Sulfuric acid, fuming alcohols

A. Dinitrodurene.—A solution of 13.4 g. (0.1 mole) (Notes 1,2) of durene (p. 32) in 100 cc. of chloroform is added to 75 cc. of concentrated sulfuric acid in an 800-cc. beaker provided with a thermometer and an efficient mechanical stirrer. The mixture is cooled to io°, and 16 g. (10.7 cc.) of fuming nitric acid (sp. gr. 1.5) (Note 3) is added drop by drop, with stirring, from a 125-cc. separatory funnel, the mixture being cooled in an ice-salt bath and the nitric acid added at such a rate that the temperature does not rise above 50° (about fifteen minutes is required for the addition). As soon as all the acid has been added the mixture is poured into a separatory funnel, the sulfuric acid layer is removed and the upper chloroform layer is immediately (Note 4) run into 500 cc. of 10 per cent sodium carbonate solution. The sulfuric acid layer is discarded because it contains very little dinitrodurene. Four portions are nitrated and the combined chloroform solutions are washed twice with 2.5 per cent sodium carbonate solution, dried over night with 30 g. of anhydrous calcium chloride, filtered, and the chloroform distilled off until crystals of dinitrodurene begin to appear. At this point four times the volume of hot 95 per cent ethyl alcohol is added (about... 

Trinitrobenzene can be prepared by heating w-dinitro-benzene with nitric acid and sulfuric acid to 1200 1 by heating 2, 4, 6-trinitrotoluene with fuming nitric acid in a sealed tube at 180° for three hours 2 by heating 2, 4, 6-trinitrobenzoic acid or its sodium salt with water, alcohol, dilute sodium carbonate or other suitable solvent.3... 

The use of aqueous foams to control fume or vapour release from reactive chemicals is discussed. An acid-resistant foam NF2 controlled fume emission from 35% and 65% oleum, and from titanium tetrachloride, but was not effective for sulfur trioxide and chlorosulfuric acid. An alcohol-resistant foam NF1 suppressed ammonia vapour emission by 80%, and Universal fire foam reduced evaporation of ethylene oxide, vinyl chloride and methanethiol, and reduced vapour emission of 1,3-butadiene by 60%. Safety aspects of foam blanketing are discussed [1]. Equipment and application techniques are covered in some detail [2],... 

Mannitol hexanitrate is obtained by nitration of mannitol with mixed nitric and sulfuric acids. Similarly, nitration of sorbitol using mixed acid produces the hexanitrate when the reaction is conducted at 0—3°C and at —10 to —75°C, the main product is sorbitol pentanitrate (117). Xylitol, ribitol, and L-arabinitol are converted to the pentanitrates by fuming nitric acid and acetic anhydride (118). Phosphate esters of sugar alcohols are obtained by the action of phosphorus oxychloride (119) and by alcoholysis of organic phosphates (120). The 1,6-dibenzene sulfonate of D-mannitol is obtained by the action of benzene sulfonyl chloride in pyridine at 0°C (121). To obtain 1,6-dimethanesulfonyl-D-mannitol free from anhydrides and other by-products, after similar sulfonation with methane sulfonyl chloride and pyridine the remaining hydroxyl groups are acetylated with acetic anhydride and the insoluble acetyl derivative is separated, followed by deacetylation with hydrogen chloride in methanol (122). Alkyl sulfate esters of polyhydric alcohols result from the action of sulfur trioxide—trialkyl phosphates as in the reaction of sorbitol at 34—40°C with sulfur trioxide—triethyl phosphate to form sorbitol hexa(ethylsulfate) (123). 

Indeed, if methanol is heated with fuming sulfuric acid, dimethyl sulfate, CH30(S02)0CH3, is obtained but other alcohols are better converted to dialkyl sulfates by oxidation of the corresponding dialkyl sulfites formed by the reaction of 1 mole of thionyl chloride (SOCl2) with 2 moles of the alcohol ... 

For commercial production the Griesheim Chem. Fabrik is reported to have used a process in which 1 part of TNT is heated at 150-200° with a mixture of 5 parts of fuming nitric acid and 10 parts of concentrated sulfuric acid. In a process devised by J. Meyer,7 picryl chloride (2,4,6-trinitrochlorobenzene) is reduced by means of copper powder in hot aqueous alcohol. The reported details are 25 kilos of picryl chloride, 8 kilos of copper 8 Ber., 9, 402 (1876) Ann., 215, 345 (1882). 

The aliphatic iodine derivatives are usually prepared by reaction of an alcohol with hydroiodic acid or phosphorus triiodide by reaction of iodine, an alcohol, and red phosphorus addition of iodine monochloride, monobromide, or iodine to an olefin replacement reaction by heating the chlorine or bromine compound with an alkali iodide in a suitable solvent and the reaction of triphenyl phosphite with methyl iodide and an alcohol. The aromatic iodine derivatives are prepared by reacting iodine and the aromatic system with oxidizing agents such as nitric acid, fuming sulfuric acid, or mercuric oxide. 

SAFETY PROFILE Poison by ingestion, intraperitoneal, intravenous, and parenteral routes. Moderately toxic by inhalation, skin contact, and subcutaneous routes. A moderate skin and severe eye irritant. Mutation data reported. Combustible liquid. IVIixtures with sulfuric acid decompose explosively at 180°. Exothermic polymerization is catalyzed by HBr + iron when heated above 100°. To fight fire, use alcohol foam, CO2, dry chemical. When heated to decomposition it emits acrid smoke and fumes. See also ALCOHOLS. 

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