- Potential Synthetic Adaptogens: V. Synthesis of Cage Monoamines by the Schwenk–Papa Reaction
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The reduction of cage ketoximes under Schwenk–Papa reaction conditions was studied to establish that the d,l, d- and l-camphor oximes are smoothly reduced to the corresponding amines in high yields. At the same time, d,l-norcamphor and adamantan-2-one oximes undergo partial catalytic deoximation to form a mixture of the corresponding amines and alcohols.
- Brunilin, R. V.,Mkrtchyan, A. S.,Nawrozkij, M. B.,Novakov, I. A.,Vernigora, A. A.,Voloboev, S. N.,Vostrikova, O. V.
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p. 1742 - 1748
(2020/01/11)
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- Synthesis and biological evaluation of phenylpropanoid derivatives
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In this work, a series of oxime ether phenylpropanoid derivatives were synthesized. Their anti-hepatitis B virus (HBV) activity in HepG 2.2.15 cells was determined, and anti-cancer potential against three human cancer cell lines was evaluated. All the synthesized derivatives showed great efficiency against HBV. Compound 4d demonstrated the most effective anti-HBV activity, performing strong potent inhibitory not only on the secretion of HBsAg (IC50?=?50.45?μM, SI?=?9.18) and HBeAg (IC50?=?50.11?μM, SI?=?9.24), but also on the HBV DNA replication (IC50?=?51.80?μM, SI?=?8.94). Besides, the synthetic compounds also displayed obvious anti-cancer activity. Moreover, the docking study of all synthesized compounds inside the related protein active site was conducted to explore the molecular interactions and a molecular target for activity using a MOE-docking technique. This study identified a new class of potent anti-HBV and anti-cancer agents.
- Liu, Sheng,Li, Yubin,Wei, Wanxing,Wei, Jingchen
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p. 1074 - 1086
(2016/07/06)
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- Ruthenium Trichloride Catalyzed Highly Efficient Deoximation of Oximes to the Carbonyl Compounds and Nitriles without Acceptors
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An acceptor-free catalysis protocol for the deoximation of ketoximes and aldoximes using RuCl3 as the catalyst has been developed. Under the optimized conditions, various oximes were converted to ketones and nitriles with excellent isolated yields. An acceptor-free catalysis protocol for the deoximation of ketoximes and aldoximes using RuCl3 as the catalyst has been developed. Under the optimized conditions, various oximes were converted to ketones and nitriles with excellent isolated yields.
- Liu, Yuxiao,Yang, Na,Chu, Changhu,Liu, Renhua
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supporting information
p. 1011 - 1014
(2015/09/28)
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- CENTRALLY ACTIVE AND ORALLY BIOAVAILABLE ANTIDOTES FOR ORGANOPHOSPHATE EXPOSURE AND METHODS FOR MAKING AND USING THEM
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In alternative embodiments, the invention provides nucleophilic hydroxyimino- acetamido alkylamine antidotes that cross the blood-brain barrier (BBB) to catalyze the hydrolysis of organophosphate (OP)-inhibited human acetylcholinesterase (hAChE) in the central nerve system (CNS). The hydroxyimino-acetamido alkylamines of the invention are designed to fit within AChE active center gorge dimensions, bind with reasonable affinity, and react with the conjugated phosphate atom in the gorge. The hydroxyimino- acetamido alkylamines of the invention are also designed to possess ionization states that govern affinity and reactivity for the two linked hAChE re-activation steps. In alternative embodiments, the invention provides pumps, devices, subcutaneous infusion devices, continuous subcutaneous infusion devices, infusion pens, needles, reservoirs, ampoules, a vial, a syringe, a cartridge, a disposable pen or jet injector, a prefilled pen or a syringe or a cartridge, a cartridge or a disposable pen or jet injector, a two chambered or multi- chambered pump, a syringe, a cartridge or a pen or a jet injector, comprising a compound of the invention.
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Page/Page column 50; 51
(2014/09/03)
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- Oxidation of primary amines to oximes with molecular oxygen using 1,1-diphenyl-2-picrylhydrazyl and WO3/Al2O3 as catalysts
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The oxidative transformation of primary amines to their corresponding oximes proceeds with high efficiency under molecular oxygen diluted with molecular nitrogen (O2/N2 = 7/93 v/v, 5 MPa) in the presence of the catalysts 1,1-diphenyl-2-picrylhydrazyl (DPPH) and tungusten oxide/alumina (WO3/Al2O3). The method is environmentally benign, because the reaction requires only molecular oxygen as the terminal oxidant and gives water as a side product. Various alicyclic amines and aliphatic amines can be converted to their corresponding oximes in excellent yields. It is noteworthy that the oxidative transformation of primary amines proceeds chemoselectively in the presence of other functional groups. The key step of the present oxidation is a fast electron transfer from the primary amine to DPPH followed by proton transfer to give the α-aminoalkyl radical intermediate, which undergoes reaction with molecular oxygen and hydrogen abstraction to give α-aminoalkyl hydroperoxide. Subsequent reaction of the peroxide with WO3/Al2O3 gives oximes. The aerobic oxidation of secondary amines gives the corresponding nitrones. Aerobic oxidative transformation of cyclohexylamines to cyclohexanone oximes is important as a method for industrial production of ε-caprolactam, a raw material for Nylon 6.
- Suzuki, Ken,Watanabe, Tomonari,Murahashi, Shun-Ichi
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p. 2301 - 2310
(2013/04/24)
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- HISTONE DEACETYLASE INHIBITORS FOR THE TREATMENT OF FUNGAL INFECTIONS
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Described are bridged compounds of the formula (I), their analogs, tautomeric forms, stereoisomers, geometrical isomers, polymorphs, hydrates, solvates, pharmaceutically acceptable salts, pharmaceutical compositions, metabolites and prodrugs thereof. The invention relates to compositions and methods to treat fungal infection. These compounds are selective HDAC inhibitors that act as inherent antifungal compounds or enhance the activity of other antifungal compounds such as azoles.
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Page/Page column 26
(2011/06/16)
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- Application of the excited state meta effect in photolabile protecting group design
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A novel photolabile protecting group for carbonyl compounds has been developed, based on the excited state meta effect.
- Wang, Pengfei,Hu, Ayou,Wang, Yun
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p. 2831 - 2833
(2008/02/07)
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- Chlorination of oximes with aqueous H2O2/HCl system: Facile synthesis of gem-chloronitroso- and gem-chloronitroalkanes, gem-chloronitroso- and gem-chloronitrocycloalkanes
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Chlorination of cyclic and linear ketone oximes with aqueous H 2O2/HCl in a two-phase dichloromethane-water system selectively affords gem-chloronitroso compounds in yields of up to 94%. One-pot oxidation of the resulting gem-chloronitroso compounds with peracetic acid, prepared in situ, gives gem-chloronitroalkanes and cycloalkanes in yields of up to 82%. The advantages of the method are that it is facile and environmentally benign and does not require gaseous chlorine. Georg Thieme Verlag Stuttgart.
- Terent'ev, Alexander O.,Krylov, Igor B.,Ogibin, Yuri N.,Nikishin, Gennady I.
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p. 3819 - 3824
(2008/02/09)
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- QUINAZOLINE DERIVATIVES AS ACETYLCHOLINESTERASE INHIBITORS
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A method of treating cognitive deficiencies is described by administering a quinazoline derivative of the general formula wherein A represents in which n is 1-10, P is a bond or (CH2)m in which m is 0-10, and M is =0 , =S , =NR, =CRR, novel compounds of the above are also described as well as methods of manufacture and pharmaceutical compositions.
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- Oxidation of Primary Aliphatic Amines to C-Nitroso Dimers
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A biphasic system of ethyl acetate or dichloromethane and water containing sodium percarbonate (Na2CO3*3/2H2O2), sodium hydrogen carbonate and N,N,N',N'-tetraacetylethylenediamine oxidizes primary aliphatic amines to aliphatic C-nitroso dimers in most cases in good to excellent yields.
- Zajac, Walter W.,Walters, Thomas R.,Woods, James M.
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p. 808 - 810
(2007/10/02)
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- REACTION D'OXIMATION DES CETONES V. MECANISME ET EFFETS DE STRUCTURE DANS LA REACTION DE DESHYDRATATION ACIDO-CATALYSEE DES CARBINOLAMINES
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The equilibrium constants of formation and the rate constants of dehydratation of carbinolamines resulting from the addition of hydroxylamine to 19 ketones, - 5 aliphatic, 5 aromatic and 9 cyclanic -, have been measured at 25 deg C in water/methanol 60/40 v/v.We show that the acid catalyzed process predominates in the range of pH 6 to 7 for acetophenones or pH 7 to 8.5 for saturated ketones.The rate constants ratios and Hammett ρ constant of the reaction suggest an sp3 (early) transition state.The changes in rate constant are discussed in terms of torsional and non-bonding steric effects.For several hindered ketones, e.g. 3,3,5,5-tetramethylcyclohexanone, we show the existence of a steric hindrance to the approach of the catalyst; in that case the result is a strong decrease of the rate of the dehydratation.
- Lamaty, G.,Roque, J. P.,Natat, A.,Silou, T.
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p. 2667 - 2676
(2007/10/02)
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- C-Nitroso compunds. Part XXXVII. The reactivity of α-chloronitroso compounds towards organoaluminium reagents
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With sterically unhindered and certain moderately hindered α-chloronitroso compounds 1 trimethylaluminium at low temperature gives, via complexes 2 and 3, the methyl nitrones 4 (Scheme 1).Several intermediate complexes 3 lose methane upon heating and rearrange to α-chloroimines 5 (Scheme 2), the structure of which is determined by that of the precursors (E- or Z-geometry; cf.Scheme 6).More sterically hindered α-chloronitroso compounds containing quaternary carbon undergo C-C rupture when treated with trimethylaluminium, thus forming hydroxamic acid chlorides, formally HCl adducts of nitrile oxides (cf. 8j in Scheme 3; 8k in Scheme 4).In the latter case, subsequent reactions lead to overall ring enlargement, i. e. formation of the seven-membered cyclic oxime 12.With triethylaluminium and triisobutylaluminium, α-chloronitroso compounds are mainly reduced to oximes and the isomeric amides (Scheme 7).
- Lub, J.,Beekes, M. L.,Boer, Th. J. de
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- SOLVOLYSIS OF SECONDARY ALKYL AZOXYTOSYLATES. A NEW REACTION RELATED TO SOLVOLYTIC DEAMINATION AND ARENESULPHONATE SOLVOLYSIS
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The rates of solvolysis of 2-adamantyl azoxytosylate have been measured in hexafluoropropan-2-ol (HFIP), trifluoroethanol (TFE), aqueous hexafluoropropan-2-ol (97HFIP), aqueous trifluoroethanol (97TFE), aqueous ethanol (50E and 80E), and aqueous methanol (80M) at 3-5 temperatures between ca. 23 and 70 deg C, and activation parameters have been determined.The O-2H solvent kinetic isotope effect has been measured for HFIP (kH/kD 1.025 +/- 0.02 at 50.8 deg C) and secondary α-deuterium kinetic isotope effects have been determined in 97HFIP (kH/kD 1.090 +/- 0.005; 40.2 deg C), 50E (1.091 -/+ 0.006; 51.0 deg C), and 80E (1.133 -/+ 0.009; 60.9 deg C).Neither methanesulphonic acid in 80M nor pyridine in TFE gives rise to a significant rate enhancement, and there is hardly any salt effect due to low concentrations of tetrabutylammonium perchlorate in 97TFE. 2-Adamantyl tosylate is formed in parallel with solvolysis product in ethanol and weakly aqueous ethanol, and is the sole organic product from reactions in chloroform and toluene.No relatively long lived intermediate such as 2-adamantyl tosylate is involved in the reaction in 97TFE, 80M, and 90M.The kinetics and product results are satisfactorily accommodated by a mechanism involving initial unimolecular rate-determining synchronous fragmentation of the substrate to give nitrous oxide and an ion-pair.This ion-pair is then either captured by solvent to give solvolysis product or, in the less polar media, undergoes ion-pair combination to yield covalent 2-adamantyl tosyate.Bicyclooctan-2-yl azoxytosylate has also been prepared, and rates and activation parameters have been determined in 97HFIP and 80M.There is no evidence from this limited study of a mechanism different from that of the 2-adamantyl analogue.Rates and activation parameters for the solvolysis of cyclohexyl azoxytosylate have also been determined in an even more limited study using only 97HFIP.Rates are slower than those for the other two compounds, but the mechanism appears to be the same.
- Maskill, H.,Thompson, John T.,Wilson, Alan A.
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p. 1693 - 1704
(2007/10/02)
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- Steroidal N-Nitroamines. Part 3. Pyrolytic Denitroamination of N-Nitroamino-adamantane and -bornane, and of Several Steroidal N-Nitroamines
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The thermal decomposition of several nitroamines has been investigated.The axial nitroamines 6β-nitroamino-5α-cholestan-3β-yl acetate (1) and 23R-nitroamino-(20S,22S,25S)-5β-spirostan-3β-yl acetate (8) gave exclusively nitrogen-free olefins.The trans-diaxial α-hydroxy nitroamines (2) and (3) afforded the 5α- and 4α-oxirane (6) and (7), and small amounts of the corresponding trans-diols (4) and (5).The 7β- and 7α-nitroaminocholest-5-en-3β-yl acetate (10) and (11) gave 7-oxocholesteryl acetate (14) and a mixture of the 7β- and 7α-alcohol (12) and (13) with 50 and 33percent inversion of configuration, respectively.The oxidation product adamantanone (16) was produced together with adamantan-2-ol (20) in the pyrolysis of 2-nitroaminoadamantane (19).Carbon-carbon rearrangement was observed in the case of exo-2-nitroaminobornane (22) and 20β-nitroaminopregn-5-en-3β-yl acetate (25).The nitroamine (25) yielded the 3-O-acetyl derivatives of pregna-5,20-dien-3β-ol, (29), pregna-5,17(20)(E)-dien-3β-ol, (30), 3β-hydroxypregn-5-en-20-one, (28), 17α-methyl-D-homoandrost-5-ene-3β,17aβ-diol, (31), and a mixture of pregn-5-ene-3β,20-diols (26) and (27).Camphene (23) and tricyclene (24) was obtained from exo-2-nitroaminobornane (22).Mechanisms for the formation of these products are discussed.
- Francisco, Cosme G.,Freire, Raimundo,Hernandez, Rosendo,Melian, Daniel,Salazar, Jose A.,Suarez, Ernesto
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p. 2325 - 2328
(2007/10/02)
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- C-Nitroso compounds. Part XXXIII. Reaction of α-chloronitrosoadamantane with Grignard reagents
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The reaction of α-chloronitrosoalkanes with aliphatic and aromatic Grignard reagents RMgX has been studied using the model compound α-choronitrosoadamantane (AdClNO)1.In addition to adamantanone oxime 7 (4-60percent) and the adamantanone oxime ether 8 (trace -28percent), the expected nitrone 2 is formed.The nitrone can be isolated for synthetic purposes using a non-chromatographic procedure in widely varying yields (6-87percent).The structure of all nitrones has been determined using spectroscopic techniques.Formation of oxime and oxime ether has been explained with the mechanism outlined in Scheme 3.This also accounts for the drastic changes in product distribution with the nature of the Grignard reagent.The mechanism involves nitrone formation via polar 1,2-addition of the Grignard reagent to the nitroso group, and single electron transfer (SET) from the Grignard reagent to the nitroso compound which leads to an iminoxy radical together with radical R..The latter combines with the multident iminoxy radical on nitrogen and oxygen (not on carbon) producing the nitrone and the oxime ether.Disproportionation can result in the formation of oxime.The oxime can also be formed when iminoxy radicals accept an electron from the Grignard reagent.As the electron donating power is strongly influenced by the nature of the Grignard reagent (i.e.SET vs. polar addition), widely varying product distributions are obtained.The phenyl Grignard reagent is amongst the poorest of electron donors, and therefore gives almost exclusively nitrone by polar 1,2-addition.Since nitroso compounds are normally excellent free radical scavengers, it is difficult to explain why trapping of transient radicals R. by the nitroso compound, followed by loss of halogen, appears to be relatively unimportant as a route to nitrone (Scheme 3, reaction iii).The formation of dibenzyl (42percent) from the reaction of AdClNO 1 with benzylmagnesium bromide is equally remarkable.
- Schenk, C.,Beekes, M. L.,Boer, Th. J. de
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p. 246 - 252
(2007/10/02)
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- 4-Azatricyclo[4.3.1.13,8 ]undecane and related compounds
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This invention relates to a novel series of compounds characterized particularly by the azatricyclo[4.3.1.13,8 ]undecane ring. These include 4-azatricyclo[4.3.1.13,8 ]undecan-5-one, 4-azatricyclo[4.3.1.13,8 ]undecane and nitrogen substituted derivatives of each of these and their salts. The compounds are useful as antiviral, cardiovascular or antiinflammatory agents, or as intermediates for such substances.
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