Methoxyl group

In the cases of 4-hydroxyquinoline and 4-methoxyquinoline the predominance of 6-nitration supports the evidence presented above that nitration in sulphuric acid proceeds via the cations. For both these compounds reaction via the neutral molecules would be expected to occur to a considerable extent at C(j) as a result of the directing properties of the hydroxyl and methoxyl groups. 

Generation of an anion at the 3-position of certain 2-methoxyisoxazolidines leads to loss of the A-methoxyl group (Scheme 92) (79T213). 

An example of this is found in the synthesis of a crown containing a mefa-xylylene unit (see also Sect. 3.5) and a convergent methoxyl group. 4-Methyl-2,6-bishydroxymethyl-anisole was treated with pentaethylene glycol and sodium hydride in THF solution to afford the crown (mp 71—73°) shown in Eq. (3.52) in 59% yield. 

CjHgONa, which is obtained from ricinine by replacement of the methoxyl group by hydroxyl, chlorine and hydrogen in succession. Ricinidine, on hydrolysis, yields first an amide, C7Hg02N, and then a carboxylic acid, by ... 

Calycotamine, CuHi5(i7)03N, occurs with calycotomine but only in traces. The hydrochloride has m.p. 206° and [a]n + 20° (HgO). The picrate is an oil the mercurichloride crystallises in needles.Two methoxyl groups are present. 

Anhalamine, C11H15O3N, occurs in microscopic needles, m.p. 187-8°. The hydrochloride, B. HCl. 2HjO, forms lustrous leaflets, m.p. 256-8° and the sulphate, Bg. H2SO4, colourless prisms the picrate has m.p. 234-6°. The base contains two methoxyl groups and one hydroxyl group. A dibenzoyl derivative, m.p. 128-9°, and a monobenzoyl derivative, m.p. 167-5°, are formed, the latter but not the former being soluble in alkalis. The methyl ether of anhalamine is identical with anhalinine, b.p. 130 0°/0-01 mm., m.p. 61-3°, and the A-methyl derivative is anhalidine, m.p. 131-3°. 

Anhalojiidine, C Hi OgN, crystallises in small octahedra, m.p. 160-1°. The hydrochloride, B. HCl, forms prisms, but the platinum and gold salts are amorphous the picrate has m.p. 201-8°. The alkaloid contains two methoxyl groups, yields a monobenzoyl derivative, m.p. 189° and with methyl iodide forms A-methylanhalonidine hydriodide (pellotine hydi-iodide), yellow prisms, m.p. 125-130°. 

HjO) picrate, m.p. 162-3°. The base eontains one methoxyl group and a methylenedioxy group. Methiodide see under anhalonine above). 

Pellotine, C13H19O3N, erystallises from aleohol in tablets, m.p. 111-2°. The hydroehloride, B. HCl, forms rhombie prisms the auriehloride melts at 147-8° and the pierate at 166-8°. The alkaloid eontains a methylimino group, two methoxyl groups and a phenolie hydroxyl group. The methiodide, B. CHgl. HjO, crystallises in small prisms, m.p. 198-9°. 

Corypalline, CnHijOjN (Corydalis spp. Nos. 9, 22 list, p. 170). This phenolic base, m.p. 168°, picrate, m.p. 178°, contains one methoxyl group and on methylation yields 2-methyl-6 7-dimethoxytetrahydrof5oquinoline, Ci2Hi,02N, m.p. 82°, and on ethylation, 2-methyl-6-methoxy-7-ethoxy-tetrahydrofsoquinoline, m.p. 65°, whence the free hydroxyl appears to be at C and this has been confirmed by the synthesis of corypalline by a method analogous with that used by Spath, Orekhov and Kuffner. Corypalline is therefore hydrohydrastinine (XII) with the methylenedioxy group replaced by MeO at C and. OH at C (Manske). ... 

Constitution. Hydrastine contains two methoxyl groups and a methylenedioxy-group, and behaves as a tertiary base. The first insight into the inner structure of the base was obtained when Freund and Will showed that with dilute nitric acid it undergoes hydrolytic oxidation, yielding opianic acid and a new base hydrastinine, CiiHigOgN. This reaction is analogous with the similar hydrolytic oxidation of narcotine (p. 201) to opianic acid and cotarnine and hydrastinine is allied to cotarnine and can be prepared from it. 

Papaveraldine (Xanthaline), C2oHij05N. This substance forms colourless scales, m.p. 210°, yields well-crystallised yellow salts, which are dissociated in water, and reacts as a tertiary base, forming a methiodide, m.p. 133-5°. It gives an oxime existing in two stereoisomeric forms, and contains foru methoxyl groups. The demethylated product, papaveraldoline, Ci0H,ON(OH)4, has been prepared by Oberlin. Miss Dobson and W. H. Perkin have shown that the alkaloid, Xanthaline, isolated from opium by T. and H. Smith, is identical with papaveraldine. On reduetion with... 

Papaverinic acid, CieHjjO N. HjO, crystallises in small tablets, m.p. 233°. It is dibasic, readily forms an anhydride, furnishes an oxime and a phenylhydrazone, contains two methoxyl groups, and on oxidation yields veratric and pyridine-2 3 4-tricarboxylic acids, and hence is represented by the following formula —... 

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-... 

To dehydrolaudanosoline chloride Robinson and Sugasawa, and independently Schopf and Thierfelder ascribe formula (VI), which makes it 2 3 11 12-tetrahydroxy-8-methyldibenzotetrahydropyrrocolinium chloride. The primary tetracetyl-derivative, m.p. 148°, is represented by (VII R = acetyl) and the second acetyl derivative, m.p. 215°, by (VII R = acetyl) with an ethylenic linkage between carbon atoms 15 and 16. Similarly, the initial tetramethoxy-derivative is to be represented by (VI) with the four hydroxyl groups replaced by methoxyl groups the primary product formed on heating, by loss of methyl chloride, will be represented by (VII R = OMe), and the second product, m.p. 201-3°, of the reaction will be represented by (VII R = OMe), with an ethylenic linkage between and C e-... 

Codamine contains one hydroxyl and three methoxyl groups. On methylation it furnishes d-laudanosine. The position of the free hydroxyl... 

Constitution. Narcotine is a weak, monoacidic, tertiary base. It contains a methylimino-group and three methoxyl groups, and, when heated in closed tubes with dilute hydrochloric acid, furnishes a series of demethylated derivatives dimethylnornarcotine, C19HJ4O4N. OH(OCH3)2, methyl-... 

Bicuculline, C2oHi,06N. (Items 1, 9, 10, 13, 14, 18, 20, 23-26, 34, 35, 38 list, p. 169). This alkaloid exists in two forms, m.p. 177° and m.p. 196°, and has [a], ° + 130- 5° (CHCI3). The hydrochloride has m.p. 259° (dec.) and from the methiodide, W-methylbicuculline, plates, m.p. 246°, has been prepared. Bicuculline contains no methoxyl groups it behaves as a lactone and is convertible by alkalis into bicucine, which is possibly the corresponding hydroxy-aeid (see below). It simulates hydrastine in its reactions and differs from that base by CH, indicating that a methylene-dioxy group replaces two methoxyl groups, and this view is supported by comparison of the products of oxidative hydrolysis of the two alkaloids. Both yield hydrastinine (p. 163) as the basic product, but while hydrastine provides as the second product, opianic acid,... 

Adlumidine, Ci9Hi50eN (items 1, 29 list, p. 169). This alkaloid crystallises in rhombic plates, m.p. 238° no methoxyl groups are present. 

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