Sulfur trioxide reaction with alcohols

ACETATO MERCURIOSO (Spanish) (21908-53-2) A strong oxidizer. Violent reaction with reducing agents, acetyl nitrate, diboron tetrafluoride, disulfur dichloride, combustible materials, fuels, hydrazine hydrate, hydrogen peroxide, hydrogen trisulfide, hypophospho-rous acid, methanethiol, phospham. sodium-potassium alloy, sulfur, sulfur trioxide. Incompatible with alcohols, alkali metals, ammonium nitrate, diboron tetrafluoride, hydrazinium nitrate, hydrogen sulfide, nitroalkanes, rubidium acetylide, selenium oxychloride. Forms heat-, friction-, or shock-sensitive explosives with anilinium perchlorate, chlorine, phosphorus,. sulfur, magnesium, potassium, sodium-potassium alloy. May increase the explosive or thermal sensitivity of nitromethane, nitroethane, 1-nitropropane and other lower nitroalkanes, silver azide, hydrazinium perchlorate. Slowly decomposes on exposure to air. 

Sulfur trioxide converts alcohols to acid alcohol sulfates directly [Eq. (1)]. It is thought that sulfur trioxide reacts with the hydroxyl group forming firstly an alkyl hydrogen pyrosulfate which decomposes to alkyl hydrogen sulfate. The first reaction ... 

Bulk aluminum may undergo the following dangerous interactions exothermic reaction with butanol, methanol, 2-propanol, or other alcohols, sodium hydroxide to release explosive hydrogen gas. Reaction with diborane forms pyrophoric product. Ignition on contact with niobium oxide + sulfur. Explosive reaction with molten metal oxides, oxosalts (nitrates, sulfates), sulfides, and sodium carbonate. Reaction with arsenic trioxide + sodium arsenate + sodium hydroxide produces the toxic arsine gas. Violent reaction with chlorine trifluoride, Incandescent reaction with formic acid. Potentially violent alloy formation with palladium, platinum at mp of Al, 600°C. Vigorous dissolution reaction in... 

This method is also used with alcohols of the stmcture Cl(CH2) OH (114). HaloaLkyl chlorosulfates are likewise obtained from the reaction of halogenated alkanes with sulfur trioxide or from the chlorination of cycHc sulfites (115,116). Chlorosilanes form chlorosulfate esters when treated with sulfur trioxide or chlorosulfuric acid (117). Another approach to halosulfates is based on the addition of chlorosulfuric or fluorosulfuric acid to alkenes in nonpolar solvents (118). 

Although widely used in the past and still used in special cases, the industrial sulfation with chlorosulfonic acid presents several problems which have caused the decline of this technique in favor of the more advantageous sulfation method with sulfur trioxide. These problems consist of evolution of the highly corrosive hydrogen chloride, heat transfer characteristics of the reaction, and the comparatively high level of chloride ion in the sulfated product compared with alcohol and alcohol ether sulfates obtained with sulfur trioxide. 

Alcohol sulfates (AS) are usually manufactured by the reaction of a primary alcohol with sulfur trioxide or chlorosulfonic acid followed by neutralization with a base. These are high foam surfactants but they are sensitive to water hardness and higher levels of phosphates are required. This latter requirement has harmed the market for this type of detergent, but they are 2% of production for the major household surfactant market. Sodium lauryl sulfate (R = Cn) is a constituent of shampoos to take advantage of its high-foaming properties. 

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). 

Silyl ethers of aliphatic alcohols are inert towards strong bases, oxidants (ozone [81], Dess-Martin periodinane [605], iodonium salts [610,611], sulfur trioxide-pyridine complex [398]), and weak acids (e.g., 1 mol/L HC02H in DCM [605]), but can be selectively cleaved by treatment with HF in pyridine or with TBAF (Table 3.32). Phenols can also be linked to insoluble supports as silyl ethers, but these are less stable than alkyl silyl ethers and can even be cleaved by treatment with acyl halides under basic reaction conditions [595], Silyl ether attachment has been successfully used for the solid-phase synthesis of oligosaccharides [600,601,612,613] and peptides [614]. 

Sulfur trioxide is one of many reagents [e.g.. DCC Ac20, (COC1) TPAA with which DMSO can be activated as an oxidizing reagent lor alcohols. Oxalyl chloride has found the widest application in the reaction named after Swem.Xi Structure 43 represents the activated species in the above oxidation. 

Parikh and Doering in 1967 described80 that DMSO can be activated for the oxidation of alcohols, using sulfur trioxide that can be conveniently added to the reaction mixture as complex with pyridine. According to the original... 

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