Methyl-N-methylanthranilate

Reactions catalyzed by (micro)peroxidases include sulfoxidation, N-demethyl-ation, oxidation, and hydroxylation. A typical example of an interesting N-de-methylation reaction is the conversion of methyl-N-methylanthranilate from citrus into the concord grape topnote N-methylanthranilate (Fig. 7.14). Florse-... 

Italian mandarin oils are characterised by the terpenes limonene (app. 70%) and y-terpinene (app. 20%). Apart from a-sinensal and long-chain saturated aldehydes there is a number of sensorially important unsaturated aldehydes with citrus-like, aldehy-dic, fatty and waxy flavour. Also the potent C-11-hydrocarbons (l,3E,5Z)-undeca-triene, (1,3E,5E,8Z)-, (l,3E,5Z,8Z)-undecatetraene and methyl N-methylanthranilate characterise the typical taste and odour of red mandarin [76]. The latter compound, which also causes the fluorescent character of mandarin oil, is a main constituent of mandarin leaf oils (see Petitgrain oils). 

When compared to Italian mandarin oils, other mandarin [77] or tangerine oils such as Dancy [76] or Murcott tangerine [78] are even more dominated by limonene (app. 95%). Moreover, the composition of the flavour compounds and, therefore, the entire flavour profile, is considerably less complex [76], This is also evident in the rather different content of methyl N-methylanthranilate and a-sinensal. Apart from the... 

The Petitgrain oils of the citrus varieties mandarin (Citrus reticulata Blanco) and lemon (Citrus limon (L.) Burm.) are also commercially available, but to a far lesser extent than for bitter orange. Mandarin Petitgrain oil is characterised by its unique sensory impact, which apart from y-terpinene (20-25%) results from its high content of methyl N-methylanthranilate (40-50%) [106-108]. 

S. Faulhaber (1997) GC/IRMS analysis of mandarin essential oils. 1. 5 Cppg and 5 N, p values of methyl N-methylanthranilate. J. Agric. Food Chem. 4 2579-2583... 

Watanabe et al. (84CPB1264) have reported a one-step synthesis of acronycine 208. Lithium methyl(2-methoxycarbonyl)phenyl amide 258 generated from methyl N-methylanthranilate 257 in situ in the presence of excess lithium cyclohexylamide (LCA), was reacted with 6-bromo-2, 2-dimethyl-7-methoxychromene 259 to produce acronycine 208. A benzyne intermediate 260 is believed to be involved in this reaction (Scheme 44). 

Pachter and Sued have prepared (80) in 68% yield by POCI3-promoted condensation of 2,3,4,9-tetrahydro-lH-pyrido[3,4-b]indol-l-one with methyl N-methylanthranilate. Catalytic reduction of (80) yields (67). Danieli and Palmisano 54) have found that (67) can be converted into (68) by a variety of oxidants. In particular, Tl(OAc)3 and DDQ give (68) in 85 and 67% yield, respectively. The yield of (68) from alkaline permanganate oxidation of (67) (in acetone at 0° 65% yield) was improved markedly to 91%, by use of dicyclohexyl-18-crown-6 (methylene chloride at room temperature). 

Content limonene 65% 75%, y-terpinene 16%-22%, methyl N-methylanthranilate 0.30%-0.60%. Matricaria oil, Matricariae aetheroleum... 

Detoxification of methyl-N-methylanthranilate to methyl-anthranilate nsing a number of microorganisms, among others Claviceps spp., is described in the patent of Page et al. (1989). The detoxification was carried out in a 4-8-day fermentation process. 

A) Preparation of 4-Acetyl-7-Chloro-1,2,3,4-Tetrahydro-1-Methyl-5H-1,4-Bemodiazepin-5-one A mixture of 68.5 g (0.37 mol) of 5-chloro-N-methylanthranilic acid, 51 g (0.51 mol) of calcium carbonate, 76 g (0.37 mol) of bromoethylamine hydrobromide and 2.5 liters of water was stirred and heated under reflux for 3 hours. A solution of 23.4 g (0.26 mol) of anhydrous oxalic acid in 250 ml of water was slowly added to the refluxing mixture. The precipitated calcium oxalate was filtered off, and the filtrate adjusted to pH 7 with concentrated ammonium hydroxide. The filtrate was then concentrated to dryness in vacuo and the residue heated on the steam bath with 400 ml of 6 N ethanolic hydrogen chloride until the residue was crystalline. Filtration gave 122 g of N-(aminoethyl)-5-chloro-N-methylanthranilic acid hydrochloride as a solid. 

Methyl-corypalline Methyl eugenol Methyl isobutyl ketone Methyl isocupressate Methyl-l-propenyl disulfide Methyl-laurate Methyl-n-amyl ketone Methyl n-nonyl ketone Methyl nigakinone Methyl palmitate Methyl-pelletierine Methyl salicylate Methyl-swertianin Methylacetic acid Methylanthranilate Methylchavicol Methylcytisine... 

METHYL-o-ANISIDINE see MGO750 p-METHYL ANISOLE see MGPOOO 9-METHYLANTHRACENE see MGP750 METHYL ANTHRANILATE (FCQ see APJ250 N-METHYLANTHRANILIC ACID, METHYL ESTER see MGQ250... 

C]Tryptophan gave inactive alkaloids but tritiated 2,4-dihydroxy-quinoline (34) and its N-methyl derivative were incorporated into (47) (0.009 % and 0.020% respectively) an early route had suggested the derivation of what was essentially (34) from tryptophan. Radioisotope dilution showed the presence of both these quinoline precursors together with iV-acetyl- and N-methyl-anthranilic acid in A. baueri. A satisfactory incorporation of N-methylanthranilic acid into (47) was found in Evodia xanthoxyloides, and this, together with its natural occurrence, indicates that early methylation may be important in the biosynthesis of acridone alkaloids. 

There are a few tetra- and pentacyclic analogues. Benzo analogues of 245 were prepared from pyridine-2,3-dicarboxylic acid anhydride and a tetralin derivative under conditions of the Friedel-Crafts reaction (85JCR(S)338). Pentacyclic compounds 258 (R = H or Me) were prepared from the bis adduct of anthranilic (or N-methylanthranilic) acid to 1,4-benzoquinone, followed by cyclization in concentrated sulfuric acid (55JCS4440 66CB1991). 6-Methylquinoline-5,8-dione dimerized in the presence of ethanolic IV-methyl-cyclohexylamine to 259 in very low yield and the dimerization is interpreted as two base-catalyzed addition reactions and three oxidation steps (71JCS(C)1253). 

Dreyer and Brenner 62) isolated two new quinazoline alkaloids from seed husks of Zanthoxylum arborescens. The major compound, C17H16N2O2 exhibits a blue fluorescence on TLC. In the H-nmr spectrum the downfield aromatic quartet at 8 8.12 (J = 7.1 Hz) and a one-proton triplet at 8 7.8 (J = 7 Hz), each further split (J = 1 Hz) suggest the presence of four adjacent aromatic protons on an ortho-substituted benzene ring. The aromatic quartet farthest downfield at 8 8.12 indicates the presence of a / r/-related carbonyl group. Two two-proton multiplets (8 2.93—4.40) are consistent with the presence of a 2-phenylethyl system. Other nmr data, in light of the mass spectrum, suggest the presence of an N-methylanthranilic acid system. These characteristics could be assembled in two different ways, leading to structures (7) (Chart 1) and (31). C-spectroscopy and synthesis from N-methylisatoic anhydride and 2-phenylethylamine finally allowed elucidation of the structure. The synthetic product, l-methyl-3-(2 -phenylethyl)-lH,3H-quinazolin-2,4-dione (7) was identical with the alkaloid. 

H-nmr 5 2.53 (3H, s, NMe) and 5.90 (IH, s, C3-H). The structure of (67) was partially revealed by alkaline hydrolysis which yields N-methyl-anthranilic acid and 3,4-dihydro-p-carboline. Boiling alcoholic potassium hydroxide degrades (67) to N-methylanthranilic acid, carbon dioxide and tryptamine. When boiled with alcoholic hydrochloric acid (67) yields optically inactive isoevodiamine [evodiamine hydrate (74)] which can be recyclized with acetic anhydride or oxalic acid to optically inactive evodiamine. (67) can be converted to rutaecarpine via the dry hydrochloride of (74), which, on heating, yields (63). The chemistry of evodiamine has been reviewed by Armarego (6) see also (25, 94, 134, 169). 

Synonyms 2-Methylamino methyl benzoate N-Methylanthranilic acid, methyl ester Methyl methylaminobenzoate Methyl 2-methylaminobenzoate Methyl N-methyl-2-ami nobenzoate... 

Synonyms Anthranilic acid, N-(3-(p-t-butyl phenyl )-2-methyl propyl idene)-, methyl ester Benzoic acid, 2-((3-(4-(1,1-dimethylethyl) phenyl)-2-methylpropylidene) amino)-, methyl ester Lilial methylanthranilate, SchifTs base Methyl-N-(p-t-butyl-a-methylhydrocinnamylidene) anthranilate Empirical C22H27NO2 Properties M.w. 337.50 flash pt. 195 C Toxicology LD50 (oral, rat) 3 g/kg, (skin, rabbit)... 

Methyl 2-anthranilate. See Methyl anthranilate Methyl anthranilate hydroxycitronellal. See Hydroxycitronellal methyl anthranilate N-Methylanthranilic acid, methyl ester. See Dimethyl anthranilate... 

Faulhaber et al. [30,31] analyzed mandarin essential oils by measuring 8 C ratios of characteristic flavor compounds of this product. Mandarin oils, which are obtained by cold-pressing the peel of the fruits of Citrus reticulata Blanco, are used in the food industry and in perfume compositions. The main constituents of mandarin essential oil are limonene (approximately 69%) and y-terpinene (ap proximately 20%), even though the fragrance of this oil is mostly determined by minor components such as methyl A-methylanthranilate (approximately 0.4%) and a-sinensal (approximately 0.3%). Evaluation of genuineness of this product is of special interest, since synthetic analogs of the essential oil components are commercially available. In this context, measurements of 8 C and 8 N of methyl -methylanthranilate [30] and of 5 C of characteristic flavor components in this oil proved helpful in the authenticity assessment of cold-pressed mandarin oil [31]. The characteristic profile of mandarin essential oil so established could be applied to the authenticity control of commercially available mandarin oils. 

Scheme 23.22 Some nitrogen-containing flavour compounds produced by microorganisms, a Methylanthranilate formation from N-methyl methylanthranilate 1 Trametes sp., Polyporus sp. b Different pyrazines produced with microorganisms in optimised media 2 mutant strain from Pseudomonas perolens ATCC 10757 3 Bacillus subtilis, Brevibacterium linens 4 mutant strain of Corynebacterium glutamicum...

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