Bromopropionyl. Chloride

A mixture of 20 g. (0.13 mole) of /J-bromopropionic acid [Org. Syntheses Coll. Vol. 1, 131 (1941)] and 10 ml. of phosphorus trichloride is refluxed for 5 hours. Distillation of the mixture gives 19.6 g. (80%) of pale, straw-colored acid chloride boiling at 65-70°/25-30 mm. 

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To a solution of 17.2g (0.10 mol) of 3-bromopropionyl chloride in 100 ml of anhydrous benzene was added dropwise with stirring a solution of 8.6 g (0.10 mol) of anhydrous piperazine in 20 ml of dry chloroform over a period of 30 minutes. The temperature rose spontaneously to 45°C during the addition. After the temperature ceased to rise, stirring was continued for another hour. The reaction mixture was then filtered to remove the piperazine hydrochloride by-product. The filtrate was evaporated to dryness and the residue recrystallized from ethanol to obtain the desired N,N -bis-(3-bromopropionyl) piperazine as a white crystalline sol id melting at 103°C to 104°C. The identity of the product was further established by elemental analysis. 

Bromopropionyl chloride (tech) was purchased from the Aldrich Chemical Company, Inc., and distilled prior to use. 

Bromopropionyl chloride Propionyl chloride, 3-bromo- (8) Propanoyl chloride, 3-bromo- (9) 15486-96-1)... 

B. Acryloyl-2-oxazolidinone (Note 8). A flame-dried, 1 -L, one-necked, round-bottomed flask, equipped with a magnetic stirring bar, is charged with 8.71 g (100 mmol) of 2-oxazolidinone (Note 3), flushed with argon (Note 9), and then 500 mL of tetrahydrofuran (Note 10) is introduced. The mixture is stirred to dissolve solids, cooled to 0°C, and 33.3 mL (100 mmol) of 3 M methylmagnesium bromide in ether (Note 3) is slowly added. After the solution is stirred for 10 min at 0°C, 11.6 mL (115 mmol) of 3-bromopropionyl chloride (Note 11) is added dropwise. The cooling bath is removed and the mixture is allowed to warm to ambient temperature over 30 min. The mixture is diluted with 600 mL of peroxide-free ether (Note 12) and washed with... 

Chloroacetyl chloride and 2-bromoacetyl bromide N-acylated without a catalyst but 2-chloroacetic anhydride required concentrated sulfuric acid. ° 3-Chloro- and 3-bromopropionyl chlorides 9-acyl-ated without a catalyst as did cinnamoyl chloride " and phosgene, the last producing 9-chloroformyIcarbazole. ... 

No resolvable separation of the signals of the diastereomers formed from reaction of the amino acid with (5)-2-bromopropionyl chloride or Mosher s acid chloride are observed. However, with common amino acids, the latter reagent can be successfully used under similar Schotten -Baumann conditions for the detection of differences in 19F spectra57. The a-alkylated amino acids are particularly challenging. However, by proper choice of solvent and signal, sufficient peak separation can be obtained. No measurable amount of kinetic resolution occurs during acylation of the acids. 

Flydroxyl-capped poly (ethylene-co-butylene), a so-called Kraton, was converted into a macroinitiator via esterification with 2-bromopropionyl chloride, and then employed for the block copolymerizations of styrene and />acetoxystyrene (B-116 and B-117).403 A similar method is utilized for B-l 18 to B-121 where the esterification is with 2-bromoisobutyroyl bromide.341 A commercially available polybutadiene is also employed for B-122 via a similar transformation into the chloroacetyl group.404... 

Other reductions. A mixed hydride of ratio 1 1 is superior to lithium aluminum hydride alone for the reduction of nitriles to amines. Unlike lithium aluminum hydride, the mixed reagent does not reduce nitro groups. Thus p-nitrobenzaldehyde is reduced by mixed hydride to p-nitrobenzyl alcohol in 75% yield. Whereas lithium aluminum hydride tends to remove halogen atoms, this reduction is retarded or prevented by the presence of aluminum chloride. Thus (8-bromopropionyl chloride is reduced by a 1 1 mixed hydride to 3-bromo-1-propanol in 77% yield in the absence of AlClj the yield is 44%. ... 

Bromopropanol-l, 598, 1232 Bromopropionic acid, 450,1118 (3-Bromopropionitrile, 77-78 Bromopropionyl chloride, 598 i9-Bromopropionyl isocyanate, 78... 

By the action of ammonia the chlorine atom is replaced by the amino group, and glycyl-alanine is formed. By condensing a-bromopropionyl chloride with glycine, and subsequent treatment with ammonia, alanyl-glycine is formed... 

Chloracetyl-chloride for the introduction of the glycyl radical. a-Bromopropionyl-chloride for the introduction of the alanyl radical. 

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