Gem-diol and Ketone Crystal-to-crystal Transition Phenomena

Abstract

The generally thought unstable diol compound tetrazyl gem-diol (1, H2DTMdiol·2H2O), was firstly obtained in crystalline form by culturing the filtrate for ten days after acidification and filtration of aqueous solution of potassium salt of ketone (2, [K(HDTMone)·2H2O]n). The stability of this novel gem-diol compound is found owning to the hydrogen bonds with lattice water molecules and electrophilic tetrazolyl groups. Meanwhile, the undissolved ketone (3, H2DTMone) was separated during the filtration in the process of gem-diol compound production. Surprisingly, the crystal-to-crystal perfect transition phenomena from gem-diol (1) to ketone (3) were firstly observed after heating up to 120 °C as evidenced by X-ray single crystal diffraction and powder X-ray diffraction. These results found here might open new revenues for methylene oxidation and alkanediol chemistry.

Aerobic Oxidation of in Situ Generated Cyanine Dyes Leading to DNA Damage

“…In addition, we studied a novel spontaneous aerobic oxidation of 4 and proposed the mechanism of the reaction based on the products and intermediate characterization. Oxidation of 4 is a rare example of a direct noncatalytic transition from CH 2 to a geminal diol, which is an important discovery for the chemistry of gem -diols . In this study, 4 and 1 demonstrated mostly unknown thermal oxidation of DNA by cyanine dyes under aerobic conditions.…”

“…Oxidation of 4 is a rare example of a direct noncatalytic transition from CH 2 to a geminal diol, which is an important discovery for the chemistry of gem-diols. 20 In this study, 4 and 1 demonstrated mostly unknown thermal oxidation of DNA by cyanine dyes under aerobic conditions.…”

A property-oriented adaptive design framework for rapid discovery of energetic molecules based on small-scale labeled datasets

“…The compound a1 was synthesized by Fischer and considered to be a promising powerful explosive, judging from some computational evidence. 46 The heat of formation of the parent ring of a10 was calculated to be 164.56 kJ mol −1 by Bo, 47 much lower than that of a10 (949.87 kJ mol −1 ) substituted by two –NHNO 2 . The heat of formation of the compound with the same parent ring as a2–a9 but with two –NO 2 substituted at the carbon atom of pyrazole was reported to be 550.84 kJ mol −1 , 48 significantly lower than those of the eight compounds (a2–a9) with the same parent ring, indicating the energetic characteristics of the –NHNO 2 and –ONO 2 substituents.…”