Chloroacetyl chloride, hydrolysis

Manufacture. Most chloroacetic acid is produced by the chlorination of acetic acid using a suitable catalyst such as acetic anhydride (9—12). The remainder is produced by the hydrolysis of trichloroethylene with sulfuric acid (13,14) or by reaction of chloroacetyl chloride with water. 

The structure of ( )-169 is determined to have a ( )-3a,3a -bispyrrolo[2,3-(j] indole skeleton by carrying out X-ray single crystallographic analysis of its derivative 252 (99H1237). Compound 252 is obtained from ( )-169 by the following sequence of reactions (1) alkaline hydrolysis of ( )-169 to 249 (88%), (2) conversion of 249 to 251 (71%) by treatment with NaH and chloroacetyl chloride, (3) substitution of chlorine on the chloroacetyl group for acetate 252 (93%) by the reaction with NaOAc. 

The electrophilic ring opening of iV-allyl HHT 53 with chloroacetyl chloride gave N-allyl- -chloromethyl-a-chloroacetamide 54, which was then alkylated with the diethyl ester of a-aminomethylphosphonic acid (AMPA) to generate the imidazolone 55. Subsequent hydrolysis of 55 gave GLYH3 (57). 

Synthesis (Moser et al., 1990) acylation of A/-phenyl-2,6-dichloroaniline with chloroacetyl chloride gives the corresponding chloroacetanilide, which is fused with aluminum chloride to give 1-(2,6-dichlorophenyl)-2-indolinone. Hydrolysis of the indolinone with dilute aqueous-alcoholic sodium hydroxide affords the desired sodium salt directly. 

The Friedel-Crafts acylation of acetanilide with chloroacetyl chloride yields l-acetamido-4-chloroacetylbenzene. The trimethylammonium group is introduced by reaction with trimethylamine, followed by hydrolysis of the acetamide group. This diazo component is a constituent of numerous yellow, orange, and red cationic azo dyes. Using diethyl- m-toluidine as the coupling component, the lightfast red dye 35 [67905-12-8] is obtained [99],... 

In a 5-1. three-necked flask mounted on a steam bath in the hood and equipped with a mechanical stirrer (Note 1) and a wide-bore condenser (Note 1) is placed 1.4 kg. (I.l I.) of carbon disulfide. Through the open neck of the flask 202 g. (1.5 moles) of acetanilide and 300 g. (2.66 moles) of chloroacetyl chloride (Note 2) are introduced. The mixture is vigorously stirred while 600 g. (4.5 moles) of aluminum chloride is added in 25-50-g. portions over a period of 20-30 minutes the neck of the flask is stoppered between additions (Note 3). After the addition of the last portion of aluminum chloride, the mixture is heated at reflux temperature for 30 minutes while stirring is continued. Heating and stirring are discontinued and the mixture is allowed to stand for 3 hours, during which time it separates into layers. The upper layer (carbon disulfide) is decanted, and the viscous red-brown louder layer is poured cautiously with stirring into about 1 kg. of finely crushed ice to which 100 ml. of concentrated hydrochloric acid has been added. After the hydrolysis of the aluminum chloride, the product crystallizes as a white solid, which is collected on a Buchner funnel and washed well with water. It is then trans-... 

The general approach was a base catalyzed condensation of the diketopiperazine with an aldehyde, followed by hydrogenation and hydrolysis. The glycine-L-aspartic acid diketopiperazine ester (5) can be prepared by standard peptide coupling procedures, but our preferred method at scale is to prepare the glycine unit from chloroacetyl chloride and ammonia (Scheme 11). 

PROBABLE FATE photolysis-, information lacking, photodissociation to chloroacetyl chloride in stratosphere is predicted oxidation-, photooxidation in troposphere may be the predominant fate, photooxidation in aquatic environments probably occurs at a slow rate hydrolysis-. unimportant compared to volatilization volatilization due to high vapor pressure, volatilization to the atmosphere should be the major transport process, if released in water, will be removed by volatilization with a half-life of 6-9 days, 5-8 days, and 23-32 hr, in a typical pond, lake, or river respectively, will be removed quickly by volatilization if released on land biological processes data is lacking, bioaccumulation not expected, biodegradation may be possible evaporation from water 25°C of 1 ppm solution 50% after 22 min, 90% after 109 min. 

PROBABLE FATE photolysis-, direct photolysis is not significant, photodissociation in stratosphere to chloroacetyl chloride oxidation photooxidation in water expected to be slow primarily removed in air by photooxidation degraded in atmosphere by reaction with hydroxyl radicals, half-life of 1 month and 1.9% loss/12 hr sunlit day products of photooxidation CO and HCl oxidation half-life 1.5 weeks-4 months hydrolysis not significant first-order hydrolytic half-life 1.1 yr volatilization high vapor pressure causes rapid volatilization, major transport process, half-life 30 min 25°C evaporation primary removal from water half-life from 1 ppm solution 25°C, still air, and an avg. depth of 6.5 cm 28 min., evaporation from water 25 °C of 1 ppm solution 50% after 29 min. and 90% after 96 min. 

DFT studies of the hydrolysis of acetyl and chloroacetyl chloride and of variously substituted benzoyl chlorides supported an S 2 mechanism. An extended Grunwald-Winstein equation correlation for the specific rates of solvolysis of 3,4,5-trimethoxybenzoyl chloride gave sensitivities towards changes in solvent nucleophilic-ity (/-value) of 0.29 and solvent ionizing power (m-value) of 0.54. The low m-value allowed specific rates to be determined in highly ionizing fiuoroalcohol/H20 mixtures. A parallel correlation of the specific rates of solvolysis of 2,4,6-trichlorobenzoyl chloride revealed that solvolyses in 100% and 90% ethanol or methanol did not appreciably follow the ionization pathway indicated for solvolyses in the other solvents and it was proposed that, despite the two or//to-substituents, the addition-elimination pathway had become dominant. ... 

The N-monosubstituted oxamic acids were converted to free amines with diphenylcarbodiimide. Treatment of 458 with this reagent in methylene chloride (0°C, 1 hr) produced 7a-methoxyamine 462. After acylation with chloroacetyl chloride (A,N-dimethylaniline, 25 C, 16 hr) amide 463 was isolated in 40% yield. Substance 458 reacts with dicyclohexylcar-bodiimide in a different and unfavorable manner to form imidazolidinone 464 (36%) and amidine 465 (6%). Hydrolysis of the former with p-TSA gave dicyclohexylimidazolidinetrione and 7-oxocephem methyl ester (466). 

Synthesis of 210 was started from preparation of chiral diamine 211 (Scheme 50) [172], In particular, D-serine methyl ester was converted to iV-benzyl derivative 212, which was transformed into carboxylic acid 212 using reaction with chloroacetyl chloride and subsequent hydrolysis. Carboxylic acid 212 was subjected to coupling with benzyl amine, reduction, reaction with ethyl oxalyl chloride and reductive cyclization to give bicyclic compound 213. Finally, 211 Two-step reduction of 213 led to the formation of diamine 211, which was isolated as dihydrochloride. Reaction of 211 with dichloro derivative 215 and then - hydrazine hydrate gave the product 216, which was coupled with carboxylic acid 217 and subjected to catalytic hydrogenation to give 210. 

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