Trimethylamine, 1,1-dimethoxy

Phenanthrenequinone (8) 9,10-Phenanthrenedione (9) (84-11-7) Lithium aluminum hydride Aluminate (1-), tetrahydro, lithium (8), Aluminate (1-), tetrahydro-, lithium, (T-4)- (9) (16853-85-3) N,/V-Dimethylformamide dimethyl acetal Trimethylamine, 1,1-dimethoxy- (8) Methanamine, 1,1-dimethoxy-(V,N-dimethyl- (9) (4637-24-5)... 

Laudanosine contains four methoxyl groups. By exhaustive methyla-tion it yields trimethylamine and laudanosene (tetramethoxy-o-vinyl-stilbene), CH2=CH—C6H2(OCH3)2—CH=CH—C6H3(OCH3),. On oxidation with manganese dioxide and sulphuric acid it furnishes, in addition to the interesting by-product 2 3 6 7-tetramethoxy-9 10-dihydroanthracene, veratraldehyde and 4 5-dimethoxy-2 )3-methyl-... 

This with potassium hydroxide in methanol forms de-OiV-dimethylarmepavine, m.p. 86-7°, (B. HCl, m.p. 229-30°) of which the methiodide, m.p. 233-4°, on treatment with alkali decomposes into trimetHylamine and a -p-anisyl-/3-(3 4-dimethoxy- 6 - vinylphenyl) -ethylene, m.p. 79°. The latter is oxidised by permanganate in acetone to anisic and m-hemipinic acids. With ethyl sulphate and alkali, armepavine gives 0-ethylarmepavine, an oil, which permanganate oxidises to p-ethoxybenzoic acid. Armepavine is similarly oxidised to p-hydroxybenzoic acid and l-keto-6 7-dimethoxy-2-methyl-1 2 3 4-tetiahydrowoquinoline and is therefore 6 7-dimethoxy-l-p-hydroxybenzyI-2-methyI-l 2 3 4-tetrahydrowoquinoline, i.e., it is laudanosine (p. 187) with MeO. at C replaced by H and MeO at C changed to HO. ... 

The reaction of trans-dimethoxy tellurium tetrafluoride with pyridine produced pyridinium /ra .v-(methoxy)oxo(tetrafluoro)tell urate (VI). The tetramethylammonium salt was obtained, when trans-dimethoxy tellurium tetrafluoride was reacted with trimethylamine in dichloromethane2. Treatment of these salts with 96% sulfuric acid gave trans-hydroxy methoxy tellurium tetrafluoride. ... 

By reaction with phenyl lithium, mesembrine produced phenyl-mesembrinol (XVI) which was dehydrated with thionyl chloride to a mixture of two isomeric phenylmesembrenes (XVII). Methylation and Hofmann degradation of the mixture of methiodides afforded a uniform des-iV-methylphenylmesembrene (XVIII). Methylation of XVIII and Hofmann degradation of the resulting methiodide yielded, besides ethylene and trimethylamine, 3,4-dimethoxy-p-terphenyl (XIX). The isolation of 3,4-dimethoxy-p-terphenyl served to locate the position of the keto group. 

In a later study of this problem Spath and Mosettig (251) by an Emde degradation obtained trimethylamine in the third stage, thus indicating that the nitrogen forms a part of two rings. They also prepared the compound LVII by first condensing l-(2,3-dimethoxybenzyl)-6,7-dimethoxy-... 

The methiodide of IV on treatment with alkali evolved trimethylamine and yielded 4,5-dimethoxy-2-vinylbenzaldehyde, a reaction strictly analogous to the decomposition of trimethylhydrastylammonium iodide (24). 

At the same time an important paper (67) appeared in which essentially the same conclusions with regard to the structure of bebeerine were arrived at by a different route. Faltis, Kadiera, and Doblhammer (67) treated the inactive a, a -dimethylbebeerine methine, obtained by a one-stage Hofmann degradation of bebeerine dimethyl ether, with ozone and obtained a mixture of two dimethylamino dialdehydes. These were not isolated but were converted to the chloromethylate derivatives, oxidized with potassium permanganate to the acids, and boiled with dilute alkah to decompose the quaternary bases. Besides trimethylamine, a mixture of two vinyl carboxylic acids were obtained. One of these proved to be 4, 6-dicarboxy-2,3-dimethoxy-5-vinyldiphenyl ether (LIX). The other vinyl carboxylic acid, which was readily separated from LIX by virtue of its low solubility, was first decarboxylated by heating with quinoline and naturkupfer C and then oxidized with potassium permanganate in acetone. This yielded 4-carboxy-2,2 -dimethoxydiphenyl ether (LXIII), the structure of which was proved by direct comparison with the synthetic compound prepared by the Ullmann condensation of o-bromoanisole and vanillic acid. 

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