Anilides addition reactions

Examples of the insertions of alkenes or alk5mes into metal-amido bonds are also rare. Examples of the insertions of alkenes into tihe M-N bonds of isolated amido complexes include the reaction of a rhodium anilide complex with alkenes to form imines witii kinetic behavior that is consistent with migratory insertion,and the formal insertion of the strongly electrophilic acrylonitrile into a platinum anilide. Additional examples include reactions of a lanthanide-amido complex generated in situ, a catalytic carboamination process in which the stereochemistry implies insertions of olefins into amides, and a catalytic hydroamination that appears to occur through an aminoalkyl complex generated by S3m addition of the iridium and amido groups across the C=C bond of norbomene. 

The first representatives of this group of compounds, 1,5-benzotelluroazepinones 57, have been prepared in 17% yield by the reaction between 2-iodopropyolanilides and NaHTe (98H631). The reaction proceeds, most probably, as nucleophilic substitution of the iodine, resulting in telluroles 58 and the subsequent nucleophilic addition of a hydrotelluride group to the triple bond. An alternative mechanism involving initial addition of NaTeH to the triple bond followed by the nucleophilic substitution of the iodine atom was mled out because the anilides PhNHCOC=CR do not react with NaTeH under the conditions at which the heterocycles 57 were obtained. Neither of the adducts PhNHCOCH=C(R)TeH or [PhNHCOCH=C(R)Te]2 was isolated. 

The pH is adjusted to 5.5 and the water phase separated and extracted with additional ether in order to remove the surplus dimethyl anilin. After addition of an excess of ammonia to the solution, the reaction product, N-methylpipecolic acid 2,6-dimethyl anilide, is recovered by extraction with isoamyl alcohol. The isoamyl alcohol solution is evaporated to dryness, the product dissolved in dilute hydrochloric acid, treated with charcoal and reprecipitated with NaOH. N-methylpipecolic acid 2,6-dimethyl anilide is obtained in crystalline form. 

One hundred seventy-seven grams (1 mole) of acetoacet-anilide 1 is added in small portions by means of a spatula to 185 ml. of concentrated sulfuric acid which has been heated previously to 75° (Note 1) in a 1-1. three-necked flask provided with a mechanical stirrer and a thermometer which extends into the liquid. The temperature of the mixture is maintained at 70-75° by intermittent cooling until nearly all the acetoacet-anilide has been added. The last 10-15 g. is added without cooling, and the temperature rises to 95° the addition requires 20-30 minutes. The heat of reaction maintains the temperature at 95° for about 15 minutes the reaction mixture is then kept an additional 15 minutes at 95° by external heating. After the solution has cooled to 65°, it is poured into 5 1. of water with vigorous stirring. 

Acidic work-up of 18 furnishes ketone 22. Further addition of HC1 and acetic acid at 70 °C results in cleavage of the pivaloyl anilide to yield the unprotected orf/io-ketoaniline as hydrochloride hydrate 5, since ketones with neighboring electron-withdrawing groups undergo nucleophilic addition of water. 5 directly crystallized from the reaction mixture and was obtained in 87 % yield with a purity of > 98 %. These three steps were carried out on a 3,700 g scale. 

The action of a Zn/Cu couple on 1,3-dibromo ketones and secondary amides yields 2-dialkylamino-1,3-dioxolanes (451 equation 208). Fluorosulfonic peracid anhydride adds to trifluoroacetonitrile to give an amide acetal (452 equation 209). In the addition of (Z)-2-butene-l,4-diol to trichloroacetoni-trile, catalyzed by sodium, the 1,3-dioxepin (453 equation 210) is produced. Bicyclic amide acetals (454 equation 211) are byproducts in the reaction of lactim ethers with diketene. TTie methyl esters of perfluorinated carboxylic acids react with diethanolamine to afford bicyclic amide acetals (455 equation 212). Heating of maleic anilides (456 equation 213) with acetic acid anhydride/sodium acetate gives heterocyclic compounds (457) containing an amide acetal structure. ... 

Analyzing the frequency factor v, Bursey43 was able to show that the details of the reaction mechanisms of the electron impact induced ketene elimination from ortho substituted phenyl acetates and from acetanilides, 36, are dramatically influenced by the nature of the substituent R = F, Cl, Br, J. The results demonstrate that the decrease of v going from the voluminous iodine to the small fluorine is not caused by steric effects (which should operate in an opposite direction) but is the result of an electronic interaction of both substituents, leading to a tighter transition state in the case of the more electronegative fluorine. Additional factors which are not yet completely understood play a decisive part in the fragmentation of the anilides. 

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