Indole carboxylic add

Indole-3-aldehyde, 879 Indole-3-carbonitrile, 745-746 Indole-3-carboxaldehyde, 745-746 Indole-2-carboxylic add, 839 Indoles, 642 Indolines, 642... 

Jones and Chapman, (1993) developed a method for the decarboxylation of indole-2 carboxylic adds derivatives by microwave-assisted thermolysis using copper (5-25 mol%) in the presence of quinoline (Scheme 3.7). 

Xanthine Indazole Indoleacetic add hydrazide 3-Indoleacetone Indole-2-carboxylic add (337 nm) 7,7,8,8- +... 

Indole carboxylic acid 187 was converted via a Barton ester to fused indole 194 (11 examples, 5-79% yield). Barton ester 189 was formed by treatment of indole 187 with S-(l-oxido-2-pyridinyl)-l,l,3,3-tetramethyl thiouronium hexafluorophosphate (188, Garner s HOTT reagent) in the absence of light. Upon refluxing in MeCN, the Barton ester 189 decomposes to give nucleophilic ethyl radical 190, which adds to the unsubstituted carbon of alkyne 191 furnishing vinyl radical 192.This species cyclizes onto the C2 position of the indole to provide 193, which aromatizes to dehver the final product 194. The sequence proceeds without the need for an initiator or metal catalyst (14JOC5903). 

A mixture of 9.5 g pyrrolyl-2-aldehyde, 29.2 g dimethyl-succinate and NaH (9.6 g of 50% suspension in oil) in 100 ml benzene is stirred at room temperature 6 hours, cooled and carefully acidified with glacial acetic acid. Add water and ether and dry, evaporate in vacuum or work up (JACS 72,501 (1950), JCS 1025(1959)) to get ca. 17 g (80%) 3-methoxycarbonyl-4-(2 -pyrrolyl)-3-butenoic acid (I) (recrystallize-acetone-benzene). A mixture of 12 g (I), 7 g sodium acetate and 70 ml acetic anhydride is left overnight at room temperature with occasional shaking. Then gradually raise the temperature to 70-75° over 2 hours, maintain for 4 hours and work up (see JCS 1714(1955), 986( 1958)) to get ca. 8 g (60%) methyl-4-acetoxy-indole-6-carboxylate (II) (recrystallize-petroleum ether). If desired, this can be converted to 4-OH-indole-6-COOH and 4-methoxyindole-COOH as described in the ref. or decarboxylated as described elsewhere here. If the 1-methyl cpd. is used, 1-Me-indole results. 

Aliphatic and aromatic amines, alkaloids, amino adds, amino sugars, carboxylic and sul-fanfiic adds, drugs, indole derivatives, nucleobases, nucleosides, nucleotides, peptides, dipeptides, polypeptides, phenols, phenothiazine bases, steroids, sulfonamides, water-soluble food dyes... 

Haitnup Disease 1 4a. Type I (kidney 4- gut) ( 4b. Type II (kidney) f (recessive) Neutral monoamino, mono-carboxylic acids (except imino adds, methionine and ar nine) Neutral amino adds (atmormal urinary indole pattern due to bacteria] tamv on of tryptophan) Mental retardation and psychosis, episodic cerebellar ataxia, pellagraUke sjmaptoins and abnormal plantar reflex (nicotinamide therapy) Chromatography shows increase of urinary monoamino, mono-carboxyHc adds (B2, B20, E5. E12. H17, H18, H19, J5. M8. M8, P12, R9.T3a... 

Indoline-2-carboxylic acid (2,3-dihydro-lH-indole-2-carboxylic acid) [78348-24-0] M 163.2, m 168°(dec), pKEst(i) 2.1, pKesi(2) 3.8. Dissolve the acid in hot EtOH, add excess of dry Et20 and cool to... 

Indoline-2-carboxylic acid (2,3-dihydro-lEf-indole-2-carboxylic acid) [78348-24-0] M 163.2, m 168°(dec), pKEst(i) 2.1, pKesi(2) 3.8. Dissolve the acid in hot EtOH, add excess of dry Et20 and cool to yield colourless plates that decompose in the range of 120-150°. The amide (m 208-209°) crystallises as colourless plates which sublime at 150°/1.0mm and has vmax at 1625cm i (paraffin mull) [Hudson Robertson AustJ Chem 20 1935 1967], [Beilstein 22/2 V 421.] See Chapter 6, Catalysts-Part 1 for optical isomers... 

Alford and Davies reported the aminoacylation of indoles and pyrroles via a three-component reaction with ynol ethers and sulfonyl azides. In the presence of copper(I) thiophene-2-carboxylate (CuTC), alkyne 221 and azide 222 react to form an intermediate Al-sulfonyltriazole. N-Methylin-dole (220) adds into this species, which after quench, affords acylated indole 223 in good yield. Various substitution patterns on the indole are tolerated unprotected indole also works and delivers the expected product in 57% yield (14JA10266). 

These workers expanded their carbolithiation chemistry to ortto-aminostibenes (e.g., 16) in the synthesis of C-3 functionalized indoles (Scheme 5) [14]. Thus, Uthiation of 16 in the presence of pentamethyldiethylenetriamine (PMDTA) gave 17 as the major species in equilibrium with the Z-isomer. The structure of 17 was established by an x-ray structure determination of the carboxylic acid obtained upon quenching with carbon dioxide. Exposure of 17 to DMF yielded 18 (equation 1), which upon reaction with ethanol/p-toluenesulfonic add, thionyl chloride, and allyl-trimethylsUane/BFj-EtjO gave 19-21, respectively [14]. 

Rauwolscine gires colour leactions like those of yohimbine and the absorption curves of the hydrochlorides of the two alkaloids are very similar. Heated to 300°j5 mm. rauwolscinic acid forms barman (p. 490) and 3-ethylindole and on fusion with potassium hydroxide decomposes into indole-2-carboxylic acid, isophthalic add, barman and an unidentified indole derivative.. Rauwolsdne itself on distillation with zinc dust produces barman, 2-methylindole (scatole) and isoquinoline. It is suggested that the alkaloid has the skeletal structure suggested by Scholz (formula XIV, p. 508) for yohimbine, the positions of the hydroxyl and carbomethoxy groups being stUl undetermined. 

Hartnup disease Indole-3-acetic add Indole-3-lactic adds Indole-3-acetylglutamine Neutral monoamino mono-carboxylic acids except glycine and the iminoacids. Indican Neutral amino add-transport system ... 

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