Butyryl chloride

Burano/I chloride is a clear colorless liquid with o chorocteristic pungent odor. It reocts with woter and olcohol and is infinitely soluble in ether. It is used for orgonic synthesis to introduce the butyryl group. 

Submitted by B. Helferick and W. Schaefer. Checked by Henry Gilman and S. A. Harris. 

In a 125-cc. distilling flask, provided with a water-cooled side arm to act as reflux condenser (Note 1), is placed 56 g. (0.47 mole) of thionyl chloride (Note 2). This is heated on a water-bath and to it is added during the course of an hour 35.2 g. (0.4 mole) of -butyric acid (Note 3) by means of a separatory funnel attached to the neck of the flask. The evolved gases are absorbed in water. 

When all the acid has been added, the mixture is heated for one-half hour on the water bath and then distilled directly from an oil bath into a second distilling flask. The crude acid chloride thus obtained boils between 70-1 io° it is purified by distillation through a column and boils almost entirely at ioo-ioi0, only a few drops of forerun being obtained. The yield is 36 g. (85 per cent of the theoretical amount). 

If a Claisen distilling flask is used for the preparation of the acid chloride the side-arm is plugged the short neck holds the reflux condenser, and the long neck the separatory funnel. 

The yield is influenced by the purity of the thionyl chloride the results reported above were obtained with a pure product which boiled over a two-degree range. 

---

CH3CH2CH3COOH + SOClj —> CH3CH3CH3COCI + SOj + HCl n.But3rric acid n-Butyryl chloride (b.p. 101")... 

Prepare n-heptoyl chloride from the acid by treatment with thionyl chloride as detailed for n-butyryl chloride (Section 111,87) b.p. 173-175°. 

Several methods are available to supplement the phenol alkylations described above. Primary alkylphenols can be produced using the more traditional Friedel-Crafts reaction. Thus an -butylphenol can be synthesized direcdy from a butyl haUde, phenol, and mild Lewis acid catalyst. Alternatively, butyryl chloride can be used to acylate phenol producing a butyrophenone. Reduction with hydrazine (a Wolff-Kishner reduction) generates butylphenol. 

This technique can be applied to prepare DL-a-fluoromethylputrescme (5-fluoropentane 1,4-diamine), a potent irreversible inhibitor of E colt ornithine decarboxylase, from 4-phthalimido-l -butyryl chloride, diazomethane, and hydro gen fluonde-pyridine [94 95]... 

The initial series of major tranquilizers consists of alkylated derivatives of 4-aryl-4-hydroxypiperidines. Construction of this ring system is accomplished by a set of rather unusual reactions. Condensation of methylstyrenes with formaldehyde and ammonium chloride afford the corresponding hexahydro-1,3-oxazines (119). Heating these oxazines in the presence of acid leads to rearrangement with loss of water to the tetrahydropyridines. Scheme 1 shows a possible reaction pathway for these transformations. Addition of hydrogen bromide affords the expected 4-bromo compound (121). This last is easily displaced by water to lead to the desired alcohol (122) The side chain (123) is obtained by Friedel-Crafts acylation of p-fluorobenzene with 4-chloro-butyryl chloride. Alkylation of the appropriate arylpiperidinol with 123 affords the desired butyrophenone derivative. Thus,... 

The 2,3-dichlorophenoxyacetic acid and n-butyryl chloride are placed in the reaction vessel and stirred while the aluminum chloride is added portionwise over a 45-minute period. The mixture then is heated on the steam bath for 3 hours and allowed to cool to room temperature. The gummy product obtained is added to a mixture of 300 ml of crushed ice and 30 ml concentrated hydrochloric acid. The resulting mixture is extracted with ether and the extract evaporated at reduced pressure. The residue Is suspended in boiling water and dissolved by addition of a minimum quantity of 40% sodium hydroxide. After treatment with decolorizing charcoal and filtering, the hot filtrate is made acid to Congo red paper and chilled in ice. 

Methohexital sodium Butyramidophenol Acebutolol Butyric anhydride lopanoic acid Tyropanoate sodium n-Butyryl chloride Ethacrynic acid... 

Acetyl chloride, a-tert butyl-o-cyano- [Butyryl chloride, 2-cyano-3 3-dimethyl-], 55,38... 

C4H7N 709-74-0) see Etifelmine 2-butyrylbenzofuran (C12H12O2 85614-50-2) see Amiodarone butyryl chloride... 

Acetic anhydride Propionic anhydride Butyric anhydride Maleic anhydride Phthalic anhydride Acetyl chloride Propionyi chloride Butyryl chloride Hexonyl chloride Benzoyl chloride Oxalyl chloride Chloroacetyl chloride Dichloroacetyl chloride Trichloroacteyl dtloride... 

---