Syntheses based on anabasine

N-Phenacyl salts of acetyl-, benzoyl-, and methylanabasine were synthesized for the first time. Their reactions with unsaturated carbonyl compounds of the ethylene and acetylene series and acrylonitrile were studied. Methods for the synthesis of 6- and 8-(2-piperidyl)indolizines were developed. For Part 1, see Ref. 1. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 135–145, January, 2008.     

Modification of salsoline, salsolidine, and anabasine with dibenzo-24-crown-8-dicarboxylic acid dichloride

New derivatives of dibenzo-24-crown-8-dicarboxylic acid diamide with salsoline, salsolidine, and anabasine moieties were prepared by condensation of the alkaloids with 4′,4″(5″)-dibenzo-24-crown-8-dicarboxylic acid dichloride. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 471–473, September–October, 2006.     

Syntheses based on (N,N-difluoroamino)dinitroacetonitrile

High reactivity of the nitrite group in (NN-difluoroamino)dinitroacetonitrile was demonstrated. Based on its reaction with HN₃, a new preparative method for the synthesis of 5-[(N,N-difluoroamino)dinitromethylltetrazole was developed; some derivatives of the latter compound have been obtained.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8. pp. 2056–2058, August, 1996.     

Oxidation of secondary alcohols byN-methylmorpholine-N-oxide (NMO) catalyzed by atrans-dioxo ruthenium(VI) complex or perruthenate complex: A kinetic study

Thetrans-dioxo ruthenium (VI) complex, [P(C₆H₅)₃C₆H₅CH₂]⁺[Ru(O)₂OAcCl₂] or tetrapropylammonium perruthenate catalyzes the oxidation of secondary alcohols to ketones byN-methylmorpholine-N-oxide (NMO). Kinetic studies showed the formation of a complex between catalyst and substrate (alcohol) as the first step in the mechanism.     

Syntheses and transformations of novel nitrogen and sulfur containing morphinanedienes

Summary The synthesis of 6-azido-6-demethoxythebaine (10) has been performed starting from thebaine (1). Compound10 undergoes a cycloaddition reaction with the azadienophilePTAD to form bridgehead azide14. The acid catalyzed rearrangement of isothiocyanato diene11 obtained from azido diene10 and thiocyanato dienes8 and9 leads to sulfur containing derivatives of apocodeine (17–20).

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Darstellung und Reaktionen stickstoff- und schwefelhaltiger Morphinandiene

Zusammenfassung 6-Azido-6-demethoxythebain (10) wurde ausgehend von Thebain (1) hergestellt. Verbindung10 wurde in einer Cycloadditionsreaktion mit dem AzadienophilPTAD zum Brückenkopfazid14 umgesetzt. Das aus dem Azidodien10 erhältliche Isothiocyanatodien11 und die bereits früher gewonnenen Thiocyanatodiene8 und9 liefern bei säurekatalysierter Umlagerung die Apokodeinderivate17–20.

     

Preparation of a thermosensitive cobalt phthalocyanine/N-isopropylacrylamide copolymer and its catalytic activity on thiol

A thermosensitive copolymer of cobalt tetra(N-acryliccarbonyl)aminophthalocyanine (Co-TACAPc) and N-isopropylacrylamide (NIPA) was prepared through redox polymerization in aqueous solution, and its catalytic activity for oxidation of 2-mercaptoethanol was investigated. The products of Co-TACAPc and its copolymer were characterized by elemental analysis, IR, UV/vis, and TGA. The copolymer can be dissolved into most solvents, particularly into water over a wide range of pH. The copolymer also revealed a lower critical solution temperature (LCST) phenomenon at 32.6 degrees C in water; i.e., it was soluble in cold water (below 32.6 degrees C) but insoluble in hot water (above 32.6 degrees C). As a result, in contrast to Co-TACAPc, the copolymer is able to serve as a homogeneous catalyst on oxidation of 2-mercaptoethanol below 31.0 degrees C and be recovered with increasing temperature due to its lower solubility above 31.0 degrees C.     

Oxidation of secondary alcohols byN-methylmorpholine-N-oxide (NMO) catalyzed by Ru(II) halosulfoxide complexes. A kinetic study

RuX₂(DMSO)₄ (X=Cl,cis; Br,trans) undergoes ligand substitution in N,N-dimethylformamide (DMF) to give RuX₂(DMSO)₃DMF, which catalyzes the oxidation of secondary alcohols by NMO to ketones. Kinetics of the reaction catalyzed bytrans-RuBr₂(DMSO)₄ differed from that ofcis-RuCl₂(DMSO)₄. A mechanism is proposed involving the formation of Ru(IV)oxo species as the active intermediate and a rate expression is derived.     

Interaction of cellulose with amine oxide solvents

Cellulose I, mainly as ramie or as Avicel microcrystalline cellulose, has been monitored by optical microscopy and by ¹³C CPMAS NMR, over the course of its dissolution in hot N-methylmorpholine N-oxide solvent. Its interaction with the near-solvent N-ethylmorpholine N-oxide and related non-solvents has also been investigated. NMR shows that N-methylmorpholine N-oxide partly converts crystalline cellulose I into amorphous solid cellulose. The changes in chemical shift imply increased flexibility at the glycosidic bonds. In contrast, N-ethylmorpholine N-oxide converts cellulose I to cellulose III_I, without dissolution. Microscopy shows that the ramie fibres swell laterally, and at least some also shorten longitudinally, during dissolution. Model studies using methyl--d-glucopyranose show no evidence from ¹³C chemical shifts for different modes of binding with different solvents. However, N-methylmorpholine N-oxide binds more strongly to methyl--d-glucopyranose in DMSO than does N-ethylmorpholine N-oxide, whereas N-ethylmorpholine N-oxide binds better to H₂O. Also, ¹³C T ₁ values for aqueous cellobioside show increasing rotational freedom of the –CH₂OH sidechains as N-methylmorpholine N-oxide is added. Together, these observations imply the initial penetration of solvents and near-solvents between the molecular cellulose sheets. Subsequently, N-methylmorpholine N-oxide breaks H-bonds, particularly to O-6, just sufficiently to loosen individual chains and then dissolve the sheets.     

An Efficient Synthesis of Trialkyl <Emphasis Type="Italic">N</Emphasis>-Alkyl-6-methyl-2-pyridone-3,4,5-tricarboxylates

Summary. An efficient synthesis of trialkyl N-alkyl-6-methyl-2-pyridone-3,4,5-tricarboxylates from three-component reaction of the zwitterions generated from dialkyl acetylenedicarboxylates and alkyl isocyanides with alkyl 2-chloroacetoacetates is described.     

Thermodynamic properties of copolymeric hydrogels based on 2-hydroxyethyl methacrylate and a zwitterionic methacrylate

The copolymerisation of 2-hydroxyethyl methacrylate and a zwitterionic methacrylate, namelyN,N-dimethyl-N-methacryloxyethyl-N-(3-sulphopropyl)-ammonium betaine (SPE), in the presence of a tetrafunctional crosslinker has been effected to 100% conversion by -irradiation. The resultant xerogels of different compositions were swollen to equilibrium in water to yield hydrogels. Volumetric swelling and compression-strain measurements were made over the temperature range 278–343 K. All these copolymers showed an increasing volumetric swelling with temperature, but the derived values of the partial molar enthalpy, entropy and Gibbs free energy of dilution showed certain differences which were interpreted on the basis of copolymer dyad distribution.     

Synthesis and antimicrobial activity of quinoline-based 2-pyrazolines

A series of 2-pyrazolines was prepared in a reaction of quinolinylchalcones with phenyl hydrazine under both conventional and microwave-induced heating. Structures of the synthesized compounds were characterized by spectroscopic data and CHN analyses. All prepared compounds were tested for antimicrobial activity against bacterial strains, viz. Staphylococcus aureus, Salmonella typhii, Escherichia coli, and Shigella dysentery. Almost all synthesized compounds have shown antimicrobial activity; however, compounds with a chloro group as a substituent have been found to be more effective.     

Phenazinee di-N-oxide radical cation and its reactions with hydrocarbons

The absorption spectra of phenazine di-N-oxide radical cation (OPO^+·) in dichloromethane were recorded by the spectroelectrochemical method in the range from 300 to 700 nm. The reactions of the electrochemically generated OPO^+· withpara-substituted toluenes, ethylbenzene, and cumene were studied. Using differential cyclic voltammetry, relative rate constants of reactions of OPO^+· with substrates were determined; their correlations with ⁺ para constants of substituents gives p = -2.7, which attests to the nonradical character of the reaction of OPO^+· with RH. This conclusion is confirmed by the study of the effect of O₂ on oxidation of ethylbenzene and cumene.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1992–1998, August, 1996.     

Synthesis and some transformation ofN-allyl-N′-methoxy-andN-allyl-N′-tosyloxydiazeneN-oxides

The first representatives ofN-2-alkenyl-N′-alkoxydiazeneN-oxides andN-2-alkenyl-N′-sulphonyloxydiazeneN-oxides have been synthesized. Some reactions of the double bond in these compounds have been studied. The possibility of isomerization ofN-2-alkenyl-N′-alkoxydiazeneN-oxides toN-alk-1-enyl derivatives has been discovered. See Ref. 1 and the references therein. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2262–2265, November, 1998.     

Reactions of Cinnoline, Cinnoline N-Oxides, and Their Chloro Derivatives with Alkylamines: the First Case of Nucleophilic Substitution of Hydrogen in the Cinnoline Series

In contrast to cinnoline and cinnoline N₍₁₎-oxide, cinnoline N₍₂₎-oxide reacts with primary and secondary amines on prolonged heating or in the presence of oxidants to give 3-alkylaminocinnolines.     

Preparation of substituted ionic carbohydrate polymers and their interactions with ionic surfactants

The formation of micelles of hexadecyltrimethylammonium chloride (CTAC) and sodium dodecylsulfate (SDS) in aqueous solutions containing charged polysaccharides was studied by steady-state and time-resolved fluorescence measurements using pyrene as a photophysical probe. Micropolarity studies using the I₁/I₃ ratio of the vibronic emission bands of pyrene and the behaviour of the I_E/I_M ratio between the excimer and monomer emissions show the formation of hydrophobic domains. The interactions between the polyelectrolytes and surfactants of opposite charge lead to the formation of induced pre-micelles at surfactant concentrations lower than the critical micellar concentration (cmc) of the surfactants. At similar concentrations, the I_E/I_M ratio shows a peak. This aggregation process is assumed to be due to electrostatic attractions. At higher surfactant concentrations, near the critical micellar concentration, micelles with the same properties as those found in pure aqueous solution are formed. On the other hand, systems containing polyelectrolytes and surfactants of the same charge do not show this behaviour at low concentrations. The presence of long alkyl chains bound to the polyelectrolytes also induces the formation of free micelles at concentrations somewhat below the aqueous cmc.     

Zur Ringumwandlung von 2-Amino-thiophen-3-carbonsäureestern: Pyridon- und Pyridazinon-Derivate

Whereas treatment of the ethyl 5-acetyl-2-amino-4-methyl-thiophene-3-carboxylate (1) with potassium hydroxide yields the 2-hydroxy-thiophene-3-carbonitrile4 its hydrazone2 is converted into the 1-amino-5-mercapto-2-pyridone derivative6. The transformation of the 2-amino-5-phenylazo-thiophene derivative9 by potassium hydroxide yields the substituted 3-mercapto-pyridazin-6(1H)one10, with sodium ethoxide the 5-phenylhydrazono-2-oxo-thiolen-3-carbonitrile11 is formed. From6 the 5-mercapto-2-pyridone derivatives7 d,e can be obtained.

     

Synthesis ofN-3-chloroalkoxy-2-nitroxypropyl-N-alkylnitramines and their subsequent azidation

Nitration ofN-3-chloroalkoxy-2-hydroxypropyl-N-alkylsulfamates gave the correspondingN-3-chloroalkoxy-2-nitroxypropyl-N-alkylnitramines. Azidation of the latter resulted inN-azido-3-azidoalkoxypropyl-N-alkylnitramines. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 673–676, April, 1998.     

Swelling and dissolution of cellulose, Part V: cellulose derivatives fibres in aqueous systems and ionic liquids

The swelling and dissolution mechanisms of several cellulose derivatives (nitrocellulose, cyanoethylcellulose and xanthate fibres) are studied in aqueous systems (N-methylmorpholine-N-oxide—water with various contents of water, hydroxide sodium—water) and in ionic liquids. The results are compared with the five modes describing the swelling and dissolution mechanisms of cotton and wood cellulose fibres. The mechanisms observed for the cellulose derivatives are similar to the ones of cotton and wood fibres. Swelling by ballooning is also seen with cellulose derivatives, showing that this phenomenon is linked to the fibre morphology, which can be kept after undergoing a heterogeneous derivatisation. Patrick Navard and Thomas Heinze—Members of the European Polysaccharide Network of Excellence (EPNOE),     

Ag-Pd/g-C3N4的制备及在水溶液中选择性氧化苯甲醇

采用硼氢化钠还原法在g-C₃N₄的表面负载Ag和Pd纳米颗粒制备Ag/g-C₃N₄、Pd/g-C₃N₄、Ag-Pd/g-C₃N₄光催化剂.采用能谱仪、X射线衍射、高分辨透射电子显微镜等技术对样品进行表征.结果显示,Ag-Pd/g-C₃N₄复合材料中C、N、Ag和Pd元素的质量百分数分别为22.718%、59.966%、9.132%和8.184%.Ag和Pd纳米颗粒负载在g-C₃N₄表面可提高材料在可见光区域的吸收以及提高苯甲醇的转化率,生成苯甲醛的选择性为85.6%.     

Syntheses of angular condensed ring systems combining a benzodiazepinic,or benzothiazepinic,and a coumarinic moiety

Summary The title compounds were prepared via intermediates resulting from reactions of 3-formyl-4-hydroxycoumarin (1) witho-phenylenediamine,o-aminophenol, ando-aminothiophenol, respectively. Intramolecular ring closures were effected between the free hydroxy and amino or thiol groups.

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Synthese von kondensierten Heterocyclen, die ein Benzodiazepin oder Benzothiazepin angular mit dem Coumarinsystem verknüpfen

Zusammenfassung Die Titelsubstanzen werden über Zwischenverbindungen erhalten, die aus der Reaktion von 3-Formyl-4-hydroxycoumarin (1) mito-Phenylendiamin,o-Aminophenol undo-Aminothiophenol enstehen. Der Ringschluß erfolgt über die freie Hydroxylgruppe und der Amino- bzw. Thiolgruppe.