An efficient method for the synthesis of quinoxaline derivatives catalyzed by titanium silicate-1

Research on Chemical Intermediates - A series of quinoxaline derivatives were efficiently synthesized by convenient and simple procedure in excellent yields using 1 wt.% of titanium silicate (TS-1)...     

Photochemistry of trifluromethyl substituted 1‐methylpyrazoles

Trifluromethyl substitution on the pyrazole ring was found to enhance photoreactivity via the P₄ pathway which involves interchange of the N2‐C3 ring atoms. Thus, 1‐methyl‐3‐(trifluromethyl)pyrazole (1) and 1‐methyl‐5‐(trifluromethyl)pyrazole (3) transposed with a P₄/P₆ or P₄/P₆+P₇ ratio of 2.1:1. 1‐methyl‐4‐(trifluromethyl)pyrazole (2) transposed regiospecifically by the P₄ transposition pathway. Compounds 2 and 3 were also observed to undergo photocleavage to yield enaminonitrile and enaminoisocyanide products.     

The Statistical Mechanics of Semiflexible Equilibrium Polymers

We give an overview of studies of models for semiflexible, equilibrium polymers with special emphasis on our work on both lattice and continuum models for such systems. We show, principally by Monte Carlo simulations, that, once monomers self assemble to form polymers, their semiflexibility leads to nematic phases at low temperatures. Attractive wall potentials encourage the adsorption of these equilibrium polymers on surfaces. Rapid cooling leads to the formation of glasses with entangled polymers. Shear promotes nematic ordering, but, at high shear rates, this tendency decreases since the equilibrium polymers are torn apart. A version of our model in which the polymers are directed shows the polymer analog of bosonic Mott-insulating, mass-density-wave, and supersolid phases. We give a brief comparison of our work with other studies and also explore the experimental implications of our study.     

Reaction of β-amino-α,β-unsaturated esters and amides with aryl diazonium salts : Synthesis of cinnoline derivatives

Conjugated esters and amides react with aryldiazonium salts at room temperature (MeCN) to form the corresponding iminium hydrazone derivatives, which can be thermally cyclized to cinnoline-3-esters and cinnoline-3-amides. In general the intermediate iminium salts derived from the enamine amides cyclize faster than those from the enamine esters. Furthermore, the ease of cyclization depends upon the structure of the base-component of the enamine ester or the amide and the substituent in the aryl moiety of the diazonium salt. The configurational structure of the iminium hydrazones, studied by NMR spectroscopy, has been shown to involve H-bonding of the hydrazonyl N-H with the ester or the amide CO group.     

Study of the development of thermoresistance in human pancreatic carcinoma cell lines using proteome analysis

In order to find candidate proteins that are potentially associated with the thermoresistant phenotype in combination with drug resistance, we analyzed the differential protein expression in vitro in the human pancreatic cancer cell line EPP85-181-P and classical and atypical multidrug-resistant variants and their thermoresistant counterparts using proteomics. This study identifies sets of proteins that may lead to the development of thermoresistance. These results provide a fundamental basis to elucidate the molecular mechanism of thermoresistance and chemoresistance phenomena that may assist the therapy of inoperable cancers.     

Highly rapid and direct synthesis of monoacylated piperazine derivatives from carboxylic acids under mild conditions

A series of monoacylated piperazine derivatives were obtained by the reaction of carboxylic acids with 2-chloro-4,6-dimethoxy-1,3,5-triazine in dichloromethane at room temperature. Good to excellent yields, short reaction times and mild reaction conditions are important features of this methodology.     

A facile two synthon approach to the camptothecin skeleton

A synthesis of deethyldesoxycamptothecin via the reaction of two readily accessible synthons is described. One of the synthons constitutes the ABC ring system of camptothecin, while the second provides all the C atoms of the rings D and E. The synthetic approach is suited for the total synthesis of camptothecin analogues.     

Functionalized enamines—XV: Reactivity patterns of carbene addition to morpholine enamine of 1-β-acetoxy-6-oxo-8a-methyl-Δ-octalin

Carbenes3a-e add to the α-side of the first double bond of dienamine2 (title compound) to give 1 : 1 adducts4a-e, Chlorofluorocarbene3e gives, in addition, ketone7, corresponding to β-addition at the second double bond of2, and a 2 : 1 adduct8. The reaction of2 with dichlorocarbene3a yields, besides4a, novel ring-expansion products5 and6 corresponding to addition of two moles of3a. Ethoxycarbonylcarbene3f reacts with the dienamine (2) to give isomeric esters9 and10a,b. The structure assignments and the mechanism of formation of the reaction products are discussed.     

Unconventional nucleotide analogues. 3. 4-(N1-pyrimidyl)-2-aminobutyric acids

Alkylation of 4-ethoxy-2-hydroxypyrimidines (10a, b), via their anions, provides a convenient procedure for preparing N₁-substituted derivatives. Reaction of 10a, b with t-butyl 4-bromo-2-benzyloxycarbamidobutyrate (17) gives good yields of the N₁-alkylated products 18a, b. The latter have been converted to uracil- (20a), thymine- (20b) and cytosine- (21) substituted -aminobutyric acids.