2-methyl-5-ethylaniline

After a few minutes 2,4-diamino-6-methylphenol (hRf 5-10), 3-chloro-4-methoxy-aniline (hJ f 25-30), aniline (hRf 35-40), 4-bromoaniline (hRf 40-45), 3-chloroaniline (hJ f 50-55), 2,6-dimethylaniline (hi f 60-65), 2-methyl-6-ethylaniline (hi f 65-70) and 2-chloroaniline (hRj 70-75) yielded orange-colored chromatogram zones on a yellow background. The detection limits were between 5 ng (2,4-diamino-6-methylphenol) and 30 ng (2,6-dimethylaniline) substance per chromatogram zone. 

Fig. 1 Reflectance scans of a chromatogram track with 100 ng each of 1 = 2,4-diamino-6-methylphenol, 2 = 3-chloro-4-methoxyaniline, 3 = aniline, 4 = 4-bromoaniline, 5 = 3-chloro-aniline, 6 = 2,6-dimethylaniline, 7 = 2-methyl-6-ethylaniline and 8 = 2-chloroaniline.

We found a solution with new, doubly promoted platinum catalysts on silica and reported their scope and limitations for the synthesis of various aniline derivatives (ref. 5). In the following communication we describe the development of the most effective catalyst using as model reaction the N-alkylation of 2-methyl-6-ethylaniline with methoxy-2-propanol. 

The N-alkylation of 2-methyl-6-ethylaniline (MEA) with methoxy-2-propanol (MOIP) was investigated in the same flow microreactor under atmospheric pressure. Feed MEA MOIP = 0.5 (3 ml/h) and hydrogen (4,7 ml/min). The reaction product was condensed in a cooling trap. Each catalyst was tested for 24 h and 7 samples were collected and analyzed separately by GLC on a fused silica capillary column with methylsilicon fluid (Hewlett Packard) as stationary phase. 

Orf/zo-alkylated anilines, such as 2-methyl-6-ethylaniline (96), and 2,6-diethylaniline (97), are used in the production of acetanil-like pre-emergence herbicides, applied to corn, soyabeen, etc. The amine 97 is the starting point for the selective systemic alachlor (98) (Scheme 21). Acylation of 38 with phthalic anhydride affords the pre-emergence herbicide naptalam (AM-naphthylphthalamic acid) (99). 

Beilstein Handbook Reference) Aniline, 2-methyl-6-ethyl- Benzenamine, 2-ethyl-6-methyl- BRN 2079468 C 25702 EINECS 246-309-6 2-Ethyl-6-methylaniline 6-Ethyl-2-toluidine 6-Ethyl-o-toluidine 2-Methyl-6-ethylaniline o-Toluidine, 6-ethyl-. 

Methylaniline Ethylaniline n-Propylaniline n-Butylaniline Benzylaniline 2 -MethyIbenzylamine N-Ethylbenzylamine 2 -Methyl o-toluidine N-Methyl m-toluidine 2 -MethyI p-toluidine N-Ethyl o-toIuidine N-Ethyl m-toIuidine 2S -Ethyl p-toluidine 2 -MethyI a-naphthylamine N-Methyl p-naphthylamine N-Phenyl- a-naphthylamine 2 -Phenyl-P-naphthylamine... 

Quaternary salt formation in 4-quinazoline 3-oxide and its 4-amino and 4-methyl derivatives has been studied by Adachi. These N-oxides, prepared by reaction of the simple quinazoline with hydroxylamine, react with ethyl iodide at N-1, although only in the case of the 4-amino derivative could the ethiodide be purified. The salts are degraded by alkali yielding derivatives of ethylaniline [Eq. (4)]. 

FIGURE 6.16 Rp values of aromatic amines obtained on silica gel plate 1, 3 — isocratic development with 5 and 50% solutions of methyl ethyl ketone in cyclohexane, respectively, 2 — two-stepwise gradient development with both solvents open squares, N, N-dimethyla-niline, open triangles, iV-ethylaniline, open circles, aniline, diamonds, 2-phenylenediamine, filled squares, 3-phenylenediamine, filled triangles, 4-phenylenediamine, filled circles, 3-aminopyridine. (From Soczewinski, E. and Czapinska, K., J. Chromatogr. 168, 230-233, 1979. With permission.)... 

Ethylamine, 2-chloro-N,N-dimethyl-, HYDROCHLORIDE, 31, 37 N-methyl-1,2-diphenyl-, 34, 64 N-Ethylaniline, 36, 22 Ethyl benzalmalonate, 37, 5 Ethyl benzoylacetate, 32, 85 37, 3 Ethyl benzoylacetate, 37, 32 Ethyl N-benzylcarbamate, 35, 91 Ethyl 3-benzyl-2-cyano-3-methylpenta-noate, 35, 7... 

N-Methylethylamine has been prepared by heating ethyl-amine with methyl iodide in alcohol at 100° 3 by the hydrolysis of N-methyl-N-ethylarenesulfonamides,4-5 -nitroso-N-methyl-N-ethylaniline,6 or methylethylbenzhydrylidene ammonium iodide 7 by catalytic hydrogenation of ethyl isocyanate or ethyl isocyanide 8 and by the reduction of ethyl isocyanate by lithium aluminum hydride,9 of N-methylacetisoaldoxime by sodium amalgam and acetic acid,10 or of a nitromethane/ethylmagnesium bromide adduct by zinc and hydrochloric acid.11... 

Consider 7V-ethylaniline (17) in concert with 16. The literature enthalpy of formation of 17 is 56.3 5.9 kJmol-1. The calculated 5(sec/Ph, Et) of ca —48 kJmol-1 is not incompatible with the values in Table 2 and their aromatic extensions calculated above. One can estimate the enthalpy of formation 17 by assuming methyl/ethyl difference quantities are reasonably constant. Two such are equations 15 and 16. 

Ethylaniline from ethylaniline, diethylaniline NaY Methyl alcohol [201]... 

Purification of /V-methylaniline. The laboratory preparation of Af-methyl-and AT-ethylanilines is hardly worth while since commercial grades of good quality (97-99% pure) are available. The following procedure, however, illustrates a useful and instructive method of purifying crude samples of secondary alkylarylamines via the derived AT-nitroso compound [CAUTION (1)]. 

Fig. 6.24. Electrochromatographic separation of aromatic acids (a) and anilines (b) on monolithic capillary columns. (Reprinted with permission from [14]. Copyright 2000 Elsevier). Conditions monolithic poly(butyl methacrylate-co-ethylene dimethacrylate) stationary phase with 0.3 wt. % 2-acrylamido-2-methyl-l-propanesulfonic acid pore size, 750 nm UV detection at 215 nm voltage, 25 kV pressure in vials, 0.2 MPa injection, 5 kV for 3 s. (a) capillary column, 100 pm i.d. x 30 cm (25 cm active length) mobile phase, 60 40 vol./vol mixture of acetonitrile and 5 mmol/L phosphate buffer pH 2.4. Peaks 3,5-dihydroxybenzoic acid (1), 4-hydroxybenzoic acid (2), benzoic acid (3), 2-toluic acid (4), 4-chlorobenzoic acid (5), 4-bromobenzoic acid (6), 4-iodobenzoic acid (7). (b) capillary column, 100 pm i.d. x 28 cm (25 cm active length) mobile phase, 80 20 vol./vol mixture of acetonitrile and 10 mmol/L NaOH pH 12. Peaks 2-aminopyridine (1), 1,3,5-collidine (2), aniline (3), N-ethylaniline (4), N-butylaniline (5).

Fig. 5.5. GC separation of TFA derivatives of arylamines. Peak 1 = solvent (CH2CI2) 2 = N-methyl-aniline 3 = N,N-dimethylaniline 4 = N-ethylaniline 5 = N-methyl-o-toluidine 6 = N-methyl-m-toluidine 7 = N-methyl-p-toluidine 8 = o-toluidine 9 = o-ethylaniline 10 = aniline 11 = 2,5-dimethyl-aniline 12 = 2,6-dimethylaniline 13 = 2,4-dimethylaniline 14 = m- toluidine 15 = p-toluidine 16 = 2,3-dimethylamline 17 = 3,5-dimethylaniline 18 = m-ethylaniline 19 = p-ethylaniline 20 = 3,4-dimethylaniline. Conditions stainless-steel column, 18 ft. X 0.125 in. O.D., 9.5% Apiezon L + 3.6% Carbowax 20M on Aeropack 30 (80—100 mesh) helium flow-rate, 100 ml/min column temperature, 152°C. (Reproduced from Anal. Chem., 39 (1967) 1188, by courtesy of the American Chemical Society.)...

Indeed, within 4 kJ mol-1, and so within the error bars, this is true and so gives us confidence in both the recent measurements of liquid and gaseous IV-ethylaniline and its 3-methyl isomer. 

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