Brunner J, Senn H, Richards F M
J Biol Chem. 1980 Apr 25;255(8):3313-8.
The synthesis of 3-trifluoromethyl-3-phenyldiazirine (TPD) is reported in an overall yield of 60% based on 2,2,2-trifluoroacetophenone as starting material. TPD is rapidly photolyzed on irradiation near 350 nm to yield 35% of the diazoisomer and 65% of the corresponding carbene. No internal rearrangement of the latter compound by fluorine migration was detected. Photolysis in methanol yielded the product of a formal OH insertion in greater than 95% yield. Photolysis in cyclohexane gave at least a 50% yield of the CH insertion product at a diazirine concentration of 15 mM. The products were identified by gas chromatographic mass spectra and by 19F NMR spectra. In the dark the diazirine is stable in 1 M acid or base and at temperatures as high as 75 degrees C for at least 30 min. The diazoisomer is much less photolabile and is stable in 0.1 M acetic acid for at least 12 h. The synthesis of a derivative of TPD containing the 2-hydroxyethyl[O-tosylate] group on the para position of the phenyl ring is described. This compound permits the easy attachment of the TPD function to other molecules. It is suggested that the ease of synthesis, dark stability, rapid photolysis, and reactivity of the carbene may make this group useful in the preparation of various photochemical probes.
据报道，以2,2,2-三氟苯乙酮为起始原料，3-三氟甲基-3-苯基重氮甲烷（TPD）的合成总产率为60%。TPD在350nm附近照射时会迅速光解，生成35%的重氮异构体和65%的相应卡宾。未检测到后一种化合物通过氟迁移发生的内部重排。在甲醇中光解得到的正式OH插入产物产率大于95%。在环己烷中，当重氮甲烷浓度为15mM时，CH插入产物的产率至少为50%。产物通过气相色谱质谱和19F NMR光谱进行鉴定。在黑暗中，重氮甲烷在1M酸或碱中以及在高达75℃的温度下至少30分钟是稳定的。重氮异构体的光稳定性要低得多，在0.1M乙酸中至少12小时是稳定的。描述了一种在苯环对位含有2-羟乙基[O-甲苯磺酸酯]基团的TPD衍生物的合成。该化合物允许将TPD官能团轻松连接到其他分子上。有人认为，这种基团易于合成、黑暗稳定性好、光解迅速以及卡宾的反应活性可能使其在制备各种光化学探针中有用。
