Esters anthranilic acid

Other discretes from chemical assessment (a-Amino Ester, Anthranilic Acid (AA), Alkylating Agent, Yield of purified material) ... 

Anthranilic acid, 1,5-dimethyl-1-vinyl-4-hexenyl ester Anthranilic acid linalyl ester. See Linalyl anthranilate... 

Synonyms 2-Aminobenzoic acid-3-phenyl-2-propenyl ester Anthranilic acid cinnamyl ester Cinnamyl alcohol anthranilate Cinnamyl-2-aminobenzoate Cinnamyl-o-aminobenzoate... 

Synonyms Anthranilic acid, 1,5-dimethyl-l-vinyl-4-hexenyl ester Anthranilic acid linalyl ester 3,7-Dimethyl-1,6-octadien-3-ol 2-ami nobenzoate 3,7-Dimethyl-1,6-octadien-3-yl anthranilate 1,5-Dimethyl-1-vinyl-4-hexen-1-yl-o-aminobenzoate... 

Synonyms 2-Aminobenzoic acid methyl ester o-Aminobenzoic acid methyl ester Anthranilic acid methyl ester Benzoic acid, 2-amino-, methyl ester 2-Carbomethoxyaniline o-Carbomethoxyaniline 2-(Methoxycarbonyl) aniline Methyl 2-ami nobenzoate Methyl-o-aminobenzoate Methyl 2-anthranilate Neroli oil, artificial... 

The benzoic acid derivative 457 is formed by the carbonylation of iodoben-zene in aqueous DMF (1 1) without using a phosphine ligand at room temperature and 1 atm[311]. As optimum conditions for the technical synthesis of the anthranilic acid derivative 458, it has been found that A-acetyl protection, which has a chelating effect, is important[312]. Phase-transfer catalysis is combined with the Pd-catalyzed carbonylation of halides[3l3]. Carbonylation of 1,1-dibromoalkenes in the presence of a phase-transfer catalyst gives the gem-inal dicarboxylic acid 459. Use of a polar solvent is important[314]. Interestingly, addition of trimethylsilyl chloride (2 equiv.) increased yield of the lactone 460 remarkabiy[3l5]. Formate esters as a CO source and NaOR are used for the carbonylation of aryl iodides under a nitrogen atmosphere without using CO[316]. Chlorobenzene coordinated by Cr(CO)j is carbonylated with ethyl formate[3l7]. 

Esterification. The formation of an ester from an acid (or its derivative) and an alcohol is of limited appHcation siace carboxyUc esters are comparatively rare substitueats ia dyes. Esters of A/-(3-hydroxyethylaniLiaes are important iatermediates for azo disperse dyes for polyester. Another example is methyl anthranilate, formed by the classical esterification of anthranilic acid usiag methanol and sulfuric acid. 

The pyrazole analogues of anthranilic acids or anthranilonitriles are a convenient source of [5.6] fused systems (for a general review see (80T2359)). Thus 5-amino-4-cyanopyrazoles (in some examples an ester or a hydrazido group replaced the cyano group) have been transformed into pyrazolo[3,4-d]pyrimidines (552) and into pyrazolo[2,3-e]diazepinones (553), and 4-amino-5-methoxycarbonylpyrazoles have been converted into pyrazolo[4,3-d]pyrimidines (554). 

It was found inadvisable to use more than four molecules of form-amide [ (47) when R = H] per molecule of anthranilic acid and the condensation produces best results when the mixture is heated at 120 -130°C for 2 hr followed by further heating at 170°-180 C for 2 hr. Other variants of this reaction involve the use of ammonium o-acylaminobenzoates, anthranilic acid in the presence of nitriles and acetic anhydride, o-acetamidonitrile with acetic anhydride or hydrogen peroxide, anthranilic esters and aliphatic or aromatic amides or amidines, isatoic anhydride with amides or amidines, and anthranilic esters with aryl iminochlorides in acetoned The mechanism proposed by Bogert and Gotthelf has had experimental supporR and is represented in Scheme 12. 

Indazoles can be considered as either azaindoles or azaisoindoles depending on the reader s prejudice. Benzydamine (54) represents a drug with this heterocyclic nucleus. Alkylation of the amine of anthranilic acid methyl ester with benzyl chloride in the presence of sodium acetate gives 52. Treatment with nitrous acid leads to the nitrosoamine, which cyclizes spontaneously to the 3-ketoindazole system, 53. This intermediate forms an ether of its enol form on heating the sodium salt with 3-dimethylaminopropyl chloride. There is thus obtained benzydamine (54), a fairly potent nonsteroidal antiinflammatory agent with significant antipyretic and analgesic properties. 

Nucleophilic aromatic substitution of the anthranilic acid derivatives, 72, on ortho-bromonitrobenzene affords the diphenyl-amine, 73. The ester is then saponified and the nitro group reduced to the amine (74). Cyclization of the resulting amino acid by heat affords the lactam (75). Alkylation on the amide nitrogen with 2-dimethylaminoethyl chloride by means of sodium amide affords dibenzepine (76). ... 

Anthranilic acid, or o-amidobenzoic acid, C H (NH2)(COOH),. is the-acid constituent of the ester found in neroli, petit-grain, jasmin, and mandarin oils. It is a solid crystalline substance melting at 145°. It is prepared artificially, and then converted into synthetic methyl anthranilate.. To prepare anthranilic acid, o-nitrobenzaldehyde is reduced by tin and hydrochloric acid to anthranil,... 

This product was dissolved in 10 ml of chloroform. To this solution were added 10 ml of a 10% aqueous solution of caustic soda and the mixture was warmed at 50°C to effect hydrolysis of the ester group. After completion of the reaction, the organic phase was separated, washed with water and distilled to remove the solvent whereby 2.1 g (yield 4B%) of the end product, i.e., N-(3, 4 -dimethoxycinnamoyl)-anthranilic acid, were obtained. This product had a melting point of 211°C to 213°C. 

V-methyl-7V-(o-aminophenyl)anthranilic acid methyl ester... 

For the preparation of the 2,5-diketopiperazines 9-57 and 1,4-benzodiazepine-2,5-diones 9-58, respectively, the isocyanide 9-54 was either treated with an aldehyde and an amino acid, or with an aldehyde and an anthranilic acid, to give either 9-55 or 9-56, using the conditions depicted in Scheme 9.11. Further transformations include liberation from the resin with KOtBu forming N-acyloxazolidones and treatment with NaOMe to afford the corresponding esters, which are then cy-clized to the desired products 9-57 and 9-58 under acidic conditions. 

Anthranilic acid reacts with the fused-ring chloroimine 155 in ethanol at 170°C to give the pentacycle 156 (Equation 38), and similar compounds can be prepared from the keto-ester 157 by reaction with hydrazine in acetic acid (Equation 39) <2003HC0181>. 

A number of new conditions and catalysts have been used for the synthesis of quinazolinones 50 from anthranilic acids, amines and ortho esters, including bismuth trifluoroacetate with an ionic liquid <06TL3561>, lanthanum nitrate or tosic acid under solvent-free conditions at room temperature <06TL4381> and Nafion-H <06SL2507>. 

Solid-liquid phase systems with no added solvent produce esters in high yield [e.g. 2, 3] and are particularly Useful when using less reactive alkyl halides [e.g. 15], for the preparation of sterically hindered esters [16], or where other basic sites within the molecule are susceptible to alkylation, e.g. anthranilic acid is converted into the esters with minimal A-alkylation and pyridine carboxylic acids do no undergo quat-emization [17]. Excellent yields of the esters in very short reaction times (2-7 minutes) are also obtained when the two-phase system is subjected to microwave irradiation [18]. Direct reaction of the carboxylic acids with 1,2-dichloroethane under reflux yields the chloroethyl ester [19], although generally higher yields of the esters are obtained under microwave conditions [20]. 

N-3-Substituted 2-thioxo-4-quinazolinones 859 are formed when alkyl or aryl isothiocyanates are reacted with anthranilic acids or esters 857, <2001JME1710, 2002AP556, 2004JC0584, 2006JME2440>. The intermediate di-substituted thiourea 858 is normally not isolated, but is directly ring-closed in situ to the thioxoquinazolinone product 859. When 3-unsubstituted products are required, benzoyl isocyanate can be used <20008714>. 

Chem. Abstr. Name 3-Phenyl-2-propen-l-ol, 2-aminobenzoate lUPAC Systematic Name Anthranilic acid, cinnamyl ester Synonyms Cinnamyl alcohol anthranilate 3-phenyl-2-propenyl 2-aminobenzoate 3-phenyl-2-propenyl anthranilate... 

In a separate experiment, groups of male CDl mice were given intraperitoneal injections of 0-200 mg/kg bw ciimamyl anthranilate daily for three days. At doses of 20 mg/kg bw and above, there were dose-dependent increases in relative liver weight, total cytochrome P450, and cyanide-insensitive palmitoyl-CoA oxidation. The hepatic effects of cinnamyl anthranilate are apparently due to the intact ester, since neither its expected metabolites alone nor an equimolar mixture of the hydrolysis products, cinnamyl alcohol and anthranilic acid, had a significant effect on the weight or marker enzyme content of mouse liver (Viswalingam Caldwell, 1997). 

Cinnamyl anthranilate has the characteristic effects of a peroxisome proliferator on mouse liver, increasing the activity of peroxisomal fatty acid-metabolizing enzymes and microsomal CYP4A and increasing hepatocellular proliferation. These effects are mediated by the intact ester, and were not seen after administration of the hydrolysis products, cinnamyl alcohol and anthranilic acid. The corresponding effects on rat liver were very much weaker. No relevant data from humans were available. 

The reactions of anthranilic acids and esters (65CB983, 75BSF(2)283) with halohydrins give the 4,l-benzoxazepin-5-one system (357). o-Methylaminobenzamide reacts with ethylene oxide to give (358) which can be cleaved to (359) by treatment with aqueous ammonia (66JOC4268). 

At a finer level of resolution, compounds with similar hydrocarbon skeletons may vary in functional group, degree of unsaturation, or oxidative state. For example, the volatile methyl esters of benzoic, salicylic and anthranilic acids (1 Fig. 5.1) differ only in -position functionality, but they are olfactorily distinct to humans and at least to some phytophagous insects (Raguso et al, 1996 Maekawa et al., 1999). Furthermore, many scent compounds have positional isomers and enantiomers that elicit different behavioral responses from flower visitors (Williams and Whitten, 1983 Hick et al, 1999). The refinement of capillary gas chromatography-mass... 

Because benzanilides exhibit fungicidal activity 38) and anthranilic acid esters have fungicidal and bactericidal activities 39,40), Kirino et al. attempted to derive a new class of fungicides from those having a hybrid structure, methyl N-(substituted benzoyl)anthranilates 41. Among various derivatives, m-substituted compounds (19) were shown to exhibit appreciable preventive activity against powdery mildew of cucumber. 

Laser irradiation of isatin (70) gave 71 as a result of bimolecular condensation (78TL3007). The diazine ring of 73 was formed during the cyclocondensation of anthranilic acids with the imidate esters derived from indolinone (72) (81AP271). 

A remarkably simple and efficient method for preparing oxazolo[2,3- >]quinazoline (208) is the reaction of anthranilic acids or their esters with /3-haloisocyanates, followed by base-catalyzed cyclization of the intermediate urea derivatives (207) [74GEP(0)2252122 76S469 80JHC1553]. 

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