Hydroxyls etherification

Etherification and esterification of hydroxyl groups produce derivatives, some of which are produced commercially. Derivatives may also be obtained by graft polymerization wherein free radicals, initiated on the starch backbone by ceric ion or irradiation, react with monomers such as vinyl or acrylyl derivatives. A number of such copolymers have been prepared and evaluated in extmsion processing (49). A starch—acrylonitrile graft copolymer has been patented (50) which rapidly absorbs many hundred times its weight in water and has potential appHcations in disposable diapers and medical suppHes. 

Reaction of olefin oxides (epoxides) to produce poly(oxyalkylene) ether derivatives is the etherification of polyols of greatest commercial importance. Epoxides used include ethylene oxide, propylene oxide, and epichl orohydrin. The products of oxyalkylation have the same number of hydroxyl groups per mole as the starting polyol. Examples include the poly(oxypropylene) ethers of sorbitol (130) and lactitol (131), usually formed in the presence of an alkaline catalyst such as potassium hydroxide. Reaction of epichl orohydrin and isosorbide leads to the bisglycidyl ether (132). A polysubstituted carboxyethyl ether of mannitol has been obtained by the interaction of mannitol with acrylonitrile followed by hydrolysis of the intermediate cyanoethyl ether (133). 

Every polysaccharide contains glycosyl units with unsubstituted hydroxyl groups available for esterification or etherification. Polysaccharide derivatives are described by their degree of substitution (DS), which is the average number of substituent groups per glycosyl unit. Because each monomeric unit of cellulose molecules has free hydroxyl groups at C-2, C-3, and C-6, the maximum DS for cellulose, and all polysaccharides composed exclusively of neutral hexosyl units, the majority of polysaccharides, is 3.0. 

Etherification. The accessible, available hydroxyl groups on the 2, 3, and 6 positions of the anhydroglucose residue are quite reactive (40) and provide sites for much of the current modification of cotton ceUulose to impart special or value-added properties. The two most common classes into which modifications fall include etherification and esterification of the cotton ceUulose hydroxyls as weU as addition reactions with certain unsaturated compounds to produce ceUulose ethers (see Cellulose, ethers). One large class of ceUulose-reactive dyestuffs in commercial use attaches to the ceUulose through an alkaH-catalyzed etherification by nucleophilic attack of the chlorotriazine moiety of the dyestuff ... 

Etherification of the epoxy group by hydroxyl groups (Figure 26.8). 

Symmetrical labile ethers such as cycloalkenyl ethers (15) or mixed acetals (16) can also be prepared from the 3-hydroxyl group by acid-catalyzed exchange etherification or by acid-catalyzed addition to cyclohexanone methyl enol ether. 

The hydroxylation reaction, whose stereochemical course is controlled by the strong inherent preference for the formation of a cis-fused 5,5 ring system, creates a molecule which would appear to be well suited for an intramolecular etherification reaction to give ring E of ginkgolide B (1). Indeed, when a solution of 11 in methylene chloride is exposed to camphorsulfonic acid (CSA), a smooth cycli-zation reaction takes place to give intermediate 10 in an overall yield of 75% from 12. The action of CSA on 11 produces a transient oxonium ion at C-12 which is intercepted intramolecularly by the proximal hydroxyl group at C 4. 

Due to the high reaction temperatures required during the last stages of these syntheses, side reactions cannot be avoided. Acetaldehyde, carboxyl endgroups, and vinyl endgroups are formed during PET and PEN synthesis. The formation of 2,2/-oxydiethylene moieties in polymer chains by etherification of hydroxyl endgroups is also a well-known side reaction of EG polyester syntheses.264 These reactions should be carefully controlled since they can exert an important influence on polymer properties such as Ts, mechanical properties, hydrolytic stability, and discoloration. 

Two of the hydroxyl groups present in each glucose unit of the cellulose are secondary, one is primary. Studies on the relative rates of etherification of the three hydroxyls are not conclusive. Mahoney and Purves,18 using a method which takes advantage of the rapid reaction between tosyl chloride and a primary hydroxyl, combined with a determination of unsubstituted glycol groups, have studied the relative num-... 

The hydroxyl groups of the cellulose appear to be somewhat acidic. While studies of the composition of alkali cellulose and adsorption of sodium hydroxide have not clearly proved the presence of any sodium compound in alkali cellulose, the reactions of alkali cellulose with carbon disulfide and with etherifying agents would seem to justify the assumption that such an intermediate exists or that the hydroxyl hydrogen at least ionizes. This view is strengthened by the fact that the rate of etherification is proportional to a high power of the concentration of alkali.19... 

In selective etherification, it is important to distinguish between reversible and irreversible reactions. The former class comprises etherifications with dimethyl sulfate, halogen compounds, oxirane (ethylene oxide), and diazoalkanes, whereas the latter class involves addition reactions of the Michael type of hydroxyl groups to activated alkenes. In this Section, irreversible and reversible reactions are described separately, and a further distinction is made in the former group by placing the rather specialized, diazoalkane-based alkylations in a separate subsection. 

Normalized to k3 = I. 6 For entries 4 and 7-9, the numbers represent the relative distribution of the substituents between 0-2, 0-3, and 0-6, at degrees of substitution of 0.07, 0.048, 0.14, and 0.034, respectively thus, the relative rate-constants are only approximate. c The relative rate-constant for HO-3 was assumed to be doubled after methylation at HO-2. d The relative rate-constant at one of the secondary hydroxyl groups was assumed to be 0.3 when the other one is substituted. e The relative rate-constant for etherification of the 2-hydroxyethyl group is 10. f The relative rate-constants found are now thought to have been erroneous, as the formation of internal acetals300,301 was not taken into account. 

In carbohydrate chemistry, the preparation of ethers that are stable in the presence of acids, bases, and aqueous alkali is an important analytical and synthetic tool. The methods used for the etherification of hydroxyl groups51 generally employ reactions of unprotected sugars and glycosides with methyl, allyl, benzyl, triphenylmethyl, and alkylsilyl halides in the presence of a variety of aqueous and nonaqueous bases. 

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