纳米晶TiO2电极上半菁衍生物光敏染料

合成了具有不同共轭链长度的吡啶盐类及喹啉盐类半菁染料(E)-N-(4-磺酸丁基)-4-[2-(4-N, N-二甲基氨基苯基)乙烯基]吡啶鎓盐(P1)、(E)-N-(4-磺酸丁基)-4-[2-(4-N, N-二甲基氨基苯基)丁二烯基]吡啶鎓盐(P2)、(E)-N-(4-磺酸丁基)-4-[2-(4-N, N-二甲基氨基苯基)乙烯基]喹啉鎓盐(Q1)以及(E)-N-(4-磺酸丁基)-4-[2-(4-N, N-二甲基氨基苯基)丁二烯基]喹啉鎓盐(Q2).研究了它们的光物理性质，并将它们用作TiO2纳米晶电极的光敏化剂引入光电化学电池.与含有乙烯基共轭桥的染料P1和Q1相比，含有丁二烯基共轭桥的染料P2和Q2在甲醇和氯仿中的最大吸收均发生一定程度的红移，而且吸收光谱变宽.这两类染料都能很好地吸附于TiO2电极上.在比较了四个染料的吸收光谱、摩尔消光系数以及在TiO2电极表面的吸附量后，发现Q1具有最好的光电转化性质.     

SYNTHESIS OF 2-γ-N-(AMINOETHYL)AMINOPROPYL-2-METHYL-6-ALKYL(ARYL,H)-1,3-DIOXA-6-AZA-2-SILACYCLOOCTANES

Some new 2-γ-N-(aminoethyl)aminopropyl-2-methyl-1,3-dioxa-6-aza-2-silacyclooctane and 2-γ-N-(aminoethyl)aminopropyl-2-methyl-6-alkyl(aryl)-1,3-dioxa-6-aza-2-silacyclooctanes have been synthesized from γ-chloropropyldimethoxymethyl silane by ethylenediamine substitution and diethanolamine or N-alkyl(aryl)diethanolamines substitution. The resulting silocanes have been characterized by elemental analyses, IR, and ¹H NMR.     

Synthesis,Structure, and Biological Activity of Mixed-Ligand Amine-Containing Copper(II) Coordination Compounds with 2-(2-Hydroxybenzylidene)-N-(prop-2-en-1-yl)hydrazinecarbothioamide

Russian Journal of General Chemistry - Сopper(II) nitrate reacts in ethanol with 2-(2-hydroxybenzylidene)-N-(prop-2-en-1-yl)hydrazinecarbothioamide H2L in an 1 : 1 molar ratio to form the...     

Calorimetric Investigations of the Lipase-catalysed Hydrolysis of Acylated Acyclonucleosides

Thermal power accompanying the hydrolysis of mono- and bi-acylated acyclonucleosides:(R,S)-1-N-(1-O-acetyl-3-hydroxypropoxymethyl)-thymine (ThL),1-N-(1,3-di-O-acetylpropoxymethyl)-thymine (ThAc), and1-N-(1,3-di-O-acetylpropoxymethyl)-5-fluorouracil (FAc), catalysed by lipase from Candida Cylindracea (Rugosa) was investigated by isothermal heat conduction microcalorimetry. Changes of the thermal power in time and the total heat effects were determined in long-lasting measurements. Hydrolysis of these compounds was examined also by TLC. For all three esters the thermal power curves reveal both a relatively intensive and slow heat evolutions. It is suggested that this complexity results from a superposition of: (i) a stereospecific hydrolysis of the ester bond connected to the heterocyclic moiety by a chain endowed with an appropriate chirality, and (ii) a non-specific hydrolysis of another ester bond. A partial chemical degradation of reactants in the buffer was also observed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ceramide constituents from five mushrooms

Five mushrooms, Panellus serotinus, Lyophyllum connatum, Amanita pantherina, Sarcodon aspratus and Lepista nuda, have been investigated chemically. Two new ceramides, (2S,3R,4E,8E)-N-hexadecanoyl-2-amino-9-methyl-4,8-octadecadiene-1,3-diol (1) and (2S,3R,4E,8E,9'Z,12'Z)-N-9',12'-octadecadienoyl-2-amino-9-methyl-4,8-octadecadiene-1,3-diol (2), have been isolated from Panellus serotinus. Compound 2 was also isolated from Lyophyllum connatum. Two new ceramides, (2S,2'R,3R,4E,8E)-N-2'-hydroxypentadecanoyl-2-amino-9-methyl-4,8-octadecadiene-1,3-diol (4) and (2S,2'R,3R,4E,8E)-N-2'-hydroxytetradecanoyl-2-amino-9-methyl-4,8-octadeca-diene-1,3-diol (5), have been isolated from Amanita pantherina with (2S,2'R,3R,4E,8E)-N-2'-hydroxyhexadecanoyl-2-amino-9-methyl-4,8-octadecadiene-1,3-diol (3), a known synthetic compound. Compounds 3 and 4 were also isolated from Sarcodon aspratus and compound 3 was isolated from Lepista nuda. The structures of the new compounds were elucidated on the basis of their spectral data.     

Use of ESI-MS to determine reaction pathway for hydrogen sulphide scavenging with 1,3,5-tri-(2-hydroxyethyl)-hexahydro-s-triazine

To study the reaction between hydrogen sulphide and 1,3,5-tri-(2-hydroxyethyl)-hexahydro-s-triazine, which is an often used hydrogen sulphide scavenger, electro spray ionisation mass spectrometry (ESI-MS) was used. The investigation was carried out in positive mode, and tandem mass spectrometry was used to investigate the nature of unknown peaks in the mass spectra. The reaction was found to proceed as expected from theory with the triazine reacting with hydrogen sulphide to form the corresponding thiadiazine. This species subsequently reacted with a second hydrogen sulphide molecule to form the dithiazine species, hereby confirming previously obtained results and showing the ability of the ESI-MS method for studying the scavenging reaction. The final theoretical product s-trithiane was not detected. Furthermore, fragmentation products of thiadiazine and dithiazine were detected in the solution, and possible pathways and structures were suggested to describe the observed fragments. In these, thiadiazine fragmented to 2-(methylidene amino)-ethanol and 2-(1,3-thiazetidin-3-yl)-ethanol and N-(2-hydroxyethyl)-N-(sulfanylmethyl)-ethaniminium, which underwent a further fragmentation to N-methyl-N-(2-oxoethyl)-methaniminium. Dithiazine fragmented to N-methyl-N-(2-oxoethyl)-methaniminium as well. The by-product from this reaction is methanedithiol, which was not detected due to its low polarity.     

Zur Bestimmung von Carbamaten 2-(1,3-Dioxolan-2-yl)-phenyl-N-methyl-carbamat in Reaktionsgemischen

Zusammenfassung Am Beispiel von 2-(1,3-Dioxolan-2-yl)-phenyl-N-methyl-carbamat werden Hydrolyse-bedingungen und spezifische Bestimmungsverfahren für Carbamate beschrieben. Besonders günstig verläuft die Hydrolyse unter Verwendung von Kaliumhydroxid in Propylenglykol oder von konz. Phosphorsäure. Wegen der erhöhten Reaktionstemperaturen verlaufen die Reaktionen rasch.Eine für 2-(1,3-Dioxolan-2-yl)-phenyl-N-methyl-carbamat gültige Bestimmungsmethode beruht auf der Umsetzung des Acetalringes mit Hydroxylaminhydrochlorid [8]; es entsteht direkt das entsprechende Oxim. Möglicherweise vorhandene Nebenprodukte, welche die gleiche Reaktion geben, sind Salicylaldehyd und 2-(1,3-Dioxolan-2-yl)-phenol; sie lassen sich colorimetrisch als Eisen(III)-Komplexverbindung bestimmen.

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The determination of carbamates. 2-(1,3-dioxolane-2-yl)-phenyl-N-methyl-carbamate in reaction mixtures

Hydrolysis procedures for carbamates have been investigated, using 2-(1,3-dioxolane-2-yl)-phenyl-N-methyl-carbamate as an example. Phosphoric acid (85% w) and potassium hydroxide in propylene glycol are suitable hydrolyzing agents. Due to the elevated reaction temperature, hydrolysis is fast.A method applicable to the determination of 2-(1,3-dioxolane-2-yl)-phenyl-N-methyl-carbamate is based on direct conversion of the acetal group to the related oxime, with hydroxylamine hydroehloride as reagent.Salicyl aldehyde and 2-(1,3-dioxolane-2-yl)-phenol, which are potential by-products, give the same reaction. They form a coloured iron(III)-complex and can thus be determined.

     

Synthesis and crystal structure of β-N-(5-methyl-4-oxo-5,6-dihydro-4H-1,3-thiazin-2-yl)isonicotinohydrazide

In the presence of amines under mild conditions, β-N-(methacryloylcarbamoythioyl)isonicotinohydrazide underwent intramolecular heterocyclization to give β-N-(5-methyl-4-oxo-5,6-dihydro-4H-1,3-thiazin-2-yl)isonicotinohydrazide, the spatial structure was confirmed by X-ray crystallography.     

Synthesis of (S)-(-)-N-acetylcolchinol using intramolecular biaryl oxidative coupling

An asymmetric synthesis of the tubulin polymerisation inhibitor (S)-(-)-N-acetylcolchinol is reported based on an intramolecular biaryl oxidative coupling of a 1,3-diarylpropyl acetamide intermediate using phenyliodonium bis(trifluoroacetate) as the final step. Three syntheses of the penultimate 1,3-diarylpropyl acetamide intermediate (S)-(-)-N-[1-[3-(tert-butyldimethylsilyloxy)phenyl)]-3-(3,4,5-trimethoxyphenyl)propyl] acetamide are described which differ in the means by which the stereogenic centre was introduced.     

新型S(N)-β-D-葡萄糖苷-4-N-(取代邻羟苯基)亚胺基-5-(4-甲基-1,2,3-噻二唑)-1,2,4-三唑的合成及生物活性

在KOH/acetone体系中,4-N-(取代邻羟苯基)亚胺基-5-(4-甲基-1,2,3-噻二唑)-1,2,4-三唑-3-硫酮(3a～3d)与溴-α-D-四乙酰葡萄糖发生Kenigs-Knorr反应,合成了8个未见报道的S(N)-β-D-乙酰葡萄糖苷,其结构经1H NMR、13C NMR、红外光谱及元素分析等确定.目标化合物的生物活性测试结果表明,它们对金黄色葡萄球菌、白色念珠菌和大肠杆菌均显示了较好的抑菌活性,其效果接近或优于对照药物三氯生和氟康唑的抑菌效能.其中,化合物2-N-(2’,3’,4’,6’-O-四乙酰基-β-D-吡喃葡萄糖基)-4-N-(3,5-二溴邻羟苯基)亚胺基-5-(4-甲基-1,2,3-噻二唑)-1,2,4-三唑-3-硫酮(4d)及3-S-(2’,3’,4’,6’-O-四乙酰基-β-D-吡喃葡萄糖硫基)-4-N-(3,5-二溴邻羟苯基)亚胺基-5-(4-甲基-1,2,3-噻二唑)-1,2,4-三唑(5d)具有较强的抑菌活性.     

β-Dicéto énamines hététrocycliques: 1. Indanediones-1,3 substituées en 2 par un hétérocycle azoté

The condensation of methylated N-heterocycles and espically monomethyl- and polymethylpyridinets on phthalic enhydrides leads to 2-ary1-1,3-indanediones. The 3alklidenylphthalides formed in an intermediary state have been isloated. The influence of solvents and temperature on the velocity and yeild of formation of 2-(2- and 4-pyridyl)-1,3-indandiobnes has been studies. The ir and nmr spectra confirm taht these compunds exist under a β-diketoenamine form resonating witj a betaine form.     

Synthesis of aromatic aldehydes via 2-aryl-n,n'-diacyl-4-imidazolines

Diacylimidazolium ions yield adducts with aromatic compounds. Thus the N,N'-diacetylimidazolium ion and indole gives 1,3-diacetyl-2-(3-indolyl)-4-imidazoline. Less reactive substrates such as thiophene, anisole and 1,3-dimethylbenzene fail to react with this reagent but do form adducts (e.g. 1,3-bis-(trifluoroacetyl)-2-(2-thienyl)-4-imidazoline) with an imidazole/trifluoroacetic anhydride reagent. All of the adducts could be converted to the corresponding aldehyde under mild conditions. The synthetic scope of the new synthesis is similar to that of the Vilsmeier-Haack reaction.     

Stereochemical studies, 88. Saturated heterocycles, 83: Synthesis of stereoisomeric condensed-skeleton 2-imino-substituted 1,3-oxazines

Thiourea ( - , - ) and urea ( - , - ) derivatives have been prepared from - and -2-aminomethyl-1-cyclopentanols, and -l-cyclohexanols and their -methyl derivatives with phenyl isothiocyanate and phenyl isocyanate, respectively. Treatment of and with methyl iodide and then with alkali furnished - with the exception of the - -methyl derivative - 2-phenylimino-1,3-oxazines ( , , - ). The remarkable fact that the ring closure of -2-amino-methyl-1-cyclopentanols gives 1,3-heterocycles with -anellation supports the assumption that the -1,2-disubstituted-1,3-difunctional cyclopentanes undergo ring closure when 1,3-heterocycles with a delocalized pπ bond system are formed. With thionyl chloride the -urea derivatives - afforded an elimination product ( ), whereas the isomers yielded the oxazines by inversion. ¹H and ¹³C NMR spectroscopic studies indicated that in - , the “O-in” conformers are favoured (the methylene group of the hetero ring is , while the oxygen atom is ) and all 3-unsubstituted-2-phenylimino-1,3-oxazines exist exclusively in the tautomeric form with an C=N bond.     

1-Oxa-3-azapentalen-2-ones as Precursors of cis-2-Amino Alcohols: Synthesis from Propargyl Alcohols, CO2, and Amines Using an Intramolecular Amidoalkylation Reaction of Oxazolidin-2-ones

The reaction of 5-methyl-5-(4-methyl-3-pentenyl)-4-methylene-1,3-dioxolan-2-one with primary amines gives the corresponding 4-hydroxy-4-methyloxazolidin-2-ones. These undergo an intramolecular amidoalkylation reaction to form 1-oxa-3-azapentalen-2-ones which are potential precursors of cyclopentanyl cis-2-amino alcohols.     

Free-radical addition of phenyl- and diphenylphosphines to 2-vinyl-1,3-dioxa-6-aza-2-silacyclooctanes

Conclusions Phenyl- and diphenylphosphines add to 2,6-dimethyl-2-vinyl-1,3-dioxa-6-aza-2-silacyclooctane upon the action of UV irradiation to form 2,6-dimethyl-2-[(2-phenylphosphino)ethyl)]-1,3-dioxa-6-aza-2-silacyclooctane and 2,6-dimethyl-2-[(2-diphenylphosphino)ethyl]-1,3-dioxa-6-aza-2-silacyclooctane, respectively.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2615–2616, November, 1985.     

Structure and reactivity of a pyridine-1-imido-2-thiolato complex of iridium(III), CpIr(1-N-2-Spy), generated by photolysis of the (azido)(pyridine-2-thiolato) complex, CpIr(2-Spy)(N3)

Photolysis of the (azido)(pyridine-2-thiolato)iridium(III) complex CpIr(2-Spy)(N3) (1) gave a pyridine-1-imido-2-thiolato complex, CpIr(1-N-2-Spy) (2), in which one of the nitrogen atoms of the azide ligand has been inserted into the Ir-N(py) bond (Cp = eta5-C5Me5). Complex 2 reacted quantitatively with methyl iodide to give the N-methylated product, [CpIr(1-NMe-2-Spy)]I (3). X-ray crystallography revealed that both 2 and 3 have similar two-legged piano stool structures with planar 1-N-2-Spy2- or 1-NMe-2-Spy- ligands, which form iridacyclopentadienyl-like rings by moderate S(ppi)/N(ppi) to Ir(dpi) pi donation.     

Reactions of 2-diaminomethylidenecyclohexane-1,3-diones with diethyl malonate

The debenzoylation of 2-[(amino)(benzoylamino)methylidene]cyclohexane-1,3-diones (addition products of cyclohexane-1,3-diones with benzoylcyanamide) affords the corresponding 2-diaminomethylidenecyclohexane-1,3-diones. The latter act as N,N-dinucleophiles in reactions with diethyl malonate in the presence of MeONa to form 6-hydroxy-2-(2,6-dioxocyclohexylidene)-1,2-dihydropyrimidin-4(3H)-ones. This reaction performed at 200 °C in the absence of bases results in the subsequent self-condensation of the dihydropyrimidinones to give 4,5′-bipyrimidine derivatives.     

Reactions of 2-hydroxybenzonitrile with isocyanates

Triethylamine catalyzes the reaction of 2-hydroxybenzonitrile ( 1 ) with aryl isocyanates to form the corresponding carbamates 2a-c , as well as the cyclization of the latter compounds to either 4[N-(N-arylcarbamoyl)-imino]-3-aryl-2H-1,3-benzoxazin-2-ones 4a-c , or 4-arylamino-2H-1,3-benzoxazin-2-ones 7a-c , depending on the reaction temperature. Under analogous conditions, the carbamates obtained from 1 and 2-chloroethyl isocyanate, 3-chloropropyl isocyanate and ethyl isocyanatoacetate undergo a double cyclization yielding imidazo- and pyrimido[1,2-c|1,3]benzoxazinones 13a,b,17 . Upon heating in phenyl ether, compounds 7a-c , rearrange to 2-(2-hydroxyphenyl)-4(3H)-quinazolinones 10a-c .     

Synthesis of 1-halophenyl 4-(2-imidazolyl)-1-butanones and 5-(2-imidazolyl)-1-pentanones and their ketalization with glycerol

An alternate synthesis of 1-(2,4-dichlorophenyl)-4-(2-imidazolyl)-1-butanones 5d is presented after 1-[(dimethylamino)methyl- and 1-methyl]-2-lithioimidazole failed to be substituted satisfactorily by 2-(2,4-dichlorophenyl)-2-(3-iodopropyl)-1,3-dioxolane ( 3b ). The Pinner addition of ethanol to 2-(2,4-dichlorophenyl)-2-(3-cyanopropyl)-1,3-dioxolane yielded the corresponding imidate which was reacted with 1-amino-2,2-dimethoxyethane to form an amidine. Hot dilute hydrochloric acid converted this ami-dine to the 2-imidazolyl ketone 5b . Syntheses of homologous 1-(4-chloro- and 2,4-dichlorophenyl)-4-(2-imidazolyl)-1-pentanones 20 are described. Ketalizations of 5 and 20 with glycerol formed imidazolyl 1,3-dioxolanyl alcohols. Selective N- and O-alkylations of some of these imidazolyl alcohols are described.     

Reaction of 2-Chloro-5-(chloromethyl)thiophene with Monoethanolamine Vinyl Ether

At the alkylation of monoethanolamine vinyl ether with 2-chloro-5-(chloromethyl)thiophene in ethyl alcohol (60-70°C) a product of disubstitution and transvinylation, viz. N,N-bis(5-chloro-2-thienylmethyl)-N-(2-hydroxyethyl)ammonium chloride is formed. The analogous reaction in the absence of solvent proceeds with the formation of N-(5-chloro-2-thienylmethyl)-N-(2-vinyloxyethyl)amine.