2 -4,5,6 trimethoxy

Asaronealdehyde (2,4,5-trimethoxy-benzaldehyde) can be produced in the following way Methylate resorcinol. Product is 1,3-di-MeO-benzene. Do a Vilsmeyer aldehyde synthesis with POCI3/N-methylformanilide to obtain 2,4-di-MeO-benzaldehyde. Brominate and treat as described above to obtain asaronaldehyde. 

A solution of sodium methoxide (25% w, 115 ml, 532 mmol) in methanol (187 ml) was cooled to — 8 "C under nitrogen. A solution of 2,4,5-trimethoxy-benzaldehyde (25 g, 128 mmol) and methyl azidoacetate (59 g, 513 mmol) in a 1 2 mixture of methanol-THF (50 ml 4- 100ml) was added dropwisc to the sodium methoxide solution with stirring at — 8°C over a period of 45 min. The solution was stirred and kept below 5°C for 2 h. The mixture was then poured onto ice (1 kg) and stirred. The precipitate which resulted was collected by filtration, washed with water and dried over CaCl in a vacuum desiccator. The dried precipitate was dissolved in EtOAc (600 ml) and dried over Na2S04. 

ALKANOLAMNES - ALKANOLAMINES FROM OLEFIN OXIDES AND AL ONIA] (Vol 2) (3-(2-Aminoethyl)aminopropyl)trimethoxy silane... 

Pyridine 1-oxide, 2,4,6-trimethoxy-rate eonstants, 2, 190 (75JCS(P2)1600)... 

Chromone, 3-(tetrazol-5-yl)-antiallergic activity, 5, 836 degradation, 5, 815 Chromone, 3,5,7-trimethoxy-2-methyl-photolysis, 3, 695... 

The trimethoxy derivative is too labile for most applications, but the mono and diderivatives have been used extensively in the preparation of oligonucleotides and oligonucleosides. The monomethoxy derivative has been used for the selective protection of a primary allylic alcohol over a secondary allylic alcohol (MMTr, Pyr, -10°). ... 

Anhalamine. When mezcaline is condensed with formaldehyde it yields 6 7 8-trimethoxy-l 2 3 4-tetrahydrowoquinoline and the quaternary iodide obtained from this is identieal with dimethylanhalamine methiodide. It follows that 0-methylanhalamine must be 6 7 8-trimethoxy-1 2 3 4-tetrahydrot5oquinoline. The free hydroxyl group was shown to be at C by Spath and Beeke, who found that the produet (II R = Et), formed by 0-ethylation of anhalamine, gave 4 5-... 

Pellotine and Anhalonidine. The A -acetyl derivative of mezcaline (I NHj— NHAc), on treatment with phosphoric oxide, yields 6 7 8-trimethoxy-l-methyl-3 4-dihydrowoquinoline (picrate, m.p. 181-2°), which, on successive catalytic hydrogenation and treatment with methyl sulphate, yields 6 7 8-trimethoxy-l 2-dimethyl-l 2 3 4-tetrahydro-isoquinoline identical with 0-methylpellotine (picrate, m.p. 167-8°), whence it appears that pellotine must be a dimethyl ether of 6 7 8-trihydroxy-1 2-dimethyl-l 2 3 4-tetrahydrowoquinoline. Pellotine and anhalonidine on complete methylation yield the same product, and as anahalonidine is a secondary base and differs from pellotine by containing —CHj less, it must be a dimethyl ether of 6 7 8-trihydroxy-l-methyl-1 2 3 4-tetrahydrowoquinoline, and pellotine should be A -methyl-anahalonidine. 

IV-Methyllaurotetaninc, C20H23O4N. This alkaloid was obtained by Spath and Suominen from Litsea citrata. It distils at 205-15° (air-bath temperature) urder a pressure of 0-01 mm. and is dextro-rotatory. Diazomethane converts it into glaucine and Hofmann degradation of the ethyl ether yields 3 5 6-trimethoxy-2-ethoxy-8-vinylphenanthrene, m.p. 140-1°, identical with that obtained from laurotetanine (see above). The alkaloid is therefore represented by formula II (NMe replacing NH). 

Similarly, reaction of (3) with methyl orthoformate yields the trimethoxy compound (6) via the intermediate 1,4-adduct (5). 

Even polyalkoxy-s-triazines are quite prone to nucleophilic substitution. For example, 2,4,6-trimethoxy-s-triazine (320) is rapidly hydrolyzed (20°, dilute aqueous alkali) to the anion of 4,6-dimethoxy-s-triazin-2(l )-one (331). This reaction is undoubtedly an /S jvr-4r2 reaction and not an aliphatic dealkylation. The latter type occurs with anilines at much higher temperatures (150-200°) and with chloride ion in the reaction of non-basified alcohols with cyanuric chloride at reflux temperatures. The reported dealkylation with methoxide has been shown to be hydrolysis by traces of water present. Several analogous dealkylations by alkoxide ion, reported without evidence for the formation of the dialkyl ether, are all associated with the high reactivity of the alkoxy compounds which ai e, in fact, hydrolyzed by usually tolerable traces of water. Brown ... 

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