Nitro-m-Cresol

N 3.38% pale red plates mp, darkens at 220° and explds violently at 228°. Sol in chlf, carbon tetrachloride toluene insol in It petr. Prepn is by reacting an aq soln of Tl diethyl hydroxide with 4-nitro-m-cresol Ref A. Goddard, JCS 119,1310-15 (1921) CA 15,3635 (1921)... 

Fenitrothion is one of the very important outlets for m-cresol and is widely used throughout the world. As stated in an earlier chapter, m-cresol on nitration gives 4-nitro-m-cresol which is then converted to fenitrothion. 

Zincke, Schuimann, Ann., 1918,417,24L 6-Chloro-4-nitro-m-cresol CTa Clil" ... 

Dibromo-4>nitro>m>cresol (2 6 2>i bromO 4-nitro-i-hydroa ytdtiene). 

In addition, m-cresol is used to produce plant protection agents such as feni-trothion. The manufacturing process involves nitrosation of m-cresol with nitrous acid esters in isopropanol, and subsequent oxidation of the nitroso compounds with nitric acid to yield 4-nitro m-cresol (or its sodium salt), which, when acted upon by 0,0-dimethyl thiophosphoric acid chloride, gives fenitrothion. 

Ethyl-(4 nitro-3-methylpbenyl)-etber, C6H3(CH3)(N02)0C2H5 mw 181.18, N7.73% prisms (pet eth), mp 55°. Prepd from ethyl iodide in eth and the silver salt of 6-nitro m-cresol... 

Tetrani trocresol (TeNCrs). Only one isomer is known 2,4,5,6 Tetranitro-m-cresol, CH3.Cg(N02)4.0H mw 288.13, N 19.45% col crysts (from chlf) having a bitter taste, mp 175°, bp explodes readily sol in ale or w, giving yel solns was prepd by nitrating 5-nitro-m-cresol with coned HN03 coned H2S04 at 50°. This compd is a powerful expl (Refs 1 2) Refs 1) Beil 6, 388 2) J.J. Blanksma, Rec 27,... 

The addition of mercuric nitrate is here written as a 1,4-addition, but 1,2-addition would give the same final product, and there is no evidence in the facts concerning benzene which enables us to choose between the alternative hypotheses. Toluene yields tri-nitro-m-cresol by a similar series of reactions, and it is clear that the nitro group in the addition product of mercuric nitrate and toluene has taken either the 2-, the 4-, or the 6-position, that is, one or the other of the positions activated by the methyl group. In the addition of mercuric nitrate to naphthalene, the nitro group correspondingly may be supposed to go to the active a-position. If the addition is 1,2-, the product on oxidation will yield a derivative of /J-naphthol. If it is 1,4-, it will yield a derivative of a-naphthol. The two possibilities are indicated below. 

C7H5N30 benzoyl azide 582-61-6 35.00 1.1680 1 10247 C7H6CIN03 4-chloro-6-nitro-m-cresol 7147-89-9 25.00 1.4048 2... 

Chemical/Physical. Products identified from the reaction of toluene with nitric oxide and OH radicals include benzaldehyde, benzyl alcohol, 3-nitrotoluene, p-methylbenzoquinone, and o, m, and p-cresol (Kenley et ah, 1978). Gaseous toluene reacted with nitrate radicals in purified air forming the following products benzaldehyde, benzyl alcohol, benzyl nitrate, and 2-, 3-, and 4-nitro-toluene (Chiodini et al., 1993). Under atmospheric conditions, the gas-phase reaction with OH radicals and nitrogen oxides resulted in the formation of benzaldehyde, benzyl nitrate, 3-nitrotoluene, and o-, m-, and p-cresol (Finlayson-Pitts and Pitts, 1986 Atkinson, 1990). 

Problem 19,14 Assign numbers from 1 for least to 4 for most to indicate the relative acid strengths in the following groups (a) phenol, m-chlorophenol, m-nitrophenol, m-cresol (b) phenol, benzoic acid, p-nitro-phenol, carbonic acid (c) phenol, p-chlorophenol, p-nitrophenol, p-cresol (d) phenol, o-nitrophenol, m-nitrophenol, p-nitrophenol (e) phenol, p-chlorophenol, 2,4,6-trichlorophenol, 2,4-dichlorophenol (/) phenol, benzyl alcohol, benzenesulfonic acid, benzoic acid. ... 

Of the three isomeric cresols ortho-, meta-, and para-, only m- cresol can be used as the starting material for introducing three nitro groups, viz. in the 2,4,6-positions. Ortho and p- cresols are able to form stable nitro group systems only when no more than two nitro groups are introduced. Under the conditions of the nitration of m- cresol to its trinitro derivative the o- and p- isomers are oxidized to oxalic acid. 

The direct nitration of m-cresol is unsatisfactory for obtaining 4-nitro-3-methylphenol (29%). A better procedure is to form the nitroso compound and oxidize it to the nitro compound (66% over-all). ... 

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