Butyric acid, bromination

Preparation of 2-bromobutyric acid by hydrolysis of the crude bromide (obtained from butyric acid, bromine, and red phosphorus) by hot water is described by Fischer and Mou-neyrat.560... 

Bromination of the substituted butyric acid, 26, by the Hell-Volhardt-Zelinsky procedure affords the a-halo acid bromide (27). Reaction of this with urea affords directly bromisovalum (28). 

Chau and Terry [146] reported the formation of penta-fluorobenzyl derivatives of ten herbicidal acids including 4-chloro-2-methyl-phenoxy acetic acid [145]. They found that 5h was an optimum reaction time at room temperature with pentafluorobenzyl bromide in the presence of potassium carbonate solution. Agemian and Chau [147] studied the residue analysis of 4-chloro-2-methyl phenoxy acetic acid and 4-chloro-2-methyl phenoxy butyric acid from water samples by making the pentafluorobenzyl derivatives. Bromination [148], nitrification [149] and esterification with halogenated alcohol [145] have also been used to study the residue analysis of 4-chloro-2-methyl phenoxy acetic acid and 4-chloro-2-methyl phenoxybutyric acid. Recently pentafluorobenzyl derivatives of phenols and carboxylic acids were prepared for detection by electron capture at very low levels [150, 151]. Pentafluorobenzyl bromide has also been used for the analytical determination of organophosphorus pesticides [152],... 

Bromine (dry gas) Bromine (liquid) Bromobenzene Butanol Butyl acetate Butylamine Butylchloride Butyric acid Calcium chloride Carbon tetrachloride Castor oil Cellosolve Cellosolve acetate Chlorine (dry gas) Chlorine water Chloroacetic acid Chlorobenzene Chloroform Chlorosulfonic acid Chromic acid Citric acid Colza oil Copper sulfate Cyclohexane Cyclohexanol Cyclohexanone... 

NIOSH REL (Chromium(VI)) TWA 0.025 mg(Cr(VI))/mh CL 0.05/15M SAFETY PROFILE Confirmed human carcinogen. Poison by subcutaneous route. Mutation data reported. A powerful oxidizer. A powerful irritant of skin, eyes, and mucous membranes. Can cause a dermatitis, bronchoasthma, chrome holes, damage to the eyes. Dangerously reactive. Incompatible with acetic acid, acetic anhydride, tetrahydronaphthalene, acetone, alcohols, alkali metals, ammonia, arsenic, bromine penta fluoride, butyric acid, n,n-dimethylformamide, hydrogen sulfide, peroxyformic acid, phosphorus, potassium hexacyanoferrate, pyridine, selenium. 

A powerful oxidizer. Explosive reaction with acetaldehyde, acetic acid + heat, acetic anhydride + heat, benzaldehyde, benzene, benzylthylaniUne, butyraldehyde, 1,3-dimethylhexahydropyrimidone, diethyl ether, ethylacetate, isopropylacetate, methyl dioxane, pelargonic acid, pentyl acetate, phosphoms + heat, propionaldehyde, and other organic materials or solvents. Forms a friction- and heat-sensitive explosive mixture with potassium hexacyanoferrate. Ignites on contact with alcohols, acetic anhydride + tetrahydronaphthalene, acetone, butanol, chromium(II) sulfide, cyclohexanol, dimethyl formamide, ethanol, ethylene glycol, methanol, 2-propanol, pyridine. Violent reaction with acetic anhydride + 3-methylphenol (above 75°C), acetylene, bromine pentafluoride, glycerol, hexamethylphosphoramide, peroxyformic acid, selenium, sodium amide. Incandescent reaction with alkali metals (e.g., sodium, potassium), ammonia, arsenic, butyric acid (above 100°C), chlorine trifluoride, hydrogen sulfide + heat, sodium + heat, and sulfur. Incompatible with N,N-dimethylformamide. 

Derivation By heating bromine and butyric acid. Hazard Toxic by ingestion. 

Bleach (chloride of lime) Bromine Butyl acetate Butyl phthalate Butyric acid Calcium carbide Calcium cyanamide Calcium hypochlorite Calcium nitrate Calcium potassium ferrocyan-ide (double salt)... 

A stream of air, charged with bromine vapor, introduced into a vigorously stirred 0.34 M aq. soln. of crotonic acid over a period of 5 hrs., then air bubbled rapidly through the reaction mixture for an additional 30 min. to remove any excess bromine —a-bromo- -hydroxy-n-butyric acid. Y 79%. (H. E. Carter and C. L. Zirkle, J. Biol. Chem. 178, 709 (1949).). ... 

Methyl 2-bromobutyrate Butyric acid (70.4 g) is added to technical SOCl2 (112 g) during 75 min, with stirring, at room temperature, then the mixture is heated on a boiling water-bath for 30 min, after which the SOCl2 excess is distilled off. Bromine (135 g) is added to the residue at 80-90°, with stirring, and the whole is heated for 5 h on a boiling water-bath, then cooled. Methanol (46 ml) is added, and the solution is heated under reflux for 2 h. A small upper layer is formed and is separated in a separatory funnel and discarded. The remainder is distilled in a vacuum after a small forerun has been removed at 100° under atmospheric, pressure. The bromo ester (75-86%) has b.p. 70-75°/15 mm. 

Ammonium chloride Ammonium hydroxide Ammonium phosphate Ammonium sulfate Amyl acetate Amyl chloride Aqua regia Barium hydroxide Body fluids Bromine, wet or dry Butyric acid Calcium bisulfate Calcium chloride Calcium hydroxide Calcium hjpochlorite Carbon tetrachloride Carbonic acid Carbon dioxide Chloric acid... 

It seems not unlikely that a similar catalytic role is played by an alkaloid in the asymmetric synthesis of d-phenyl-n-butyric acid recorded by Lipkin and Stewart (76), by a reduction of the hydrocinchonine salt of /9-methylcinnamic acid, and also in the optically selective bromination of cinchotine cinnamate and glucosamine cinnamate noted by Erlenmeyer (38). A more complicated example recorded by Stewart and Lipkin (136) may perhaps be an extension of the same principle here, j8-methylcin-namic acid was selectively reduced by glucose in the presence of Raney nickel. 

Aluminum phosphide Amyl trichlorosilane Benzoyl chloride Boron tribromide Boron trifluoride Boron trifluoride etherate Bromine pentafluoride Bromine trifluoride n-Butyl isocyanate Butyllithium Butyric anhydride Calcium Calcium carbide Chlorine trifluoride Chloro silanes Chlorosulfonic acid Chromium oxychloride Cyanamide Decaborane Diborane... 

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