Trimethylacetic acid

Highly Branched Acids. These acids, called neoacids, are produced from highly branched olefins, carbon monoxide, and an acid catalyst such as sulfuric acid, hydrogen fluoride, or boron trifluoride. 2,2,2-Trimethylacetic acid (pivaUc acid) is made from isobutylene and neodecanoic acid is produced from propylene trimer (see Carboxylic Acids, trialkylacetic acids). 

Pivalic acid (trimethylacetic acid) [75-98-9] M 102.1, m 35.4", b 71-73"/0.1mm, pK 5.03. Fractionally distd under reduced pressure, then fractionally crystd from its melt. Recrystd from benzene. 

Neopentyl alcohol has been made by lithium aluminum hydride reduction of trimethylacetic acid and by treating ferf-butyl-magnesium chloride with methyl formate. ... 

Neopentanoic acid (trimethylacetic acid) is an intermediate and an ester-ifying agent used when a stable neo structure is needed. 

After surrounding the flask with ice, the reaction mixture is hydrolyzed (Note 4) with 25 per cent sulfuric acid. The reaction mixture is transferred to a 2-1. separatory funnel and the ether layer separated (Note 4). The water layer is extracted with four 100-cc. portions of ether. The combined ether extracts are then washed with four 100-cc. portions of 25 per cent sodium hydroxide solution to remove the trimethylacetic acid from the ether. 

The aqueous alkaline extract is heated to ioo° to remove ether and volatile impurities. The solution is then cooled with ice and acidified with 25 per cent sulfuric acid, and the organic acid separated. The water layer is distilled from a 2-1. flask until no more oily solution comes over, The distillate is saturated with salt and the acid layer is separated. This water layer together with the low boiling fraction from distillation of the crude trimethylacetic acid is distilled and the distillate salted out as before. 

The combined acid layers are distilled from a 250-cc. Claisen flask connected to an air condenser, which in turn is connected to a side-arm flask cooled by running water. The trimethylacetic acid is collected at i62-i6s°/a-tm. press., no-ii2/ i24mm. The yield, which depends somewhat on the form of magnesium, is 157-162 g. (61-63 Per cent of the theoretical amount based on tert-butyl chloride) when ordinary magnesium turnings are used and 177-178 g. (69-70 per cent) when 200-mesh magnesium powder is used. The acid melts at 34-350. 

The burner is then removed, the mixture is cooled to 50°, and 400 cc. of concentrated sulfuric acid (Note 4) is added through the separatory funnel. The heat of neutralization causes some trimethylacetic acid to distil with water. When all the acid is added the flask is heated again and the trimethylacetic acid comes over with about 400 cc. of water. When... 

The trimethylacetic acid is dried very easily by distilling with about 50 cc. of benzene at ordinary pressure until all of the water is removed and then the residue is distilled under reduced pressure. 

Trimethylacetic acid may be made by the hydrolysis of tert-butyl cyanide with weak hydrochloric acid at ioo0.1 It is also obtained by oxidation of trimethylpyroracemic acid with silver oxide or potassium dichromate and sulfuric acid,2 by oxidation of tertf-butylethylene with permanganate solution,3 or by oxidation of dimethyl 2,2-propanol with chromic acid.4 Schroeter reports the formation of trimethylacetic acid by rearrangement of the oxime of trimethylacetophenone to give the anilide of trimethylacetic acid, which can be hydrolyzed to give the acid.5... 

The general plan of Organic Syntheses has been discussed in the prefaces of the previous volumes. In this volume are published two distinctly different methods of preparation for each of two compounds. The directions for producing /3-chloro-propionic acid first from acrolein and second from trimethylene chlorohydrin, and for producing trimethylacetic acid first from terJ-butyl chloride and second from pinacolone, have been included. This has been deemed advisable since in some countries one raw material is more readily available than the other. 

Por the formylation of amines with the mixed anhydride of formic and trimethylacetic acid, see Vlietstra, E.J. Zwikker, J.W. Nolte, R.J.M. Drenth, W. Reel. Trav. Chim. Pays-Bas, 1982, 101, 460. 

S = substrate = p-nitrophenyl trimethylacetate P = product = p-nitrophenol A = trimethylacetic acid kx = 150 m3/mole-ksec k2 = 2.60 ksec-1... 

During homologation of higher MW acids, e.g., starting from propionic acid or trimethylacetic acid, the product... 

The trimethylacetic acid is isolated from the used ruthenium catalyst and unreacted iso-butyric acid by fractional distillation in vacuo, and identified by NMR and FTIR analyses. 

Trimethylacetamide, d678 Trimethylacetic acid, d679 Trimethylacetic anhydride, d680 Trimethylacetyl chloride, d681... 

A large amount of trimethylacetic acid and a small amount of at least one C9-acid and one Ci3-acid are formed from the /-butyl alcohol. The treatment with ammonia separates 1-ada-mantanecarboxylic acid from these acids, the ammonium salts of which remain in solution. 

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