Perfluorophenyl azide

Also unexpected is the formation of the 2,2 -(3,4,5,6,7-pentafluoroazepin-2-ylidene) (35) during the flow pyrolysis of perfluorophenyl azide over platinum at 300 C.6°... 

The following references provide further information on the use of Sulfo-SFAD and perfluorophenyl azide photoreactive groups Pandurangi et al. (1995a, b, 1996, 1997a, b, 1998) Yan etal. (1994). 

Yan, M., Cai, S.X., Wybourne, M.N., and Keana, J.F.W. (1994) N-Hydroxysuccinimide ester functionalized perfluorophenyl azides as novel photoactivatable heterobifunctional cross-linking reagents. The covalent immobilization of biomolecules to polymer surfaces. Bioconjugate Chem. 5, 151-157. 

An increase of triplet nitrene absorption relative to azepine absorption was observed upon LFP of perfluorophenyl azide in methanol. This effect was not observed in acetonitrile, which has a similar dielectric constant, or in... 

It was mentioned previously that, unlike most arylnitrenes, polyfluorinated arylnitrenes have bountiful bimolecular chemistry. Banks and Sparkes found that pyrolysis of 4-azido-2,3,5,6-tetrafluoropyridine in cyclohexane produced the product of formal CH insertion in 45% yield. Tetrafluoropyridyinitrene was also captured by alkenes, dimethyl sulfoxide and even benzene. Pyrolysis of perfluorophenyl azide (15e) yields a product of formal insertion with a CH-bond of benzene and the formation of adducts with dimethyl sulfoxide.Abramovitch et demonstrated that... 

It is known that irradiation of perfluorophenyl azide in the presence of diethylamine results in the formation of hydrazine along with some other products. LFP of azides 16f, 16g demonstrates that in the presence of amines (piperidine and morpholine) the decay of the aryinitrene absorption (Figure 17, Spectrum 1) is accompanied by formation of the transient absorption with maximum at 320 nm (Figure 17, Spectrum 2). Unlike the adduct of singlet aryinitrene with pyridine (ylide 22e), this intermediate is unstable and its lifetime is about 2.5 ps. The product of its transformations absorbs slightly in the near-UV region (Figure 17, Spectrum 3), which is typical of hydrazines (24). 

Cai, S. X. Glenn, D. J. Kanskar, M. Wybourne, M. N. Keana, J. F. W. Development of highly efficient deep-UV and electron beam mediated cross-linkers synthesis and photolysis of bis(perfluorophenyl) azides, Chem. Mater. 1994, 6, 1822-1829. 

Perfluorophenyl azide was not pyrolyzed in an alkane solvent. However thermolysis of perfluoroazidotoluene 12 in cyclohexane produced the product of CH insertion in 30% yield [95]. 

Russell Poe demonstrated that photolysis of perfluorophenyl azide in pyridine produces ylide 19 with X = 390 nm. This ylide is isolable and its structure obtained by x-ray crystallography. [27]... 

YAN 94] Yan M., Cai S.X., Wybourne M.N. et al., N-Hydroxysucdnimide Ester Functionalized Perfluorophenyl Azides as Novel Photoactive Heterobifunctional Crosslinking Reagents. The Covalent Inunobilization of Biomolecules to Polymer Smfaces , Bioconjugate Chemistry, vol. 5, pp. 151-157, 1994. 

A comparative study of polystyrene (PS) with bis(perfluorophenyl) azides 1-2 and the corresponding non-fluorinated bisazides 3-4 as deep-UV resists is reported. Inclusion of as low as 1.2 wt-% of 1 in PS led to 70% retention of thickness after photolysis and development. PS containing 2.4 wt-% of 1 is > 100 times more sensitive as a deep-UV negative resist than PS itself. The presence of 1 in PS also increased the contrast of the resist. On a molar basis, 1 was about 10 times as effective as non-fluorinated bisazide 3 in cross-linking PS while 2 was about 6 times as effective as 4. PS containing 2.4 wt-% of 1 was found to have a deep-UV sensitivity of 5-10 mJ cm and resolution of about 0.5 /tm. 

We 12y 13) and others 14) have developed perfluorophenyl azides (PFPAs) as a new class of photolabeling agents (i5) with improved CH insertion efficiency in hydrocarbon solvents over nonfluorinated analogues. The nitrene intermediates derived from photolysis of PFPAs do not undergo ring expansion 12) y which is probably the main wasteful reaction pathway of nonfluorinated... 

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