Phenyl acetic acid, 4-nitro

Cohare and co-workers reported that aristolactam BU (22) was prepared, following Kupchen s method, by Perkin condensation of 6-bromo-3,4-di-methoxy phenyl acetic acid (119) and o-nitrobenzaldehyde (120) (Scheme 14). The 2-bromo-4,5-dimethoxy-2 -nitro-ds-stilbene-a-carboxylic acid (121) was obtained. The nitro group of 121 was reduced with ferrous sulfate and ammonium hydroxide, and the resulting 2-bromo-4,5-dimethoxy-2 -amino-cw-stilbene-a-carboxylic acid (122) without purification was submitted to the Pschorr phenanthrene synthesis to yield l-bromo-3,4-dimethoxyphen-anthrene-lO-carboxylic acid (123). The phenanthrylamine 124 was prepared from 123 via a Schmidt reaction, and, by treatment with n-butyllithium and CO2, 124, afforded 22 (42). 

H0.N CH.CgH3(N02).N( N).Cl mw 228.60, N 24.51% pink ndls, mp stable at 60-80° but expl on strong heating. Can be prepd from 2-nitro-4-amino-phenyl acetic acid in cold coned HC1 by reaction with amyl nitrite. On heating with ale, this eompd forms 2-nitrobenzaldehyde-anti-oxime(qv)... 

Nitro-phenyl)-acetic acid methyl ester (24)... 

To a solution of (4-nitro-phenyl)-acetic acid methyl ester 24 (8.11 g, 41.6 mmol) in ethanol (208 mL) was added 10% Pd/C (3.20 g) and NH4HCOO (14.0 g in 10 equal portions every 5 min) while stirring at room temperature. The reaction was stirred for 24 h, followed by... 

Oxindole.—When ortho-nitro phenyl acetic acid is reduced to the ortho-amino phenyl acetic acid, the latter, being a gawwa-amino acid, loses water yielding a lactam which is known as oxindole. 

From ortho-Nitro Phenyl Acetic Acid.—Several other syntheses were developed by Baeyer. Starting with ortho-nitro phenyl acetic. CH2—COOH (i)... 

Several enzyme-linked immunosorbent assays (ELISAS) have been developed for trinitrotoluene, trinitrobenzene, 2,4-dinitrotoluene, and 2,6-dinitrotoluene using polyclonal antibodies raised in New Zealand white rabbits. Nitro substituted benzoic and phenyl acetic acids were used as haptens by conversion to the correspond NHS esters followed by coupling to protein carriers.The antibodies which were developed to 1,3-dinitroaromatic haptens had the greatest specificity and sensitivity when the nitroaromatic analytes contained a 1,3-dinitro functionality. In one ELISA system a lower detection limit for various 1,3-dinitroaromatics analytes of 1 ng/mL with an I50 of 5 ng/mL was observed. No cross reactivity with mononitroaromatic compounds was observed. Antibodies developed to mononitroaromatic haptens showed high affinity for a variety of coating antigens but would not compete with nitroaromatic analytes in a normal ELISA. 

Phenol B.P. M.P. Bromo Com. pound Acetate Benzoate p-NItro benzoate 3 5 D. nltro- benzoate Aryloxy- acetic Acid NN-DI- phenyl- carba- mate N-O- naphthyl carba- mate p-Tolu- enesul- phonate 2 4- Dlnltro- phenyl Ether... 

The migration aptitudes in the reaction of ketones with peracetic acid in acetic acid as a solvent are in the order -anisyl > phenyl > >-nitro-phenyl.82 Cyclohexyl and phenyl are about equal in migration aptitude... 

The nitration of dimethyl (Af-phenyl-Ar-methylamino)methylthiomethy-lenemalonate with nitric acid in acetic acid at room temperature for 24 hr gave the 4-nitro derivative (1577) in 38% yield (69T4649). 

Subjected to a mixture of nitric acid/acetic acid, ethyl l,4-benzodioxin-2-carboxylate did not lead to the expected 6-substituted product but led to a complicated mixture from which 52% of ethyl 3-nitro-l,4-benzodioxin-2-carboxyate was isolated <1997SC431>. Under acidic conditions, addition of water at the double bond of 2-phenyl-3-formyl-l,4-benzodioxin 33 afford an hemiketal which recyclized. After dehydration, the 2-benzoyl-l,4-benzodioxin 34 was isolated in very good yield <2000CHE351>. 

Nitration of benzo[6]furan may be achieved with nitric acid in acetic acid and affords the 2-nitro compound, although nitrogen dioxide in benzene is reported to give the 3-nitro compound. 2-Phenylbenzo[6]furan with nitric acid in acetic acid yields the 3- and 6-nitro compounds. Treatment of 2-bromobenzo[6]furan with nitric acid and sodium nitrite yields 2-nitrobenzo[6]furan. The only electrophilic substitution reported with a benzo[c]furan is nitration of 1,3-diphenylbenzo[c ]furan with sodium nitrate and sulfuric acid, and this occurs on a phenyl group. 

Nitration of indolizines is seldom attempted in view of accompanying oxidation reactions. Thus the synthesis of 6- and 8-nitro-2-phenyl-indolizine has been achieved by the cyclization of appropriately substituted 2-methyl-1-phenacylpyridinium bromide.179 However, 1-nitro and 1,3-dinitro compounds have been prepared.4 From the behavior of the indolizine nucleus toward other electrophiles, 3-nitroindolizine might be expected to be the primary product. This compound has been synthesized using a dilute solution of nitric acid in acetic acid at - 70°C where the substrate could well be the base and not the 3-protonated cation as in a nitric acid-sulfuric acid mixture.180... 

Amino-4-methoxy-l-methoxymethylnaphthalene 120, obtained from the chloromethyl derivative 111, is transformed into azide 121. The latter undergoes photolytic heterocyclization to the labile 5-methoxyben-zo[cd]indole 117 which, on reduction by lithium aluminium hydride followed by acetylation, is converted into the stable l-acetyI-5-methoxy-l, 2-dihydrobenzo[o/]indole 119 (R = OMe) [71JCS(C)721]. The reduction of methyl or phenyl 8-nitro-1 -naphthyl ketones by hydrogen and platinum dioxide or by iron in acetic acid leads to a mixture of products (59M634). 

Nitro-2-phenylindoles are obtained by electrophilic ipso-nitration of arylazo, hydroxymethyl, and acyl groups on treatment with two equivalents of 70% nitric acid in acetic acid at 25°C. No attack on the phenyl ring is observed under these conditions [80MI1 81JCS(P2)628]. Indolenines undergo nitration mainly at the 5-position (77-85%) (64TL803). 

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