4.7- dinitro-2-methyl

Beim Austausch der Nitro-Gruppe in 1-Position von 1,4-Dinitro-imidazol oder 1,4-Dinitro-2-methyl-imidazol mit Methanol oder Ethanol werden als Produkte 4(5)-Methoxy-5(4)-nitro-, 4(5)-Ethoxy-5(4)-nitro-, 4(5)-Methoxy-2-methyl-5(4)-nitro- bzw. 4(5)-Ethoxy-2-methyl-5 (4)-nitro-imidazol erhalten972. 

Dinitro Methyl Anisole (4-Nitro-2-nitromethyl anisole, 3-Nitro-6-methoxynitromethyI toluol. or Methyl-[5-nitro-2-nitromethylphenyl] -ether). CH3.0.(N02)C6H3.CH2N02, mw 212.18, N 13.21%, OB to C02 —113.11%, cryst, mp 93—94°. Prepd from 4-nitro-2(lodomethyl) anisole in ether-ben2ene soln by treatment for 3 days at RT with Ag nitrate. The sodium salt explodes violently on heating Refs 1) Beil, not found 2) G. Bendy,... 

MMED Benzoic acid, 2-(l,l-dimethylethyl)-4,6-dimethyl-3,5-dinitro-methyl ester... 

Bntansaure 2,2-Dinitro- -methyl-ester E19a, 493 (H - N02) Cyclopenten 4-Nitro-3-nitrylperoxy-E13/1,295 (1,3-Dien + N2O4/02) Peroxid... 

Formula M.p. Methyl ester M.p. Ethyl ester M.p. Acetyl deriv M.p. Benzoyl deriv M.p 3.5 Dinitro. benzoyl deriv. M.p. Naphthal- ene sulphonyl deriv. M.p. 

The benzoyl compounds frequently occlude traces of unchanged benzoyl chloride, which thus escape hydrolysis by the caustic alkali it is therefore advisable, wherever possible, to recrystaUise the benzoyl derivatives from methyl, or ethyl alcohol or methylated spirit, since these solvents will esterify the unchanged chloride and so remove the latter from the recrystalKsed material. Sometimes the benzoyl compound does not crystallise well this difficulty may frequently be overcome by the use of p-nitrobenzoyl chloride or 3 5-dinitro-benzoyl chloride, which usually give highly crystalline derivatives of high melting point (see Section IV,114j. 

Compounds containing two primary amino groups attached to a benzene ring can be prepared by the reduction of dinitro compounds and of nitroanilines, usually with tin or stannous chloride and hydrochloric acid or with iron and very dilute hydrochloric acid. / ara-diamines may also be obtained by the reduction of aromatic amino-azo compounds (e.g., p-aminodimethylanihne from methyl orange, see Section IV,78). p-Phenylenediamine may also be prepared from p-nitroacetanilide reduction with iron and acid yields p-amino-acetaniUde,.which may be hydrolysed to the diamine. 

Another significant use of 3-methylphenol is in the production of herbicides and insecticides. 2-/ f2 -Butyl-5-methylphenol is converted to the dinitro acetate derivative, 2-/ f2 -butyl-5-methyl-4,6-dinitrophenyl acetate [2487-01 -6] which is used as both a pre- and postemergent herbicide to control broad leaf weeds (42). Carbamate derivatives of 3-methylphenol based compounds are used as insecticides. The condensation of 3-methylphenol with formaldehyde yields a curable phenoHc resin. Since 3-methylphenol is trifunctional with respect to its reaction with formaldehyde, it is possible to form a thermosetting resin by the reaction of a prepolymer with paraformaldehyde or other suitable formaldehyde sources. 3-Methylphenol is also used in the production of fragrances and flavors. It is reduced with hydrogen under nickel catalysis and the corresponding esters are used as synthetic musk (see Table 3). 

With mixed acid 1-methylpyrazole 2-oxide (268) gives high yields of l-methyl-5-nitropyrazole 2-oxide (269) (B-76MI40402). The form undergoing the reaction is the base, for which first-order kinetics are observed in the Hq range from -5 to -6.5 a dinitro derivative is also formed under slightly different conditions. The reaction of indazole with fuming nitric acid affords a nearly quantitative yield of 5-nitroindazole (Section 4.04.2.3.2(i)). 

Nitration of a series of methyl-1,2-benzisoxazoles was studied by Tahkar and Bhawal using fuming nitric acid and sulfuric acid in acetic acid at 100 °C. 3-Methyl-1,2-benzisoxazole gave a mixture of 5-nitro- and 5,7-dinitro-3-methyl-l,2-benzisoxazole, with the 5-nitro isomer predominant. The product obtained from 3,5-dimethyl-1,2-benzisoxazole was the 4-nitro derivative and not the 7-nitro compound as proposed by Lindemann (26LA(449)63). The synthesis of the 7-nitro compound by an alternative method was used as structural proof. Two products were obtained from 3,6-dimethyl-l,2-benzisoxazole and these were the 5-nitro and 5,7-dinitro derivatives. 3,7-Dimethyl-l,2-benzisoxazole was converted into the 5-nitro derivative (Scheme 25) (77lJC(B)l06l). 

Nitration of 3-phenyl-1,2-benzisoxazole with fuming nitric acid has been shown to give dinitro products of undetermined substitution pattern (67AHC(8)277, p. 290>. However, more satisfactory studies have now been described, especially on the kinetics and mechanism of nitration of 3-methyl-l,2-benzisoxazole (77JCS(P2)47). Nitration in cold, concentrated mixed acids yields the 5-nitro derivative exclusively, nitration in 80-90% sulfuric acid occurring on the free base whereas at higher acidities the conjugate acid is the species involved in the nitration. 

However, other studies on the nitration of a series of 3-methyl- and 3-ethyl-1,2-benzisoxazoles have shown that a mixture of the 5-nitro and 5,7-dinitro derivatives is formed (77IJC(B)1058, 77IJC(B)1061). The effect of substituents in the benzene ring is also of interest. If the 5-position is blocked, e.g. by a chloro group or by alkyl groups, nitration then occurs at the 4-position. 3-Alkyl-7-chloro and 3,7-dialkyl derivatives result in the formation of the appropriate 5-nitro derivative. The isomeric 3-alkyl-6-chloro- and 3,6-dialkyl-1,2-benzisoxazoles yield a mixture of the 5-nitro and 5,7-dinitro compounds. Both H NMR measurements and alternate syntheses were used in establishing the structures of these substitution products. 

Benzo[6]furan, trans-3-acetoxy-2,3-dihydro-2-methyl-5,7-dinitro- H NMR, 4, 571 (713001805)... 

Imidazole, 2-methyl-1,4-dinitro-rearrangement, 5, 378 Imidazole, 5-methyl-1,4-dinitro-denitration, 5, 378 Imidazole, l-methyl-4,5-diphenyl-synthesis, 5, 478... 

Phenols Apply sample solution and spray with saturated sodium methylate solution and then treat with 4% 2,4-dinitrofluorobenzene in acetone and heat to 190°C for 40 min. Chromatograph the dinitro-phenyl ethers so produced. [79]... 

Only 22-45% yields of m-fluoronitrobenzene are obtained from the fluoro-denitration of m dinitrobenzene by potassium fluoride in Af-methyl-2-pyrrolidone or hexamethylphosphoramide, along with significant amounts of 3,3 dinitro-diphenyl ether [107, 108, 109] (equation 32)... 

Chloro- and 5-methylbenzofuroxans are readily nitrated in the 4-position the product rearranges easily to form 7-substituted 4-nitro compounds (see Section VIII), also obtained by nitration of the corresponding 4-substituted benzofuroxans. Dinitration of 5-methylbenzofuroxan is said to give a product of m.p. 133°, while the 4-methyl gives a dinitro compound m.p. 122°-123°. For other benzofuroxans to have been nitrated see refs. 19, 36, 81, 97,121. There appears to be some confusion over the site of electrophilic substitution of naphtho[l,2-c]furoxan. Early reports in the literature state that nitration gives the 5,6-dinitro derivative (47). However, sulfona-... 

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