Indeno- quinoxalines

If the heterocyclic base contains several pyridine-type nitrogens select can also be observed. Indeno[l,2-b]quinoxalines, for example, are quaternized at the N-10 atom.110 The alkylation of heterocycles conta one pyrrole-type nitrogen and several pyridine-type nitrogens is appar selective (e.g., indolo[2,3-b]quinoxaline).201 The yields of quaternary however, are extremely low,201 even if phenacyl halides or a-halo ester used.207 Perhaps the resultant quaternary salts are dealkylated.200,207... 

Azizian, J., Karhni, A.R., Kazemizadeh, Z., Mohammadi, A.A., Mohammadizadeh, M.R. 2005. Silica snlfuric acid-catalyzed reaction of 4-hydroxy proUne with llH-indeno[l,2-b] quinoxalin-ll-one and isatin derivatives A novel synthesis of new pyrrole compounds. Synthesis 1095-1097. 

Scheme 38 Substituted-1 l/-/-indeno[l,2-5]quinoxaline-l 1-ones from o-phenylenedi-amine and 3.

New spiro[indeno[l,2-fe]quinoxaline-l l,2 -pyrrolidine] derivatives 548 were prepared stereoselectively in high yields from the efficient multicomponent 1,3-dipolar cycloaddition reaction between ninhydrin 545, 1,2-DABs 155a, b, sarcosine 546, and chalcones 547 (Scheme 2.130) (Moemeni et al. 2012). In this case the car-bocyclic system of the ninhydrin contributes to the construction of the pyrazine ring system, as distinct from the above reaction of tetrachlorocyclohexanedione 539. 

Scheme 2.130 Synthesis of spiro[indeno[l,2- ]quinoxaline-ll,2 -pyrrolidine] 548...

Moemeni M, Arvinnezhad H, Samadi S, Tajbakhsh M, Jadidi K, Reza Khavasi H (2012) An efficient multicomponent and stereoselective synthesis of new spiro[indeno[l,2-h] quinoxaline-ll,2 -pyrrolidine] derivatives. J Heterocycl Chem 49(1) 190-194. doi 10.1002/ jhet.685... 

An efficient, three-component method for the construction of ll-(lH-pyrrol-l-yl)-llH-indeno-[l,2-li]quinoxalines has been worked out by Azizian et al. [60]. The reaction, catalyzed by montmorillonite KIO (Mont K-10) under MW irradiation, is carried out via condensation of ninhydrin, 1,2-phenylenediamine, and 4-hydroxyproline. The authors propose that an azomethine ylide 42 is formed as the intermediate, which undergoes dehydration (catalyzed by Mont K-10) spontaneously to produce the conjugated azomethine ylide 43. Proton transfers could then give azomethine ylide 44, which in turn furnishes the desired product (Scheme 38). 

SCHEME 38 MW-assisted synthesis of indeno-[l,2-fc]quinoxalines and the proposed mechanistic pathway. 

J. Azizian, A.R. Karimi, Z. Kazemizadeh, A.A. Mohammadi, M.R. Mohammadizadeh, A synthetic route to ll-(lH-pyrrol-l-yl)-llH-indeno[l,2-i)]quinoxaline derivatives exploiting a three-component coupling strategy under microwave irradiation. Tetrahedron Lett. 46 (2005) 6155-6157. 

Perumal et al. prepared a library of l-methyl-4-arylpyrrolo-(spiro[2.2 ]indan-l, 3 -dione)-spiro[3.3"]-l"-methyl/ benzyl-5 -(arylmethylidene)piperidin-4"-ones 185 and l-methyl-4-arylpyrrolo-(spiro[2.11 ]-llH-indeno[l,2-b] quinoxaline)-spiro[3.3 ]-l"-methyl/benzyl-5 -(arylmethylidene)piperidin-4 -ones 186 in good yield (Scheme 109) via 1,3-dipolar cycloaddition of azomethine ylide in the IL [BMIM][Br]. The reactions were realized by heating an equimolar mixture of the reactants in IL in an oil bath at 100 °C for 1-2 h. After completion of the reaction, the products were isolated and purified by simple recrystallization from ethanol, while the IL could be recovered and reused further without appreciable decrease in the catalytic activity [289]. 

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