L-Methyl-2-nitrobenzene

Preparation 226.—o- and p-Nitrotoluenes (l-Methyl-2-nitrobenzene and 1 -methyl-i-nitrobenzene). 

Scheme 6.93. The formation of the nitronium ion (NO2 ) from nitric (HONO2) and snlfuric (H2SO4) acids in the presence of methylbenzene (tolnene [C6HSCH3]) and the snbseqnent reaction of N02" to prodnce l-methyl-2-nitrobenzene (orf/jo-nitrotolnene), l-methyl-4-nitrobenzene (para-nitrotolnene), and l-methyl-3-nitrobenzene (mefa-nitrotolnene). Using the curved arrow to indicate the movement of a pair of electrons (as nsual) there is a resonance form in which the positive charge is formally placed on the ring carbon bearing the methyl (CH3-) group for the first two. No such form can be written for the last.

Methyl-2-nitrobenzene, see 2-Nitrotoluene l-Methyl-3-nitrobenzene, see 3-Nitrotoluene... 

SYNS l-METHOXY-2-NITROBENZENE 2-METHOXYNITROBENZENE NCI-C60388 2-NITROANISOLE o-NITROPHENYL METHYL ETHER... 

It is a general rule that imidazoles and benzimidazoles are resistant to Friedel-Crafts reactions. This is not surprising since such basic compounds must be markedly deactivated in the presence of Lewis acids. Imidazolin-2-ones appear to be an exception and apparently possess sufficient activation to react. Reactions between imidazoles and Af-methylfor-manilide and phosphoryl chloride are also unproductive. With 4,5-diphenylimidazole, phenyl isocyanate at 80 °C gives products of both N- and C-substitution, but in boiling nitrobenzene only the latter (86) is formed. 2-Methyl-4-phenylimidazole gives (87) under the same conditions, and 1,3-diphenylimidazolium perchlorate is transformed by potassium t-butoxide into a ylide which reacts at C-2 with phenyl isothiocyanate. Sufficient activation is present in l-methyl-2-phenyl-4-phenylaminoimidazole for it to react by substitution at C-5 with acetic anhydride (71JOC3368). 

Tseng and colleagues [58] reported a three-step synthesis of fused tetrahydro-P-carbolinequinoxalinones, solely based on the use of ionic liquids as solvents. Tetrahydro-P-carboline is a central core for many biologically important indole alkaloids, and the moiety of quinoxalinone often exhibits a wide spectrum of biological activities such as being anti-HIV, antihypertensive, and a ligand for a number of protein receptors. As a first step, tryptophan methyl ester was reacted with an aldehyde to form tetrahydro-p-carboline by Pictet-Spengler cyclization that further reacted with l-fluoro-2-nitrobenzene to form iV-aryl-tetrahydro-P-carboline. Intramolecular cyclization upon a reduction reaction in step three provided the desired tetrahydro-P-carbolinequinoxalinones. The entire process was based on the use of 1-n-butyl-... 

Figure 2.7 shows several examples of [bis(acyloxy)iodo]arenes whose X-ray crystal structures have been reported in literature. These structures include the chiral diacetate 31 [191], p.-oxodiiodanyl diacetate 57 [117], A-tosyM-(diacetoxyiodo)pyrazole (58) [133], l,3,5,7-tetrakis[4-(diacetoxyiodo)phenyl]adamantane (59) [154], tetrakis[4-(diacetoxyiodo)phenyl]methane (60) [155], 3-[bis(trifluoroacetoxy)iodo]benzoic acid (61) [186], l-(diacetoxyiodo)-2-nitrobenzene (62) [94] and the chiral (diacetoxyiodo)arene 63 [165] derived from methyl lactate. 

Palladium catalyst foe partial ee DUCTION OF ACETYLENES, 46, 89 Palladium on charcoal, catalyst for reductive methylation of ethyl p-mtrophenylacetate, 47, 69 in reduction of l butyl azidoacetate to glycine J-butyl ester 4B, 47 Palladium oxide as catalyst for reduction of sodium 2 nitrobenzene sulfinate, 47, S... 

Other compounds containing a nitrobenzene unit like substituted benzamides145, azobenzenes146, iV - ben zy I i den can i I i n cs147 and donor-acceptor cyclophanes148 have been investigated by PES. The PE spectrum of l-methyl-3-nitro-2-phenylindole (68) has been measured130. 

An intramolecular hydrogen abstractions has also been claimed to occur from one methyl group of l,3,5-tri-ethyl-2-nitrobenzene. The photochemistry of o-nitro-fer<-butylbenzenes has been studied in some detail 42,48,52-60,62) ... 

Biological In an in vitro study, the soil fungi Fusarium oxysponim and Paecilomyces varioti degraded pendimethalin to W(l-ethylpropyl)-3,4-dimethyl-2-nitrobenzene-l,6-diamine and 3,4-di-methyl-2,6-dinitroaniline. The latter compound was the only metabolite identified by another soil fungus namely, Rhizoctonia bataticola (Singh and Kulshrestha, 1991). 

Gas chromatographic examination of another reaction mixture run on a 10-mmol scale with undecane as an internal standard indicates that 2-methyl-4 -nitrobipheny1 is formed in 90% yield based on l-bromo-4-nitrobenzene. The product obtained by this procedure shows the following properties mp 99-101 C (lit., mp 103-105°C) IR (neat) cm l 1600 (s), 1510 (s), 1480 (s), 1340 (s),... 

Although the preparation has been repeated, there have been no other reports of the type of reaction, (described in 1923) in which carbazole in the presence of excess potassium hydroxide and nitrobenzene at only 50°C gave a good yield of 9-(4-nitrophenyl)-carbazole, presumably via an adduct such as 43 subsequently oxidized by excess nitrobenzene and/or air. More recent examples of N-arylation of carbazoles have involved copper catalysis in reaction of aryl halides with carbazoles. Thus, copper bronze and potassium carbonate heated with the carbazole and the appropriate aromatic halide have produced 9-(4-methoxyphenyl)- and 9-(2-tolyl)carbazoles 9-(4-phenylphenyl)carbazole, l,4-di(carbazol-9-yl)benzene, 4,4 -di(carbazol-9-yl)biphenyl, and 9-(2-pyridyl)- and 9-(2-quinolyl)carbazoles 9-[2-(2-phenylphenyl)phenyl]- and 9-[2-(4-methylphenyl)phenyl] carbazoles 9-(3-bromo-6-nitrophenyl)-, 9-[3-(carbazol-9-yl]-, 9-(2-nitrophenyl)-, 9-(4-methyl-2-nitrophenyl)-, 9-(4-methoxycarbonyl)-l-nitro-, and l-nitro-9-(4-tolyl)carbazoles 9-(2-methoxycarbonylphenyl)carbazole 9-[2- 2-... 

Dinitrobenzene (5) has been converted to l-fluoro-3-nitrobenzene (6) with potassium fluoride in jV-methyl-2-pyrrolidone. Hexamethylphosphoramide can also be used as a solvent for this displacement reaction. Besides 5 some heterocyclic nitro compounds 7,9 were also converted to their respective fluoro analogs 8 and 10 by treating with potassium fluoride. 

Called in Beil N-[3 Nitro-phenyl]-2,4,6-trinitropheny endiamin-( 1,3)1, H2N(02N)2-C4H-NH-C6H4 N02. Oysts(from et acet), mp 272°(decomp). Can be prepd either by heating 2,3,4,6-tetranitroaniline with 3 nitrobenzene in benzene or by fusing N-nitro N-methyl-2,4,6-trinitro-l,3-phenylenediamine with 3-nitroaniline at 110—120°. Its expl props were not reported... 

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