Ethylene derivatives glycol esters

Chung, Y. and H. Cho. 2004. Preparation of highly water soluble tacrolimus derivatives poly(ethylene glycol) esters as potential prodruofteh. Pharm. Re 7 878-883. 

A soln. of 1-hexene in 4 1 acetic acid/anhydride containing NaCl (partially dissolved) and catalytic amounts of PdCl2 and CuCl2 heated at 80° for 24 h under ca. 2/1 v/v of CO and O2 acetic p-acetoxyheptanoic anhydride. Y 84%. Functionalized ethylene derivs., e.g. allyl and vinyl acetate, gave the corresponding glycol ester derivs., while 2-ethylenealcohols in ethanol afforded p,Y-dialkoxycarboxylic acid esters. F.e.s. H. Urata et al.. Tetrahedron Letters 29, 4435-6 (1988). 

Sulfuric acid peroxyacetic acid Glycol esters from ethylene derivs. 

Stereospecific reactions alcohols from ethylene derivatives 19, 188 amines, axial, from sulfonic acid esters 19, 418 ethylene derivatives from glycols 19, 962... 

Lead(lV)salt acetic anhydride Glycol esters from ethylene derivatives... 

The most important derivatives of the carboxyl group are formed by esterification with monohydric or polyhydric alcohols. Typical alcohols used iaclude methyl alcohol, ethylene glycol, glycerol, and pentaerythritol. These rosia esters have a wide range of softening poiats and compatibiUties. 

CF,C02)2lPh, H2O, CH3CN, 85-99% yield. In the presence of ethylene glycol the dithiane can be converted to a dioxolane (91% yield) or in the presence of methanol to the dimethyl acetal. The reaction conditions are not compatible with primary amides. Thioesters are not affected. A phenylthio ester is stable to these conditions, but amides are not. The hypervalent iodine derivative l-(t-butylperoxy)-l,2-benziodoxol-3(l/f)-one similarly cleaves thioketals."... 

The reaction of the p-nitrophenyl esters with the polymer (4) was studied in dimethyl sulfoxide ( DMSO ) solution in the presence of triethylamine at 25°C. The poly-L-lysine derivatives obtained have different IR absorption spectra from those of the starting compounds, and have absorptions assigned to the nucleic acid bases. Poly( e,N-Ade-L-lysine )(5) was soluble in DMSO and ethylene glycol, and also in water below pH 3, where it was present as a protonated form. In dimethylformamide (... 

The signal molecule, 30,C6-HSL and number of its analogues, with variations in the acyl chain and the hetero-ring, have been prepared [15,56,57] to investigate the mechanism of induction of carbapenem and luminescence in Erwinia carotovora and V.fischeri respectively. Essentially, the acylation of l-HSL with 3-oxoalkanoic acid by the same method as outlined for the preparation of AT-acyl-L-HSL delivers the desired derivatives. However, as the p-keto acids are thermally labile, these were prepared from the corresponding p-keto ester after the initial protection of the p-keto function as ethylene glycol ketal (route a, Scheme 6). 

Macrocyclization of esters of allylglycine with diols has been successfully used to prepare derivatives of 2,7-diaminosuberic acid [861,864]. The latter are surrogates of cystine, and therefore of interest for the preparation of peptide mimetics. For unknown reasons protected allylglycine derivatives can not be directly dimerized by self metathesis [864]. However, catechol [864], ethylene glycol [861], and 1,2- or 1,3-di(hydroxymethyl)benzene derivatives [860] of allylglycine are suitable templates for the formal self metathesis of this amino acid via RCM. 

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