Pyrimido indole

Heating an intimate mixture of bis(2,4,6-trichlorophenyl)malonate and the appropriate 3-aminotriazinoindoles 657 afforded pyrimido-[3, 2 2,3][ 1,2,4]triazino[5,6-fe]indole-2,4-diones 658 (88JHC475). 

The cyclocondensation of 3-aminopyrido[3,4-h]indole (1090) and EMME in boiling acetic acid and propionic acid for 8 hr or 4 hr gave pyrimido[2, 1 6,1 ]pyrido[3,4-b]indolecarboxylate(1091) in52%and65% yields, respectively [87MIP4, 87MIP5 881JC(B)484]. 

Carboxy substituted diazepines 226 and 229 react with phenyl isocyanate to afford pyrimido diones 227 and 230, correspondingly (Scheme 48, Section 3.1.1.3 (1993JHC897)). N-Hydroxymethylation on an indole ring annulated to benzaze-pinone, as well as formation of the corresponding carbamate and urea, has been described (2004MI1076). 

Methyl-l, 2,3,4-tetrahydro-yrido[4,3-b]indoiy (80%) umgelagert2. 

Tetracyclic pyrimido[l, 2 l,2]pyrido[3,l- >]indole derivative 606 (R = H) was obtained when 9-bromotetrahydropyrido[ 1,2- ]pyrimidin-4-one 604 (R = H) reacted with Af-methylaniline in boiling ethanol for 8 hours under nitrogen in 37% yield (Scheme 40) (91JHC1405). In the reac-... 

Alkylation of 8-(un)substituted-10,10,10a-trimethyl-1,2,3,4,10-1 Oa-hexahydro-pyrimido[l,2-a]indol-2-ones (46) gave (unlike the five-membered ring case) chiefly the O-ethers (47), and gave them exclusively when triethyloxonium fluoroborate was the alkylating agent. Upon treatment with acid, these similarly gave the 1-alkoxy-carbonylethyl-2-methylene-3,3-dimethyl-5-substituted indolines (45, n = 2).50... 

P. Tardieu, R. Dubest, J. Aubard, A. Kellmann, F. Tfibel, A. Samat, and R. Guglielmetti, Synthesis Mid photochromic characteristics of l,3-dihydrospiro[2fir-indole-2,3 -[3 /7]pyrimido[5,4-/7[l,4]benzoxa-zines] and 1,3-dihydrospiro[2/f-indole-2,7 -[7/f]thiazolo[5,4-/][l,4]benzoxazines], Helv. Chim. 

The mechanism of the photochemically induced conversion of vinylazides into 2H-azirines has been examined using ab initio MO calculations. A new approach to the elusive thionitrosobenzene system has been reported. Direct irradiation of the 3-azido-2,l-benzisothiazole (88) affords a transient 2-cyanothionitrosobenzene (89) which can be trapped as the cycloadduct (90) with cyclopentadiene. Nitrene cyclization is the preferred pathway on irradiation of the 5-formyl- or 5-benzoyl-6-azidouracils (91) and yields the isoxazolo[3,4-d]pyrimidines (92). In contrast, 5-phenyl- and 5-benzyl-6-azidouracils were converted into pyrimido[4,5-b]indoles and pyrimido[4,5-ti Jquinolines, respectively, by a pathway involving photochemically induced loss of nitrogen and intramolecular nitrene insertion. 

On irradiation with a high-pressure mercury lamp, 9-phenyl-8-azapurine in dioxane gave 9i/-pyrimido[4,5-i>]indole in 33% yiel whereas 54% was obtained in methanol. Nine derivatives of this azapurine, carrying various substituents in the 6 position, behaved similarly (32-91% yields). The principal by-products arose from (1) replacement of hydrogen in the 4 position of the pyrimidoindole by dioxane or methanol residues, (2) reaction with benzene, when used as a solvent, to yield 4-anilino-5-phenylpyrimidine, and (3) reaction with dioxane to furnish 4-anilinopyrimidines. l,3,7-Trimethyl-8-azapurine-2,4-dione, irradiated with diethylamine in acetonitrile, gave 6-diethylamino-1,2-dimethyl-5-methylaminopyrimidine-2,4-dione (66% yield). However, photolysis in methanol gave 5-hydroxy-l,3-dimethyl-6-methoxypyrimidine-2,4- one (22% yield). 

With (305) the azavinamidinium salt (7u) yields (150—160°, 2 h in quinoline) the pyrimido(3,4-c)indole-4-carbonitrile (309) mp. 160—161°, orange needles (47%), besides a not very soluble, yellow substance, not identified. 

Photo-oxidative decarboxylation of indole-3-acetic acid in the presence of pyrimido[5,4-g]pteridine W-oxide has been described. Photoelimination of carbon dioxide has been observed in a variety of esters including aromatic esters, substituted l-naphthylmethyl alkanoates and ethyl a-oxocarboxylates,and is one pathway described in a review of the photochemistry of 2(3H)- and 2(5H) furanones.Ethylene, ethanol and carbon dioxide are the only... 

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