p-Azidotetrafluoroaniline (1) was synthesized in 65-73% yield by two different methods employing a stable carbamate intermediate. The first method trapped the intermediate isocyanate generated via a modified Curtius rearrangement with 2-methyl-2-propanol or 2-(trimethylsilyl)ethanol to form the stable carbamates 2d and 2e, respectively. Benzoic acid 2c was first converted to its acid chloride with PCl(5). Displacement of the chloride by NaN(3) in acetone/water formed the acyl azide. Thermal rearrangement followed by the addition of the appropriate alcohols provided the carbamates. The acid labile carbamate 2d was deprotected with HCl/AcOH to provide 1, while trifluoroacetic acid was required to deprotect 2e and afford 1. In the second path, 1 was synthesized in five steps from pentafluoronitrobenzene (3a) in 65% overall yield. Compound 3a was converted into 4-azidotetrafluoronitrobenzene (3b) with NaN(3) in 93% yield and was used without further purification to form 1, 4-diaminotetrafluorobenzene (3c) by Sn/HCl reduction in 85% yield. The mono-9-fluorenylmethoxycarbonyl (FMOC) derivative 3d was formed from 3c with FMOC-Cl and pyridine in EtOAc in 92% yield. Diazotization of 3d under anhydrous conditions with TFA/NaNO(2) and NaN(3) gave 3e in 87% yield. The aryl azide was formed with concurrent nitration of the 2-position of the fluorenyl system. The protecting group was removed with piperidine to afford 1 in 93% yield. Irradiation of 1 with 254 nm light in cyclohexane gave cyclohexylamine 11, diamine 3c, and azobenzene 12 as the primary products. The formation of C-H insertion product 11 indicates that 1 forms a singlet nitrene upon photolysis. Two heterobifunctional photoaffinity reagents iodoacetamide 9 and dansyl derivative 10 were prepared.

中文翻译：

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高效合成4-叠氮基四氟苯胺：一种新型光亲和试剂。

通过使用稳定的氨基甲酸酯中间体的两种不同方法，以65-73％的产率合成了对叠氮基四氟苯胺（1）。第一种方法用2-甲基-2-丙醇或2-（三甲基甲硅烷基）乙醇捕获通过改性库尔修斯重排生成的中间体异氰酸酯，分别形成稳定的氨基甲酸酯2d和2e。苯甲酸2c首先用PCl（5）转化为其酰氯。NaN（3）在丙酮/水中的氯化物置换形成酰基叠氮化物。热重排，然后添加适当的醇，得到氨基甲酸酯。将酸不稳定的氨基甲酸酯2d用HCl / AcOH脱保护，得到1，而需要三氟乙酸将2e脱保护，得到1。在第二种方法中，由五氟硝基苯（3a）分五步合成1，总产率为65％。用NaN（3）将化合物3a转化为4-叠氮基四氟硝基苯（3b），产率为93％，无需进一步纯化即可使用，通过Sn / HCl降低产率为85％，形成1，4-二氨基四氟苯（3c）。由3c用FMOC-Cl和吡啶在EtOAc中以92％的收率形成单-9-芴基甲氧基羰基（FMOC）衍生物3d。在无水条件下用TFA / NaNO（2）和NaN（3）重氮化3d，得到3e，产率为87％。芳基叠氮化物与芴基系统的2位同时硝化而形成。用哌啶除去保护基，以93％的收率得到1。在环己烷中用254 nm光照射1，得到环己胺11，二胺3c和偶氮苯12作为主要产物。CH插入产物11的形成表明1在光解时形成单线态氮。