Azides Azido compounds

This change in editorial leadership has resulted, perhaps inevitably, in a change in editorial policy which is reflected in the contents of Volume 8. There has been a marked de-emphasis on the inclusion of organic parent compounds followed by an exhaustive and voluminous cataloging of azide, azido, azo, diazido, diazonium, diazo, nitro, dinitro, polynitro, hitr amine, nitrate (esters and salts), dinitrate, poly nitrate, nitroso, polynitroso, chlorate, perchlorate, peroxide, picrate, etc, derivatives — regardless of whether any of these derivatives exhibit documented explosive or energetic properties. Only those materials having such properties have been included in this volume... 

Hydrazoic acid can be added to certain Michael-type substrates (Z is as defined on p. 975) to give 3-azido compounds. The reaction apparently fails if R is phenyl. Ammonia also adds to enol ethers CH2=CHOR to give CH3—CH(OR)N3, and to silyl enol ethers, but it does not add to ordinary alkenes unless a Lewis acid catalyst, such as TiCU, is used, in which case good yields of azide can be obtained. Ammonia can also be added indirectly to ordinary alkenes by azidomercuration, followed by demercuration, analogous to the similar procedures mentioned in... 

Reaction of N,N-dimethylaniline with 1-cyanobenziodoxol 1783 to afford N-methyl-N-cyanomethylaniline 1784 in 97% yield has been discussed in Section 12.1 [31]. Analogously, oxidation of dimethylaniline with iodosobenzene and trimethylsilyl azide 19 at 0°C in CDCI3 gives the azido compound 2040 in 95% yield, iodobenzene, and HMDSO 7 [194, 195] (Scheme 12.56). Likewise, the nucleophilic catalyst 4-dimethylaminopyridine (DMAP) is oxidized, in 95% yield, to the azide 2041, which is too sensitive toward hydrolysis to 4-N-methylaminopyri-dine to enable isolation [194, 195]. Amides such as 2042, in combination with tri-... 

A way to introduce the primary amino group directly onto the selenophene ring is via the azido compound, obtained by nucleophilic substitution of the bromo derivative with sodium azide. Useful transformations of the azido group are shown in Scheme 12.117 The amino aldehyde (109) is a suitable starting material for the preparation of selenolo[3,2-b]pyridine (110) by the Friedlander reaction.138 Not only can the azido be reduced to an amino... 

Cyclization of 776 with ortho-esters gave (83JOC1628) [l,2,4]triazolo-[4,3-fc]pyrimido[5,4-< ][ 1,2,4]triazines 777, whereas reaction with sodium nitrite afforded the corresponding tetrazolopyrimidotriazine 778.3-Azido-pyrimido[4,5-e][l, 2,4]triazine 779 exists in a cyclic form as tetrazolo derivative 780, as shown by X-ray analysis (86KGS114). In solution the position of the 779 780 equilibrium depended on temperature and solvent. Higher temperatures favored 779. Azido compound 779 predominated in water, and tetrazolo compound 780 predominated in pyridine. Addition of sodium azide to the aqueous solution shifted the equilibrium toward 780. The... 

Alkyl azides are conveniently prepared from the reaction of alkali metal azides with an alkyl halide, tosylate, mesylate, nitrate ester or any other alkyl derivative containing a good leaving group. Reactions usually work well for primary and secondary alkyl substrates and are best conducted in polar aprotic solvents like DMF and DMSO. The synthesis and chemistry of azido compounds is the subject of a functional group series. ... 

Michael addition of sodium borohydride or piperidine across 3-methyleneazetidin-2-one (60) affords the adducts (61) (85T375). 4-(Iodomethyl)azetidin-2-one undergoes nucleophilic substitution by sodium azide in DMF to give the azido compound (88JOC4006). 

As depicted in Scheme 10, displacement of the 2-imidazylate ester of a p-L-arabino-pyranoside derivative with azide ions occurred readily in refluxing toluene to afford a 2-azido-2-deoxy-L-ribopyranoside [84], Treatment of the corresponding triflate with sodium azide gave the same azido compound in only 27% yield [84],... 

Hydrazono-4-oxo-4ff-pyrido[l,2-u]pyrimidines were transformed by sodium nitrite in hydrochloric acid at 0-5 C to the corresponding 2-azido compound (102).166-287 2-Azido-4-oxo-4//-pyrido[l,2-azide-tetrazole tautomerism.290... 

Triazoates. See Azides, Inorganic A520-L Triazo Compounds. See Azido Compounds A626ff... 

Azido-3,5-dinitrofuran [70664-49-2] +-.N N o 0-N+ V O Sitzmann, M. E., J. Heterocycl. Chem., 1979, 16, 477—480 Very sensitive to heat and impact. See other ORGANIC AZIDES, POLYNITROARYL COMPOUNDS c4hn5o5... 

Treatment with azido compounds, such as azide ion [Eq. (65)], halidoazide [reaction (66)], or trimethylsilylazide [reaction (67)], which is the most common nitride-forming pathway. 

In Section 3.5, only the most generally useful methods for making azides, diazo compounds and diazirines can be covered. In the unlikely event that these methods fail the reader may wish to try less commonly used alternatives. These may be found by searching for the syntheses of analogous compounds in Chemical Abstracts, or by consulting the appropriate volumes in Houben-Weyl Methoden der Organischen Chemie, Beilstein , and The Chemistry of. .. series, e.g. The Chemistry of the Azido Group, S. Patai, ed., Interscience (1971). 

Acetoxylation. Transformations of Carbonyl Compounds. Phenolic Oxidation. Oxidation of Nitrogen Compounds. Hypervalent iodine Reagents in Combination with Azido Compounds. DIB and Sodium Azide in Combination with Other Reagents. Transformations of Alkynes Involving Thiophenols and Diphenyl Diselenide. Miscellaneous Reactions. 

The 3-chloro-l,7-dimethylpyridazino[3,4-(7][l,3]oxazine-4,5-dione (149) was prepared in a four-step synthesis starting with (Z)-methyl-3-(3,6-dichloro-l-methyl-4-oxo-l,4-dihydropyridazin-5-yl)-2-methylacrylate (146) which is converted with sodium azide into the 6-azido compound (147). Heating in o-dichlorobenzene at 150°C results in cyclization to methyl 3-chloro-l,6-dimethyl-4-oxo-1,4-dihydro(7//)pyrrolo[2,3-c]pyridazine-5-carboxylate (148) via a nitrene intermediate. Ozonolysis effects ring-enlargement of the pyrrole ring into the 3-chloro-l,7-dimethylpyridazino[3,4-d][l,3]oxazine-4,5-dione (149) (Scheme 26) <79JHC1213>. 

The 3-azido compound (125) exists in equilibrium with its cyclized isomer (126) and the position of equilibrium varies with both temperature and solvent (Equation (3)). The azido isomer (125) predominates in aqueous solution, and is also favored by higher temperatures. Addition of sodium azide shifts the equilibrium towards the tricyclic isomer (126) <86KGS114>. 

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