Acid chlorides oximes, preparation from

This method is an adaptation of that of Dengel. -Methoxy-phenylacetonitrile can also be prepared by the metathetical reaction of anisyl chloride with alkali cyanides in a variety of aqueous solvent mixtures by the nitration of phenylaceto-nitrile, followed by reduction, diazotization, hydrolysis, and methylation 1 by the reduction of ct-benzoxy- -methoxy-phenylacetonitrile (prepared from anisaldehyde, sodium cyanide, and benzoyl chloride) and by the reaction of acetic anhydride with the oxime of -methoxyphenylpyruvic acid. ... 

Toluenesulfonic anhydride has been prepared from the acid by the use of thionyl chloride and phosphorus pentoxide. It has also been obtained by heating oxime -toluenesulfonates, by reaction of -toluenesulfonic acid with di- -tolylcarbodiimide, and by the interaction of methoxyacetylene and -toluenesul-fonic acid. ... 

Chlorophenyl)-5-(4-methoxyphenyl)isoxazole has also been prepared from the dilithio derivative of 4-ehloroacetophenone oxime by two other methods (a) reaction with anisonitrile (4-methoxybenzoni-trile) followed by acid-catalyzed cyclization8 and (b) condensation of anisolyl chloride (4-methoxybenzoyl chloride) followed by acid-catalyzed cyclization. ... 

The incorporation of complex side chains at the 7 position based on alkyloximes of 2-amino-thiazole-5-gyloxylamides has provided drugs with very wide antibacterial activity that extend to hitherto resistant species such as pseudomonas. The preparation of one of the simpler side chains involves, first, the formation of the methyl ether from the oxime obtained by the nitrosation of methyl acetoacetate. Chlorination of the product, for example with sulfuryl chloride, gives the intermediate (21-1). The aminothiazole ring is then formed by reaction of that with thiourea to give (21-2). The free acid (21-3) is obtained by saponification of the product. The protected acid chloride (21-5) is obtained by sequential acylation of the amino group with chloroacetyl chloride and then reaction with thionyl chloride. 

Recently, it has been shown that acyl chlorides may be prepared from cyanuric chloride and carboxylic acids (79TL3037). Cyanuric chloride is also valuable for effecting the formation of macrocyclic lactones (Scheme 44) (80TL1893). Similarly, aryl oximes may be converted to... 

Thus the 3-substituted isoquinolinium iodide 64, prepared from deoxypi-peroin 20 via the oxime 62 and the amine 63 as outlined in Scheme 11, was treated with an excess of ethereal diazomethane. When the resulting crude aziridinium iodide 65 in 6 iVhydrochloric acid was kept at room temperature for 1 week, ( )-reframidine (27) was isolated in 20% yield. Reframi ne was also formed, in 35% yield, when the 3-benzazepine 67, obtained in 20% yield by refluxing the crude aziridinium iodide 65 with 1% methanolic hydrogen chloride, was treated with 6 iVhydrochloric acid at ambient temperature for 1 week. 

The oxime 7, prepared from salicyl aldehyde, is converted with iV-chlorosuccinimide into the hydrox-amic acid chloride 8. From this, the nitrile oxide is obtained with KHCO3, which reacts regioselec-tively with styrene to give the 3,5-diaryl-4,5-dihydroisoxazole 9. Catalytic hydrogenation leads to the y -hydroxy ketone 10, which on acid-catalysed cyclodehydration gives the flavanone 11. 

A range of 0-alkyl thiazolethiones such as (44) have been prepared from 4-chloroacetophenone. Bromination of 4-chloroacetophenone and reaction with hydroxylamine hydrochloride afforded the bromo oxime (42). (42) is then treated with potassium ethyl xanthate and oximino dithiocarbonate, followed by zinc chloride to afford the thiohydroxamic acid (43), which is then alkylated to give (44). These derivatives are a useful source of alkoxy radicals eg, photolysis of (44) leads to the alkoxy radical (45) <97SL848>. 

Amides can be easily prepared under mild conditions from acid chlorides with ammonium acetate and from oximes by a mild modification of the Beckmann rearrangement Lactams can be prepared by this method from cyclic oximes. and 7-Lactams have been synthesized in a simple manner from aminomalonates a-Aminoacids can be converted into a-ketoacids and related compounds through 2-trifluoromethyl-5-oxazolones... 

In the preparation of tetrazoles from oximes, monosubstituted amides, and amidoximes the use of acid chlorides such as thionyl chloride, ben-zenesulfonyl chloride, or phosphorus chlorides transforms the compounds into imide chlorides, which then yield tetrazoles upon treatment with sodimn azide. ... 

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