Wibaut, J. P. published an article in 1914, the title of the article was Quantitative researches on the nitration of chlorotoluenes.HPLC of Formula: 38939-88-7 And the article contains the following content:
The o-ClC6H4Me used was obtained by converting com. o-H2NC4H4Me into the oxalate (van der Laan, Idem, 26, 1 (1908)) and the NH2 replaced by Cl by Erdmann’s method (Ann., 272, 145). It b759 159-5° (corrected), n59.4° 1.4977. o-H2NC6H4Me nitrated with HNO3 + H2SO4 gave 4,2-O2N(H2N)C6H3Me, m. 107°, which, treated with 25% HCl, diazotized and treated With CuCl2, gave 2,4-Cl(O2N)C6H3Me. m. 62.3° (not 65° nor 68°), n69.4° 1.5470. 2,4-Cl(H2N)C4H3Me was prepared from 15 g. of the preceding in 1 l. H2O + 30 g. powdered Fe + H2SO4. With Ac2O it gave 4-acetylamino-2-chlorotoluene, m. 105°; similarly Bz3O gave 4-benzoylamino-2-chlorotoluene, m. 122°. 2,6-(O2N)2C6H2Me reduced with H2S in EtOH in the presence of NH3 gave 6,2-O2N(H2N)C4H3Me, m. 9t°, which, diazotized, etc., gave 6-nitro-2 chlorotoluene, m. 35-3°, n69.6° 1.5377; reduced, the latter gave 2,6-Cl(H2N)C6H3Me, m. 2.8°, which with Ac2O gave 2,6.Cl(AcNH)C6H3Me, m. 156°, and with Bz2O gave 2,6-Cl(BzNH)C6H3Me, m. 170°. 5,2-O2N(H2N)C6H3Me was prepared by the method of Goldschmidt and Hönig (Ber., 20, 200) from o-AcNHC6H4Me, and when diazotized, etc., gave 2,5-Cl(O2N)C6H3Me, m. 42.9°, n69.4° 1.5511. The latter on reduction gave 2,5-Cl(H2N)C6H2Me, m. 83°, which with Ac2O gave 2,5-Cl(AcNH)C6H3Me, m. 92°, and with Bz2O gave 2,5-Cl(BzNH)C6H2Me. m. 119.5°. 3,2-O2N(H2N)C6H3Me (obtained along with the 5-NO3 derivative), diazotized, etc., gave 2,3-Cl(O2N)C6H3Me, m. 22.1°, n69.4° 1.5327, which on reduction gave 2,3-Cl(H2N)C6H3Me, m. 6.6°; this, with Ac2O, gave 2,3-Cl(AcNH)C6H3Me, m. 133°, or with Bz2O gave 3-benzoylamino-2-chlorotoluene, m. 125°. The o-ClC6H4Me (n69.4° 1.4977) was nitrated with 4 times as much HNO3 (d. 1.52) at 0° ƛ 1°; after standing some time at 0° the mixture was poured on crushed ice, extracted with C6H6, etc., the C6H6 distilled off under reduced pressure and the nitration product (60 g. from so g. o-ClC6H4Me) distilled fractionally under 30 mm.; fraction (1) 120-30°, n69.4 1.5428; (2) 130-7°, n69.4 1.5438; (3) 137-40°, n69.4 1.5447; (4) above 140°, n69.4 1.5462. The values for n show that there is no unchanged o-ClC6H4Me nor was 3,4,6-Cl(O2N)2C6H2Me (n69.4 1.5723) formed. No attempts at direct isolation or identification of the complex mixtures of mono-NO2 derivatives were successful. The mixture was reduced with Fe + H2SO4, distilled with steam, etc. (crystals of 2,5-Cl(H2N)C6H2Me separated at this point, m. 81-2°), finally dissolved in C6H6 and treated with the calculate amount of Ac2O. This solution deposited white crystals which proved to be 2,6-Cl(AcNH)C6H3Me, m. 156°. The mother liquor was concentrate and gave 2,3-Cl(AcNH)C6H3Me, m. 133-4°. Attempts to isolate the 4th isomer in this way failed. A number of ways were tried but finally 120 g. of the nitration product were reduced and subjected to an elaborate fractional crystallization (for details see original) by which the presence of the 4th isomer was established, although it was not isolated. For a quant. study of the nitration products the fusion curve method used by Valeton (C. A., 5, 1283) was applied. When one has to do with a mix. of 4 compounds, A, B, C and D, the branch A of the crystallization curve of A-B is easily confused with branch A of A-C or A-D. The effect of a quantity of B on the f. p. of A is the same if a mixture of B, C and D is substituted for the same amount of either pure B, C or D. So that in order to determine the amount of A in any mixture add to a known amount of the mixture a known amount of A, such that A seps. first from the fused mass, and from the f. p. thus observed deduce the amount of A present on the basis of a binary solidification curve and from this calculate the amount of A present in the original mixture The 6 binary curves of solidification of the 4 isomeric Cl(O2N)C6H3Me were worked out and afterwards it was attempted to determine the comp. of complex mixtures of known comp. It was found that 3 of the isomers (all but 2,3-Cl(O2N)C6H3Me) could be accurately determined in this way. 10.3 g. o-ClC3H4Me nitrated for 1.5 hrs. with 41.3 g. HNO3 (d. 1.52) at 0° gave 10.3 g. nitration products (74%), m. 2-3°, which on analysis by the above method gave: 43.6% 2,5-, 16.9% 2,4-, 20.6% 2,6-, and 18.9% 2,3-Cl(O2N)C6H3Me. Another portion nitrated for 3 hrs. gave 43.2, 17.2, 20.9 and 18.7%, resp. Nitration of m-chlorotoluene. The m-ClC6H4Me used b. 229.5-30°, m. 15.2°. 45 g. m-AcNHC6H4Me were dissolved a little at a time in 300 cc. concentrate H2SO4 with cooling in ice + NaCl and 21 g. HNO3 (d. 1.52) + 50 cc. concentrate H2SO4 added slowly at 5° to -3°. This finally gave an 80% yield of 6,2-O2N(AcNH)C6H3Me. The Ac was removed by b. until dissolved in 100 cc. H2O + 100 cc. concentrate H2SO4. The NH2 was replaced with Cl by diazotizing, etc., which gave 6-nitro-3-chlorotoluene, m. 24.9° (and a metastable form, m. 24-2°). n65.6 1.5495. 2,6-(O2N)2C6H3Me was reduced electrolytically to 2,6-O3N(HONH)C6H3Me (Brand, Zoller, Ber., 40, 3332) which with HCl gives 3,2,6-Cl(O2N)(H2N)C6H2Me; this, diazotized, etc., gives 3,2-Cl(O2N)C4H3Me, dimorphous, m. 23.4° (the m. p. of the metastable form was not accurately determined), n68.5 1.5204. o-AcNHC6H4Me was chlorinated with Ca(OCl)2, the Ac eliminated with KOH in aqueous EtOH, the Cl(H3N)C6H3Me converted into the nitrate and this into 3,4,6-Cl(O2N)(H2N)C3H2Me according to Claus and Stapelburg (Ann., 274, 285), of which 20 g. were dissolved by b. in 160 cc. 50% H2SO4, diazotized and the 300 cc. of solution obtained added drop by drop to 600 cc. b. EtOH, which finally gave 4-nitro-3-chlorotoluene, m. 24.2°, n68.5° 1.5428. 3,5-Cl(O2N)C6H3Me, prepared by Hönig’s method (Ber., 20, 2419), m. 58.4°, n68.5° 1.5404. m-ClC6H4Me was nitrated like the o-derivative The nitration product was distilled fractionally at 8 cm.: (1) up to 173°, n68.5° 1.5447; (2) 173-8°, n68.5° 1.5453; (3) 178-80°, n68.5° 1.5448; (4) 180-5°, n68.5° 1.5448; (5) n68.5° 1.5452. The values of n show that m-ClC6H4Me and 3,4,6-Cl(O2N)2C6H2Me (n69.6 1.5723) are not present. The 6 binary curves of solidification of the 4 isomers of Cl(O2N)C6H3Me were worked out as for the o-derivatives and the nitration mixtures analyzed as above. The result shows 58.9% 3,6-, 32.3%, 3,4-, and 8.8% 3,2-Cl(O2N)C6H3Me; the presence of 3,5-Cl(O2N)C6H3Me could not be established experimentally but cannot exceed a few %. The latter part of the paper is devoted to a theoretical discussion in which it is shown that the quant. results obtained in the nitration of m- and o-ClC6H4Me are in perfect agreement with the theoretical predictions of Holleman and a formula is proposed which permits a satisfactory calculate of the proportions of the isomers formed. (For details see the original.) The experimental process involved the reaction of 2-Chloro-4-methyl-1-nitrobenzene(cas: 38939-88-7).HPLC of Formula: 38939-88-7
2-Chloro-4-methyl-1-nitrobenzene(cas:38939-88-7) belongs to chlorides. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. However, the extent of chlorination is difficult to control. Aryl chlorides may be prepared by the Friedel-Crafts halogenation, using chlorine and a Lewis acid catalyst. HPLC of Formula: 38939-88-7
Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics