Untersuchungen zur Silicationenkonstitution in N-(2)Hydroxyethyl- und N-(2)Hydroxypropylpyridiniumsilicatlösungen. Bildung von N-(2)Hydroxypropylpyridiniumsilicathydrat

Investigations on the Silicate Ion Constitution in N-(2)hydroxyethyl- and N-(2)hydroxypropylpyridinium Silicate Solutions Crystallization of N-(2)hydroxypropylpyridinium Silicate Hydrate In N-(2)hydroxyethyl- and N-(2)hydroxypropylpyridinium silicate solutions are present mainly double three-ring and double four-ring silicate ions. With increasing concentration their molar ratio shifts in direction to double four-ring silicate. Simultaneously the amount of the low-condensed silicates decreases. An increasing concentration of the alkali hydroxide destroys the double ring cages. From solutions of N-(2)hydroxypropylpyridinium silicate with molar ratios of the pyridinium base to silicon dioxide of 0.5 to 2 and from solutions with a certain amount of alkali hydroxide an acid- N-(2)hydroxypropylpyridinium-double-four-ring silicate hydrate is obtained by crystallization.     

N-(polyfluoroalkyl)imidazolium-2-carbodithioates

Chemical properties of carbenes derived from 1-methyl-3-polyfluoroalkylimidazolium salts were studied. These unstable intermediate products reacted with carbon disulfide to give the corresponding imidazolium-2-carbodithioates which were subjected to methylation at the sulfur atom.     

N－（2－环戊酮基丙酰基）－及N－（2－环己酮基丙酰基）－四氢噻唑－2－硫酮的合成及其醇解与胺解

以碘化－Ｎ－甲基－２－氯吡啶盐为缩合剂，在三乙胺存在下由３－（２－环戊酮基）丙酸及３－（２－环己酮基）丙酸分别同四氢噻唑－２－硫酮反应，得到新化合物Ｎ－（２－环戊酮基内酰基）四氢噻唑－２－硫酮（２ａ）及Ｎ－（２－环己酮基丙酰基）四氢噻唑－２－硫酮（２ｂ），产率分别为５２．９％和５１．０％，２ａ，ｂ分别同甲醇、乙醇反应得到相应的３－（２－环戊酮基）丙酸酯３ａ，ｂ及３－（２－环己酮基）丙酸酯３ｃ，ｄ，３ａ～ｄ的产率为７５～８７％；２ａ、ｂ分别同胺反应得到３－（２－环戊酮基）内酰胺４ａ、ｂ及３－（２－环己酮基）内酰胺４ｃ、ｄ，４ａ～ｄ产率为７８～９３％。     

Vibrational and 1H NMR spectra of N-(2-pyridyl)-thioformamide and N-(2-pyridyl)thioacetamide

The Raman and infrared spectra of N-(2-pyridyl)thioformamide and N-(2-pyridyl)-thioacetamide have been measured. The assignment of the bands is aided by the complete normal coordinate treatment for all the vibrations of N-(2-pyridyl)thioformamide and its N-deuterated molecule using a Urey—Bradley force function for the in-plane vibrations and a valence force function for the out of plane vibrations. Variable temperature ¹H NMR study of the two pyridylthionamides has also been performed. It is inferred that while N-(2-pyridyl)thioformamide favours a cis —CSNH— group, the other compound favours a trans —CSNH— grouping at ambient temperature.     

Synthesis of N-(2-Hydroxyalkyl)trimethylsilylpropynamides

A number of previously unknown N-(2-hydroxyethyl)trimethylsilylpropynamides were synthesized by reactions of 2-aminoethyl trimethylsilyl ethers with trimethylsilylpropynoyl chloride. 2-Hydroxyethylamine reacts with trimethylsilylpropynoyl chloride at both nitrogen and oxygen atoms to afford 2-(3-trimethylsilylpropynoylamino)ethyl trimethylsilylpropynoate.