Anilines, o alkylation

Amyl bromide [Pentane, 1-bromo-], 82 Aniline [Benzenamine], 122 Anilines, o-alkylation of, 15 Anisole [Benzene, methoxy-], 48 Amsyl chloride [Benzene, l-(chloromethyl)-... 

Aniline, N-alkyl-o-allyl-indole synthesis from, 4, 321 Aniline, N-allyl-... 

The reaction of the O-alkylated cyclohexan-l,3-diones 73 with p-substituted anilines in the presence of acetic acid is influenced by the nature of R in 73, yielding 4-anilinoxanthones 74 when R = H, but the condensed y-lactams 75 when R = Me (Scheme 51) <00T5947>. 

Illustrative examples of the acylation of support-bound amines with carbodiimides as coupling agents are listed in Table 13.3. Difficulties are usually encountered in the acylation of a-alkylamino acid derivatives (which are significantly less nucleophilic than simple secondary amines Entries 3 and 4) and Al-alkyl (Entries 5 and 6) or iV-aryl anilines. Acylations with haloacetic or related acids containing a leaving group prone to nucleophilic displacement should not be performed with the aid of HOBt and bases because O-alkylation of HOBt by the product occurs readily. 

The lactim/lactam tautomerism of hydroxamic acids and their O-alkyl and O-acyl derivatives has also been studied [146], Hydroxamic acids exist in the solid state and in polar solvents as the lactam tautomer only, whereas in nonpolar solvents the hydroximic tautomer is also present. Further analogous solvent-dependent lactim/lactam equilibria have been observed for certain Schiff bases (prepared from anilines and 2(4)-hydroxybenzaldehyde [256] or 2-hydroxynaphthaldehyde [257]), for 3-hydroxypyrazole [258], and for 3-methyl-l-phenylpyrazolin-5-one [259]. 

Aniline, JV-alkyl-o-allyl-indole synthesis from, 4, 321 Aniline, N-allyl-indole synthesis from, 4, 326 Aniline, AT-allyl-o-bromo-indole synthesis from, 4, 327 Aniline, N-allyl-o-iodo-indole synthesis from, 4, 327 Aniline, o-bromo-in indole synthesis, 4, 340 Aniline, o-halo-cyclization, 4, 340 Aniline, m-nitro-in indole synthesis, 4, 338 Aniline black, 3, 197 Anilines... 

Carbazoles. o-Alkylation of p-substituted anilines with a cationic (1,3-... 

Al-HMS mesoporous molecular sieves with Si/Al ratio in the range 10-40 were synthesized by using dodecylamine as template. They were characterized by XRD, N2 adsorption, MAS NMR, and DRIFT, and their acid properties were determined by pyridine (PY) adsorption. Aniline methylation was a pseudo-first-order process with respect to aniline concentration. Alkylation is a sequential reaction process, in which methylation of aniline produces N-methylaniline (NMA), then N,N-dimethylaniline (NNDMA) and subsequently N,N-dimethyltoluidines (NNDMT, p- > o-). N-methylation products (NMA+NNDMA) were predominant with a selectivity over 97 mol% at 573 K. 

This procedure illustrates a general method for the ort o-alkylation of anilines. It can be utj EdTfty.Jigbli. iuiilines nd mono-A-substituted... 

Phosphorylation. The compound reacts with an alcohol or a phenol at 0° in pyridine to form O-alkyl-O-phenyl N-phenylphosphoromidates (2) in 70-867o yield. The aniline group in (2) is removed by treatment with isoamyl nitrite (excess). ... 

In a series of papers, Blechert and coworkers reported several closely related indole syntheses involving, for example, the reaction of IV-phenylhydroxyamines with electron-withdrawing aUenes to give o-alkylated aniline intermediates, which cycUzed to 1,2-disubstituted indoles in an oxy-Cope rearrangement (Scheme 7, equation 1)... 

The protected aminoalcohols 65 are prepared from N-Boc-(o-alkyl)anilines 64 by benzyUc metalation with tBuLi and addition to aldehydes. N-Deprotection with TFA leads to the free aminoalcohols 66, which are oxidized by mesityl bromide in the presence of Pd(PPh3)4 and K2CO3 the resulting (o-aminophenyl)ketones 67 cyclize in situ to the indoles (68). 

A simple preparation of indoles from anilines is based on a specific o-alkylation of ar. amines with sulfides in the presence of an active chlorine source such as tert-hwtyl hypochlorite . A lactamol has been obtained by double ring closure of a diketone in one operation combining 4 simple steps, all of which occur stereospecifically in high yield in the same medium . Another multiple reaction is the stereospecific rearrangement of an epoxytetrahydrofuranolactone in the course of synthetic studies on tetrodotoxin. A new riboflavin synthesis via its 5-oxide has been reported . 

What in your estimation would be the effect of a copolymerization, e.g. of 3-alkyl and unsubstituted thiophene, o-methoxy and unsubstituted aniline, 3-alkyl and unsubstituted pyrrole, on the morphology, as compared to the corresponding unsubstituted homopolymers. Discuss in detail with structures. 

Thus, the synthesis of 2,1-benzisothiazoles by the action of thionyl chloride on o-toluidines (see Vol. 2, p. 576) has found further application. o-Benzylaniline affords 3-phenyl-2,l-benzisothiazole (72 R = Ph) nearly quantitatively, but < -toluidines functionally substituted in their methyl group yield only tars or iV-sulphinyl-derivatives. o-Ethylaniline gives several products 3-methyl-2,l-benzisothiazole (72 R = Me) may first be formed, but is rapidly chlorinated at its methyl group, to produce, after hydrolysis, 2,l-benzisothiazole-3-carboxylic acid (30%) (72 R = COaH). Another product, previously erroneously regarded as 3-methyl-2,l-benzisothiazole (72 R = Me), appears to be 2-(2,l-benziso-thiazol-3-yl)-7-ethylbenzothiazole. More highly substituted o-alkyl-anilines produce, apart from traces of 2,1-benzisothiazoles, merely A-sulphinyl-amines. ... 

The compound (3) is a useful intermediate for the synthesis of mixed diesters of phosphoric acid (4). There are several methods of cleaving the N-P bond, of which the method of Ikehara is the most convenient. Reaction of (3) with a 40 molar excess of 3-methylbutyl nitrite in acetic acid-pyridine (1 1 v/v) is successful in removing the aniline protecting group from the phosphoryl moiety in almost quantitative yields, giving the O-alkyl/aryl-O-phenyl hydrogen phosphate. 

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