Methyl-anthranilate

Orange Flower. Extraction of freshly picked flowers of the bitter orange tree, dims aurantium (subspecies amard) for the production of concrete is carried out mainly ia Morocco and Tunisia. Most of this material is processed further to give orange flower absolute, one of the most important absolutes used ia perfumes after rose and jasmine. It is highly valued ia perfumery, even when used at low levels, for its long-lasting, rich, warm, yet dehcate and fresh floralcy. The material is a complex mixture, to which methyl anthranilate [134-20-3] linalool (3), methyl jasmonate (15), and iadole (16) are important odor contributors. 

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. 

Isatin (190) is a compound with interesting chemistry. It can be iV-acetylated with acetic anhydride, iV-methylated via its sodium or potassium salt and O-methylated via its silver salt. Oxidation of isatins with hydrogen peroxide in methanolic sodium methoxide yields methyl anthranilates (81AG(E)882>. In moist air, O-methylisatin (191) forms methylisatoid (192). Isatin forms normal carbonyl derivatives (193) with ketonic reagents such as hydroxylamine and phenylhydrazine and the reactive 3-carbonyl group also undergoes aldol condensation with active methylene compounds. Isatin forms a complex derivative, isamic acid (194), with ammonia (76JCS(P1)2004). 

These formulae explain the scission products of the two alkaloids and the conversion of evodiamine into rutaecarpine, and were accepted by Asahina. A partial synthesis of rutaecarpine was effected by Asahina, Irie and Ohta, who prepared the o-nitrobenzoyl derivative of 3-)3-amino-ethylindole-2-carboxylic acid, and reduced this to the corresponding amine (partial formula I), which on warming with phosphorus oxychloride in carbon tetrachloride solution furnished rutaecarpine. This synthesis was completed in 1928 by the same authors by the preparation of 3-)S-amino-ethylindole-2-carboxylic acid by the action of alcoholic potassium hydroxide on 2-keto-2 3 4 5-tetrahydro-3-carboline. An equally simple synthesis was effected almost simultaneously by Asahina, Manske and Robinson, who condensed methyl anthranilate with 2-keto-2 3 4 5-tetrahydro-3-carboline (for notation, see p. 492) by the use of phosphorus trichloride (see partial formulae II). Ohta has also synthesised rutaecarpine by heating a mixture of 2-keto-2 3 4 5-tetrahydrocarboline with isatoic anhydride at 195° for 20 minutes. 

Substituted 2-mercapto-4(3i/)quinazolinones were prepared by condensing methyl anthranilate with isothiocyanates (see 7c). 

The alkaloid rutaecarpine (111) was synthesized from l-oxo-1,2,3,4-tetrahydro-)3-carboline (183 R = H) by condensation with methyl anthranilate in the presence of phosphorous chloride or by heating... 

The reaction of methyl anthranilate and 3-amino-2-chloropyridine in 1,2,4-trichlorobenzene in the presence of KOt-Bu at 50 °C gave 5,1 l-dihydro-6//-pyrido[2,3-Z)]benzodiazepin-6-one and 6-amino-ll//-pyr-ido[2,l-Z)]quinazolin-l 1-one as a by-product (99BMCL3031). 

Altanserin (100) is a representative of the thiaquinazolinones. This serotonin antagonist is said to prevent gastric lesions. One method for preparation of this compound involves first preparation of isothiocyanate derivative 99, by reacting 4-fluorobenzoylpiperidine with 2-bromoethylamine and then converting the intermediate to the isothiocyanate with thionyl chloride and base. Condensation of 99 with methyl anthranilate (98) probably proceeds initially to a thiourea. Cyclization by ester-amide interchange leads to altanserin (100) [28]. 

Methyl Anthranilate.—This ester is one of extreme importance, and to it is largely due the possibility of manufacturing artificial neroli oils. It was discovered as a constituent of neroli oil in 1895 by Walbaum, and has since been identified in numerous other flower oils, such as tuberose, ylang-ylang, jasmin, and gardenia. Its value in synthetic perfumery is therefore obvious. Its constitution is that of a methyl ester or orthp-amido-benzoic acid, of the formula here shown —... 

Methyl Methyl-anthranilate.—This ester is quite similar in all its characters to methyl anthranilate. It has the constitution—... 

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,... 

Methyl anthranilate from Eastman Kodak Company was used without further purification. 

Methyl anthranilate Acetic acid Unknown, CHCL3-soluble 0.033<—... 

Because we were unable to identify the methyl anthranilate component within the sensitivity of the equipment used for these tests, we resorted to an examination of the ethanol loss (Figure 11). After a sampling time of 65 hours for each sample, the sample of CC14 was injected. The amplitude of the peak at 1 minute 58 seconds retention time (peak for ethanol) was examined. The two tests proved that the corrective action on the container was effective. Less than 10 6 grams of ethanol (the sensitivity limit of the system) had escaped from the corrected sample container, whereas 1.5 X 10 4 grams of ethanol had escaped from the uncorrected sample. (See Figure 11, which shows the two traces.)... 

Fortunately, such sophistication is not always necessary to compare containers. For example, a few days after the gas chromatography tests were completed, we opened the jars and were able to detect by sniffing that the grape odor from one container was noticeably more distinct than from the other. The methyl anthranilate, which had eluded the gas chromatograph, could be detected qualitatively and, for comparative purposes, quantitatively by the human nose. 

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