M-Nitroacetanilide

Problem 18.49 Outline the steps in the syntheses of the following compounds from C H, C HjCH, and any readily available aliphatic compound (a) p-aminobenzoic acid, (b) m-nitroacetanilide, (c) 1-amino-l-phenyl-propane, (d) 4-amino-2-chlorotoluene. M... 

Early publications on [VO(/3-diketonato)2] have been reviewed.355 More recently, complexes with benzoyl m-nitroacetanilide, benzoyl acetanilide545 and l,l -(l,3-phenylene)-bis(butane-1,3-dione546 have been synthesized. Other [VO(/S-dik)2] adducts have been isolated, for example [VO(acac)2] adducts with a series of pyridine N-oxides547 and several pyridine carboxamides, 48 and [VO(bzac)2] adducts with pyridine, methylamine, isoquinoline and 4-picoline.549 Equilibrium constants of 1 1 and 2 1 adducts of pyrazine with [VO(tfacac)2] have been determined (equation 38).550 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 N-oxide also forms an adduct with [VO(hfacac)2] in which there is a strong interaction between the electrons on the metal and nitroxide.551... 

The nitrosation is carried out by passing nitrous fumes into an ice-cold solution or suspension of the acetylamine in acetic acid and acetic anhydride, or by adding a solution of nitrosyl chloride to the acetylamine and sodium acetate in acetic acid. The nitroso derivative is precipitated by pouring the solution into ice water and is extracted by the aromatic liquid or filtered and added to the liquid with which it reacts. In the example given, 3-nitrobiphenyl is obtained from m-nitroacetanilide in 83% yield. 

Vorozhtsov [21] referred to the nitration of m- nitroacetanilide (XIV) as an example of inconsistency between the results obtained and predicted, viz. ... 

The procedure described for the preparation of l-(ra-nitro-phenyl)-3,3-dimethyltriazene is the method of Elks and Hey,2 and the preparation of m-nitrobiphenyl is also a modification of their procedure. The other principal methods for the preparation of m-nitrobiphenyl are the decomposition of N-nitroso-m-nitroacetanilide in benzene 3 and the decomposition of alkaline w-nitrobenzenediazohydroxide in benzene.4 Other methods that have been reported include the decomposition of potassium m-nitrobenzenediazotate in benzene with acetyl chloride,6 the decomposition of m-nitrobenzoyl peroxide in boiling benzene,6 the decomposition of benzenediazonium borofluoride in nitrobenzene 7 at 70°, and the reduction of 4-(3 -nitrophenyl) -benzenediazonium acid sulfate in boiling ethanol.8... 

---