R'3 when x is 1, has one of the meanings given for R3, or R'3 in formula (IV) and when x is 2 in formula (I), is for example C2-C12 alkylene, phenylene; R4 and R5 are independently of each other for example hydrogen, halogen, C1-C6alkyl; R6 is for example hydrogen, phenyl; R7 and R8 are independently of each other for example hydrogen or C1-C12alkyl; R9 is for example C1-C12alkyl; A is S, O, NR6, or a group of formula (A1), (A2), (A3) or (A4); R10 and R11 independently of each other have one of the meanings given for R4; R12, R13, R14 and R15 independently of one another are for example hydrogen, C1-C4alkyl; Z is CR11 or N; Z1 is -CH2-, S, O or NR6, are useful as latent sulfonic acids, especially in photoresist applications

Abstract: A novel non-symmetrical polydentate Schiff base ligand 3-({2-[(1-methyl-3-oxobut-1-enyl)amino]ethyl}imino)butan-2-one oxime (H2L) comprising an oxime function among various donor sites yields neutral [NiIIL] and [CuIIL] complexes. The structural determination of [NiL] confirms the deprotonation of the oxime function. The deprotonated oxime oxygen atom can react with auxiliary complexes to give homo- and hetero-di- and tri-nuclear entities. The structural determination of a homodinuclear copper complex clearly shows the presence of the expected oxime bridge, along with an unexpected ketonic bridge between the two copper centres leading to a Cu[O,NO]Cu core. A moderate antiferromagnetic interaction is present in the di- and tri-nuclear copper complexes. A similar interaction is also observed in the heteronuclear complexes (CuIINiII and CuIIMnII) and, more surprisingly, in the heterodinuclear CuIICrIII entity. A generalization of the Cu[O,NO]Cu structure leads to a justification of these magnetic properties.

Abstract: The vapor‐phase Beckmann rearrangement of cyclohexanone oxime to ɛ‐caprolactam catalyzed by mesoporous molecular sieves was studied. The proton‐form mesoporous molecular sieves, H‐MCM‐41 and H‐FSM‐16, exhibited extremely high activity, selectivity and stability for ɛ‐caprolactam formation when 1‐hexanol was used as diluent. The weak acid sites and/or surface silanol groups of mesoporous molecular sieves play an important role in the selective ɛ‐caprolactam formation.

Abstract: 1-Benzyl-4-aza-1-azoniabicyclo[2.2.2]octane periodate (BAABCP) (1), readily prepared from commercially available 1,4-diazabicyclo[2.2.2]octane (DABCO) and sodium periodate, converts oximes and α-sulfinyl oximes to the corresponding carbonyl compounds and β-keto sulfoxides, respectively, in high yields and high enantiomeric purity.

Abstract: Cyclization of 2-(3-hydroxyphenyl)ethyl ketone O-2,4-dinitrophenyloximes proceeds on the oxime nitrogen atom by the treatment with NaH and then with 2,3-dichloro-5,6-dicyano-p-benzoquinone and acetic acid to yield quinolin-8-ols regioselectively. The reaction in the presence of Na[BH3(CN)] affords 1,2,3,4-tetrahydroquinolin-8-ols. The present cyclization proceeds via alkylideneaminyl radical intermediates generated by the single electron transfer between 3-hydroxyphenyl and 2,4-dinitrophenyl moieties.

Abstract: The first direct observation of oxidative addition of an oxime upon N–O bond cleavage has been reported in the reaction of Me2CNOH with trans-[ReCl(N2)(Ph2PCH2CH2PPh2)2] in the presence of Tl[BF4]–Tl[HSO4], to form, in a single-pot experiment, the methyleneamide complexes trans-[Re(OH)(NCMe2)(dppe)2][A] (A = BF4 1a or HSO4 1b) which undergo ready replacement of hydroxide by fluoride upon reaction with HBF4; X-ray crystallography (1b) showed that the linearly bound methyleneamide behaves as an effective π acceptor and exerts a significant trans influence on the hydroxide ligand.

Abstract: Efficient syntheses of ω-halo-, phenylseleno-, and vinylacylgermane hydrazones and oxime ethers have been developed, and the radical cyclizations of these substrates have been studied. The preparation of substituted triphenylacylgermanes has been improved through a copper-mediated coupling of acid chlorides and LiGePh3. Condensation of various acylgermanes with O-benzyl hydroxylamine or N,N-dimethylhydrazine efficiently generates the new acceptor systems, which undergo 5-exo cyclizations in good yields. The acylgermane hydrazone and -oxime ether radicals have cyclization rate constants of about 107 s-1 and are thus better acceptors than the parent acylgermanes.

Abstract: Two oxime-urethane derivatives, benzophenone oxime N-cyclohexylurethane (1) and dibenzophenone oxime N,N′-hexamethylenediurethane (2), were used as photobase generators Photolysis of these derivatives results in the formation of amines which induce cross-linking of poly(glycidyl methacrylate) (PGMA) upon heating The bifunctional derivative 2 is more efficient than the monofunctional derivative 1 in inducing thermal cross-linking of PGMA, with a maximum degree of insolubilization increasing up to ca 90%

Abstract: Theoretical studies on intramolecular nucleophilic displacement of the protonated oxime oxygen with an aryl ring revealed that the substitution reaction on the sp2 nitrogen atom is a low energy process. This seemingly anomalous substitution is due to the low-lying σ*-orbital of the O-protonated oxime. The theoretical conclusion received experimental support.

Abstract: 1-Aryl-2,2-dichloro-7, 1-aryl-2,2-dibromo-8, 1-aryl-2-bromo-2-fluoro-9 and 1-aryl-2-chloro-2-fluoro-ethanone oximes 10 have been prepared by allowing the corresponding ketones to react with hydroxylamine hydrochloride in EtOH at room temperature. Stereochemical assignments for the oximes were made on the basis of 1H NMR spectroscopic evidence and an X-ray crystallographic analysis of 1-(3-chlorophenyl)-2,2-dichloroethanone oxime 7f. The 1-aryl-2,2-dihalogenoethanone oximes react with tetrasulfur tetranitride in refluxing 1,4-dioxane to give 3-aryl-4-chloro-1, 3-aryl-4-bromo-2, and 3-aryl-4-fluoro-1,2,5-thiadiazoles 3 in 69–98, 49–99, and 32–65% yields, respectively. A mechanism for the formation of the 1,2,5-thiadiazoles is proposed.

Abstract: Chemiluminescence signals were obtained when aqueous propan-2-ol solutions of phenylhydrazine, 2-nitrophenylhydrazine, 4-nitrophenylhydrazine, 2,4-dinitrophenylhydrazine and hexanal oxime or aqueous solutions of hydroxylamine and dimethylglyoxime were injected into a carrier stream of formic acid which merged with acidified potassium permanganate solution. Rhodamine-B was present in the carrier stream as a sensitiser. The chemiluminescence was deduced to originate from the oxidation of the hydrazine or amine functional groups. For phenylhydrazine oxidation, dinitrogen was proposed as the emitting molecule; in the oxidation of hydroxylamine, a nitrogen oxide emitter was proposed. The role of the formic acid was as a source of formate ions, which are oxidised to carbon dioxide in a relatively slow reaction. It is further proposed that excited carbon dioxide molecules, as well as producing a feeble emission in what seems to be an autocatalytic reaction, transfer energy to the emitting products of analyte oxidation, thus enhancing their chemiluminescence. Injection of formate ions, or their massive production by injections of strong alkali, cause chemiluminescence signals which would interfere with those from the analyte. Iron salts, which catalyse the permanganate–formic acid reaction, have a similar effect but at much lower concentrations.

Abstract: PROBLEM TO BE SOLVED: To obtain the subject new compound having excellent inhibitory effect on P38 MAP kinase especially activating a certain kind of transcription factor, and useful as a treatment agent for tumor necrosis factor(TNF)-α-related diseases, interleukin-1-related diseases, cyclooxigenaseII-related diseases, or the like based on the above inhibitory activity. SOLUTION: This new compound (or a salt thereof) is represented by formula I (X is H or a halogen; R1 is H or a lower alkyl; R2 is H, an organic sulfonyl or the like; wherein, when X is H, R1 and R2 are each not H at the same time), e.g. 3-(4-fluorophenyl)-5-methylamino-4-(4-pyridyl) isoxazole. The compound of formula I where R1 and R2 are each H is obtained by treating an aldehyde compound of formula II with hydroxylamine (salt) to form an oxime compound, which is then halogenated, and the resulting halide of formula III is then reacted with acetonitrile. A dose of the compound of formula I is pref. 0.1-2 mg/kg.

Abstract: Thermally induced cyclization of the anti-alkenyl oximes E-7a,b and E-17a,b affords cyclic α-alkoxycarbonylnitrones 8 and the 6,7-bicyclic nitrones 18, respectively. The syn-oximes Z-7b and Z-17b react via an alternate pathway to give exclusively the fused isoxazolidine derivatives 10b and 19b, respectively. These oximes are configurationally stable at high temperatures with the energy barrier to isomerization being significantly greater than that to cyclization/cycloaddition. Neither the tert-butyl derivative 7c nor the Iµ-alkenyl oxime 7d share this characteristic and in these cases the products of thermal activation are independent of the geometry of the starting oxime. For 7c the energy barriers to oxime rotation and cyclization or cycloaddition are sufficiently close to allow all three reactions to proceed. With 7d, cis–trans isomerization and cyclization are the only observed reactions.

Abstract: Just one of the ten methyl groups of deca-B-methyl-1,12-dicarba-closo-dodecarborane(12) (1) is selectively functionalized in a reaction sequence in which photolysis of a nitrite of 1 is the key step. Reduction of the resulting aldoxime with LiAlH4 generates, by way of the first Beckmann rearrangement of a boron-substituted oxime, the methylamino alcohol 2.

Abstract: 8-Hydroxy-1,2,3,4-tetrahydroquinolines are synthesized from m-hydroxyphenethyl ketone O-2,4-dinitrophenyloximes by the cyclization on the sp2 nitrogen atom of the oxime derivatives using sodium hydride and sodium cyanoborohydride.

Abstract: This invention discloses a process for the synthesis of stable aryl nitrile oxides which comprises the sequential steps of (1) halomethylating a halomethyl group onto a substituted aromatic compounds wherein said halomethyl group is halomethylated onto a position that is ortho to at least one of the substituent groups on the substituted aromatic compound; (2) converting the ortho halomethylated-substituted aromatic compound into an ortho-substituted aromatic aldehyde by reacting the ortho halomethylated-substituted aromatic compound with a salt selected from the group consisting of sodium 2-nitropropane and potassium 2-nitropropane in a lower alcohol solvent; (3) converting the ortho-substituted aromatic aldehyde into an ortho-substituted aromatic; and (4) converting the ortho-substituted aromatic oxime into the ortho-substituted aryl nitrile oxide by reacting the ortho-substituted aromatic oxime with an aqueous sodium hypochlorite solution

Abstract: A series of adamantane-containing molecules consisting of two lipophilic centers which are linked by different bridges (oxime esters, oxime ethers, amides, and symmetric alcohols), were designed and synthesized as anti-inflammatory agents. Their anti-inflammatory activity was evaluated as their ability to inhibit phlogistic-induced mouse paw edema. Some of the tested compounds exhibited activity comparable to that of diclofenac, others had a weaker activity, while some oxime esters proved to enhance the inflammatory response. In all cases, activity was dose-dependent. The deacylated compound 10 was found to be the most active of the series, inhibiting inflammation due to Baker's yeast, the mechanism of which involves mainly the activation of lipoxygenase and/or complement systems, a property which is absent from most selective cyclooxygenase only inhibiting non-steroidal anti-inflammatory drugs (NSAIDs).

Abstract: The additions of organolithium reagents to the CN bond of several chiral oxime ethers derived from erythrulose afforded protected amino polyols with high diastereoselectivity. Four of the latter compounds have been converted into the α,α-disubstituted α-amino acids ( R )-2-(−)-methylserine, ( S )-2-(+)-methylserine, ( R )-(+)-2-phenylserine and ( R )-(−)-2- n -butylserine.

Abstract: Reactivation of organophosphate (OP)-inhibited acetylcholinesterase (AChE) by oximes is the primary reason for their effectiveness in the treatment of OP poisoning. Reactivation is reported to accelerate by quaternary ligands such as decamethonium, which is devoid of nucleophilicity. The mechanism of this enhancement is not known. To better understand the acceleration phenomenon, we examined ligand modulations of oxime-induced reactivation of methylphosphonylated AChE using 7-(methylethoxyphosphinyloxy)-1-methylquinolinium iodide and fetal bovine serum AChE. Edrophonium, decamethonium, and propidium, three quaternary AChE ligands of different types, were tested as potential accelerators. Experiments were carried out with both soluble enzyme preparation and AChE conjugated to polyurethane. Kinetic measurements with oximes 2-[hydroxyiminomethyl]-1-methylpyridinium chloride, 1,1′-trimethylene bis-(4-hydroxyimino methyl)-pyridinium dibromide, and 1,1′-[oxybis-methylene)bis[4-(hydroxyimino)methyl]pyridiniuum dichloride showed that in the presence of 50 μmedrophonium, the reactivation rate constants increased 3.3–12.0-fold; 200 μm decamethonium produced a 1.6–3.0-fold enhancement of reactivation rate constants by the same oximes. Reactivation of the inhibited enzyme by 1-(2-hydroxyiminomethyl-1-pyridinium)-1-(4-carboxy-aminopyridinium)-dimethyl ether hydrochloride, 1-(2-hydroxyiminomethyl-1-pyridinium)-1-(3-carboxy-aminopyridinium)-dimethyl ether hydrochloride, and 1-[[[4-(aminocarbonyl)pyridino]methoxy]methyl]-2, 4,-bis(hydroxyimino)methyl pyridinium dichloride was not affected by either ligand. Propidium slowed the reactivation of 7-(methylethoxyphosphinyloxy)-1- methylquinolinium iodide-inhibited AChE by all oximes. Results suggest that the accelerator site may reside inside the catalytic gorge rather than at its entrance and acceleration may be due to the prevention of reinhibition of the regenerated enzyme by the putative product, the phosphonylated oxime. In addition to the nucleophilic property of the oximate anion, some of the reactivators may carry an accelerating determinant, as characterized with respect to edrophonium and decamethonium. Results offer possible explanations for the superiority of 1-(2-hydroxyiminomethyl-1-pyridinium)-1-(4-carboxy-aminopyridinium)-dimethyl ether hydrochloride over other oximes in the reactivation of specific AChE-OP conjugates.