Hexyl triflate

Table 7.4 Values of diffusion coefficients and solubilities for (A) oxygen and (B) carbon dioxide in various RTIL compared with conventional solvents. Pyi4 = A-methyl butyl pyrrolidinium P14666 = tris( -hexyl)tetradecylphosphonium Tf = triflate MIM = methyl imidazolium FAP = fluoroethyl phosphate (adapted from Buzzeo et al., 2004)...

Since the addition of dimethylpyrazole to an isocyanate is reversible by heating at 60°C, the product (10) is known as a blocked isocyanate . Now, it has been shown that magnesium triflate, Mg(OTf)2, is highly active as a catalyst in the reaction at 60 °C between an acid and a blocked isocyanate to give an amide. Thus blocked hexyl isocyanate (10) and heptanoic acid (11) when heated in equimolar quantities in CHCI3 at reflux for 1 h in the presence of 1 mol% Mg(OTf)2 gave a quantitative yield of IV-heptyloctamide (12) with evolution of CO2.6... 

PALLADIUM-CATALYZED AMINATION OF ARYL HALIDES AND ARYL TRIFLATES N-HEXYL-2-METHYL-4-METHOXYANIUNE AND... 

In the area of organometallic chemistry, we begin with a procedure for the palladium-catalyzed animation of aryl halides and aryl triflates, illustrated by syntheses of N-HEXYL-2-METHYL-4-METHOXYANIUNE and N-METHYL-N-<4-CHLOROPHENYL)-ANILINE. The next procedure describes the synthesis of 1,2,3,4-TETRAHYDROCARBAZOLE by the palladium-catalyzed annulation of ketones with o-iodoaniline. Next, a procedure for the synthesis of 2,7-DIMETHYLNAPHTHALENE via the nickel-catalyzed coupling of aryl O-carbamates with Grignard reagents is presented. The fourth procedure in this section describes the synthesis of 5-METHYL-2,2 -BIPYRIDINE by a Negishi cross-coupling reaction... 

TRIFLATES N-HEXYL-2-METHYL-4-METH0XY ANILINE AND N-METHYL-N-(4-... 

Abbreviations Ac acetyl Bn benzyl Cu(OTf)2 copper triflate Et ethyl HOTf trifluoromethanesulfonic acid KHMDS potassium hexamethyldisilazane Kim potassium imidazole / Hx / Hexyl Me methyl ... 

Even though most of the supported ionic liquid catalysts prepared thus far have been based on silica or other oxide supports, a few catalysts have been reported where other support materials have been employed. One example involves a polymer-supported ionic liquid catalyst system prepared by covalent anchoring of an imidazolium compound via a linker chain to a polystyrene support [79]. Using a multi-step synthetic strategy the polymeric support (e.g. Merrifield resin among others) was modified with l-hexyl-3-methylimidazolium cations (Scheme 5.6-4) and investigated for nucleophilic substitution reactions including fluorina-tions with alkali-metal fluorides of haloalkanes and sulfonylalkanes (e.g. mesylates, tosylates and triflates). 

Figure 1.26 Synthesis of (A) poly(dipropargylhexylamine) and (B) poIy(dipro-pargyl-N-hexyl-N-methyl ammonium triflate. (Reprinted with permission from Chemistry of Materials, 5, 1598. Copyright (1993) American Chemical Society.)...

Previously, the alkynylation had heen reported with other attached hydrocarbon groups (R = Ph and / hexyl in eq 1). The presence of a second acetylene group in the hydrocarbon group R was successful only with four methylenes, but not fewer, separating the two acetylenes. However, with enough separation the outer acetylene succeeded with only H-substitution to yield 8 in eq 2 and the product could be carried through triflation and a second alkynylation to form 9. 

Treatment of the polymer with methyl trifluoro-methanesulfonate resulted in the corresponding poly-(dipropargyl-iV-hexyl-A/-methylammonium triflate) polymer (Figure 20.63) which was reportedly thermally and environmentally stable with respect to the untreated polymer. The methyl trifluoromethanesulfonated polymer possessed a conductivity of < 10 S cm but upon reduction with a THF solution of sodium sulfide, the conductivity increased to approximately 0.1 S cm with a corresponding change in the UV/ vis absorption spectrum as shown in Figure 20.64. 

Figure 20.63. Formation of poly(dipropargyl-V-hexyl-V-methylammonium triflate. (Reprinted by permission of ref. 46)...

---