Anilide substituted

The formation of the products 43 and 45 has also been studied from a mechanistic point of view. Labeling studies with H2180 revealed that two molecules of acetyl-2-iodoxybenzoic acid (formed by the reaction between Dess-Martin Peri-odinane 8 and water) are involved in para-quinone formation. It is suspected that the substituent in 2-position in 42 blocks another molecule of acetyl-2-iodoxybenzoic acid attacking the initially formed product leading to the formation of ortho-imidoquinones. Anilides substituted in the 3-position does lead to complex mixtures in the oxidation reaction. 

Rintoul and Cross patented gelatinized blasting explosives with small amounts of accelerants for gelat-inization (urethans, anilides, substituted ureas). Shilling patented a propellent explosive powder containing nitrocellulose and nitroguanidine, superficially impregnated with a deterrent material such as dinitrotoluene. 

B) anilides substituted at 2.6 in the aromatic ring, of the lidocaine/butanilicaine type [1707, 1703]. 

Anilides substituted in 2- or 3-positions are monoarylated. 4-Substituted anilides can be either mono- or diarylated. For slower reactions or diarylation, use of silver trifluoroacetate instead of silver acetate is beneficial by increasing the reaction rate. The products can be deprotected by base hydrolysis to afford 2-aryl- or 2,6-diarylanilines. 

Similar sulfenylation reactions of the 2-subsdtuted cyclic enamines of -keto carboxylic acid anilides are also possible, The trifluoromethanesulfenyl substitution takes place according to ring size Sulfenylation occurs at positions 2 and 5 with five-membered rings, at posibon 6 with six-membered tings, and at position 7 with seven-membered rings [5J (equation 4) (Table 1). Acid hydrolysis of the enamines proceeds readily to form the corresponding keto compounds. 

A variety of aryl systems have been explored as substrates in the Knorr quinoline synthesis. Most notable examples are included in the work of Knorr himself who has demonstrated the high compatibility of substituted anilines as nucleophilic participants in that reaction. In the case of heteroaromatic substrates however, the ease of cyclization is dependent on the nature and relative position of the substituents on the aromatic ring." For example, 3-aminopyridines do not participate in ring closure after forming the anilide... 

The first representatives of this group of compounds, 1,5-benzotelluroazepinones 57, have been prepared in 17% yield by the reaction between 2-iodopropyolanilides and NaHTe (98H631). The reaction proceeds, most probably, as nucleophilic substitution of the iodine, resulting in telluroles 58 and the subsequent nucleophilic addition of a hydrotelluride group to the triple bond. An alternative mechanism involving initial addition of NaTeH to the triple bond followed by the nucleophilic substitution of the iodine atom was mled out because the anilides PhNHCOC=CR do not react with NaTeH under the conditions at which the heterocycles 57 were obtained. Neither of the adducts PhNHCOCH=C(R)TeH or [PhNHCOCH=C(R)Te]2 was isolated. 

The mechanism for the conversion of the A -oxide (94) to the o-methylaminophenylquinoxaline (96) involves an initial protonation of the A -oxide function. This enhances the electrophilic reactivity of the a-carbon atom which then effects an intramolecular electrophilic substitution at an ortho position of the anilide ring to give the spiro-lactam (98). Hydrolytic ring cleavage of (98) gives the acid (99), which undergoes ready dehydration and decarboxylation to (96), the availability of the cyclic transition state facilitating these processes. ... 

Most of the subsequent work on this reagent was concerned with the formation of aryl radicals (see review by Cadogan, 1971). However, 2-terf-butyl-A-nitrosoacet-anilide was found to decompose in benzene to give, instead of 2-tert-butylbiphenyl, as expected for a substitution of benzene by a 2-tert-butylphenyl radical, a mixture of isomeric tert-butylphenyl acetates. A careful reexamination (Cadogan and Hib-bert, 1964) suggested that the ratio of 2- and 3-tert-butylphenyl acetates was consistent with the involvement of 2-tert-butylbenzyne, i.e., the product of an ionic dediazoniation, as an intermediate. This was later confirmed by trapping experiments designed to detect aryne intermediates. 

There is little mention in the literature of the use of amide salts in substitution reactions on chlorophosphazene precursors. The anilide anion was shown to be a powerful nucleophile in substitution reactions on various trimer derivatives, but investigations of such reactions with the high polymer have not been reported.22 Where strong nucleophiles (such as amide salts) with low steric requirements are employed, the usual pentacoordinate transition state (Scheme 1), may be a viable reaction intermediate which can undergo alternative modes of decomposition, perhaps involving chain cleavage and/or cross-linking. 

Substituted adducts similar to 50 have been obtained from the reactions carried out in chlorobenzene and in toluene 19>. Whereas methanesulphonyl azide does not thermolyze appreciably below 120 °C, when a solution of CH3SO2N3 in benzene was heated at 80 °C for 100 hr, 47 (ca. 0.5%) could be detected by thin layer chromatography but no 49 38>. Almost all the azide remained undecomposed. Similarly, very small, amounts of 47 were observed, together with much tar and undecomposed azide, on photolysis of CH3SO2N3 in benzene at room temperature or at 80 °C 10). This confirms that azepine formation is the kinetically controlled process, while the anilides are the products of thermodynamic control. 

The thermal, but not the photochemical, decomposition of ferro-cenylsulphonyl azide (14) in benzene gave some intermolecular aromatic substitution product FCSO2NHC6H5 (6.5%) but no intermolecular cyclization product (17). Contrariwise, photolysis of 14 in benzene gave 17 but no anilide 1 ). 

Amination of aromatic nitro compounds is a very important process in both industry and laboratory. A simple synthesis of 4-aminodiphenyl amine (4-ADPA) has been achieved by utilizing a nucleophilic aromatic substitution. 4-ADPA is a key intermediate in the rubber chemical family of antioxidants. By means of a nucleophibc attack of the anilide anion on a nitrobenzene, a o-complex is formed first, which is then converted into 4-nitrosodiphenylamine and 4-nitrodiphenylamine by intra- and intermolecular oxidation. Catalytic hydrogenation finally affords 4-ADPA. Azobenzene, which is formed as a by-product, can be hydrogenated to aniline and thus recycled into the process. Switching this new atom-economy route allows for a dramatic reduction of chemical waste (Scheme 9.9).73 The United States Environmental Protection Agency gave the Green Chemistry Award for this process in 1998.74... 

Quinazolines 51 have been prepared by the condensation of A-aryl carbamates with hexamine, followed by aromatisation of the dihydro intermediate. A variety of mono- and di-substituted anilides were used, mefa-substituted starting materials giving 7-substituted quinazolines <06T12351>. Benzoquinazolines were also prepared similarly from naphthylamine carbamates <06OL255>. 

This procedure may be used to prepare other substituted anilides. If one of the components is a solid, it can be dissolved in an excess of the other. For instance, 46 g. of 2-amino-5-nitroanisole in 285 ml. of hot ethyl bcnzoylacetate is passed through in 30 minutes, with a transformer setting of 70 volts then the column is rinsed with 50 ml. of the ester. The product crystallizes in the receiver and is... 

Studies on competitive inhibition of Bi2 activity show that certain substituted benzimidazoles, purines, and pteridines have weak inhibitory effects in bacterial systems (SlOa). Substituted amides of Bi2 (S9) inhibited the growth-promoting effects of vitamin B12 in protozoic and bacterial systems (B5, B6). The anilide of B12 shows a definite inhibitory effect on maturation and proliferation of blood-forming cells of the chick embryo an opposite effect is induced by vitamin Bi2 (E2). 

These pigments are obtained by coupling substituted aryl diazonium salts with ary-lides of 2-hydroxy-3-naphthoic acid (2-hydroxy-3-naphthoic acid anilide = Naph-tol AS). They provide a broad range of colors from yellowish and medium red to bordeaux, carmine, brown, and violet their solvent fastness and migration resistance are only marginal. Naphthol AS pigments are used mainly in printing inks and paints. 

Substitution in the anilide ring affords a series of Naphthol AS derivatives, although only a limited number are commercially recognized. 

The synthesis involves nitrosating the corresponding substituted acetoacetic anilide with sodium nitrite in acetic acid and subsequently, by adding hydroxyl-amine to the same reaction vessel, converting the compound to the oxime. Finally, complexation is achieved by means of a Ni(II) salt. 

The most important substituted anilide herbicides (Fig. 10, Table 3) are Propanil,Propachlor,and Alachlor [43,151,175-178]. 

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