Benzoyl azide, derivatives

Some further details about the Curtius reaction with boron halides are given by Fahr and Neumann.1 They have found that benzoyl azide and substituted derivatives react with boron... 

When the triazolinic nucleus carries electron-withdrawing groups at the position, it is far more labile.250 This is attributed to the increased stabilization of the betaine intermediate (53). Thus, triazoline 52 formed by reaction of benzoyl azide with norbornene already decomposes from 40° into N-benzoylaziridine 54.107 This compound isomerizes by distillation under normal pressure quantitatively into an exo-oxazoline derivative (55). 

Vasilevskii et al(Ref 2) studied the expl props of this compd from the viewpoint of its structure and from measurements of N evolution at 20 35° and found the trinitro deriv and benzoyl azide to have the same order of stability. However, both compds were less stable than the ortho-nitro and meta-nitro derivs the meta or 3-nitrobenzoyl azide was the most stable deriv Refs l)Beil- not found 2)V.V.Vasilevskii et al, ZhObshchKhim 5,1652(1935) CA 30,3416(1936) 3)C.Naegeli et al.Helv 21,1138-9(1938) CA 33, 540(1939)... 

Dinitro-4-bromobenzoyl Azide, col fine ndls (from petr eth), mp 116° was prepd by addn of Na azide to 4-bromo-3,5-dinitrobenzovl chloride suspended in glac AcOH. Although its expl props were not investigated this compd is an expl. Compare with the props of 3,5-dinitrobenzoyl azide under Benzoyl Azide and Derivatives (Ref... 

Aroyl azides (ArCON3) have been studied by some Japanese workers Benzoyl azide is reported to have a maximum at 245-5 nm while substitution in the para position causes a shift to longer wavelength. Methoxy changes the maximum to 283 nm while fluorine moves it to 251 and nitro to 260-5. Other substituents such as Cl, Br, I, methyl, and CON3 caused the maximum to fall between that of the p-Y and -OMe derivatives. 

Triazole Derivatives. Triazole derivatives are known to possess tumor necrosis factor-a (TNF-a) production inhibitor activity. The synthesis of triazole derivatives can be achieved from alkynes or diynes by a tandem cascade reaction involving 1,3-dipolar cycloaddition, anionic cyclization and sigmatropic rearrangement on reaction with sodium azide. Some of the benzoyl triazole derivatives were considered to be potent local anaesthetics and are comparable with Lidocaine. The triazoles can also be prepared from benzoyl acetylenes,triazoloquina-zoline derivatives, 2-trifluoromethyl chromones, aliphatic alkynes, 2-nitroazobenzenes, ring opening of [ 1,2,4]triazolo [5,1-c] [2,4]benzothiazepin-10 (5//)-one, alkenyl esters and dendrimers. A number of these reactions are outlined in eqs 44 8. 

Preparations of azide derivatives from styrene-maleic anhydride copolymers, cellulose, and gelatin by attaching aromatic azide compounds are described in the literature. Most of the resultant polymers crosslink rapidly when exposed to light of 260 wavelength. Also, as much as 90% of the hydroxy groups of poly(vinyl alcohol) can be esterified withp-azido-benzoyl chloride. These reactions must be carried out in mixtures of chloroform and aqueous sodium hydroxide. Based on infrared spectroscopy, the following crosslinking mechanism was proposed ... 

For convenience of synthesis the preparation of a tritiated photoactive GA-derivative involved slight modification of the C-17 side chain. The GA4-photoaffinity probe, GA4-17-S-propyl-S-benzoyl azide (structure III, Fig. 3) was thus tritiated to 1.79 TBq/mmol. 

Heating benzoyl azide with ethanol or benzoylhydrazine gave the corresponding urethane (5) or benzoylphenyl semicarbazide (6), respectively. The explosive diacyl azide 8, prepared from fumaric acid-derived 7, underwent double rearrangement in ethanol to the dicarbamate 9. ... 

The structures of donor-acceptor complexes of iyn-benzoyl azide, its 2-methyl- and 2,6-dimethyl-substituted derivatives with BF3, AICI3, and SbCls, and the transition states of the rearrangement into isocyanates have been reported by computational methods. The reaction of donor-substituted alkenes with a-diazo-a-nitro ethyl acetate under Rh catalysis have been reported which show that the nitro group is inserted forming cyclic nitronates, whereas the ester moiety was not incorporated into the ring system (Scheme 198). ... 

The yields of the isocyanates produced upon photolysis of benzoyl azide (R=Ph, 31b) and its pam-methoxy, para-chloro and meta- uoro derivatives were found to be in the range of 40-50% in both inert solvents and in solvents that intercept acylnitrenes. Similar results were obtained for 2-naphthoyl azide (35). Irradiation of 35 in cyclohexane at room temperature produces isocyanate (36, -45%), A-cyclohexyl-2-naphthamide - the product of 2-naphthoylnitrene (37) insertion (-50%), and a trace (<1%) of 2-naphthamide (38). Therefore, it was concluded that carbonylnitrenes (R-CO-N) do not rearrange to isocyanates (R-N=C=0) at a rate that is competitive with their capture by trapping agents. ... 

Diazido-4,4 -dideoxy-ga/acto-trehalose was synthesized from a known partially benzoylated trehalose derivative by formation and azide ion displacement of a 4,4 -ditriflate, and was claimed to have antimicrobial properties. ... 

The uniquely distinguished axial alcohol at C5 was activated by triflation and the resultant triflate was displaced by the action of tetra n-butylammonium azide in benzene at room temperature. Compound 25 was thus available in 86% yield from alcohol 24. Hydrogenolysis ((H24 d(OH)2C) followed by acetylation afforded compound 26 in 96% yield. TTie richly detailed NMR spectrum (490 MHz) of 26 was identical in every respect with that of the L-antipode derived from reaction of NeuSAc, first with acidic methanol and then with benzoyl chloride under the influence of DMAP. The infrared and mass spectra, as well as the chromatographic characteristics of the two materials, were identical. 

The addition reactions of aryl azides onto enamines bearing a carbonyl, sulfonyl, or nitro group in the 0 position with respect to the nitrogen atom have been investigated by Italian authors.240-241 The expected triazoline derivatives could not be isolated but were immediately converted into the corresponding 1,2,3-triazoles (49) and secondary amines. The reaction of p-nitrophenyl azide with l-benzoyl-2-morpholino-l-propene (48) is given as a typical example. 

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