J-Nitrotoluene

While the direct halogenation of toluene gives a mixture of isomers that is difficult to separate into the pure isomers, the isomeric o- and /r-nitrotoluenes 6a and 6b, formed by nitration, are easy to separate from each other. Thus reduction of the single o- or /j-nitrotoluene 6 to the o- or /j-toluidine 7a or 7b respectively, followed by conversion into the corresponding diazonium salt 8 and a subsequent Sandmeyer reaction leads to the pure o- or /j-halotoluene 9. 

A kinetic study of the deprotonation-reprotonation behavioru of (4-nitrophenyl)-nitromethane in 50% H2O-50% Me2SO mixtures promoted by bases (phenoxide and carboxylate ions, primary amines) has revealed a one-step equilibration at pH > 4.2 the equilibration in acidic media is complicated by protonation of the exocychc nitro group.The results suggest that the substrate acts essentially as a nitroalkane rather than a /j-nitrotoluene. A further study of kinetics of deprotonation of (4-nitrophenyl)nitromethane has provided evidence of a steric effect on proton tunnelling on reaction with A/ -propyl-A,A/-dipropylbenzimidamide. " ... 

Table 9.7. When the aromatic reactant carries an EWG, the selectivity increases, since the TS occurs later. For example, while toluene is about 20 times more reactive than benzene, /j-nitrotoluene is about 200 times more reactive than nitrobenzene. The effect of the methyl substituent is magnified as a result of the later TS. 

The synthesis of Benzocaine starting from /j-nitrotoluene is usually accomplished by means of three sequential reactions i.e., Eq. (a) through Eq. (c) as given above. 

Hydrogenation of ]j-nitrotoluene MSR made of stack of aluminum wafers [78]... 

Spiess T, F Desiere, P Fischer, JC Spain, H-J Knackmuss, H Lenke (1998) A new 4-nitrotoluene degradation pathway in a Mycobacterium strain. Appl Environ Microbiol 64 446-452. 

An D, DT Gibson, JC Spain (1994) Oxidative release of nitrite from 2-nitrotoluene by a three component enzyme system from Pseudomonas sp strain JS42. J Bacterial 176 7462-7467. 

Rhys-Williams W, SC Taylor, PA Williams (1993) A novel pathway for the catabolism of 4-nitrotoluene by Pseudomonas. J Gen Microbiol 139 1967-1972. 

Some examples 4-Chloro-2-methylaniline 2-Chloro-4-nitrotoluene Sodium hydro-J xide 2-Nitrobenzaldehyde (reference 4) 4-Nitrophenylacetic acid Acetic anhydride, Pyridine 4-Nitrotoluene (reference 3)... 

Lenchitz, C. and Velicky, R.W. Vapor pressure and heat of sublimation of three nitrotoluenes, J. Chem. Eng. Data, 15(3) 401-403, 1970. 

Robertson, J.B., Spain, J.C., Haddock, J.D., and Gibson, D.T. Oxidation of nitrotoluenes by toluene dioxygenase evidence for a monooxygenase reaction, AppL Environ. Microbiol, 58(8) 2643-2648, 1992. 

Similarly with the raising of the b.p. in violet or reddish-violet soln. of iodine in benzophenone, carbon disulphide, ethyl chloride, chloroform, carbon tetrachloride, ethylene chloride or benzene or in brown soln. of ethyl alcohol, methyl alcohol, thymol, ethyl ether, methylal, or acetone. The values for the last three solvents were rather low, presumably because of the chemical action of solute on solvent. High values with benzene are attributed to the formation of a solid soln. of solvent and solid. Confirmatory results were found by J. Hertz with naphthalene, and by E. Beckmann and P. Wantig with pyridine. The results by I. von Ostromisslensky (o-nitrotoluene), by G. Kriiss and E. Thiele (glacial acetic acid), and by H. Gautier and G. Charpy indicate polymerization, but they are not considered to be reliable. 

The values for toluene, nitrobenzene, and p-nitrotoluene are from McClellan, Ref. 32. The values for phenol and p-cresol were determined by Goode lbbitson J. Chem. Soc. 1960, 4265. 

Abstract—The equilibrium diagrams of the binary systems of sulphuric add with nitromethane and with o-y m- and p-nitrotoluene have been investigated. It has been shown that addition compounds of the type 1 1 are formed in these systems, analogous to the compound sulphuric acid-nitrobenzene (Chebbuuez Helv, Chim, Acta 1923 6 281 and Masson J. Chem. Soc. 1931 3201)t The formation of these addition compounds is due to hydrogen bonding between the components, rather than to proton transfer. Their stability in the crystalline phase seems to be contradictory to the known basicities of mononitrocompounds (Gillespie and Solomons J. Chem. Soc, 1957 1796), because of the effect of temperature on the equilibria in the liquid phase. 

Biazzi, Mario, of Vevey, Switzerland, is the in-ventor(l935) and producer of apparatus for continuous manuf of expls, such as NG, DFGDN, Nitrobenzene, Nitrotoluene, PETN, RDX, etc Re/s l)W.B.Littler D.B.Clapp,BIOS Final Rept 1842kl946) 2)Stettbacher (1948), Advertisement at the back of the book 3)J-C.Smith, Chemlnds 62,929-31(1948) CA 43,1711(1949) (Biazzi pro- cess for continuous nitration) 4)H.J.Klassen ... 

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