Methyl methylanthranilate

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...

The distillate exhibits faint blue fluorescence—which becomes more pronounced OP addition of alcohol—owing to the presence of methyl methylanthranilate. 

UnKke other citrus essential oils, tangerine essential oil contains about 0.85% of N-methyl methylanthranilic acid (8-187), which is the key component. Other important substances are terpenic hydrocarbons, such as y-terpinene and -pinene, terpenic aldehyde a-sinensal and other terpenoids. 

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. 

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. 

Evidence from nanosecond flash photolysis studies indicates that an oxa-ziridine precursor to the diazoketone is unlikely. Photoelimination of nitrogen is also observed in 4-methyl-1,2,3-benzotriazine 3-oxide and affords 3-methylanthranil a mechanism involving loss of nitrogen from an intermediate oxaziridine has been proposed.74... 

The main components are limonene (65-75%) and q-terpinene (16-22%). The characteristic feature of mandarin oil is its content of a-sinensal (0.2-0.5%), methyl A-methylanthranilate (0.3-0.6%, which is responsible for fluorescence), and long-chain unsaturated aliphatic aldehydes [369, 370a, 370d, 370e, 381, 394c, 414-421b]. 

Petitgrain oils are obtained by steam distillation of the leaves of citrus trees. The oils derived from the bitter orange tree are the most important. Other petitgrain oils (mandarinier, citronnier, and bergamottier) are less important. Petitgrain oil mandarinier is a source of natural methyl A -methylanthranilate, which is present at a concentration of nearly 50%. Petitgrain oils are essential constituents of eau de cologne. 

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... 

Methylanthracene [779-02-2] M 192.3, m 77-79°, b 196-197 /12mm, d 1.066. Chromatographed on silica gel with cyclohexane as eluent and recrystd from EtOH [Werst JACS 109 32 1987. V-Methylanthranilic acid see V-methyl-oaminobenzoic acid. 

IV-Methyl-o-aminobenzoic acid (/V-methylanthranilic acid) [119-68-6] M 151.2, m 178.5°. Crystd from w ater or EtOH. 

Wilson, C.W. and Shaw, P.E. 1981. Importance of thymol, methyl V-methylanthranilate and monoterpene hydrocarbons to the aroma and flavor of mandarin cold-pressed oils. J. Agric. Food Chem. 29 494-496. 

Anthramycin 11-methyl ether (25), which is formed during crystallization of anthramycin (8) in methanol-water, is more stable and hence easier to characterize than anthramycin (Fig. 4a). This ether compound was converted with diazomethane to the dimethyl ether (26), which, after hydrolysis with 6 N HCI and subsequent esterification with diazomethane, yielded methyl 3-methoxy-4-methylanthranilate (27). The relative configuration of the two asymmetric centers C-11 and C-lla of the anthramycin molecule was assigned from H-NMR spectra which indicated the absence of coupling between the protons at C-11 and C-lla 28). Similarly, the ethyl ether (28) of tomaymycin (12) was converted by alkaline hydrolysis to 4-ethoxy-5-methoxyanthranilic acid (29) (26). 

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