Alkyl sulfites

The reactions of thionyl chloride with organic compounds having hydroxyl groups are important. Alkyl chlorides, alkyl sulfites, or alkyl chlorosulfites form from its reaction with aUphatic alcohols, depending on reaction conditions, stoichiometry, and the alcohol stmcture ... 

Heating the adduct of ethylene oxide and sulfur dioxide with primary alcohols in the presence of alkaH hydhdes or a transition-metal haHde yields dialkyl sulfites (107). Another method for the preparation of methyl alkyl sulfites consists of the reaction of diazomethane with alcohoHc solutions of sulfur dioxide (108). 

The usual etherifying agents are the alkyl chlorides or sulfates. The advantage, usually found in organic reactions, of using the alkyl iodides and bromides because of their greater reactivity as compared to the chlorides is overshadowed by their much slower diffusion rate, lower solubility in the alkali and greater rate of saponification. The sulfates are relatively costly. Alkyl sulfites have also been proposed ... 

From Reference 14d, the gaseous a values are —18.19 for di-tt -alkyl sulfites and —18.10 for din-alkyl sulfates. The a values were calculated from the diethyl, dipropyl and dibutyl substituted species in each of the homologous series. 

Secondary alkyl sulfites are produced if the formed hydrogen chloride is removed by carrying out the reaction at reduced pressure (aspirator) [9], Examples of the preparation of cyclic sulfites from 1,2-diols are shown in Table II. Other examples involving the preparation of cyclic sulfites are found in a recent patent [20],... 

Sulfonic Esters by Rearrangement of Alkyl Sulfites (RO)jSO RSOjR (56%) ... 

The thermal decomposition of the alkyl sulfites is expected to be similar to that of chlorosulfites . This system has received little attention either qualitatively or quantitatively. Desulfonylation occurs with the formation of (i) approximately equimolar proportions of alkene and alcohol or ( ) ether, in varying proportion depending on the structure of the sulfite - , viz. 

Berti explored use of the reagent for the conversion of secondary alcohols into olefins by reaction of the alcohol with methyl chlorosulflte in ether containing pyridine to produce the methyl alkyl sulfites and pyrolysis of these esters, but the results were not impressive. 

Alkyl phosphates, preparation, 16, 9 Alkyl sulfates, preparation, 19, 27 Alkyl sulfides, preparation, 15, 72 Alkyl sulfites, preparation, 19, 29 Ai-AlkyW -toluidines, 18,42 Allanioin, 13,1 Allyl alcohol, 10, 107 16, 85 Allylamine, 18, 5 Allyl cyanide, 16, 85 Allyl isothiocyanate, 18, 5 Alumina, 17, 27... 

In addition to the organic solvents described above, there are quite a few more organic compounds considered as solvent candidates for Li-ion battery electrolytes. In many cases, these molecules are more appropriate as additives instead of solvents due to the inferior physical and electrochemical properties of the resulting electrolyte if such molecules are used in high concentration. These molecules include the non-fluorinated and fluorinated varieties of alkyl sulfates [113], alkyl sulfites [21, 59, 63], alkyl phosphates [66], and phosphazenes [84]. Some of them have been employed as SEI formation additives or flame retardant additives and will be discussed in the respective sections of Chap. 9. 

Mao L, Li B, Cui X, Zhao Y, Xu X, Shi X, Li S, Li F (2012) Electrochemical performance of electrolytes based upon lithium bis(oxalate)borate and sulfolane/alkyl sulfite mixtures for high temperature lithium-ion batteries. Electrochim Acta 79 197-201. doi 10.1016/j. electacta.2012.06.102... 

The structure of linear alkyl sulfites is similar to that of linear alkyl carbonates, but the electrochemical properties as a single solvent for an electrolyte are not good. EC can be used as an additive to improve the ionic conductivity and performance at low temperature. 

Secondary alkyl sulfites are produced if the formed hydrogen chloride is removed by carrying out the reaction at reduced pressure (use HCl trap). 

---