2.6- Dichloro-3-methylaniline

Ullman condensation of m-trifluoromethylaniline (13) with o-iodobenzoic acid in the presence of copper-bronze affords flu-fenamic acid (14). An analogous reaction of o-chlorobenzoic acid with 2,3-dimethylaniline (15) gives mefenamic acid (16) meclofenamic acid (18) is obtained by Ullman condensation employing 2,6-dichloro-3-methylaniline (17). 

Meclofenamic acid Meclofenamic acid, iV-(2,6-dichloro-m-tolyl)anthranylic acid (3.2.20), is synthesized analogous to flufenamic acid, by the reaction of potassium salt of 2-bromobenzoic acid with 2,6-dichloro-3-methylaniline in the presence of copper (11) bromide in a mixture of iV-ethylmorpholine and diglyme [82,83]. 

Synthesis By condensation of 2-bromobenzoic acid with 2,6-dichloro-3-methylaniline by means of CuBr2 in diethyleneglycol dimethyl ether containing N-ethylmorpholine, and heating at 145-155 °C (Scherrer and Short (Parke Davis), 1961 1967) Juby et al., 1968 Arrigoni-Martelli, 1978b Kleemann et al., 1999). 

A mixture consisting of 22.7 g potassium o-bromobenzoate, 16.6 g 2,6-dichloro-3-methylaniline, 12 ml N-ethylmorpholine, 60 ml diethylene glycol dimethyl ether, and 1.0 g anhydrous cupric bromide is heated in a nitrogen atmosphere at 145°C to 155°C for 2 hours. The reaction mixture is diluted with 60 ml diethylene glycol dimethyl ether and acidified with 25 ml concentrated hydrochloric acid. The acidic mixture is diluted with 100 ml of water and the liquid phase decanted from the insoluble oil. The insoluble oil is stirred with methanol and the crystalline N-(2,6-dichloro-3-methylphenyl) anthranilic acid which separates is collected and washed with methanol. The product, after recrystallization from acetone-water mixture, melts at 248°C to 250°C. 

In this solvent the reaction is catalyzed by small amounts of trimethyl-amine and especially pyridine (cf. 9). The same effect occurs in the reaction of iV -methylaniline with 2-iV -methylanilino-4,6-dichloro-s-triazine. In benzene solution, the amine hydrochloride is so insoluble that the reaction could be followed by recovery. of the salt. However, this precluded study mider Bitter and Zollinger s conditions of catalysis by strong mineral acids in the sense of Banks (acid-base pre-equilibrium in solution). Instead, a new catalytic effect was revealed when the influence of organic acids was tested. This was assumed to depend on the bifunctional character of these catalysts, which act as both a proton donor and an acceptor in the transition state. In striking agreement with this conclusion, a-pyridone is very reactive and o-nitrophenol is not. Furthermore, since neither y-pyridone nor -nitrophenol are active, the structure of the catalyst must meet the conformational requirements for a cyclic transition state. Probably a concerted process involving structure 10 in the rate-determining step... 

The removal of 2,4-, 2,6-dichloroaniline, and 2,6-dichloro-4-methylaniline at an aged contaminated site was accomplished by the fungi Allescheriella sp., Stachybotrys, and Phlebia, although their ultimate fate was not determined (D Annibale et al. 2006). PCNA was removed only by the second of these. 

Clomeprop Parent and 2-(2,4-dichloro-3-methylphenoxy)propionic acid Naproanilide Parent and 2-(2-naphthoxy)propionic acid Propanil Parent and 3,4-dichloroaniline Pentanochlor Parent and 3-chloro-4-methylaniline Etobenzanid Parent... 

Fig. 1.11 Dissociation ranges of colour indicators for determination of the acidity function H0 in H2S04-H20 mixtures (1) p-nitroaniline, (2) o-nitroaniline, (3) p-chloro-o-nitroaniline, (4) p-nitrodiphenylamine, (5) 2,4-dichloro-6-nitroaniline, (6) p-nitroazobenzene, (7) 2,6-dinitro-4-methylaniline, (8) benzalacetophenone, (9) 6-bromo-2,4-dinitroaniline, (10) anthraquinone, (11) 2,4,6-trinitroaniline. (According to L. P. Hammett and A. J. Deyrup)...

Diloxanide Diloxanide, 2,2-dichloro-iV-(4-furoyloxyphenyl)-Af-methylacetamide (37.2.4), is made by acylating 2,2-dichloro-iV-(4-hydroxyphenyl)-iV-methylacetamide (37.2.3) with -2-furoyl chloride. The 2,2-dichloro-iV-(4-hydroxyphenyl)-iV-methylacetiamide (37.2.3) is made by iV-acylating 4-hydroxy-Af-methylaniline with either dichloroacetyl chloride, or by an extremely original method of using chloral cyanohydrin [41 3]. 

Treatment of veratrole (191) with excess of 2,5-dichloro- (192) or 2,6-dichloro-1,4-benzoquinone in 70% sulfuric acid yields dibenzofurans and other products. Thus 2,5-dichloro-1,4-benzoquinone (192, Scheme 49) affords the dibenzofuran 193, the diarylquinone 194 and the triphenylene 195. The quinol formed by acid-catalyzed addition of veratrole (191) to the quinone 192 is presumably oxidized to the arylquinone 196, which can form the dibenzofuran 193 or undergo further arylation. The quinone 196 is also available by arylation of 2,5-dichloro-1,4-benzoquinone (192) with 3,4-di-methoxybenzenediazonium chloride in buffered solution. On treatment with 70% sulfuric acid, the arylquinone 196 affords the dibenzofuran 193 (88%). The cyclization can also be effected photochemically. The aryl-quinones available by treatment of 2,5- and 2,6-dichloro-1,4-benzoquinones with buffered solutions of diazotized 4-methoxy-3-methyl- and 3-methoxy-4-methylaniline have been cyclized to 2-dibenzofuranols by the agency of aluminum chloride in hot benzene. ... 

The reaction of A-methylaniline with 1,1,2,2-tetrachlorodimethyldisilane in presence of NEts gives the mono-, di- and triaminodisilanes depending on the reactant ratio. The tetraamide 3 is only formed in the reaction with lithium A-methylanilide. The compounds possess very different reactivity. l-Chloro-l,2,2-tris(lV-methylanilino)dimethyldisilane (2) is rather inert towards nucleophilic reagents. 1,2-Dichloro-l,2-bis(iV-methylanilino)dimethyldisilane (1) reacts with nucleophiles with substitution of both chlorine atoms (see Scheme 1). The products formed during... 

Cyanobenzal chloride (a,a-Dichloro-o-tolunitnle) N-Methylani-linonitrile (N-Cyano-N-methylaniline) 3>(2-Chloro-phenyllpropio-nitrile... 

I N-Methylaniline mixed with 2,6-dichloro-3-(2-chlorethyl)-4-methylpyridine, and heated 7 hrs. at 190°... 

Of greater interest is the catalysis observed by Bitter and Zollinger (78,87) for the reactions of trichloro-s-triazene and 2-anilino-3,5-dichloro-s-triazene with aniline and of l-JV-methylanilino-3, 5-di-chloro-s-triazerie with A-methylaniline, all in benzene. These reactions, which are catalyzed by amines such as pyridine and tri-... 

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