4-butylaniline

Pure dialkylanilines may be prepared by refluxing the monoalkylaniline (1 mol) with an alkyl bromide (2 mols) for 20-30 hours the solid product is treated with excess of sodium hydroxide solution, the organic layer separated, dried and distilled. The excess of alkyl bromide paases over first, followed by the dialkylaniline. Di-n-propylaniline, b.p. 242-243°, and di-n-butylaniline b.p. 269-270°, are thus readily prepared. 

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... 

C-Alkylations may be discussed under the headings of alkene reactions and A/-alkyl rearrangements. The isopropylation of benzene and naphthalene are two important examples of alkylation with alkenes (see Alkylation). Manufacture of j butylaniline, by heating /V-butylaniline with 2inc chloride, typifies the rearrangement reaction appropriate to and higher alkyl derivatives. 

The feasibility of this approach was demonstrated with a model library of 36 compounds prepared from a combination of three Boc protected L-amino acids (valine 23, phenylalanine 24, and proline 25) and 12 aromatic amines (3,4,5-trimethoxyaniline (26), 3,5-dimethylaniline (27), 3-benyloxyaniline (28), 5-aminoindane (29), 4-tert-butylamline (30), 4-biphenylamine (31), 1-3-benyloxyani-line (28), 5-aminoindane (29), 4-tert-butylaniline (30), 4-biphenylamine (31), 1-aminonaphthalene (32), 4-tritylaniline (33), 2-aminoanthracene (34),... 

EBBA 4-ethoxybenzylidene-4 -n-butylaniline 4-n-pentyl-4 -cyanobipbenyl [90] 60 NpT MC (all atom)... 

The hydrogenation of toluene, aniline, /r-toluidine, and 4-tert-butylaniline was examined over catalyst M1273. The reaction profile for the reactions is shown in Figure 2. From this it can be seen that the order of reactivity is aniline > toluene > /Moluidinc > 4-fer f-butylaniline. The hydrogenation products were methylcyclohexane from toluene, cyclohexylamine from aniline, 4-methyl-cyclohexylamine (4-MCYA) from /Holuidine. and 4-feri-butylcyclohexylamine (4-tBuCYA) from 4-tert-butylaniline. At 50 % conversion the cis trans ratio of 4-MCYA was 2, while tBuCYA it was 1.6. 

Figure 2 Hydrogenation of aniline, toluene, p-toluidine, 4-tert-butylaniline, over M1273. Temperature 338 K and 2 barg hydrogen pressure.

The effect of catalyst pore size on the hydrogenation of 4-tert-butylaniline was examined using catalysts M1081, M1272, M1079, and M1273. The effect on the rate is shown in Table 2. 

The TOF was calculated for the 4-fert-butylaniline hydrogenation over each of the four catalysts. Using the relationship between metal crystallite size and TOF shown in Figure 3, the TOF for each catalyst was normalised to 1 nm and back calculated to a rate expression to remove the metal ciystallite size effect from the rate. With the rate expressed in this way the effect of the pore size is clearly seen (Figure 4). 

Aromatic amines RNH2 (R = Ph, 2-MeCgH4 or 4-MeOCgH4) are phenylated by triphenylbismuth in the presence of 0.5 equivalent of copper(II) acetate to yield diarylamines RNHPh. Butylamine yields a mixture of TV-butylaniline and N-butyldiphenylamine in this reaction and piperidine gives TV-phenylpiperidine36. A similar alkylation of the secondary amines pyrrolidine, piperidine and morpholine with trimethylbismuth or tris(2-phenylethyl)bismuth in the presence of copper(II) acetate affords tertiary amines, e.g. 14. The reaction proceeds by way of transient pentavalent bismuth compounds37. 

The pH dependence of the regioselectivity for the nucleophilic photosubstitution of 3,4-dimethoxy-l-nitrobenzene by n-butylamine gives21 2-methoxy-5-nitro-Af-butylaniline as the major product at pH = 11 (equation 19). At pH = 12, the ratio of the major product to 2-methoxy-4-nitro-7V-butylaniline increases to 12 1 the increased selectivity is caused by hydroxide ion, which can either promote exciplex formation or act as a base catalyst in deprotonation steps following the cr-complex formation22. 

A kinetic smdy of the formation of zwitterionic adducts (28) from 1,3,5-trinitrobenzene and diazabicyclo derivatives indicates that reactions are surprisingly slow, with rate constants many orders of magnitude lower than those for related reactions with primary or secondary amines. The use of rapid-scan spectrophotometry was necessary to study the kinetics of reaction of 4-substimted-2,6-dinitro-A -n-butylanilines (29) with n-butylamine in DMSO the two processes observed were identified as rapid deprotonation to give the conjugate base and competitive a-adduct formation at the 3-position. The reactions of MAf-di-n-propyl-2,6-dinitro-4-trifluoromethylaniline (30), the herbicide trifluralin, and its A -ethyl-A -n-butyl analogue with deuteroxide ions and with sulfite ions in [ H6]DMS0-D20 have been investigated by H NMR spectroscopy. With deuteroxide a-adduct formation at the 3-position is followed by... 

Other aromatic nitramines have not found use as practical explosives. Ethyltetryl (232) is prepared from the nitration of 2,4-dinitro-A-ethylaniline, A,A-diethylaniline or N-ethylaniline. Butyltetryl (233) can be synthesized from the nitration of 2,4-dinitro-A-butylaniline, which is attainable from the reaction of n-butylamine with 2,4-dinitrochlorobenzene. 

This product has been prepared both by the nitration of N-n-butylaniline and by the action of n-butylamine on chlorodinitrobenzene followed by nitration of dinitro-N-n-butylaniline. 

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