Nitro derivatives of diphenyl

Diphenyl is nitrated with nitric acid in the presence of acetic acid to form a mixture of mononitro derivatives  

By boiling with nitric acid (98%) or with a mixture of nitric (77%) and sulphuric acids, diphenyl yields a mixture of 2,4 - and 4,4 -dinitrodiphenyl  

By direct nitration no more than four nitro groups can be introduced into diphenyl, 2,4,2 ,4 -tetranitrodiphenyl being formed (Losanitsch [36] Ulhnann and Bielecki [37]). 

Nowadays the compound is not used in the explosives industry since its explosive power is only slightly higher than that of dinitrobenzene, while on the other hand its melting point is too high, and diphenyl, the raw material for its manufacture, is available only in small quantities. 

The compound may be obtained by Ullmann and Bielecki s [37] method, which consists in heating picryl chloride with copper powder in a high boiling solvent like nitrobenzene, toluene or xylene. 

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NOTE No higher nitro derivs of Diphenyl-tetrazole were found in the literature thru 1°66... 

Nitro derivatives of benzene Nitro derivatives of diphenyl... 

Jackson-Meisenheimer complexes can serve in obtaining nitro derivatives of diphenyl. An original approach to this type of reaction was given by Wenner-ttrom [52]. He reacted a derivative of phenylsUver with 1,3,5-trinitrobenzene in the presence of pyridine. The oxidation of the o-complex yielded compound VI. 

The harsh conditions needed to introduce five or more nitro groups into diphenyl ether lead to the destruction of the aromatic ring. Highly nitrated derivatives of diphenyl ether can be prepared by an indirect route 2,2, 4,4, 6-pentanitrodiphenyl ether (92) is the product from the controlled nitration of (91), which is obtained from the reaction of picryl chloride (87) with sodium o-nitrophenolate. ... 

A study was made of the ultraviolet spectra of benzene, alkyl-, amino-, and nitro-derivatives of benzene, diphenyl-amine, triphenylmethane, triphenylcarbinol, and anthra-quinone adsorbed on zeolites with alkali exchange cations, on Ca- and Cu-zeolites, and on decationized zeolites. The spectra of molecules adsorbed on zeolites totally cationized with alkali cations show only absorption bands caused by molecular adsorption. The spectra of aniline, pyridine, triphenylcarbinol, and anthraquinone adsorbed on decationized zeolite and Ca-zeolite are characterized by absorption of the corresponding compounds in the ionized state. The absorption bands of ionized benzene and cumene molecules appear only after uv-excitation of the adsorbed molecules. The concentration of carbonium ions produced during adsorption of triphenylcarbinol on Ca-zeolite and on the decationized zeolite depends on the degree of dehydroxyla-tion of the zeolite. 

Polynitro derivatives of diphensi ether Pen t a ni trod i phenyl ether Hexanitrodiphenyl ether Nitro derivatives of various phenolic ethers Hexanitro diphenyl sulphide Hexanitrodiphenyl sulphone Literature... 

Niiro derivatives of mesitvlene Nitro derivatives of ethylbenzene Nilrosolvem-naphthi Hexanitrostilbene Niiro derivatives of diphenyl Nitration of mixtures Nitre derivatives of polymers Literature... 

ArN-NCRNNHAr by M. Ragno S. Bruno who prepd various nitro derivs [Gazz Chimltal 76, 485—99(1946) and CA 41, 6542(1947)]. For instance, the compd PhN=NC(CN)= NNHPh may be called N,N -Diphenyl-C-cyano formazan or N, N7-Di phenyl-formazylcyanide. Some of the formazan or formazyl derivs give expl salts while others form tetrazoles or other ring compds Note C Metby I formazan is called Acetazidin or Azidin in Beil 2, 4, but the name azidin has been suggested for the radical NgC(—)=NH, which is entirely different... 

Heating diethyl (l-isoquinolylamino)methylenemalonates in diphenyl ether gave ethyl 4-oxo-4//-pyrimido[2,l-a]isoquinoline-3-carboxylates (97) (78USP4127720). Cyclization of diethyl[(4-amino-l-isoquinolyl)amino] methylenemalonate in a mixture of acetic anhydride and pyridine in methylene chloride at ambient temperature afforded ethyl 7-acetylamino-4-oxo-4//-pyrimido[2,l-a]isoquinoline-3-carboxylate [84JAP(K)84/172472]. The 7-nitro derivative was prepared similarly. Cyclization of diethyl [(7-methoxy-3-methyl-l-isoquinolyl)amino]methylenemalonate in polyphos-phoric acid at 130°C for 6 h gave 10-methoxy-6-methyl-4//-pyrimido[2,l-a]isoquinolin-4-one in 29% yield [94IJC(B)795]. 

The nitration of 1,2,3,5-tetraphenylpyrrole, using nitric acid acetic acid, gives the 4-nitro derivative (66MI1) as does 1-methyl-2,5-diphenyl-3-(2-pyridyl)pyrrole (9). The action of fuming nitric acid at 0°C on ethyl... 

The nitration of l,2-diphenyl-3,5-dioxopyrazolidine with mixed acid at 0°C gives the 4-nitro derivative, whereas sulfonation (20% oleum) results in both 4- and phenyl substitution to form 4-sulfo-l,2-bis (4-sulfophenyl)-3,5-dioxopyrazolidine (58ZOB3027). 

In the nitration of 2,5-diphenyl-3-pyrryl-3, 51-dimethyl (or diphenyl)-4-isoxazolylketone (52), the only reaction that is detected is the formation of the 4-nitro derivatives (53a,b)(77JHC 1021). 

Nitrations of phenyl derivatives of small ring heterocycles have been little studied. The nitration of 3-(4-nitrophenyI)-l-phenyl-2,2-dichloroaziri-dine (90) using potassium nitrate in sulfuric and acetic acids yields 1,3-bis(4-nitrophenyl)-2,2-dichloroaziridine and 3-(4-nitrophenyl)-l-(2-nitro-phenyl)-2,2-dichloroaziridine in 65 35 ratio. Under the same conditions the diphenyl derivative undergoes cleavage of the aziridine ring to give a mixture of nitrated anilides. 

Diphenyl-diacetylene is the parent hydi ocarhon of indigo blue, and the dye itself can be prepared by means of tliis reaction, starting with o-nitro-phenyl-propiolic acid. By loss of carbon dioxide the acid becomes o-nitro-phenyl-acetylene, the copper derivative of which passes to di-ortho-nitrophenyl-diacety-lene ... 

Diphenyl-4-nitrosoimidazole is oxidized by amyl nitrate to the corresponding 4-nitro derivative [592], An unusual reaction is observed when 4,5-diphenylim-idazole and 2-bromo-4,5-diphenylimidazole are boiled with amyl nitrite. Instead of nitrosation the substrate undergoes nitration with the formation of 2-nitro-4,5-di-phenylimidazole [593] (Scheme 115). 

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