Acetanilide, a-BENZOYL

Acetal formation from pentaerythritol and benzaldehyde, 38, 65 Acetamide, 31, 17 Acetamide, N-bromo, 31,17 a-PHENYL-, 32, 92 Acetanilide, cz-benzoyl-, 37, 2 a -ben zoyl-2-mcth oxy-4-ni tro, 37, 4 Acetic acid, benzoyl-, ethyl ester, 37, 3, 32... 

Friedel-Crafts allq lations and acylations ofA -aiylamides also proceed normally. For example, benzoylation of acetanilide (A/-acetylaniline) under Friedel-Crafts conditions gives 4-aminobenzophenone in 80 yield after hydrolysis ... 

Yellow Couplers. The most important classes of yeHow dye-forming couplers are derived from P-ketocarboxamides, speciftcaHy the benzoyl acetanilides (6) (66) and the pi val oyl a ceta n il i des (7) (67). Substituents Y and Z can be used to attach baHasting or solubilization groups as weH as to alter the reactivity of the coupler and the hue of the resulting dyes. Typical coupling-off groups (X) cited in the Hterature are also shown. 

The relatively low pX values seen for the benzoyl acetanilides, especiaHy as two-equivalent couplers, minimize concerns over slow ionization rates and contribute to the couplers overaH reactivity. But this same property often results in slow reprotonation in the acidic bleach, where developer carried over from the previous step can be oxidized and react with the stiH ionized coupler to produce unwanted dye in a nonimage related fashion. This problem can be eliminated by an acidic stop bath between the developer and the bleach steps or minimized by careful choice of coupling-off group, coupler solvent, or dispersion additives. 

The lack of a second aryl group flanking the active methylene site, however, means that the pX values of the pi val oyl a ceta n il i des tend to be considerably higher than those of the benzoyl acetanilides. As a result, these couplers are rarely used as thek four-equivalent parents. Rather, the coupling... 

Substituted amides suffer hydrolysis with greater difficulty. The choice of an acid or an alkaline medium vill depend upon (a) the solubility of the compound in the medium and (b) the effect of the reagent upon the products of hydrolysis. Substituted amides of comparatively low molecular weight (e.g., acetanilide) may be hydrolysed by boiling either with 10 per cent, sodium hydroxide solution or with 10 per cent, sulphuric acid for 2-3 hours. Other substituted amides are so insoluble in water that little reaction occurs when they are refluxed with dilute acid or dilute alkali for several hours. These include such substances as benzanilide (C(H(CONHC,Hg) and the benzoyl derivative of a naphthylamine (C.HjCONHCioH,) or a toluidine (C gCONHCjH,). For these substances satisfactory results may be obtained with 70 per cent, sulphuric acid this hydrolysis medium is a much better solvent for the substituted amide than is water or more dilute acid it also permits a higher reaction temperature (compare Section IV 192) ... 

This reaction has been applied to a great number of carbonyl compounds, e.g., cyclopentanone,27 1,3-cyclohexanedione,36 5,5-dimethyl-l,3-cyclohexanedione,S5 1-acenaphthenone,24,25 1,3-indane-dione,35 1,3-phenalanedione,85 86 sodium salts of 3-aryl-3-oxo-propanals,39 2,3-dihydrobenzo[6]thiophen-3-one,40 sodium benzoyl-acetate,41 benzoylacetonitrile,29 30,88 ethyl cyanoacetate,30 35 cyano-acetanilide,30 barbituric acid,35 rhodanine,35 jV-phenylrhodanine,37 and iV-methylenebenzothiazoline.37... 

Idemify and account for the producl(s) expected from each of the following reactions (a) benzene + benzoyl chloride + AlCI (b) acetanilide + nitric acid + sulfuric acid (c) bromobeiizene + sulfuric acid (d) l-melhoxy-2-nitrobenzene + nitric acid + sulfuric acid (e) (trif1 uoromethyI)benzene + Bi + Fe powder. 

A very efficient cyclization of o-acyl-cu-substituted acetanilides is effected by heating them with a base the cu-substituent should be electron-withdrawing. Suitably positioned acetyl and benzoyl functions undergo an aldol condensation alumina as a base gave better results than potassium carbonate. 

To a solution of 14.5 g of 2-bromo-2 -(2-chlorobenzoyl)acetanilide in 100 ml of tetrahy-drofuran, an excess of liquid ammonia (ca 150 ml) was added, The ammonia was kept refluxing with a dry-ice condenser for 3 hours after which time the ammonia was allowed to evaporate and the solution was poured into water. Crystals of 2-amino-2 -(2-chloro-benzoyl)acetanilide were collected, which after recrystallization from ethanol melted at 162 to 164 C. 

Early publications on [VO(/3-diketonato)2] have been reviewed. More recently, complexes with benzoyl m-nitroacetanilide, benzoyl acetanilide and l,l -(l,3-phenylene)-bis(butane-1,3-dione have been synthesized. Other [VO(jS-dik)2] adducts have been isolated, for example [VO(acac)2] adducts with a series of pyridine AT-oxides and several pyridine carboxamides, and [VO(bzac)2] adducts with pyridine, methylamine, isoquinoline and 4-picoline. Equilibrium constants of 1 1 and 2 1 adducts of pyrazine with [VO(tfacac)2] have been determined (equation 38). ° In the 2 1 complex, the pyrazine bridge between two equatorial sites of adjacent vanadium atoms promotes a weak exchange interaction. The nitroxide radical 2,2,6,6-tetramethylpiperidinyl iV-oxide also forms an adduct with [VO(hfacac)2] in which there is a strong interaction between the electrons on the metal and nitroxide. ... 

A,A-Dialkyl-benzoylacetamides and -acetoacetamides and iV-benzoyl acetanilide underwent photocyclization involving S-hydrogen abstraction by the ketone carbonyl group to give high yields of N-substituted 4-hydroxypyrrolid-2-ones (Scheme 75).i 9... 

In 2008, Fagnou et al. reported that acetanilide couples with alkynes in the presence of a Cp Rh catalyst and a copper salt oxidant through ortho C—H bond cleavage to produce Al-acetylindole derivatives [Eq. (a) in Scheme 25.36] [28a]. In contrast, the authors found that benzanilide, which possesses two types of cleavable ortho C—H bonds on anilino and benzoyl moieties, undergoes annulation accompanied by the selective cleavage of the benzoyl C—H bond to give isoquinolinone derivatives [Eq. b] [20]. 

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