Para-toluidine

Hexamethylene tetramine Mercapto benzo thiazole Ortho-toluidine Para-toluidine... 

The first report of this new type of kinetic isotope effect in a Menshutkin reaction was published by Matsson and coworkers in 198744. In this study, the alpha carbon kll/ku kinetic isotope effect was measured for the Menshutkin reaction between N,N-dimethyl-para-toluidine and labelled methyl iodide in methanol at 30 °C (equation 35). The carbon-11 labelled methyl iodide required for this study was prepared from the nC atoms produced in the cyclotron in three steps45 (equation 37). 

Janini, G.M., Muschik, G.M., andZielinski, W.L., A,A -i>w[para-butoxybenzylidene)-alpha,alpha -bi-para-toluidine—thermally stable liquid-crystal for unique gas-liquid-chromatography separations of polycyclic aromatic-hydrocarbons, Anal Chem., 48, 809, 1976. 

Figure 21. Conversion of substituted anilines (OT, MT, and PT are respective ortho-, meta-, and para-toluidine, PA = p-anisidine, and PAA = p-aminoacetophenone), corresponding mono-N-methylated anilines selectivity and yield obtained on Cu0.5Zn0.5Fe204 at 300oC with methanol. Only in the case of PAA, feed with CH30H PAA = 6 was employed to avoid solubility problem, and in all other cases a CH30H Sub. Amline H20 = 3 1 1 was maintained. Reprinted from Applied Catalysis A General, 320, Vijayaraj M., et al., 2007, 64-68 with permission from Elsevier.

Sample N-methylaniline conversion, % anillne+N. N-dlme thylanil ine para-toluidine % mol. 

Table 8. Catalytic properties of zeolites studied in para-tolui-dine conversion. T . =400°C, para-toluidine benzene=1 4(mol), WHSV=1 h...

Sample Para-toluidine conversion, % Products composition. %wt. 

ANILINE — N-METHYLANILINE — N,N-DIME FHYLANILINE OR THO-TOLUIDINE PARA-TOLUIDINE... 

N-METHYL-ORTHO-TOLUIDINE N-METHYl-PARA-TOLUIDINE N, N-DIME PHYL-ORTHO-a OLUIDINE 2.4-XYLIDINE N, N-... 

Cheever, K.L., Richards, D.E. Plotnick, H.B. (1980) Metabohsm of ortho-, meta-, and para-toluidine in the adnlt male rat. Toxicol, appl. Pharmacol, 57, 361-369 Cheever, K.L., DeBord D.G, Sweaiengin, T.F. Booth-Jones, A.D. (1992) ortho-Toluidine blood protein addnets HPLC analysis with fluoreseenee deteetion after a single dose in the adult male rat. Fundam. appl Toxicol, 18, 522-531 Chemfinder (2000) ortiho-Toluidine Hydrochloride [http //www.ehemfinder.com/result.asp] Chemieal Information Serviees (1999) Directory of World Chemical Producers (Version 99.1.0) [CD-ROM], Dallas, TX... 

Examjdes.—Aniline is rapidly tribrominated at room temperature, the end point is very sharp, and this estimation of aniline is preferable to the nitrous acid method. At ordinary temperature ortho- and para-toluidines are dibrominated and meta-toluidine is tribrominated. Dimethylaniline is monobrominated at 0°—5°, dibrominated at 40°—50° and tribrominated at 60°—70°, an interesting example of the effect of temperature. Sulphanilic acid at 60°—70° yields tribromoaniline, and at this temperature p-nitroaniline reacts quantitatively. Phenol at about 22° yields tribromophenol. For reference to the estimation of m-diamines, m-dihydroxy compounds, R salt, cresols, p nitroaniline, diphenylamine, p-nitrophenol, and other notes, see J. S. C. I., 41, 161. 

Oxyiodination by oxygen is a relatively simple process that takes place under mild conditions. NaV03 catalyzes the oxyiodination of benzene in CF3S03H260. para Toluidine is iodinated by ammonium iodide under air pressure in presence of Cu(I) catalyst (equation... 

Iron(II) sulfate forms compounds of the type [Fe(S04)(L)2] by direct reaction with aniline and para-toluidine. In solution, the affinity of iron(II) for pyridine is very low (log fix 0.9). In the presence of a large excess of pyridine, neutral complexes of the type [FeX2(py)4] can be prepared. Yellow trans-[FeCl2(py)4] (5.34 BM) is precipitated when a saturated solution of FeCb 4H2O is added to pyridine. It is more stable toward oxidation than simple iron(II) salts, and has the advantage of being moderately soluble in organic solvents. When heated in the absence of air, successive... 

The delta modification may be formed from 1-4-3-6 dinitrotoluic acid as in the case of the gamma isomer. Delta dinitrotoluene may also be formed by interaction of toluquinone dioxime and nitric acid. (11) Epsilon dioitrotoluene is formed to a slight extent when mononitrotoluene is further nitrated. It may also be formed in the pure state by the elimination of the amino group fromd initro-para-toluidin. 

Dyes.—The toluidines are of great importance in the manufacture of dyes. In making the dye fuchsine a mixture of aniline and ortho-and para-toluidine is used, known as aniline red. It is obtained by starting with the distillation product of coal tar known as 50 per cent benzene (p. 498), or the fraction of light oil distillate boiling at iio°-140°. This is nitrated and then reduced. In making the dye safranine a mixture of aniline and ortho-toluidine is used, and this mixture, therefore, is called aniline for safranine. 

Rearrangement of Alkyl Anilines.—Both mono-methyl aniline and di-methyl aniline undergo an interesting rearrangement when their salts are heated in sealed tubes to 250°-350°. The mono-methyl aniline yields a mixture of ortho- and para-toluidines while the dimethyl aniline yields first a mixture of ortho- and para-mono-methyl toluidines and then finally from each of these intermediates there is obtained unsymmetrical meta-xylidine only. 

When the dye that was made by oxidizing crude aniline was studied and the facts which we have stated were determined, it was also found that the dye was not one compound but that two were present as a mixture. Originally the mixture of the two was called simply rosani-line, but to distinguish the two compounds the one we have been studying because of its relation to para-toluidine is called para-rosaniline while the other is named simply rosaniline. Sometimes the name rosaniline is applied to the former and the latter is then called homoros-aniline. The first names are the better and are now generally adopted.. 

In the preparation of commercial fuchsine aniline is heated with a mixture of ortho and para toluidine. p-Toluidine is oxidized to the aminoaldehyde which condenses with one molecule of both aniline and o-toluidine to form homorosaniline hydrochloride- At the same time there is also formed pararosaniline hydrochloride owing to the reaction of two molecules of aniline with the aldehyde. The differences in the structure of leuco base, color base, and dye are shown by comparison of their respective formulas (1), (2), and (3). 

The red oil used in the manufacture of rosaniline is a mixture containing aniline, ortho- and para-toluidine in varying proportions. 

Some knowledge of the structure of the very complex molecules of the sulphur dyes is being accumulated gradually. It has, for example, been established that one of the reactions which takes place when sulphur is heated with para-toluidine is the formation of dehydrothio-toluidine ... 

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