Dehydrate agent

Crystalline solid m.p. 35-36 "C, b.p. 154--156 C, prepared by oxidizing A,A -dicycIo-hexylthiourea with HgO in carbon disulphide solution, also obtained from cyclohexylamine and phosgene at elevated temperatures. Used as a mild dehydrating agent, especially in the synthesis of p>eptides from amino-acids. Potent skin irritant. 

At temperatures of 220-240 C it functions as an efficient, neutral dehydrating agent, amides yielding nitriles and alcohols yielding alkenes. 

McjC = CHCOCH3. Colourless liquid b.p. 129"C, with a strong peppermint-like odour. Prepared by distilling diacetone alcohol in the presence of a trace of iodine. Converted to phorone by heating in propanone with dehydrating agents such as sulphuric acid. It is a solvent For cellulose acetate and ethyl-cellulose and other polymers. 

CaHjNCO, PhNCO. A pungent lachrymatory almost colourless liquid m.p. — 33 "C, b.p. 162°C. Used as a dehydrating agent and for characterization of alcohols. Prepared from aniline and phosgene in the presence of hydrogen chloride. 

Uses of hydrogen chloride—Hydrogen chloride is sometimes used in the preparation of an ester, for example ethyl benzoate, where it acts as both an acid catalyst and a dehydrating agent. Hydrochloric acid is used primarily to produce chlorides, for example ammonium chloride. It is extensively used in the manufacture of anilme dyes, and for cleaning iron before galvanising and tin-plating. 

Directly from the corresponding acid and alcohol, in the presence of a dehydrating agent. Thus when ethanol and acetic acid are mixed, ethyl acetate and water are formed, but in addition an equilibrium is established. 

Dehydration of the corresponding acid amides. This process usually requires phosphorus pentoxide (correctly termed phosphoric anhydride) as a dehydrating agent. 

Phosphoric acid method. The advantages of phosphoric acid as a dehydrating agent in this preparation are the absence of carbonisation and the freedom of the product from sulphur dioxide. 

The phosphorus oxychloride formed in the reaction is a dehydrating agent also. 

It may be pointed out that dehydration of p hydroxy esters with fused potassium hydrogen sulphate, acetic anhydride, phosphoric oxide or with tliionyl chloride in benzeue solution leads to ap unsiiturated esters containing some PY-unsaturated ester the proportion of the latter depends not only upon the structure of the ester but also upon the dehydrating agent used. Elehydration occasionally occurs during the reaction itself or upon attempted distillation. 

Pyruvic acid is conveniently prepared by the distillation of tartaric acid with a dehydrating agent, such as potassium bisulphate ... 

The widely used Moifatt-Pfltzner oxidation works with in situ formed adducts of dimethyl sulfoxide with dehydrating agents, e.g. DCC, AcjO, SO], P4O10, CCXTl] (K.E, Pfitzner, 1965 A.H. Fenselau, 1966 K.T. Joseph, 1967 J.G. Moffatt, 1971 D. Martin, 1971) or oxalyl dichloride (Swem oxidation M. Nakatsuka, 1990). A classical procedure is the Oppenauer oxidation with ketones and aluminum alkoxide catalysts (C. Djerassi, 1951 H. Lehmann, 1975). All of these reagents also oxidize secondary alcohols to ketones but do not attack C = C double bonds or activated C —H bonds. 

Perchloric acid Acetic acid, acetic anhydride, alcohols, antimony compounds, azo pigments, bismuth and its alloys, methanol, carbonaceous materials, carbon tetrachloride, cellulose, dehydrating agents, diethyl ether, glycols and glycolethers, HCl, HI, hypophosphites, ketones, nitric acid, pyridine, steel, sulfoxides, sulfuric acid... 

Dehydration or Chemical Theory. In the dehydration or chemical theory, catalytic dehydration of ceUulose occurs. The decomposition path of ceUulose is altered so that flammable tars and gases are reduced and the amount of char is increased ie, upon combustion, ceUulose produces mainly carbon and water, rather than carbon dioxide and water. Because of catalytic dehydration, most fire-resistant cottons decompose at lower temperatures than do untreated cottons, eg, flame-resistant cottons decompose at 275—325°C compared with about 375°C for untreated cotton. Phosphoric acid and sulfuric acid [8014-95-7] are good examples of dehydrating agents that can act as efficient flame retardants (15—17). 

A simpler nonphosgene process for the manufacture of isocyanates consists of the reaction of amines with carbon dioxide in the presence of an aprotic organic solvent and a nitrogeneous base. The corresponding ammonium carbamate is treated with a dehydrating agent. This concept has been apphed to the synthesis of aromatic and aUphatic isocyanates. The process rehes on the facile formation of amine—carbon dioxide salts using acid haUdes such as phosphoryl chloride [10025-87-3] and thionyl chloride [7719-09-7] (30). 

Monsanto has disclosed the use of carbon dioxide—amine complexes which are dehydrated, at low temperatures, with phosphoryl chloride [10025-87-3] or thionyl chloride [7719-09-7] as a viable route to a variety of aUphatic isocyanates. The process rehes on the facile formation of the intermediate salt (30).REPLACEVariations of this process, in which phosgene is used as a dehydrating agent, have been reported earlier (84). Table 2 Hsts commercially available aUphatic isocyanates. 

Organic Reactions. Nitric acid is used extensively ia iadustry to nitrate aHphatic and aromatic compounds (21). In many iastances nitration requires the use of sulfuric acid as a dehydrating agent or catalyst the extent of nitration achieved depends on the concentration of nitric and sulfuric acids used. This is of iadustrial importance ia the manufacture of nitrobenzene and dinitrotoluene, which are iatermediates ia the manufacture of polyurethanes. Trinitrotoluene (TNT) is an explosive. Various isomers of mononitrotoluene are used to make optical brighteners, herbicides (qv), and iasecticides. Such nitrations are generally attributed to the presence of the nitronium ion, NO2, the concentration of which iacreases with acid strength (see Nitration). 

This method, however, is not industrially practical because a large amount of dehydrating agent, such as ethyl orthoformate, is required to remove water formed in the reaction. Because water is an inhibitor of the reaction, the reaction system has to be kept under substantially anhydrous conditions. 

R = alkyl, R = H) can be condensed, using acid, dehydrating agents (eg, phosphoms pentoxide), or vacuum to form polymeric peroxides (3). Most such polymeric peroxides decompose explosively. 

Potassium acetate is very soluble and is used in the manufacture of glass (qv), as a buffer (see Hydrogen-ION activity) or a dehydrating agent, and in medicine as a diuretic (see Diuretic agents). It is dehquescent and is used as a softening agent for papers and textiles. 

Pyrrohdines also can be obtained by reaction of 1,4-dihydroxyaLkanes with amines in the presence of dehydrating agents at elevated temperatures or by reaction of primary amines with 1,4-dihaloaLkanes. The dry distillation of 1,4-butanediamine dihydrochloride also generates pyrrohdine. Pyrroles can also be catalyticahy hydrogenated to pyrrohdines. 

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