W-Butyryl chloride

In a 1-1. three-necked flask fitted with a Hershberg wire stirrer, a reflux condenser equipped with a calcium chloride drying tube, and a dropping funnel, are placed 237 g. (2.21 moles) of methyl-aniline (Note 5) and 300 ml. of dry benzene (Note 6). Stirring is started, and the reaction mixture is cooled in an ice-water bath during the dropwise addition of 197 g. (1.06 moles) of a-bromo-w-butyryl chloride diluted with approximately 40 ml. of dry benzene. The addition requires approximately 1 hour, and the reaction mixture becomes thick owing to the separation of methyl-... 

BromobenzaIdehyde, 30, 100 Bromobenzene, 30, 97 a-Bromo- -butyric acid, 30, 62 a-Bromo-w-butyryl chloride, 30, 62... 

NaBH4 is superior to LiAlH4 in selective reductions. In "water or methanol soln., it is an effective reagent for the conversion of aldehydes and ketones to the corresponding alcohols. Aoid chlorides are reduced to prim, alcohols in non-aq. media, but carboxylic acids, anhydrides, esters and nitriles are practically unaffected.—E Cinnamaldehyde —> cinnamyl alcohol. Y 97%.—n-Butyryl chloride —n-butanol Y 81%. (F. e. s. S. W. Chaikin, W. G-. Brown, Am. Soc. 71,122 (1949) s. a. H. Heusser et al., Helv. 33, 1093 (1950).)... 

An ethereal suspension of thallous benzoate (prepared from benzoic acid and thallous ethoxide) treated 6 hrs. at 25° with the stoichiometric amount of iso-butyryl chloride benzoic isobutyric anhydride. Y ca. 100%. - To minimize comproportionation, the carboxylate salt of the weaker acid should be used. F. e., also phenolesters and phenyl sulfonates with thallous phenoxides, as well as sym. carboxylic acid anhydrides from thallous carboxylates with SOCU, s. E. G. Taylor, G. W. McLay, and A. McKillop, Am. Soc. 90, 2422 (1968). 

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