Bo Zhang, Sitong Chen, Weiming Guo, Weijing Zhang, Lin Wang, Li Yang, Jianguo Zhang
State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing, 100081, China.
Sci Rep. 2017 Oct 18;7(1):13426. doi: 10.1038/s41598-017-13596-6.
The generally thought unstable diol compound tetrazyl gem-diol (1, HDTMdiol·2HO), 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)·2HO]). 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, HDTMone) 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 120C 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.
一般认为不稳定的二醇化合物四唑偕二醇（1，HDTM二醇·2H₂O），是通过对酮钾盐水溶液（2，[K(HDTM酮)·2H₂O]）进行酸化和过滤后，将滤液培养十天首次以晶体形式获得的。发现这种新型偕二醇化合物的稳定性归因于与晶格水分子和亲电四唑基团形成的氢键。同时，在偕二醇化合物生产过程中的过滤过程中分离出了未溶解的酮（3，HDTM酮）。令人惊讶的是，通过X射线单晶衍射和粉末X射线衍射证明，在加热至120℃后首次观察到了从偕二醇（1）到酮（3）的晶体到晶体的完美转变现象。此处发现的这些结果可能为亚甲基氧化和链烷二醇化学开辟新的途径。
