Nitration Diphenylmethane

N 16.09% crysts (from glac acet acid or benz), mp 173—81°. It was prepd by nitrating diphenylmethane with nitric acid (d 1.53) S coticd sulfuric acid (Ref 1) and by decarboxylation of ethyl bis(2,4"dinitrophenyl-acetic acid (Ref 2). No expl props are reported... 

The first three of a series of papers by Ridd and co-workers on Inductive and Field effects in Aromatic Substitution have appeared. Results of studies of the nitration of 4-phenylp5nidine and of 4-benzylpyridine in aqueous sulphuric acid were reported and use of the usual criteria (para 8.2) showed that in each case the conjugate acid was the species undergoing nitration. The values of where fm refers to the corresponding homocyclic compound (biphenyl or diphenylmethane) when plotted against r, the distance between the... 

A suspension of sodium amide (0.275 mole) (Note 1) in liquid ammonia is prepared in the following manner in a 1-1. threenecked flask equipped with an air condenser (Note 2), a sealed mechanical stirrer, and a dropping funnel. Commercial anhydrous liquid ammonia (600 ml.) is introduced by pouring from an Erlenmeyer flask (Note 3). To the stirred liquid ammonia is added a small piece of sodium. After the appearance of a permanent blue color (Note 4) a few crystals of ferric nitrate hydrate (ica. 0.1 g.) are added, followed by small pieces of freshly cut sodium (Note 5) until 6.32 g. (0.275 g. atom) has been added. After all the sodium is converted to the amide (Note 6), 42.0 g. (0.250 mole) of diphenylmethane (Note 7) in 20 ml. of anhydrous ether is added (Note 8). The deep red suspension is stirred for 15 minutes. n-Butyl bromide (37.6 g., 0.274 mole) (Note 7) in... 

The conversion of methylene to carbonyl is especially easy when the group is flanked by two aromatic rings. Thus, diphenylmethane yields benzophenone on treatment with ceric ammonium nitrate [417, 422], selenium dioxide [509], and pyridinium chlorochromate [607. Manganese dioxide at 125 °C converts diphenylmethane into benzophenone, whereas at 211 °C, tetraphenylethylene is formed in 81% yield [814] (equation 176). 

Single-crystal X-ray structures have been reported for the following aryl- and heteroaryliodo-nium salts diphenyliodonium triiodide [412], (2-methylphenyl)(2-methoxyphenyl)iodonium chloride [413], (2-methoxy-5-methylphenyl)(4-methoxy-2-methylphenyl)iodonium trifluoroacetate [414], (2-methoxy-5-methylphenyl)(4-methoxyphenyl)iodonium trifluoroacetate [415], a complex of diphenyliodonium tetrafluoroborate with pyridine [416], a complex of diphenyliodonium tetrafluoroborate with 1,10-phenanthroline [417], a complex of diphenyliodonium tetrafluoroborate with 18-crown-6 [418], 1-naphthylphenyliodonium tetrafluoroborate [419], 3,10-dimethyl-10//-dibenzo[, e]iodinium tetrafluoroborate [420], aryl(pentafluorophenyl)iodonium tetrafluoroborates [421], 4,4 -[bis(phenyliodonium)]-diphenylmethane ditriflate [422], [bis(4-methoxyphenyl)](diethylaminocarbodithioato)iodine(in) [423], di(p-tolyl)iodonium bromide [424], diphenyliodonium chloride, bromide and iodide [425,426], diphenyliodonium nitrate [427], diphenyliodonium tetrafluoroborate [428], thienyl(phenyl)iodonium salts [401], (anft-dimethanoanthracenyl)phenyliodonium tosylate and hexafluorophosphate [429] and 3-mesityl-5-phenylisoxazol-4-yl(phenyl)iodonium p-toluenesulfonate [409]. 

Methyknediphenyldicarbamate-hzsed aromatic polycarbamate mixtures, useful for preparing polyurethanes, are prepared by nitration of diphenylmethane and reaction of the resulting dinitrodiphenylmethane-based mixtures with hydroxyl-containing organic compounds and carbon monoxide in presence of a catalyst [249]. 

---