And diazonium salts

Differences in reactivity between amino and imino isomers toward CSj and diazonium salts (199. 165). 

With l,3-dimethyl-2,l-benzisoxazolium salts, however, considerable reactivity has been reported. Condensation occurs readily with aldehydes, ketones, orthoesters and diazonium salts to yield styryl, cyanine and azo compounds, respectively (78JOC1233). In the presence of triethylamine, dimerization was observed, and the reactions of the cation were considered to involve the intermediacy of the anhydro base (77JOC3929). 

Thiazolotriazines 636 (R = CO,Me) were prepared [84JCS(P1)2707] by cycloaddition of dimethyl acetylenedicarboxylate with triazine derivative 632. Derivatives of thiazolo[3,2-b][l,2,4]triazin-3,7-diones 637 have been formed (74JPR163) on reaction with aromatic aldehydes and diazonium salts to give 636 (R = Ar) and 638, respectively. Regioselective catalyzed... 

Aryl radicals are produced in the decomposition of alkylazobenzenes and diazonium salts, and by f)-scission of aroyloxy radicals (Scheme 3.73). Aryl radicals have been reported to react by aromatic subsitution (e.g. of Sh) or abstract hydrogen (e.g. from MMA10) in competition with adding to a monomer double bond. However, these processes typically account for <1% of the total. The degree of specificity for tail vs head addition is also very high. Significant head addition has been observed only where tail addition is retarded by sleric factors e.g. methyl crotonate10 and -substituted methyl vinyl ketones 79, 84). 

Diazonium ions, see Arenediazonium ions and Diazonium salts... 

Reaction between aromatic amines and diazonium salts Reaction between amines and diazonium salts... 

Disubstituted tetrazoles are conveniently prepared from acyl hydrazines (98) and diazonium salts.166 The reaction proceeds through the intermediate tetrazenes (99) followed by cyclization to the tetrazole (100) (Scheme 13). The intermediate can be isolated under mildly basic conditions. Symmetrically 1,2-diacylated hydrazines yield 1-substituted tetrazoles through the elimination of one of the acyl groups.166 - 168 Diformyl-hydrazine is a very convenient starting material for 1-substituted tetrazoles.166, Unsymmetrically 1,2-diacylated hydrazine usually results in mixtures.169... 

The first CEM system described by Griffing and West (84) consisted of an organic dye dispersed in an inert polymer film that is spin coated onto the surface of a resist and subsequently removed following exposure but prior to resist development. The chemistry of this system is based on the photoisomerization of an aromatic dye to an oxaziridine (87) (Figure 10). Other workers have evaluated polysilanes (88) and diazonium salt chemistry (89,90) for CEM applications. 

Hydrazones from a-ketoesters and diazonium salts with the acid of base. 

Diazoazoles find wide application in the preparation of azolo-triazenes, which have shown several biological activities expecially as antineoplastic agents. Triazenes are, in effect, latent diazo compounds because they decompose to give amino derivatives and diazonium salts so they can be employed as a carrier group for the diazo compounds (66JMC34). 

The only published method available for the determination of personal exposure to benzidine-based dyes utilized the analysis of urine for benzidine and benzidine metabolites (JO, J 1 ). This method does not allow for quantitation of a daily exposure, since benzidine and its metabolites have been found in the urine of hamsters fed a benzidine-based dye up to 168 hours after a single dosing (J 2). A method for the determination of personal exposure to azo dyes and diazonium salts has been developed (J 3), but it is not specific enough to determine an exposure to a benzidine-based dye. 

This method has been used to analyze both symmetrical (C.I. Direct Red 28 and C.I. Direct Blue 6) and unsymmetrical (C.I. Direct Black 38 and C.I. Direct Brown 95) benzidine-based dyes. Based on this work, the application of the method to other benzidine-based dyes should be straightforward. When field samples are submitted for benzidine-based dye analysis, bulk samples of the dyes present in the sample also should be submitted. With these bulk samples, the analyst should be able to determine if this method is applicable to the various dyes submitted and if any interferences are present. The method presently has not been tested on field samples. An existing sampling method (J 3) for azo dyes and diazonium salts should be directly applicable to this method with a change from a cellulose ester to a Teflon filter. This change is necessary to insure quantitative recovery of the sample from the filter. 

See also Diazochemistry, Diazo hydrocarbons and Diazonium Salts Refs 1) E. von Herz, BritP 207563(1922)... 

The equilibrium existing between nitrosamines and diazonium salts of 1,2,4-thiadiazoles in acid media was mentioned in Section III,E. Diazonium salt solutions may be directly prepared from the amines in concentrated sulfuric, phosphoric, or acetic acid.6 80> 17°-191 Most of... 

DIAZO COMPOUNDS AND DIAZONIUM SALTS. See Azo and Diitzn Compounds. 

Diazonium salts can be regarded as combinations of carbocations R with N2 and, because of the considerable stability of nitrogen in the form of N2, we would expect diazonium salts to decompose readily with evolution of nitrogen and formation of carbocations. This expectation is realized, and diazonium salts normally decompose in this manner in water solution. The aliphatic diazonium ions decompose so rapidly that their presence can only be inferred... 

Macrae and Wright (96) demonstrated that visible light irradiation of xanthene dyes (eosin, erythrosin, rhodamine B, or RB) in ethanolic solutions of 4-(N,N-diethylamino)benzene-diazonium chloride (as the zinc chloride double salt) resulted in decomposition of the diazonium salt. Electron transfer from the dye excited state(s) to the diazonium salt was postulated and dye-diazonium salt ion pair formation in the ground state was shown to be important. Similar dyes and diazonium salts were claimed by Cerwonka (97) in a photopolymerization process in which vinyl monomers (vinylpyrrolidone, bis(acrylamide)) were crosslinked by visible light. Initiation occurs by the sequence of reactions in eqs. 40-42 ... 

Ring closure reactions taking place by intramolecular addition of an aromatic radical to a double bond have been widely studied on both their regio- and stereochemical aspects [93]. Aryl halides and diazonium salts substituted at ortho- position with a 0-allyl or TV-allyl chain were used for the preparation of 2,3-dihydrobenzofuranes and 2,3-dihydro-1/7-indoles under different reaction conditions. The reaction pattern involves the generation of an aryl radical 20, which reacts with the double bond in a 5-exo trig fashion to afford the exocyclic radical 21, plausible of reduction by a hydrogen donor to obtain the reduced-cyclized product 22 (Sch. 23) [93d,94]. 

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