Chloro acetic acid amide

This compound is similar in type to the sodium acet-bromoamide, CHjCONNaBr, which is an intermediate compound in Hofmann s amine synthesis (p. 127). If a weak acid (such as acetic acid) is now added to the solution of the chloro-sodio-amide, the latter compound reacts with the hypo-chlorous acid giving the sulphon-dichloro amide, which being insoluble in water, rapidly separates ... 

A solution of 54 g (0.64 mol) of propyl isocyanate in 60 ml of anhydrous dimethylform-amide was added to a cold, well-stirred suspension of 81 g (0.42 mol) of dry p-chloro-benzenesulfonamide in 210 ml of anhydrous triethylamine during the course of 20 to 30 minutes. The mildly exothermic reaction was completed by allowing it to stand at room temperature for about 5 hours. The reaction mixture was then slowly added to 3 liters of cold 20% acetic acid during the course of about one hour, constant agitation being maintained throughout the addition. 

The earliest oxidations were effected with nitrous fumes and later with mercuric oxide and isoamyl nitrite.74 Lead tetraacetate in acetic acid is in many cases the reagent of choice, but the removal of by-products can present some difficulties.75 IV-Haloimides and amides in alcoholic solutions have been reported to yield essentially pure tetrazolium salts76 and have been found specially useful in the preparation of heteroaryl-substituted tetrazolium salt.77,78 The novel formazans 49 have been successfully oxidized to 50 using 7V-chloro succinimide (Eq. II).79 tert-Butyl hypo-... 

Aromatic and aliphatic aldehydes have been prepared in good yields by the decarboxylation and isomerization of the corresponding glycidic acids. Esters of the latter are obtained by treating a ketone with ethyl chloro-acetate in the presence of sodium amide (method 127). The glycidic esters are first converted to the sodium salts with sodium ethoxide and then treated with aqueous hydrochloric acid under gentle reflux. By this procedure, a-phenylpropionaldehyde has been prepared from acetophenone in an over-all yield of 38%. Other details have been discussed. ... 

Chloro- and methyl-substituted acetic and propionic acids Amide, thioamide, and amidine herbicides Amides Ureas... 

More complex products are obtained from cyclizations in which the oxidizable functionality and the alkene are present in the same molecule. y9-Keto esters have been used extensively for Mn(III)-based oxidative cyclizations and react with Mn(OAc)3 at room temperature or slightly above [4, 10, 11, 15], They may be cyclic or acyclic and may be a-unsubstituted or may contain an a-alkyl or chloro substituent. Cycloalkanones are formed if the unsaturated chain is attached to the ketone. y-Lactones are formed from allylic acetoacetates [10, 11]. Less acidic /3-keto amides have recently been used for the formation of lactams or cycloalkanones [37]. Malonic esters have also been widely used and form radicals at 60-80 °C. Cycloalkanes are formed if an unsaturated chain is attached to the a-position. y-Lactones are formed from allylic malonates [10, 11]. yff-Diketones have been used with some success for cyclizations to both alkenes and aromatic rings [10, 11]. Other acidic carbonyl compounds such as fi-keto acids, /3-keto sulfoxides, j8-keto sulfones, and P-nitro ketones have seen limited use [10, 11]. We have recently found that oxidative cyclizations of unsaturated ketones can be carried out in high yield in acetic acid at 80 °C if the ketone selectively enolizes to one side and the product cannot enolize... 

It may be prepared by the diazotization and subsequent treatment with sulphur dioxide in glacial acetic acid in the presence of cupric chloride of 3-amino-4-chloro-benzophenone-2-carboxylic acid to yield 4-chloro-2 -carboxy-benzophenone-3-sulphonyl chloride. This on treatment with thionyl chloride followed by amidation in aqueous ethanol and finally with HCl gives crude chlortalidone which is recrystallized from aqeous ethanol. 

Michael addition of the (S nitroester 95 to the unsaturated ketone 96 gave a mixture of 97 and the (22S)-isomer (207, 208). Sodium borohydride reduction of 97 in an acidic medium afforded the nitrodiol 98 in excellent yield. Reduction of the nitro group and subsequent lactam formation (99) proceeded smoothly when the nitrodiol 96 was refluxed with zinc and acetic acid. Further reduction of the amide 99 with LAH yielded the piperidine 100, which was converted into its iV-chloro derivative. Treatment of this compound with sodium methoxide effected dehydrochlorination which was... 

Lanthanide bis(trifluoromethylsulfonyl)amides Ln[N(S02CF3)2] catalyse the acetylation of anisole by acetic anhydride in good yield with easy catalyst recovery. The Friedel-Crafts acetylation of (3-bromopropyl)benzene by acetyl chloride to form p-(3-bromopropyl)acetophenone together with a little of the 3-chloro analogue has been studied. The acylation of phenol by acetic acid has been subject to... 

The chemical transformations of the carboxyl group include formation of halo[ C]acetyl halides, amides, imides, alcohols, aldehydes and amines. Methods for the preparation of halo[ " C]acetyl halides from [ " C]acetic acid have already been mentioned. In addition, chloro[ " C]acetyl chloride has become available through treatment of chloro[ C]acetic acid with thionyl chloride or phthaloyl chloride, whereas for bromo[ " C]acetyl chloride, thionyl chloride or phosphorus pentachloride is recommended. Numerous applications of halol Clacetyl halides have been published, out of which the following C-, N- and 0-acylations may illustrate their versatility. 

A related agent, g1 icetanile sodium (42), is made b / a variant of this process. Methyl phenyl acetate is reacted with chlorosulfonic acid to give 38, which itself readily reacts with aminopyrimidine derivative 39 to give sulfonamide Saponification to acid 4 is followed by conversion to the acid chloride and amide formation with 5-chloro-2-methoxyaniline to complete the synthesis of the hypoglycemic agent glicetanile (42). ... 

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