Nitration hydroxyl group

Nitrocellulose of 12.65% N, according to this nomenclature, is called 2i-nitrate, etc. The degree of nitration can also be designated by the degree of substitution (D.S.) which is the average number of nitrated hydroxyl groups in one anhydroglucose unit. 

The hydroxyl groups on glycols undergo the usual alcohol chemistry giving a wide variety of possible derivatives. Hydroxyls can be converted to aldehydes, alkyl hahdes, amides, amines, a2ides, carboxyUc acids, ethers, mercaptans, nitrate esters, nitriles, nitrite esters, organic esters, peroxides, phosphate esters, and sulfate esters (6,7). 

The aromatic nature of lignin contrasts with the aliphatic stmcture of the carbohydrates and permits the selective use of electrophilic substitution reactions, eg, chlorination, sulfonation, or nitration. A portion of the phenoUc hydroxyl units, which are estimated to comprise 30 wt % of softwood lignin, are unsubstituted. In alkaline systems the ionized hydroxyl group is highly susceptible to oxidative reactions. 

Cationic, anionic, and amphoteric surfactants derive thek water solubiUty from thek ionic charge, whereas the nonionic hydrophile derives its water solubihty from highly polar terminal hydroxyl groups. Cationic surfactants perform well in polar substrates like styrenics and polyurethane. Examples of cationic surfactants ate quaternary ammonium chlorides, quaternary ammonium methosulfates, and quaternary ammonium nitrates (see QuARTERNARY AMMONIUM compounds). Anionic surfactants work well in PVC and styrenics. Examples of anionic surfactants ate fatty phosphate esters and alkyl sulfonates. 

The indolinol character of eseretholemethine is indicated by the fact that the methiodide on treatment with picric acid yields a diquaternary pierate (m.p. 170°) with the loss of the hydroxyl group. More definite proof is afforded by the oxidation of eseretholemethine with ammoniaeal silver nitrate or potassium ferricyanide, when a dehydroeseretholemethine (oxyeseretholemethine of Polonovski), pierate, m.p. 199°, is produced which is assumed to have formula (VI), since on exhaustive methylation it yields trimethylamine and an unsaturated product (deep-red pierate, m.p. 103°), which absorbs two atoms of hydrogen, forming 5-ethoxy-l 8-dimethyl-S-ethyl-2-indolinone (VII), colourless cubes, m.p. 68°. The... 

Nitrates have only been prepared from saturated equatorial 3-hydroxyl groups by reaction with concentrated nitric acid and acetic anhydride at low temperature.Electrophilic substitution at C-6 precludes the satisfactory formation of nitrates from A -3j5-ols. 

Generally, the successful conversion of 20-ketopregnanes to 17-hydroxy-androstanes with peracids requires the protection of other ketones, with the exception of those at C-11, and possibly C-12 e.g., as ketals or cyanohydrins ) and isolated double bonds e.g., as dibromides). Unprotected hydroxyl groups do not interfere, except, as expected, a 17a-hydroxy-20-keto steroid is oxidized to the 17-ketone. The use of nitrate esters to protect... 

As an alternate route to functionalized morphinans, the intermediate, 38, is first nitrated, the group entering para to the methylene bridge (44). Reduction of the nitro to the aniline (45) followed then by diazotization and replacement by hydroxyl gives intermediate, 46. Cyclization as above again gives racemorphan. 

The hydroxyl group is a strongly activating, ortho- and para-directing substituent in electrophilic aromatic substitution reactions (Section 16.4). As a result, phenols are highly reactive substrates for electrophilic halogenation, nitration, sulfonation, and lTiedel-Crafts reactions. 

Nitric acid also undergoes reactions with organic compounds wherein the acid serves neither as an oxidizing agent nor as a source of hydrogen ions. The formation of organic nitrates by esterification (O-nitration) involves reaction with the hydroxyl group ... 

C-Nitration does not involve the hydroxyl group but is a reaction with an aliphatic or aromatic hydrocarbon or a substituted derivative to produce such compounds as the nitroparaffins and the nitrotoluenes ... 

Polyhydric Alcohols. (Polyols). An alcohol with three or more hydroxyl groups, each attached to a different carbon atom. They are w-sol and of sweetish taste, which tends to intensify with increasing hydroxyl content. Examples of polyols of ordn interest are listed below. Polyvinyl alcohol is considered in a separate entry as a polymer although it is defined as a polyhydric alcohol. Polyols, when nitrated, make excellent expls, proplnt binders, plasticizers, etc. Prepn can follow the procedure of Lenth DuPuis (Ref 3) which uses a methanol suspension of either sucrose or dextrose and a special Cu-Al oxide catalyst to yield 60-65% distillable polyols at 240° and 1500psi Refs 1) Beil — refs found under individual compds 2) CA, under Alcohols, Polyhydric for compds of current ordn interest 3) C.W. Lenth R.N. DuPuis, "Polyhydric Alcohol Production by Hydrogenolysis of Sugars in the Presence of Copper-Aluminum Oxide , IEC 37, 152-57 (1945) CA 39, 1391 (1945)... 

Chhatre et al. (1993) have reported that highly selective ort/io-nitration of phenol with dilute nitric acid can be realized by using a microemulsion medium. It seems that in the microemulsion medium, phenol orients in such a way that the phenyl group remains extended towards the side of the organic phase, whereas the hydroxyl group protrudes in the aqueous... 

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