Isoamyl nitrate

Other methods of nitration that Laali investigated were with isoamyl nitrate in combination with a Bronsted or Lewis acid in several ionic liquids, with [EMIM][OTf] giving the best yields (69 %, 1.0 1.0 o p ratio). In the ionic liquid [HNEt( Pr)2] [CE3CO2] (m.p. = 92-93 °C), toluene was nitrated with a mixture of [NH4][N03] and trifluoroacetic acid (TEAH) (Scheme 5.1-37). This gave ammonium trifluoroacetate [NH4][TEA] as a by-product, which could be removed from the reaction vessel by distillation (sublimation). 

Nitrocyclopropane-l-carboxylate is prepared in 71% yield by nitration of the enolate derived from the cyclopropane carboxylate with isoamyl nitrate (Eq. 2.24). It is a precursor of... 

Nobel proposed using as antifreezes in Dynamites methyl-, ethyl-, amyl-, or isoamyl-nitrates, but these substances were too volatile (Vol 5, p D1589-L)... 

N22.03% red ndles (from ethanol) mp, explds on heating without melting. Sol in hot ethanol, chlf and warm w si sol in benz and eth insol in alkalies. Prepn is by heating N, N -diphenyl-C-nitroformazan in the presence of isoamyl-nitrate... 

CsHeO CsHuNO Furfuryl Alcohol Isoamyl nitrate 169.35 149.75 <149.6 240... 

According to Escales (Ref 2, pp 37-46) and Naoum(Ref 3, pp 15-21 356-81), the first attempt to reduce fr p of NG was made by A.Rudberg(Swed P of April 30,1866) who added materials like benz or NB and later Nobel(Swed P, July 8,1876) proposed the addn of Me and Et nitrates,acetins, or NB. A.Wahlen-berg K.Sundstrom proposed in 1877 addn of o-MNT K.Amark(1879) proposed nitrostarch, nitromannit and amyl nitrate and Liebert(l889) isoamyl nitrate. While Me Et nitrates were the most suitable from the chem point of view, their volatility was too great. The other compds were effective only in such large quantities that they reduced the sensitiveness, strength and brisance.of NG. very appreciably... 

The nitrosation of a series of 2-alkenyl-substituted 1,3-dithioles 438 was carried out with the known procedure based on the use of isoamyl nitrate. The nitroso derivatives 439 obtained are stabilized by resonance and intramolecular oxygen-sulfur interactions (Scheme 62) <1996J(P2)2367>. 

The chloroacetoxylation proceeds via the same type of intermediate as that involved in the palladium-catalyzed 1,4-diacetoxylation, i.e. via a 4-acetoxy-l,2,3-(jr-allyl)palladium intermediate (cf. Scheme 8-7). The high selectivity for iinsymmetrical product formation (usually >98%) is remarkable. Since chloride is the stronger nucleophile of the two amions present (CI and AcO ), the 4-chloro-l,2,3-( r-allyl)palladium intermediate 60 is initially formed. However, the chloride in the 4-position is rapidly exchanged for acetate to give a more stable, jr-allyl intermediate 61, which leads to product. The presence of intermediate 60 was confiimed by its trapping by a faster oxidant (isoamyl nitrate) than benzoqiiinone (BQ), which furnished l,4-dichloroalk-2-ene [78,84], In the case of cyclohexa-1,3-diene, this product was c -1,4-dichlorocyclohex-2-ene [84]. 

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