Butyl chloroacetate ether

Butyl alcohol in synthesis of phenyl 1-butyl ether, 46, 89 1-Butyl azidoacetate, 46, 47 hydrogenation of, 46, 47 1-Butyl chloroacetate, reaction with sodium azide, 46, 47 lre l-4-i-BUTYLCYCLOHEXANOL, 47,16 4-(-Butylcyclohexanonc, reduction with lithium aluminum hydride and aluminum chloride, 47, 17 1-Butyl hypochlorite, reaction with cy-clohexylamine, 46,17 l-Butylthiourea, 46, 72... 

A" 0-Butenolide, 46, 22 /-Butyl alcohol, in synthesis of phenyl /-butyl ether, 45, 89 reaction with sodium cyanate and trifluoroacetic acid, 48, 32 /-Butyl azidoacctatc, 46, 47 hydrogenation of, 45, 47 /-Butyl carbamate, 48,32 /-Butyl chloroacetate, reaction with sodium azide, 45, 47 /ra S-4-/-BuTYI,CYCLOHEXANOL, 47,16... 

These stereochemical results obtained by Bachelor and Bansal, using r-butyl alcohol as solvent, differ from those observed in a study using hexamethylphosphoramide (HMPA). In a subsequent paper, it is suggested that the differences must be attributed to differences in the degree of reversibility of the aldol step in the two solvents when irreversible aldolization is ensured (by appropriate modification of reaction conditions), the stereochemical results obtained in HMPA, ether and r-butyl alcohol/ether are essentially the same. - In HMPA, it was found that this condition is reached at ambient temperature, however in r-butanol/ether the aldol step has a significant component of reversibility above -40 C. Similar observations have been reported by Villieras and Combret in a study of the condensation of isobuty-raldehyde with alkyl chloroacetates (equation 7). The results of this study are summarized in Table 2. The results at room temperature are similar to those shown in Table 1 the ratio of c -epoxide increases as the size of the ester substituent increases. However, at low temperature the corresponding ratios of... 

Silver fluoborate, reaction with ethyl bromide in ether, 46, 114 Silver nitrate, complexing with phenyl-acetylene, 46, 40 Silver oxide, 46, 83 Silver thiocyanate, 46, 71 Sodium azide, reaction with f-butyl chloroacetate, 46, 47 reaction with diazonium salt from fi-amino-/> -nitrobiphenyl, 46,... 

A. t-Butyl azidoacetate. In a 300-ml. round-bottomed flask fitted with a reflux condenser are placed 30 g. (0.2 mole) of (-butyl chloroacetate (Note 1), 24 g. (0.37 mole) of sodium azide, and 90 ml. of 60% (v./v.) acetone-water. The heterogeneous mixture (two liquid phases and a solid phase) is heated under reflux on a steam bath for 18 hours, the acetone distilled, and IS ml. of water added (Note 2). The mixture is transferred to a separatory funnel, the layers separated, and the lower aqueous layer extracted twice with 25-ml. portions of ether. The ethereal extracts are added to the original upper layer, and the solution is dried over anhydrous sodium sulfate. The ether is distilled, and the residual oil is fractionated under reduced pressure (Note 3), the fraction boiling from 33-41° (1 mm.) being collected yield 29 g. (92%), m20d 1.4356 (Note 4). 

To 50 ml. of a well-cooled 6N sodium hydroxide solution is added, with stirring, 32 g. (0.15 mole) of the phosphite salt. The stirring is continued until all the solid has dissolved. The solution is transferred to a 125-ml. separatory funnel, extracted with three 20-ml. portions of ether, and the combined extracts dried over anhydrous sodium sulfate. The drying agent is removed by filtration, the solvent removed under reduced pressure, and the glycine 1-butyl ester distilled, b.p. 65-67° (20 mm.), ft20d 1.4237, yield 14 g. (72%, based on phosphite salt). The overall yield from 1-butyl chloroacetate is 50-55%. 

The THF supernatant was removed from a botUe of Rieke Zn and washed 3 times with anhydrous diethyl ether. A 250 ml round-bottomed flask, under Ar, was charged with 50 ml of this Rieke Zn solution (5 g at 0.1 g/ml 76.5 mmol) in diethyl ether. The flask was cooled to 0 C using an ice water bath. The tert-butyl-chloroacetate was added dropwise over 10 min. The temperature was... 

A 100-mL sample aliquot adjusted to pH 11.5 sample extracted with methyl tert-butyl ether (MTBE) chloroacetic acid partitions into aqueous phase basic and neutral compounds in MTBE phase discarded the aqueous phase now adjusted to pH 0.5 and extracted again with MTBE the MTBE extract dried and concentrated chloroacetic acid in the MTBE extract esterified with diazomethane the methyl ester determined by capillary GC on an ECD (U.S. EPA Method 552, 1990). 

The above illustrated crosslinking reactions of homopolymers, however, form elastomers with poor aging properties. Commercial acrylic rubbers are therefore copolymers of ethyl or butyl acrylate with small quantities of comonomers that carry special functional groups for crosslinking. Such comonomers are 2-chloroethylvinyl ether or vinyl chloroacetate, used in small quantities (about 5%). These copolymers crosslink through reactions with polyamines. 

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