P-Tosyl azide

Reaction of pyrido[2,l-6][l,3]thiazine-2,4-dione (105) with p-tosyl azide in the presence of triethylamine in acetonitrile at 0°C gave a 3-diazo derivative (106), which reacted with cyclohexene in the presence of a catalytic amount of rhodium acetate under reflux to yield a spiro derivative (107) [94H(39)219 95H(41)1631]. 

Compounds containing a CH2 bonded to two Z groups (as defined on p. 548) can be converted to diazo compounds on treatment with tosyl azide in the presence of a... 

Compounds containing a CH2 bonded to two Z groups (as defined on p. 464) can be converted to diazo compounds on treatment with tosyl azide in the presence of a base,164 The use of phase transfer catalysis increases the convenience of the method.165 p-Dodecylbenzenesul-fonyl azide,166 methanesulfonyl azide,167 and p-acetamidobenzenesulfonyl azide168 also give the reaction. The reaction, which is called the diazo transfer reaction, can also be applied to other reactive positions, e.g., the 5 position of cyclopentadiene.169 The mechanism is probably as follows ... 

As part of a study of the reactions of arenesulfonyl azides with indoles, Bailey et al.lu obtained a compound from the action of tosyl azide on indoline-2-thione to which they ascribed structure 114 (R = H). In contrast, N-methylindoline-2-thione gave only a low yield of 114 (R = Me) under the same conditions. Diazo-transfer via an intermediate 115 is thought to be involved when R = H, facile loss of toluene-p-sulfonamide leads to 114a, but when R = Me, loss of the same fragment leads mainly to other products. 

Diazo transfer. Tosyl azide is the most commonly used reagent for diazo Irnnsfcr, even though it is now recognized as a potentially dangerous explosive. Merck chemists have examined a number of other organic azides of these the safest is p-dodccylhciizcncsulfonyl azide, prepared from a commercial sulfonic acid mixture. 

Isopropylidene diazomalonate (1). Mol. wt. 170.13, m.p. 93-95°. This compound is prepared by diazo transfer from tosyl azide to Meldrum s acid. ... 

With the intention of extending the nitrogen chain of tetrazene, tet-razenides 62 and 64 were allowed to react with nitrogen halides as well as their derivatives. The desired objective could not be reached in any case because of decomposition of the expected compounds. Thus, reactions of 62 with nitrosyl chloride (NOX X = Cl) and 64 with isoamyl nitrite (NOX X = 0(/-CsHn)] at low temperature in ether occur according to Eqs. (95) and (96) via 73 and 74 (45), respectively, whereas reactions of 62 with phenyldiazonium chloride (PhN=N Cl ) or tosyl azide (TsN, Ts = P-T0ISO2) at — 78°C develop according to Eqs. (97) and (98), probably via 75 and 76, respectively. 

Benati, L., Calestani, G., Nanni, D., Spagnolo, P., Volta, M. Diazo transfer reaction of 2-(trimethylsilyl)-1,3-dithiane with tosyl azide. 

Diazo compounds. Doering and De Puy treated cyelopentadienyllithium with tosyl azide and obtained diazocyclopentadiene, a remarkably stable dark red compound (b.p. 53°/50 mm.) in 35% yield. The initially formed triazine decomposes... 

Tosic acid, see p-Toluenesulfonic add Af-Tosylamino adds, 1184 Tosylates, 958-959,1054 Tosyl azide, see p-Toluenesulfonyl azide Tosyl chloride, see p-Toluenesulfonyl chloride... 

Diazo transfer.1 p-Toluenesulfonyl azide (which see) is commonly used for diazo-transfer reactions however, it has the disadvantage that the p-toluenesul-fonamide formed as one product is difficult to separate from the diazo compound. Hendrickson and Wolf1 found that the lithium and triethylarnine salts of p-carboxy-benzenesulfonyl azide are soluble in THF and acetonitrile, respectively, and that the triethylarnine salt of p-carboxybenzenesulfonamide is essentially insoluble in acetonitrile. In a standard procedure a solution of the carboxy azide is prepared in acetonitrile by addition of triethylarnine. The active methylene reactant is added and the carboxyamide salt separates within an hour. It is removed by filtration and the diazo product isolated by usual procedures. 2-Diazodimedone (2) was obtained by this procedure in 86% yield (the yield with tosyl azide is 42%). Several varia-... 

Preparation.1 This N-p-toluenesulfonylsulfoximine (2) is prepared in 90% yield by the reaction of the sulfoxide (1) with tosyl azide catalyzed by copper. It is converted into its anion salt (3) by reaction with sodium hydride in DMSO. The anion salt is stable at room temperature. 

Transfer of an azide group from an azidothiazolium salt followed by cyclization in an acid medium can be a useful method of building a triazole ring (p. 263) tosyl azide is possibly a more convenient source of azide, and cyclization at ambient temperature in a basic medium is complete in about IS min. 

The possible mechanism for diazo transfer from p-toluenesulfonyl azide to active methylene compound 3 (flanked by carbonyl groups) is depicted below.1,3 Deprotonation of a-keto ester 3 with NEt3 leads to enolate 4 which attacks at the electrophilic N of the sulfonyl azide 5 to give intermediate tosyl derivative 6. Proton transfer occurs within intermediate 6 followed by elimination of p-toluenesulfonamide, leading to diazo compound 7 and the by-product -toluene sulfonamide 8.1,3... 

Dimedone provides diazo dimedone (135) with -benzoic acid sulfonylazide (84%) and with p-tolyl sulfonylazide (96%). Weak nucleophilic base such as 1,8-diazabicyclo[5.4.0]undecen-7-ene (DBU) has been used as catalyst for the diazo transfer reactions of 1,3-diketones (136 -139).55 A highly efficient methodology in solid state has been developed for the synthesis of a-diazo carbonyl/sulfonyl compounds from 1,3-diketones using tosyl azide. This method avoids any aqueous workup and diazo compounds are obtained via a column filtration over silica gel. 0... 

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