Miscellaneous Derivatives

From a cyanohydrin AC2O, FeCl3, 25-92% yield. Other anhydrides are also effective in this conversion.  

R3SiCl, KCN, Znl2, CH3CN, 86-98% yield. This method was used to prepare the r-BuPH2, /-BuMe2Si, and /-Pr3Si cyanohydrins. 

The ethoxyethyl cyanohydrin was prepared (NaCN, HCl, THF, 0°, 75% yield, followed by EtOCH=CH2, HCl, 50% yield) to convert an aldehyde ultimately to a protected ketone. It was cleaved by hydrolysis (0.01 N HCl, MeOH, 25°, followed by NaOH, 0°, 85% yield).  

The tetrahydropyranyl cyanohydrin was prepared from a steroid cyanohydrin (di-hydropyran, TsOH, reflux, 1.5 h) and cleaved by hydrolysis (cat, coned. HCl, acetone, reflux, 15 min, followed by aq. pyridine, reflux, 1 h).  

Rose Bengal, MeOH, -78°,- —20°, followed by Ph3P or Me2S, 48-88% yield.  

CHjClj, Yb(OTf)3, 55-95% yield. Aromatic ketones fail to 

reflux, 2 h, 89-95% yield.These conditions are selective for aldehydes. 

(—)-DIPT [diisopropyl L-tartrate], Ti(/-PrO)4, CH2CI2, 0°, 6 h, rt, 12 h, 95% yield. These conditions afford chiral cyanohydrins.  

Researchers at ARIAD Pharmaceuticals described the incorporation of a 3,5-dinitrotyrosine 32 into peptide inhibitors of only double-digit micromolar affinity to the SH2 domains of Syk and Src [136]. 

Due to the fact that the phosphate was replaced against entirely non-charged and phosphatase-stable analogues, the pTyr mimic is considered to have more favorable pharmacokinetic properties. However, aromatic nitro compounds bear an intrinsic potential of developing toxicological problems [136]. 

In conclusion, a variety of mutually different pTyr mimetics incorporated in peptide-type derivatives have been investigated. However, an overall satisfactory bioisosteric replacement has not yet been identified. 

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Miscellaneous Derivatives. Other derivatives of toluene, none of which is estimated to consume more than ca 3000 t (10 gal) of toluene aimuaHy, are mono- and dinitrotoluene hydrogenated to amines ben2otrich1 oride and chlorotoluene, both used as dye intermediates / 7-butylben2oic acid from / 7-butyltoluene, used as a resin modifier dodecyltoluene converted to a ben2yl quaternary ammonium salt for use as a germicide and biphenyl, obtained as by-product during demethylation, used in specialty chemicals. Toluene is also used as a denaturant in specially denatured alcohol (SDA) formulas 2-B and 12-A. 

Miscellaneous Derivatives. Fimehc acid is used as an intermediate in some pharmaceuticals and in aroma chemicals ethylene brassylate is a synthetic musk (114). Salts of the diacids have shown utUity as surfactants and as corrosion inhibitors. The alkaline, ammonium, or organoamine salts of glutaric acid (115) or C-5—C-16 diacids (116) are useflil as noncorrosive components for antifreeze formulations, as are methylene azelaic acid and its alkah metal salt (117). Salts derived from C-21 diacids are used primarily as surfactants and find apphcation in detergents, fabric softeners, metal working fluids, and lubricants (118). The salts of the unsaturated C-20 diacid also exhibit anticorrosion properties, and the sodium salts of the branched C-20 diacids have the abUity to complex heavy metals from dilute aqueous solutions (88). 

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