Glycidol derivates

Sakaguchi N, Kojima C, Harada A, Kono K (2008) Preparation of pH-sensitive poly (glycidol) derivatives with varying hydrophobicities their ability to sensitize stable liposomes to pH. Bioconjug Chem 19 1040-1048... 

Epichlorohydrin (ECH) is made from propylene, the majority is via allyl chloride intermediate. Total consumption in 1999 was about 600 million lb. Uses for ECH include epoxy resins (65%), synthetic glycerin (22%), and others (paper treatment, specialty ionic exchange resin, glycerol, and glycidol derivatives). 

Nucleophilic Additions of Carbon at C-3. One of the few reported additions of a carbon nucleophile to underivatized glycidol is that of diethyl sodiomalonate. The initial addition at C-3 is followed by lactonization between the C-2 hydroxyl group and one of the malonate carboxylic esters (eq 5). Far more numerous are the additions of carbon nucleophiles to glycidol derivatives such as O-benzyl, O-phenyl, or O-tosyl glycidol. In addition to the examples included below, many others may be found in Hanson s... 

Nucleophilic Additions of Nitrogen at C-3. Ammonia and amines add readily to glycidol and glycidol derivatives, giving the l-aminopropane-2,3-diols (eq 19). With ammonia and primary amines, an excess of the amine often is used to reduce the amount of addition by a second glycidol to the... 

If no separation is observed on Chiralpak AD, the Chiralpak AS column should be tested. It has proven to be particularly appropriate for P-lactams, glycidol derivatives, epoxides, acids, natural products, and heterocyclic compounds with a chiral centre clo.se to the ring. 

The Sharpless asymmetric epoxidation of allyl alcohol gives the glycidol derivative 61 in 90% ee after in situ tosylation of 60 [63]. This process is working on a multiton-a-year scale (Arco Co., USA), facilitating the synthesis of a variety of /0-blockers. Asymmetric dihydroxylation of the allyl ether 63 catalyzed by a combined system of OSO4 and the cinchona alkaloid-based ligand 65 allows the commercial synthesis of the propranolol intermediate 64 in 91 % (Sepracor Co., USA) [64]. 

Scheme 12.63. A synthesis of (i )-alanine (Ala, A) based upon a path utilizing the formation of morpholine derivatives and after Harding, C, L Dixon, D, J, Ley, S. V. Tetrahedron, 2004, 60,1619. Additional alkyl groups can be added to form a,a-disubstituted derivatives and, beginning with the opposite glycidol derivative, the opposite enantiomer can be obtained. HMPA = hexamethylphosphoramide,...

Scheme 2.7 Synthesis of (+)-goniothalamin from an (R)-glycidol derivative.

Glycerol Monoacyl Derivatives were prepd before WWII by IGFarbenindustrie AG, FrP 848740 (1931) CA, 35, 5912(1941), on heating Glycidol Nitrate, QI2.0.CH.CHa(QNO2) with. an org acid... 

In situ derivatization of the crude epoxy alcohol product becomes a viable alternative to isolation when 5-10 mol % of catalyst is used for the epoxidation. This procedure is especially useful when the product is reactive or is difficult to isolate because of solubility in an aqueous extraction phase [15,16]. Low-molecular-weight epoxy alcohols such as glycidol are readily extracted from the reaction mixture after conversion to ester derivatives such as the p-nitrobenzoate or 3-nitrobenzenesulfonate [4,17]. This derivatization not only facilitates isolation of the product but also preserves the epoxide in a synthetically useful form. 

Vandenberg EJ (1985) Polymerization of glycidol and its derivatives - a new rearrangment polymerization. J Polym Sci Polym Chem Ed 23(4) 915-949... 

J. M. Klunder, T. Onami, and K. B. Sharpless, Arenesulfonate derivatives of homochiral glycidol versatile chiral building blocks for organic synthesis,./. Org. Chem., 54 (1989) 1295-1304. 

Influence of Solvents. Etherification is also considerably affected by the solvent system used (211-217]. The preparation of cellulose trimethylsilyl ether derivative was considerably enhanced by conducting it in a DMSO-PF solution [212]. In a heterogeneous dihydroxypropylation of cellulose with glycidol, the DS cannot exceed the 1.5 level [215]. 

The glycidol method [Eq. (20)] and the bromoacetal method [Eq. (17)] provide general routes to N-alkyl derivatives containing almost any alkyl group. 

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