Hydroxyl accessibility

Chow, S.-Z. (1972). Hydroxyl accessibility, moisture content, and biochemical activity in cell walls of Douglas-fir trees. Tappi, 55(4), 539-544. 

During the course of the alkaline degradations, both physical and chemical structures of the hydrocelluloses were monitored. Hydroxyl accessibility (13) was determined as a practical measure of the fraction of molecules accessible to the alkaline medium. The crystalline structure was characterized by x-ray diffraction (14). 

Alkaline Degradations - Change in Physical Structure. The hydroxyl accessibility of the fibrous hydrocellulose was initially 51.4 0.8%. In contrast, the amorphous substrate had an accessibility of 99.2 1.0%. Exposure of the fibrous hydrocellulose to the alkaline media caused the accessibility to decrease slightly to 50.7 1.0% and 49.1 1.2% at 60 and 80°C, respectively, but accessibility did not change significantly during the reaction periods (0-168 hr). 

Figure 1. Hydroxyl accessibility of the amorphous hydrocellulose during degradation in l.OM NaOH.

Substituents that are otherwise accessible only with difficulty such as fluoro lodo cyano and hydroxyl may be introduced onto a benzene ring... 

During the 1980s few innovations were disclosed in the Hterature. The hydroxylation of phenol by hydrogen peroxide has been extensively studied in order to improve the catalytic system as well as to master the ratio of hydroquinone to catechol. Other routes, targeting a selective access to one of the dihydroxyben2enes, have appeared. World production capacities according to countries and process types are presented in Table 1. 

Other Methods. A variety of other methods have been studied, including phenol hydroxylation by N2O with HZSM-5 as catalyst (69), selective access to resorcinol from 5-methyloxohexanoate in the presence of Pd/C (70), cyclotrimerization of carbon monoxide and ethylene to form hydroquinone in the presence of rhodium catalysts (71), the electrochemical oxidation of benzene to hydroquinone and -benzoquinone (72), the air oxidation of phenol to catechol in the presence of a stoichiometric CuCl and Cu(0) catalyst (73), and the isomerization of dihydroxybenzenes on HZSM-5 catalysts (74). 

The other important feature of the primary stmcture of RNA is the presence of the 2 -hydroxyl group in ribose. Although this hydroxyl group is never involved in phosphodiester linkages, it does impose restrictions on the heHcal conformations accessible to double-stranded RNA. 

At low relative humidities, adsorption is due to interaction of water with accessible hydroxyl groups. These are present on the lignin and on the carbohydrates ia the noncrystalline or poorly crystalline regions. The high differential heat of adsorption by dry wood, - 1.09 kJ/g (469 Btu/lb) water. 

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 ... 

Condensation of prednisone, 40 with tetraethyl orthocarbonate leads to the cyelie ortho-carbonate 41 liydrolysis proceeds by protonation on the most accessible ether oxygen (that on carbon 21) to give the 17 mixed carbonate ester 42. Acylation with propionyl chloride proceeds on the remaining hydroxyl group to afford prednicarbate (43) [10],... 

The chiral acetate reagent is readily prepared from methyl mandelate [methyl (A)-hydroxy-phenyl acetate] which is first converted by treatment with phcnylmagnesium bromide into the triphenylglycol783, c (see Section 1.3.4.2.2.2.) and subsequently transformed into the acetate by reaction with acetyl chloride in the presence of pyridine. Thereby, the secondary hydroxyl group of the glycol is esterified exclusively. Both enantiomers of the reagent are readily accessible since both (R)- and (5)-hydroxyphenylacelic acid (mandelic acids) arc industrial products. 

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