Studies on organic fluorine compounds. LIII. Preparation of functionalized trifluoromethylated compounds using 1-phenylsulfonyl-3,3,3-trifluoropropene

Reaction of 1-phenylsulfonul-3,3,3-trifluoropropene(1) with carbonyl-stabilized enolate anions smoothly proceeded to give the addition products(7) in good yield while with an alkyl-lithium or Grignard reagent the formation of the vinyl anion(8) was one of the reaction pathways. Reaction of 1 with the chiral nucleophiles(11, 16) was carried out to give the functionalized trifluoromethylated compounds(13, 7b) in 4-43% ee     

Vaporization of a liquid injected into an immiscible liquid through a single nozzle

The basic characteristics of vaporization and flowing behavior of n-pentane injected through a single nozzle into a column of hot water have been studied photographically. Subcools at the nozzle-outlet have a strong influence on the critical temperature driving forces at over which vaporization can be maintained. The length of a Rayleigh jet is remarkably shortened when vaporization occurs, whereas mean diameters of drops are little affected whether vaporization occurs or not. A specific condition that a bubble appears in each drop is satisfied not on a specific line but over a wide region on the ΔT_∞ - U_N plane.     

The synthesis of new valence-bond isomers of pentakis(trifluoromethyl)-1,3-diazepine

A new valence-bond isomer of pentakis(trifluoromethyl)-1,3-diazepine was synthesized from tris(trifluoromethyl)cyclopropenyl trifluoromethyl ketone, and reacted with diazomethane to give an N-methylated product.     

Effect of electrostatic field on the polymer chain in the quaternized reaction of polyvinylpyridine with alkyl halides

In order to discuss the electrostatic-field effect on a polymer reaction, the quaternization of poly-4-vinylpyridine–benzyl chloride (system I) was compared to that of poly-γ-chloromethylstyrene–γ-picoline (system II). In these two systems, the reaction initially proceeded according to the simple second-order kinetics. However, after the degree of quaternization exceeded 20–30 mole-%, a deviation from simple second-order kinetics occurred. In system I negative deviation occurred, while in system II positive deviation occurred. These phenomena occurred even though the solvent or the initial concentrations of the reactants were changed. The reasons for these phenomena are given below. In system I, the quaternized pyridine nitrogens prevented the benzyl chloride from approaching the unquaternized pyridine nitrogens. However, in system II the free γ-picoline was attracted by the quaternized chloro-γ-methyl site. Furthermore, the point at which the deviation occurred was determined by the degree of chloromethylation. All these results suggest that the effect of an electrostatic field must be presumed in these two systems.     

Full-color photochromism of a fused dithienylethene trimer

A diarylethene fused trimer, 1-(5-(2-(3,5-dimethyl-2-thienyl)hexafluorocyclopententen-1-yl)-2,4-dimethyl-3-thienyl)-2-(5-(2-(2,4-dimethyl-5-phenyl-3-thienyl)hexafluorocyclopentene-1-yl)-2,4-dimethyl-3-thienyl)hexafluorocyclopentene, was synthesized. The diarylethene derivative showed full-color photochromic performance by choosing appropriate wavelength of light.     

Photochromism of single crystals composed of dioxazolylethene and dithiazolylethene

Although dioxazolylethene 1a did not show any photocoloration in the single crystalline phase, 1a displayed photochromism in the mixed crystal containing both 1a and dithiazolylethene 2a ; the mixed crystal changed color from colorless to red, orange, and yellow upon irradiation with light of appropriate wavelengths.