1-(pyridine-2-carboxymethyl)silatrane

Russian Journal of General Chemistry -     

Ring expansion of 1-(chloromethyl)silatrane

Conclusions Reaction of alkali metal sucrates and alkoxides with 1-(chloromethyl)silatrane results in expansion of one of the atrane rings to give 2-carba-3-oxahomosilatranes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1404–1408, June, 1986.     

Microwave Spectrum and Structure of 2-(Trifluoromethyl)pyridine

The high resolution rotational spectrum of 2-(trifluoromethyl)pyridine in 2\begin{document}$ - $\end{document}20 GHz was recorded and analyzed. Spectroscopic parameters including rotational constants, nuclear quadrupole coupling constants of \begin{document}$ ^{14} $\end{document}N as well as the centrifugal distortion constants were determined. The rotational spectra of five mono-substituted \begin{document}$ ^{13} $\end{document}C and one \begin{document}$ ^{15} $\end{document}N isotopologues were also measured and assigned in natural abundance. Experimental results complemented by ab initio calculations lead to an accurate determination of the skeleton structure. The values of the planar moment inertia \begin{document}$ P_{cc} $\end{document} were determined to be 44.46 u?\begin{document}$ ^2 $\end{document} for all the measured isotopologues, indicating a C\begin{document}$ _ \rm{s} $\end{document} symmetry of this molecule. The molecular electrostatic surface potential was calculated to illustrate the trifluoromethyl substitution effects on the electron distribution.     

Synthesis and Crystal Structure of 1-（Trifluoromethyl）-1-（propioloyl）-（E）-3-oxo-（2-thienyl）-（2-naphthylamine）

1INTRODUCTIONTheSchiffbasesderivedfromb-diketonesandaliphaticamineshavebeenshowntoexistastheketo-amines.However,ifsubstituentseitherattheketooraminogrouparearomatic,itmaybeexpectedtheenoliminewillbethefavoredtautomericform[1].Recently,someSchiffbasesderivedfromTTA(4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione)andPMBPhavebeenstudiedbyWang[2]andYu[3]etal.Inordertostudytherelationshipbetweenthestructuresandperformancesofthesecompounds,thetitlecom-poundwillbereportedherein.2EXPERIMENT…     

Synthesis and molecular structure of 1-(2-pyridyloxy)silatrane

1-(2-Pyridyloxy)silatrane was synthesized by trans-etherification of 1-ethoxysilatrane with 2-hydroxypyridine as well as by the reaction of the latter with tetraethoxysilane and triethanolamine. Its structure was established by the XRD analysis of a single crystal, and in solution using the methods of ¹H, ¹³C, ²⁹Si NMR and IR spectroscopy.     

Crystal and molecular structure of 1-(3-ammoniopropyl)silatrane chloride

By single crystal X-ray diffraction the crystal and molecular structure of 1-(3-ammoniopropyl)silatrane chloride (I) is determined. One of three cations in the asymmetric unit of the crystal of I differs from the other two by the length of the coordination N → Si bond. The opposite electronic effects in two geometrically similar cations are transferred inductively through a three-carbon chain.     

Thermodynamic properties of 1,3-dimethylsilatrane and 1-(2-cyanoethyl)silatrane

The heat capacities of 1,3-dimethylsilatrane and 1-(2-cyanoethyl)silatrane were measured, and their thermodynamic functions were calculated. In the intervals 12–205 and 215–315 K, the heat capacity of 1,3-dimethylsilatrane smoothly varies with temperature. A reproducible thermal effect is observed at ～315 K, and a G-type transition, in the range 205–215 K. 1-(2-Cyanoethyl)silatrane shows no anomalies in the examined temperature range. Above 260 K, the rate of the growth of the heat capacity with temperature increases.     

Synthesis of New Tandospirone Analogues Carrying 1-(3-(Trifluoromethyl)phenyl)piperazine

New tandospirone analogues containing a 1-[3-(trifluoromethyl)phenyl]piperazine (TFMPP) moiety have been synthesized by hydroarylation reactions with Pd(OAc)₂. The perhydroisoindole derivatives were obtained by the reaction of reduced starting material with aryl-(heteroaryl) iodides under the same conditions. Spiro-1,3-indandionolylpyrrolidine derivatives having an array of stereocenters are reported.     

Photochemistry of 2-(Trifluoromethyl) cyclohexanone

The photochemical behaviour of the title compound 1a is compared to that of the non-fluorinated parent ketone 2-methylcyclohexanone ( 1b ). Substitution of the CH₃- group on C(2) by a trifluoromethyl group strongly enhances 2H- and RH- reduction product formation in cyclohexane or 2-propanol and oxetane formation in the presence of 2-methylpropene as olefinic component. Under all these conditions 1b exclusively undergoes a-cleavage, a process observed for 1a only in non-reducing solvents as benzene or tert-butyl alcohol.     

3-三氟甲基联苯的合成

以3-三氟甲基苯胺为原料,叔丁醇亚硝酸酯为重氮化试剂,铜粉为催化剂,采用改良的Gomberg反应合成了3-三氟甲基联苯。最佳的反应条件为：3-三氟甲基苯胺20mmol,叔丁醇亚硝酸酯的用量为3-三氟甲基苯胺摩尔数的两倍,Cu的用量为3-三氟甲基苯胺摩尔数的0．6倍,于在40℃反应5h,其结构经^1H NMR,^13C NMR和IR表征。     

Direct Preparation of Trifluoromethyl Ketones from Carboxylic Esters: Trifluoromethylation with (Trifluoromethyl)trimethylsilane

Previously difficult to prepare , aliphatic and alicyclic trifluoromethylketones (e.g. 1 and 2 ), which are of pharmacalogic interest as potential enzyme inhibitors, can now be synthesized easily and efficiently. The one-step reaction starting with carbonic esters and trimethyl(trifluoromethyl)silane is induced by tetrabutylammonium fluoride in nonpolar, aprotic solvents and proceeds without formation of double-addition products.     

Crystal structure of 1-[N-2-aminoethyl)-aminopropyl]silatrane

The crystal structure of 1-[N-(2-aminoethyl)aminopropyl]silatrane has been determined by x-ray diffraction at room temperature. The Si←N bond distance (2.165(2) Å) is in the range observed for other 1-X-propylsilatranes (X = CN, OH, SH, Cl and SCN). The structure is partially disordered: the silatrane moiety displays a disorder that is typical for silatranes and the aminoethyl group terminating the planar chain linked to silicon is rotationally disordered.     

Synthesis and Spatial Structure of the Derivatives of 2,5-Dioxo-3,3-Bis(Trifluoromethyl)-6,7-Benzo-1,4,2-and 2,5-Dioxo-4,4-Bis(Trifluoromethyl)-6,7-Benzo-1,3,2-Oxazaphosphepines

Abstract

Hexafluoroacetone imine easily interacts with compounds (I, R = OMe, OCH₂CF₂CHF₂, NEt₂, Ph) in two directions unlike hexafluoroacttone and gives 1,4,2-oxazaphosphepines (II) (pathway I) or 1,3,2-oxszaphosphepines (III) (pathway 2). The compound (II) (R = NEt₂) lightly hydrolyzes to yield the salt (IV). The structure of heterocycles II-IV) has been confirmed by X-ray analysis (see fig. I, II, R = OMe; fig. 2, IV). The detail structural peculiarities of the compounds am discussed.