Abstract: A tetrazoyl oxime derivative which is reduced in damage to useful plants and superior in drug activity against plant diseases to conventional heterocycle-substituted oxime derivatives. The tetrazoyl oxime derivative is represented by the general formula (1): (1) wherein X is hydrogen, halogeno, alkyl, alkoxy, cyano, methanesulfonyl, nitro, trifluoromethyl, or aryl; A is 1-alkyltetrazoyl-5-yl or 5-alkyltetrazoyl-1-yl; and Het is substituted pyridyl or substituted thiazoyl. Also provided is a plant disease control agent containing the derivative as an active ingredient.

Abstract: Oxidative addition of oximes to palladium(0) complexes generates alkylideneaminopalladium‘II’ species, which are utilized as key intermediates for carbon–nitrogen bond formation. Various aza-heterocycles, such as pyrrole, pyridine, isoquinoline, spiroimine, and azaazulene, can be synthesized from O-pentafluorobenzoyloximes having an olefinic moiety via an intramolecular Heck-type reaction ‘amino-Heck reaction’ by treatment with a catalytic amount of a Pd‘0’ complex. © 2002 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 2: 268–277, 2002: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.10030

Abstract: In the presence of zinc oxide and without any additional organic solvents, Beckmann rearrangement of several ketones and aldehydes were performed in good yields.

Abstract: We previously reported the discovery of 4-[(Z)-(4-bromophenyl)(ethoxyimino)methyl]-1‘-[(2,4-dimethyl-3-pyridinyl)carbonyl]-4‘-methyl-1,4‘-bipiperidine N-oxide 1 (SCH 351125) as an orally bioavailable human CCR5 antagonist for the treatment of HIV-1 infection. Herein, we describe in detail the discovery of 1 from our initial lead compound as well as the synthesis and SAR studies directed toward optimization of substitution at the phenyl, oxime, and right-hand side amide groups in the oximino-piperidino-piperidine series. Substitutions (4-Br, 4-CF3, 4-OCF3, 4-SO2Me, and 4-Cl) at the phenyl group are well-tolerated, and small alkyl substitutions (Me, Et, nPr, iPr, and cyclopropyl methyl) at the oxime moiety are preferred for CCR5 antagonism. The 2,6-dimethylnicotinamide N-oxide moiety is the optimal choice for the right-hand side. Several compounds in this series, including compound 1, exhibited excellent antiviral activity in vitro. Compound 1, which has a favorable pharmacokinetic profile in rodents and pr...

Abstract: Dehydration of oximes and amides to nitriles was carried out using the AlCl3·6H2O/KI/H2O/CH3CN system. It produced isoquinoline derivatives 8a−c (Bischler Naperialski reaction) when reacted with amides 7a−c in hydrated media. Also, the keto oximes produced anilides (Beckmann rearrangement) with the system under the same reaction conditions.

Abstract: Si-MCM-41 and Al-MCM-41 with different Al contents (Si/Al=43.9, 23.3 and 14.3) have been prepared using cetyl trimethylammonium bromide as an organic surfactant and characterised by XRD, MAS NMR and N2 sorption studies. The transformation of cyclohexanone oxime into e-caprolactam has been studied over these molecular sieves. The influences of temperature and feed rate (WHSV) on the yield of caprolactam over the samples have been investigated at different times on stream. The studies reveal that activity and selectivity increase with Al content (investigated upto Si/Al=14) and maximum yield of e-caprolactam is obtained at ∼360 °C.

Abstract: Di[(1R)-2-Oximo-endo-3-bornyl] diselenide (4) and its benzoate derivative 5 were prepared from the corresponding known 2-keto diselenide 1. Treatment of 4 and 5 with bromine, followed by silver triflate in methanol-dichloromethane, generated the corresponding selenenyl triflates 6b and 7b. The latter reagents reacted with a variety of mono-, di-, and trisubstituted alkenes to afford the corresponding 1,2-addition products (beta-methoxy selenides) in a highly diastereoselective manner. The free oxime 6b was particularly effective in such methoxyselenenylations, giving diastereomeric ratios (d.r.s) ranging from 86:14 to > 98:2. Even cis-disubstituted alkenes, which typically give poor d.r.s in similar additions with other chiral selenium electrophiles, underwent highly stereoselective additions with this reagent. Reductive deselenizations of the adducts obtained from styrene and cis- and trans-stilbene provided the corresponding methyl ethers, whose absolute configurations were determined by comparison with authentic samples. As expected, the dominant enantiomers thus obtained from cis- and trans-stilbene, using either 6b or 7b, had opposite configurations. Moreover, each geometrical isomer of stilbene produced methyl ethers with the same configuration when treated with either the oxime 6b or the benzoate 7b. Coordination effects between the substituents at the 2-position of the camphor molecule and the positive selenium atoms in the intermediate seleniranium ions are believed to play an important role in determining the stereochemical outcome of methoxyselenenylations. Selenenyl triflate 6b and selenenyl chloride 7c were also investigated in the electrophilic cyclizations of several unsaturated alcohols and carboxylic acids. However, diastereoselectivities were typically much lower than in the methoxyselenenylations. When the selenenyl bromide 6a, derived from the addition of bromine to the corresponding diselenide 4, was allowed to stand in the absence of an alkene, it underwent intramolecular cyclization with the oxime hydroxyl group, followed by further bromination, to afford the unusual oxaselenazole 11, whose structure was determined by spectroscopic means as well as by X-ray crystallography.

Abstract: Novel homodinuclear Cu(II) (K1), heterodinuclear Cu(II)-Mn(II) (K2) and homotrinuclear Cu(II) (K3) complexes with a novel oxime-type ligand have been prepared and their nucleolytic activities on pCYTEXP were established by neutral agarose gel electrophoresis. The analyses of the cleavage products obtained electrophoretically indicate that although the examined complexes induces very similar conformational changes on supercoiled DNA by converting supercoiled form to nicked form than linear form in a sequential manner as the complex concentration or reaction period is increased, K3 is less effective than the two others. The oxime complexes were nucleolytically active at physiological pH values but the activities of K1 or K2 were diminished by increasing the pH of the reaction mixture. In contrast, K3 makes dominantly single strand nicking by producing nicked circles on DNA at almost all the applied pH values. Metal complex induced DNA cleavage was also tested for inhibition by various radical scavengers as superoxide dismutase (SOD), azide, thiourea and potassium iodide. The antioxidants inhibited the nucleolytic acitivities of the oxime complexes but SOD afforded no protection indicating that the nucleolytic mechanism involves of copper and/or manganese complex-mediated reactive oxygen species such as hydroxyl radicals being responsible for the oxidative DNA cleavage.

Abstract: Electrophilic amination of Grignard reagents is accomplished by using O-sulfonyl- oximes of benzophenone derivatives. In the presence of a catalytic amount of CuCN, O-sul- fonyloxime of 4,4'-bis(trifluoromethyl)benzophenone reacts with alkyl Grignard reagents in tetrahydrofuran (THF) and hexamethylphosphoramide (HMPA), yielding primary alkyl- amines by successive hydrolysis of the resulting N-alkylimines. Arylamines are also prepared as well as alkylamines by treating O-sulfonyloxime of 3,3',5,5'-tetrakis(trifluoromethyl)- benzophenone in toluene-ether with Grignard reagents. Various cyclic imines are synthesized by palladium-catalyzed cyclization of olefinic oxime derivatives. That is, the reaction of O-pentafluorobenzoyloximes of olefinic ketones with a catalytic amount of Pd(PPh 3 ) 4 and triethylamine in dimethylformamide (DMF) affords nitrogen-containing heterocycles, such as pyrroles, pyridines, isoquinolines, spiro- imines, and aza-azulenes. This reaction proceeds via the initial formation of alkylidene- aminopalladium species generated by oxidative addition of oximes to Pd(0), and the succes- sive intramolecular Heck-type amination occurs on the olefinic moiety.

Abstract: PROBLEM TO BE SOLVED: To provide a tetrazoyl oxime derivative which is reduced in damage to useful plants and superior in effect against plant diseases to conventional heterocycle-substituted oxime derivatives. SOLUTION: This tetrazoyl oxime derivative is represented by general formula (I) [wherein X is hydrogen, a halogen atom, alkyl group, alkoxy group, cyano group, methanesulfonyl group, nitro group, trifluoromethyl or aryl group; A is a 1-alkyltertrazoyl-5-yl or a 5-alkyltertrazoyl-1-yl group; Het is a substituted pyridyl or a substituted thiazoyl]. A plant disease controlling agent containing the derivative as an active ingredient is also provided.

Abstract: The in vitro and in vivo disposition of DPC 423 was investigated in mice, rats, dogs and humans and the metabolites characterized by LC/MS, LC/NMR and high field-NMR. The rodents produced several metabolites that included an aldehyde (M1), a carboxylic acid (M2), a benzyl alcohol (M3), glutamate conjugates (M4 and M5), an acyl glucuronide (M6) and its isomers; a carbamyl glucuronide (M7); a phenol (M8) and its glucuronide conjugate (M9), two glutathione adducts (M10 and M11), a sulfamate conjugate (M12), isomers of an oxime metabolite (M13), and an amide (M14). Humans and dogs produced less complex metabolite profiles than rats. While unchanged DPC 423 was the major component in plasma and urine samples, differences in the metabolic disposition of this compound among species were noted. M1 is believed to be rapidly oxidized to the carboxylic acid (M2), which forms the potentially reactive acyl glucuronide (M6). The formation of novel glutamate conjugates (M4 and M5) and their role in depleting endogenous glutathione have been described previously. The carbamyl glucuronide M7, found as the major metabolite in rats and in other species, was considered nonreactive and was easily hydrolyzed to the parent compound in the presence of beta-glucuronidase. The identification of GSH adducts M10 and M11 led us to postulate the existence of at least two reactive intermediates responsible for their formation, an epoxide and possibly a nitrile oxide, respectively. Although the formation of GSH adducts such as M10 from epoxides has been described before, there are no reports to date describing the existence of a GSH adduct (M11) of an oxime. The formation of a sulfamate conjugate (M12) formed by direct coupling of sulfate to the nitrogen of benzylamine is described. A mechanism is proposed for the formation of the oxime (M13) that involves sequential oxidation of the benzylamine to the corresponding hydroxylamine and nitroso intermediate. The rearrangement of the nitroso intermediate is believed to produce the oxime (M13). In vitro studies suggested that both the oxime (M13) and the aldehyde (M1) were precursors to the carboxylic acid (M2). This is the first demonstration of carboxylic acid formation via an oxime intermediate produced from an amine. The stability of DPC423 in plasma obtained from several species was studied. Significant species differences in the plasma stability of DPC 423 were observed. The formation of the aldehyde metabolite (M1) was found to be catalyzed by a semicarbazide-sensitive monoamine oxidase (SSAO) found in plasma of rabbits, dogs, and rhesus monkeys. Rat, chimpanzee, and human plasma did not form M1.

Abstract: Addition of organometallic reagents to chiral oxime ethers 1 derived from an unsaturated aldehyde, or addition of an alkene containing organometallic to chiral aldoxime ethers 2 results in highly stereoselective formation of the hydroxylamines 6. N-Allylation gives the dienes 7 which undergo ring-closing metathesis (RCM) reaction to give the 5-, 6-, and 7-membered nitrogen heterocycles 8. Likewise, the benzyl carbamates 9, also prepared by stereoselective addition to oxime ethers, were converted into dienes 10, which underwent RCM to give the 5- to 8-membered azacycles 11. The oxime addition–RCM protocol is thus a versatile method for the asymmetric synthesis of nitrogen heterocycles, further exemplified by the conversion of the unsaturated heterocycles into chiral piperidines, including the alkaloid (−)-coniine.

Abstract: The reaction between dione monoximes and platinum(IV) nitrile complexes leads, instead of the conventional substitution, to metal-mediated coupling, giving iminoacylated species which, on being liberated, undergo disintegration to the nitrile and the oxime.

Abstract: 2,3-Dibromo-6,7,13,14,15,16,22,23-octahydro-14,15-bis-(hydroxyimino)-tribenzo [e,k,q][1,4,7,10,13,16]tetraoxadiazacyclohexadecine (LH4) was prepared by condensation of 1,2-bis-(2′-aminophenoxyethoxy)-4,5-dibromobenzene with cyanogen-di-N-oxide. Mono-, di-, and trinuclear transition metal complexes of this ligand ((LH3)2Ni, (LH3)2Zn, (LH3)2Co, (LH3)2Cu, (LH3)2Fe, (LH3)2(UO2)2(OH)2, (LH)2Cu3, (LH)2Co3) were synthesized under basic conditions. The electrochemical properties of the mono- and dinuclear complexes were studied by cyclic voltammetry in DMSO solution containing TBAP. The results showed that all redox processes are based on the metal center and the oxime ligands stabilize the Ni(III), Fe(III), Co(III), and Cu(III) species formed during oxidation. The Fe(II) and U(VI)O2 complexes displayed a different behaviour: a reduction peak with the corresponding anodic signal during the reverse scan was observed. The oxime moiety also stabilizes U(V)O2 which forms during the reduction process of the uranyl complex. Cu(II) was adsorbed on the electrode surface upon scanning cathodically.

Abstract: Hydrotalcite-like compounds with boron anions in the interlayer were obtained using a coprecipitation method The effect of different pH values during the preparation was investigated and the effect on crystallinity and phase distribution studied The influence of different methods of acidity regulation was also analyzed The efficiency of synthesis of boron-containing anionic clays was evaluated, and the good thermal stability of the materials was noted Surface characteristics were determined by X-ray photoelectron spectroscopy and correlated to the bulk properties obtained by X-ray diffraction and 27Al and 11B MAS NMR The samples tested in gas-phase Beckmann rearrangement showed caprolactam formation, and the results were related to the surface features

Abstract: Structural and mechanistic aspects of orthoplatination of acetophenone and benzaldehyde oximes by the platinum(II) sulfoxide and sulfide complexes [PtCl(2)L(2)] (2, L = SOMe(2) (a), rac-SOMePh (b), R-SOMe(C(6)H(4)Me-4) (c), and SMe(2) (d)) to afford the corresponding platinacycles cis-(C,S)-[Pt(II)(C(6)H(3)-2-CR'=NOH-5-R)Cl(L)] (3, R, R' = H, Me) have been investigated. The reaction of acetophenone oxime with sulfoxide complex 2a in methanol solvent occurs noticeably faster than with sulfide complex 2d due to the fact that the sulfoxide is a much better platinum(II) leaving ligand than the sulfide. Evidence is presented that the orthoplatination is a multistep process. The formation of unreactive dichlorobis(N-oxime)platinum(II) cations accounts for the rate retardation by excess acetophenone oxime and suggests the importance of pseudocoordinatively unsaturated species for the C-H bond activation by Pt(II). A comparative X-ray structural study of dimethyl sulfoxide platinacycle 3b (R = R' = Me) and its sulfide analogue 3e (R = H, R' = Me), as well as of SOMePh complex 3c (R = H, R' = Me), indicated that they are structurally similar and a sulfur ligand is coordinated in the cis position with respect to the sigma-bound phenyl carbon. The differences concern the Pt-S bond distance, which is notably longer in the sulfide complex 3e (2.2677(11) A) as compared to that in sulfoxide complexes 3b (2.201(2)-2.215(2) A) and 3c (2.2196(12) A). Whereas the metal plane is practically a plane of symmetry in 3b due to the H-bonding between the sulfoxide oxygen and the proton at carbon ortho to the Pt-C bond, an S-bonded methyl of SOMePh and SMe(2) is basically in the platinum(II) plane in complexes 3c and 3e, respectively. There are intra- and intermolecular hydrogen bond networks in complex 3b. An interesting structural feature of complex 3c is that the two independent molecules in the asymmetric unit of the crystal reveal an extremely short Pt-Pt contact of 3.337 A.

Abstract: The extraction of nickel(II) from acidic aqueous solutions using a mixture of 2-ethylhexanal oxime (EHO) and bis(2-ethylhexyl) phosphoric acid (D2EHPA) in dodecane has been investigated as a function of total concentrations of each extractant, metal and protons. The aqueous salt concentration is proved to have no significant effect for both ammonium nitrate and chloride. The extracted organic complex is then Ni(Ox)2(HOx)2(HA)2 or Ni(HOx)4A2, where HA denotes the organo-phosphoric acid and HOx the oxime. A complementary isomolecular study has been achieved to confirm this stoichiometry. As aggregation plays a crucial role in extraction phenomenon, Vapor Pressure Osmometry (VPO) measurements have been carried out in order to determine the aggregation numbers for either the separate extractants or their mixtures. The bis(2-ethylhexyl) phosphoric acid is mainly under dimer and trimer forms, while no mixed aggregation is observed.

Abstract: New oxime sulfonate compounds of the formula (I) and (II), wherein R1 is C1-C12alkyl, C1-C4haloalkyl, hydrogen, OR9, NR10R11, SR12 or is phenyl which is unsubstituted or substituted by OH, C1-C18alkyl, halogen and/or C1-C12alkoxy; R2, R3, R4 and R5 are for example hydrogen or C1-C12alkyl; R6 is for example is C1-C18alkylsulfonyl, phenyl-C1-C3alkylsulfonyl or phenylsulfonyl; R'6 is for example phenylenedisulfonyl or diphenylenedisulfonyl; R7, R8 and R9 for example are hydrogen or C1-C6alkyl; R10 and R11, are for example hydrogen or C1-C18alkyl; R12 is for example hydrogen, phenyl or C1-C18alkyl; A is S, O, NR13, or a group of formula A1, A2 or A3, R21 and R22 independently of one other have one of the meanings given for R7; R23, R24, R25 and R26 independently of one another are for example hydrogen, C1-C4alkyl, halogen or phenyl; Z is CR22 or N; and Z1 is CR22 or N; and Z1 is CR22 or N; and Z1 is CH2-, S, O or NR13 are particularly suitable as photo-latent acids in resist applications.

Abstract: The syntheses and crystal structure determinations of three new compounds, bis-[4′-[N-(4-pyridylmethylene)]aminoacetophenone oxime] silver(I) hexafluorophosphate hydrate, bis-[4′-[N-(4-pyridylmethylene)]aminoacetophenone oxime] silver(I) perchlorate hydrate, and bis-[3′-[N-(4-pyridylmethylene)]aminoacetophenone oxime] silver(I) hexafluorophosphate hydrate, demonstrate that the desired primary supramolecular synthon, the oxime⋯oxime dimer, is not disrupted despite extensive ligand modifications (through covalent synthesis) that increase the aromatic content and introduce an additional hydrogen-bond acceptor moiety.

Abstract: Reaction of [Os3(CO)11(NCMe)] with phenyl 2-pyridyl ketoxime produced the clusters [Os3(CO)8{μ-η3-ONCPh(NC5H4)}2] 1 and [Os3H(CO)11{η2-ONCPh(NC5H4)}] 2 in 4 and 17% yields, respectively. Oxidative addition of the oximes to the clusters with O–H bond cleavage and the loss of labile acetonitrile groups, and in the case of complex 1 decarbonylation, are observed. Cluster 2 possesses an open linear metal skeleton attached to both the pyridine nitrogen and oximato nitrogen on one terminal Os atom. Heating 2 in refluxing toluene gave [Os3(μ-H)(CO)9{µ-η3-ONCPh(NC5H4)}] 3 in 13% yield. Treatment of a CH2Cl2 solution of [Os3(CO)10(NCMe)2] with phenyl 2-pyridyl ketoxime at ambient conditions afforded the bridging oximato clusters 1 and 3 in moderate yields. Cluster 3 and 1 equiv. of phenyl 2-pyridyl ketoxime in refluxing toluene led to conversion to clusters 1 and [Os3(CO)8{μ-η3-ONCPh(NC5H4)} {μ-η2-N(H)CHPh(NC5H4)}] 4 in 12 and 16% yields, respectively. In cluster 4, one of the oximato moieties is deoxygenated with N–O bond cleavage. Treatment of another oxime ligand, benzophenone oxime, with [Os3(CO)10(NCMe)2] gave [Os3(μ-H)(CO)10{μ-η2-ONCPh2}] 5 in moderate yield. On thermolysis of 5 in toluene, [Os3(μ-H)2(CO)9{μ-η3-ONCPh(C6H4)}] 6 and [Os3(CO)10(μ-OH){μ-NCPh2}] 7 were isolated in 27 and 21% yields, respectively. The oxime ligand in 6 is converted to a tridentate ligand. In addition to the μ-η2-oximato N–O bridge, the phenyl carbon on the ligand coordinates to the cluster core by ortho-metallation. Cluster 5 isomerizes thermally to 7, which is formed by oxidative addition of the oxime with N–O bond cleavage. A μ4-oxo hexaosmium cluster, [Os6(CO)16(μ4-O){μ-η3-NCPh(C6H4)}2] 8, was isolated in low yield upon refluxing 5 in octane. Vacuum pyrolysis of 5 in 140 °C yielded a pentaosmium carbonyl cluster, [Os5(CO)15{μ-η3-NCPh(C6H4)}] 9. All these clusters have been fully characterized by both spectroscopic and crystallographic techniques.