Indoles methiodides

EtOH). No methoxyl is present. It forms a series of crystalline double chlorides with cadmium, zinc or copper, does not give the thalleioquin reaction, and solutions of its sulphate are not fluorescent. It is diacidie and forms two series of salts of which the nitrate, B. HNOj, crystallises in minute prisms, m.p. 196°, insoluble in water. Cinchonamine hydrochloride, B. HCl, laminae or B. HCl. HjO, cubical crystals, has been suggested for use in the estimation of nitrates. When warmed with strong nitric acid the alkaloid furnishes dinitrocinchonamine. It gives an amorphous, monoacetyl derivative, and forms a methiodide, m.p. 208 , which with silver oxide yields an amorphous methylcinchonamine. Raymond-Hamet found that cinchonamine ves typical indole colour reactions and is probably an indole alkaloid. This seems to have been... 

The third structural possibility, the formulation of the compounds as pseudo-bases (445) was eliminated in the case of the anhydro-bases derived from p /r-iV -alkyl-l-methyl-3,4-dihydro-j8-carbolinium salts on the basis of their ultraviolet absorption spectra. A structure such as 445 demands indole-type absorption (A jax 280 mp) which was not encountered in the spectra of the anhydro-bases under discussion. This is in accord with general experience. Pseudo-bases are generally found only when dehydration to anhydro-bases is structurally impossible Indole-type absorption was indeed found in the case of the product obtained by treatment of 3,4-dihydro-)3-carboline methiodide (452 R = H) with alkali.In acid solution this compound gave the expected absorption (A jax 355 mp). In alkaline solution, however, an indole-type absorption (A jax 285 mp) was observed. On this basis formulation of the product as a derivative of 2-formylindole (454) ( max 315 mp) was rejected. Although the indole-type absorption is in accord with the pseudo-base structure 453 (R = H), the elemental analysis and molecular weight were not compatible with this formulation and the product was regarded as a dimeric anhydro-base (455). 

Allen et al mainly on the evaluation of data reported by previous workers, advanced structure (5) for 2-methylpyrrole dimer. These data were (a) the monobasic nature of the dimer and (b) the conversion by aqueous acid into an indole which they showed by elimination (i.e., by the synthesis of 2,5-, 2,6-, and 2,7-dimethylindoIes) to be 2,4-dimethyIindole (this compound has since been synthesized by Marion and Oldfield ). Structure (5) for the dimer was confirmed by Edwards and Smith by conversion, by way of the methiodide (6), into the pyrrolidinopyrrole (7), the structure of which was proved by synthesis l,5-dimethylpyrrolid-2-one was condensed with 2-methyI-pyrrole by means of POCI3 to give the cation (8), isomeric with the... 

The required chirally substituted indoloazepine 219 was prepared by reaction of (5)-l-(l-naphthyl)ethylamine with the methiodide of 4-piper-idone (223), followed by a Fischer indole reaction leading to the V-carboline 224 (Scheme 56). Chlorination and reaction with thallium dimethylmalonate, followed by decarbomethoxylation of the resulting in-... 

Arsenones react with methyl iodide at both the 1-position to give a quaternary methiodide and at the ketone to give an acetal (62JCS5110). They also fail to give isolable derivatives under the normal conditions of the Fischer indole synthesis. In these respects the chemistry of the arsenones is distinguished from that of the phosphorinanones, but closely parallels that of the piperidones. 

The first publication on the use of phosphites for the synthesis of indoles phosphorylated in the side chain relates to 1957. The authors [64, 65] showed that gramine methiodide reacts with trialkyl phosphites by the Arbuzov reaction with the formation of 3-indolylphosphonates 69 ... 

Bromolaudanosine, on treatment with potassamide or sodamide in liquid ammonia, yields the dibenzo[ >,g]indolizinium salt (21), the reaction presumably proceeding through the aryne, together with aminolaudanosine and the indoline (22) and the indole (23).32 Photolysis of laudanosine methiodide yields the base (24 R = Me) in methanol and (24 R = H) in water. The latter, on heating with... 

An efficient procedure for the nucleophilic displacement of the A, A -dimethylamino group of 1-triisopropylsilyl-gramines via the fluoride ion-induced elimination-addition reaction has been devised. 1-Triisopropylsilylgramine methiodide 1371 reacted smoothly with a variety of nucleophiles in the presence of tetrabutylammonium fluoride (TBAF) to give 3-substituted indoles 1372 (Scheme 262) <1995TL5929>. 

The base-catalyzed deamination of p-aminoketone methiodides has been elaimed to follow an E2 mechanism involving the partial carbanionic character of the intermediate 24Q 809.810 whereas the deamination of the corresponding indole derivatives would occur... 

An X-ray analysis of the tris(methiodide) showed this alkaloid to be a trimeric indole derivative (CssHsgNe) with the structure LXIX (106). 

Method One, Snyder et al. (410, 741). Ethyl acetamidomalonate -)- gramine methiodide sodium - ethyl o-acetamido-o-carbethoxy-j3-(3-indole)-propionate (A) a-acetamido-a-carbmgr-jS-(3-indole)-propionic acid -> N-acetyltryptophan -> tryptophan (81% yield based on (A)]. 

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