Compound azido

Steinbeisser, H., Mews, R., Glemser, D., Z Anorg. Allg. Chem., 406,299 (1974). 

Biener, H., Farbwerke Hoechst, A.G., unpublished results Graf, R., Angew. Chem. Int. Ed. Engl, 7, 172 (1968). 

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An intramolecular aza-Wittig reaction of the imino-A5-phosphancs 4, prepared by the action of triphenylphosphane on the corresponding azido compounds, affords l//-l,2,4-benzo-triazepines 5.346 The reactions were carried out by heating compounds 4 in acetonitrile or 2-hydroxyethyl methyl ether for the time indicated. No further details were reported. 

The presence of a 5-oxo group in the 1,2,4-triazines, as in 3-hydrazino-2,5-dihydro-5-oxo[l,2,4]triazines, does not alter the direction of cycliza-tion by the action of nitrous acid. The initial products are azido compounds 1016, which can cyclize spontaneously to tetrazolo[l,5-b][l,2,4]triazines 1017 (77JHC1221, 77JOC1866) rather than the previously reported isomeric structure. On the other hand, when the cyclization onto N-2 is impossible, as in derivative 1018, the azidotetrazolo equilibrium 1018 1019 exists (76JOC2860 77JOC1866). It exists in the solid state at least as the tetrazole derivative (Scheme 190). 

Nitroazido Compounds. See under corresponding Azido compound... 

The synthesis of aromatic amines is an active and important area of research.2 Many methods are available in the literature for the synthesis of these compounds. Though some of these are widely used, still they have limitations based on safety or handling considerations. For example, catalytic hydrogenation3 of nitro or azido compounds in the presence of metals such as palladium on carbon or Raney nickel require stringent precautions because of their flammable nature in the presence of air. In addition, these methods require compressed hydrogen gas and a vacuum pump to create high pressure within the reaction flask. To overcome these difficulties, several new methods have been reported in the... 

The azido compound IQ reacts with 1.5 equiv. of triphenylphosphine in DMF in the presence of THF and 1.5 equiv. of water to give the final product, SR 34366A with a quantitative yield. 

Scheme 5. Proposed mechanism for reaction of triphenylphosphine with the azido compound.

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-... 

Photochemical elimination reactions include all those photoinduced reactions resulting in the loss of one or more fragments from the excited molecule. Loss of carbon monoxide from type I or a-cleavage of carbonyl compounds has been previously considered in Chapter 3. Other types of photoeliminations, to be discussed here, include loss of molecular nitrogen from azo, diazo, and azido compounds, loss of nitric oxide from organic nitrites, and loss of sulfur dioxide and other miscellaneous species. 

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... 

Smalley et al. reported the synthesis of the cyano-containing keto ester 98 by reaction of o-azidobenzoyl chloride 97 with cyanoacetic ester in the presence of triethylamine. This keto ester was then heated in acetonitrile for 30 min and gave the ring closed product 99 which was isolated in the fully aromatic tautomeric form 100 <1997S773>. A similar approach to tetrazolo[l,5- ]quinolines has been applied by a Korean research group in this case a reflux of the cyano-azido compound 101 for a longer period was needed in order to accomplish the cyclization to 4-acetoxymethyl-tetrazolo[l,5- ]quinoline 102 <2003JHC1103>. 

The enantiomerically pure open-chained cyano-azido compound 103 also underwent cyclization to the tetrahy-drotetrazolo[l,5- ]pyridine derivative 104 when heated in a toluene solution at 130 °C for 7 days. The reaction was found to proceed in 75% yield and with an enantiomeric excess of 83% <2005JA1313>. 

A limited number of such reactions have been recently published, and the results are compiled in Table 5. The first example is the reduction of azido compound 76 by sodium dithionite to the corresponding amine 77. Furthermore, some nucleophilic substitutions of the chlorine substituents of heterocycles 78 and 80 have also been reported these compounds, when reacted with morpholine and w-bromoaniline, respectively, furnished the substitution products 79 and 81. 

Chloromethylphosphonamide 104 has been alkylated with diastereoselectivities up to >95%. The corresponding azido compounds 106 were obtained by nucleophilic displacement, with partial to full stereospecificity <2000HA528>. This two-step process can lead to aminophosphonic acids after reduction of the azido group and hydrolysis of the chiral appendage (Scheme 7). 

Table 1 Gel fractions of 1,2-polybutadiene containing azido compound after irradiated with the ultraviolet light...

Syntheses of 5 energetic aliphatic azido compounds are described caution is necessary in handling these because of their impact-sensitivity [1], A later symposium on energetic materials, here meaning explosives and popellants, is reported [2], Individual compounds are ... 

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. ... 

When thermolyzing azido compounds, the question arises as to whether an observed rearrangement is achieved in one step, concerted to the elimination of Nj, or whether there are two steps, elimination and rearrangement, with nitrenes as intermediates. Generally, thermolysis of azidoboranes is more probably a concerted process (22). The decomposition of (tPr2N)2BN3, however, carried out at 450°C, gives a product, besides the main product of Eq. (19), that has to be interpreted in terms of a nitrene stabilized by an intramolecular CH insertion [Eq. (19b)]. 

Table 10 Reduction of nitroso, diazonium and azido compounds...

Types of compounds are arranged according to the following system hydrocarbons and basic heterocycles hydroxy compounds and their ethers mercapto compounds, sulfides, disulfides, sulfoxides and sulfones, sulfenic, sulfinic and sulfonic acids and their derivatives amines, hydroxylamines, hydrazines, hydrazo and azo compounds carbonyl compounds and their functional derivatives carboxylic acids and their functional derivatives and organometallics. In each chapter, halogen, nitroso, nitro, diazo and azido compounds follow the parent compounds as their substitution derivatives. More detail is indicated in the table of contents. In polyfunctional derivatives reduction of a particular function is mentioned in the place of the highest functionality. Reduction of acrylic acid, for example, is described in the chapter on acids rather than functionalized ethylene, and reduction of ethyl acetoacetate is discussed in the chapter on esters rather than in the chapter on ketones. 

The method is not adaptable for phosphonodiamides having acidic hydrogens such as the a-allyl or a-benzyl derivatives. Due to the relatively harsh conditions of the substitution reaction (140 °C), elimination is the dominating process in these cases. This drawback can be circumvented by using another approach, in which the chloromethyl derivative of 1 is transformed via the azido compound 6 into the iminomethyldithiolane 7 (70- 75% yield)92. 

Plasticizers phthalate esters (DEP, DBP, DOP), , NG, liquid nitro/azido compounds etc. 

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