Low-temperature heat capacity and thermodynamic properties of crystalline 2-chloro-5-trichloromethylpyridine

The low-temperature heat capacities of 2-chloro-5-trichloromethylpyridine were measured with a high-precision automated adiabatic calorimeter in the temperature range from 80 K to 345 K. A solid-liquid phase transition was observed from 318.57 K to 327.44 K with peak temperature 324.67 K; the molar enthalpy and entropy of phase transition, DeltaH(m) and DeltaS(m), were determined to be 14.50 +/-0.02 kJ mol(-1) and 44.66 +/- 0.07 kJ K-1 mol(-1), respectively. The thermal stability was investigated through thermogravimetric analysis (TG). The TG and DTG results reveal that 2-chloro-5-trichloromethylpyridine starts to lose mass at 332 K due to evaporation and completely changes into vapour at 483 K under the present experimental conditions.

A DFT study on isomorphously substituted MCM-22 zeolite

The density functional theory has been used to study the isomorphously substituted MCM-22 zeolite for the first time. The effect of the basis sets on the calculation results is discussed in details. Data of several index properties for characterizing the relative acidity of T-MCM-22 (T = B, Al, Ga, and Fe), including proton affinity, bond length and bond angle, OH stretching frequency, and charge on the acidic proton, show that the acidity of T-MCM-22 increases in the sequence of B-MCM-22 < Fe-MCM-22 < Ga-MCM-22 < Al-MCM-22. After making a correction, the calculated OH stretching frequencies for Al-MCM-22 and Fe-MCM-22 show a reasonable agreement with the experimental data. On the basis of an equilibrium structure of the B-MCM-22 zeolite, the effect of the B element in the synthesis of the Ti-MCM-22 is also discussed. The adding of the B element during the synthesis of the Ti-MCM-22 can decrease greatly the Ti substitution energy because of the forming of a structure quite similar to the terminal silanol group. The results can provide some constructively information for zeolite synthesis.

Efficient One-Pot Synthesis of Highly Substituted Thiophene Library from 1,3-Dicarbonyl Compounds

A faccile and efficient one-pot synthesis of highly substituted thiophenes has been developed and employed for the preparation of a small focused library. Treatment of 1,3-dicarbonyl compounds 1 with CS2 in the presence of K2CO3 in DMF at room temperature, followed by stepwise addition of alkyl bromides 2 and methylene active bromides 3, provided via intramolecular cyclization 2,3,4,5-tetrasubstituted thiophenes 4 in yields of 77-94%. This protocol, combining construction and modification of the thiophene ring, increases the structural diversity of final products from readily available materials. A mechanism for the one-pot synthesis of thiophenes of type 4 has been proposed. A small focused library of thiophenes is prepared using the sequential addition of reagents to achieve unique substitution in the 2 and 5 position of the thiophene ring

Efficient and Divergent Synthesis of Fully Substituted 1H-Pyrazoles and

Efficient and divergent one-pot synthesis of fully substituted 1H-pyrazoles and isoxazoles from cyclopropyl oximes based on reaction conditions selection is reported. Under Vilsmeier conditions (POCl3/DMF), substituted 1H-pyrazoles were synthesized from 1-carbamoyl, 1-oximyl cyclopropanes via sequential ring-opening, chlorovinylation, and intramolecular aza-cyclization. In the presence of POCl3/CH2Cl2, substituted isoxazoles were obtained from the cyclopropyl oximes via ring-opening and intramolecular nucleophilic vinylic substitution (SNV) reactions

A Facile One-pot Synthesis of Substituted Pyridine-2,4(1H,3H)-diones from α-Acyl-α-carbamoyl Ketene-S,S-acetals

A facile and efficient one-pot synthesis of substituted pyridine-2,4(1H,3H)-diones has been developed. Subjected to N,N-dimethylformamide dimethyl acetal (DMFDMA) in N,N-dimethylformamide at 120 ˚C, a series of acyl(carbamoyl)ketene S,S-acetals were converted into the corresponding substituted pyridine-2,4(1H,3H)-diones in high yields.

Two novel triphenylamine-substituted poly(p-phenylenevinylene) derivatives: synthesis, photo- and electroluminescent properties

Two novel triphenylamine-substituted poly(p-phenylenevinylene) derivatives, P1 and P2, have been successfully synthesized through the Witting-Horner reaction. The structures and properties of the monomers and the resulting polymers were characterized by using H-1 NMR, FT-IR, GPC, TGA, UV-vis absorption spectroscopy, cyclic voltammetry (CV) and electroluminescence (EL) spectroscopy

(Z)-2-(2-chloro-3,3,3-trifluoroprop-1enyl)-6-methoxyphenyl acetate

The crystal structure of the title compound, C12H10ClF3O3, was determined in order to establish the configuration of the C double bond. The compound was found to be the Z isomer. The crystal structure is dominated by Cl center dot center dot center dot O halogen bonds [Cl center dot center dot center dot O = 3.111 (3) angstrom], as well as C-H center dot center dot center dot O and C-H center dot center dot center dot F hydrogen-bonding interactions, that connect neighboring molecules into a three-dimensional supramolecular network.

Ring-Enlargement of Dimethylaminopropenoyl Cyclopropanes: An Efficient Route to Substituted 2,3-Dihydrofurans

A convenient and efficient synthesis of substituted dihydrofurans is developed via ring-enlargement of 1-dimethylaminopropenoyl-1-carbamoyl/benzoyl cycloproparres catalyzed by ammonium acetate in acetic acid with high regio- and stereoselectivity. Some of the newly synthesized substituted dihydrofurans are subjected to further synthetic transformation in the presence of NaOH (aq) in ethanol to afford the corresponding 5-aryl-2,3-dihydrofuro[3,2-c]pyfidin-4(5H)-ones in high yields.

N-Acetyl-N-{2-[(Z)-2-chloro-3,3,3-trifluoroprop-1-enyl]phenyl}acetamide

The title compound, C13H11ClF3NO2, adopts a Z conformation. Halogen center dot center dot center dot oxygen interactions [Cl center dot center dot center dot O = 2.967 (3) angstrom] in the crystal packing lead to the formation of a dimer joined by two Cl center dot center dot center dot O bonds.