Ethyl a-bromoisobutyrate

Benzenediamine (228) and diethyl dibromomalonate (229) gave ethyl 3-oxo-3,4-dihydro-2-quinoxalinecarboxylate (230) (MeOH, 20°C, 24 h 40%)." The same substrate (228) with ethyl a-bromoisobutyrate gave 3,3-dimethyl-3,4-dihydro-2(17i)-qumoxalinone (231) (Me2NCHO, NEtPr j, 110°C, 7 h 76%) or with methyl 2-bromo-2-phenylacetate gave 3-phenyl-3,4-dihydro-2(l//)-quinoxalinone (232) (KI, K2CO2, AcMe, reflux, 12 h then oily product, MeONa, PhH, reflux, 7 h 89%). ... 

Ethyl a-bromoisobutyrate, 21, 53 Ethyl /3-bromopropionate, 20, 6S Ethyl caprylate, 20, 69 Ethyl carbonate, 23, 95, 97 Ethyl chlorocarbonate, 21, 81 2-Ethylchromone, 21, 42 Ethyl diacetylacetate, 21, 46 copper derivative, 21, 46 Ethyl a,a-DIMETHYL-/3-PHENYL-/3-hydroxypropionate, 21, S3 Ethylene chloride, 20, 28 22, 76 ETHYLENEDIAMINE, IV IV-DIBUTYL-, 23, 23... 

Ethyl a,a-dimethyl-/3-phenyl- 3-hydroxypropionate may be prepared in a similar manner. For instance, from 100 g. of ethyl a-bromoisobutyrate and 65 g. of benzaldehyde, 82.5 g. (73 per cent of the theoretical amount) of ethyl a,a-dimethyl-/3-phenyl-/3-hydroxypropionate, boiling at i53-i58°/n mm., is obtained. It may be recrystallized by dissolving it at 30° in 100 cc. of ligroin (30-60°), chilling the solution for several days, and decanting the clear liquid from the precipitate m.p. 38.5-39°. 

Ethyl bromoacetate, 21, 51 23, 37 Ethyl a-bromoglutaconate, 26, 44 Ethyl a-bromoisobutyrate, 21, 53 Ethyl /3-bromopropionatf., 20, 65 Ethyl-n-butylaminc, 25, 19 Ethyl w-hutylcyano acetate, 26, 31 Ethyl capkylatu, 20, 69... 

Alkylation of disubstituted acetic esters has become an important new route to trisubstituted acetic acids and their derivatives. Sodium tri-phenylmethide or potassium triphenylmethide is used to convert the ester to its enolate ion, which, in turn, is allowed to react with an alkyl iodide to form the trialkylated ester. The yields are in the range of 42-61%. Potassium hydroxide in acetal solvents serves as basic reagent in the alkylation of certain esters by reactive halides. An interesting preparation of diethyl tetramethylsuccinate involves alkylation of ethyl isobutyrate with ethyl a-bromoisobutyrate. The yield is 30%. ... 

Reaction of a variety of unsaturated methyl ketones with relatively unhindered bromo esters in refluxing ether gave only 1,2-addition products (equation 21). A similar study in refluxing THF with the more hindered ethyl a-bromoisobutyrate gave exclusively 1,4-addition products however, the conditions of work-up were such that 1,2-addition products would not have been isolated (equation 22). ... 

Reactions of Reformatsky reagents with esters or with acid chlorides generally give only low yields of P-keto esters. Hauser reported that ethyl a-bromoisobutyrate could be acylated in reasonable yields with either the acid chlorides or the phenyl esters of aromatic acids, but the reaction fails with acylating... 

Reasonable reaction parameters for the ATRP were determined first by using styrene and the commercially available ethyl a-bromoisobutyrate (EBIB) followed by small-scale reactions with 4-fluorostyrene (< 1 g), before polymerizing larger quantities of expensive halogenated styrenes with the synthesized initiator HEBIB. Similarly, suitable reaction conditions for the ROP of lactide were tested using 1-pentanol as initiator instead of the synthesized macroinitiators. 

Ethyl a-bromoisobutyrate in anhydrous anisole added to a dry mixture of o-carb-ethoxyphenylacetonitrile, Zn, a little HgCla, and benzene, heated until the reaction starts, cooled to moderate it, and refluxed 1 hr. after the exothermic reaction has subsided "> 3-(l-carbethoxy-l-methylethyl)-l-oxo-l,2-dihydroisoquinoline. Y 1A%. F. e. s. L. and V. Arsenijecic, Bl. 1968, 3403. 

---