Synthesis of new aryl(hetaryl)vinyl-substituted benzo[<Emphasis Type="Italic">f</Emphasis>]quinolines and 4,7-phenanthrolines

Previously unknown 1-[2-aryl(quinolin-2-yl)ethenyl]-3-[aryl(quinolin-2-yl)]benzo[f]quinolines and 3-aryl-1-(2-arylethenyl)-4,7-phenanthrolines were synthesized by reactions of 1-methylbenzo[f]quinolines and 1-methyl-4,7-phenanthrolines with substituted N-benzylideneanilines and N-(quinolin-2-ylmethylidene)aniline on heating in dimethylformamide in the presence of potassium hydroxide.     

Synthesis of 1,3-diazapyrenes from benzo[<Emphasis Type="Italic">f</Emphasis>]quinazolines

Methods have been developed for the synthesis of 1,3-diazapyrenes based on the reactions of 1-methylbenzo[f]quinazolines with DMF dimethyl acetal or with 1,3,5-triazine in PPA. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii. No. 2, pp. 260–262, February, 2009.     

Synthesis of new benzo[<Emphasis Type="Italic">c</Emphasis>]phenanthridine derivatives

Three-component condensation of naphthalen-1-amine with triethyl orthoformate and dimedone or cyclopentane-1,3-dione, as well as the reaction of naphthalen-1-amine with 2-acetyl-5,5-dimethylcyclohexane-1,3-dione, gave the corresponding 2-[1-(α-naphthylamino)alkylidene]cycloalkane-1,3-diones which underwent intramolecular cyclization to 7,8,9,10-tetrahydrobenzo[c]phenanthridin-7-one derivatives on heating in polyphosphoric acid. 9,9-Dimethyl-7,8,9,10-tetrahydrobenzo[c]phenanthridin-7-one was reduced to 9,9-dimethyl-7,8,9,10-tetrahydrobenzo[c]phenanthridin-7-ol with sodium tetrahydridoborate.     

Regioselective synthesis of benzo[<Emphasis Type="Italic">g</Emphasis>]- and benzo[<Emphasis Type="Italic">f</Emphasis>]quinolines by reaction of chalcones with naphthalen-2-amine

Reactions of 4- and 4′-substituted chalcones with naphthalen-2-amine afforded isomeric benzo[g]- and benzo[f]quinoline derivatives. Depending on the substituent in the initial chalcone, the cyclization follows two pathways through different intermediates. The product structure was confirmed by IR, ¹H and ¹³C NMR, and mass spectra and X-ray analysis.     

Synthesis and structures of benzo[<Emphasis Type="Italic">cd</Emphasis>]furo[2,3-<Emphasis Type="Italic">f</Emphasis>]indol-4(5<Emphasis Type="Italic">H</Emphasis>)-one derivatives

A procedure was developed for the synthesis of derivatives of the new heterocyclic system, benzo[cd]furo[2,3-f]indole, based on the cyclodehydration of 6-acylmethyloxy-1-alkyl-benzo[cd]indol-2(1H)-ones. Either 7- or 8-aryl derivatives of benzo[cd]furo[2,3-f]indol-4(5H)-ones can be prepared depending on the reaction conditions. The molecular and crystal structures of 7- and 8-phenylbenzo[cd]furo[2,3-f]indol-4(5H)-ones were established by X-ray diffraction.     

Organocatalytic approach toward the green one-pot synthesis of novel benzo[<Emphasis Type="Italic">f</Emphasis>]chromenes and 12<Emphasis Type="Italic">H</Emphasis>-benzo[5,6]chromeno[2,3-<Emphasis Type="Italic">b</Emphasis>]pyridines

An efficient tandem reaction approach is described to prepare novel benzo[f]chromenes from 2,3-dihydroxynaphthalene, malononitrile and aldehydes using 10 mol% guanidine hydrochloride as the catalyst under solvent-free conditions. The method was also extended to the preparation of novel 12H-benzo[5,6]chromeno[2,3-b]pyridines from 2-aminoprop-1-ene-1,1,3-tricarbonitrile instead of malononitrile under the same reaction conditions. The described one-pot three-component reaction is characterized by short reaction times, high-product yield, mild reaction conditions, simple workup procedure, and simple purification.     

Synthesis of New Cyclopenta[<Emphasis Type="Italic">b</Emphasis>]quinoline Derivatives

A series of new 11-(R-phenyl)-8,9-dihydro-7H-benzo[f]cyclopenta[b]quinolin-10(11H)-ones and 7,14-bis(R-phenyl)-2,3,9,10,11,14-hexahydrocyclopenta[2,3]quinolino[8,7-h]cyclopenta[b]quinoline-1,8(4H,7H)-diones were synthesized by three-component condensation of naphthalen-2-amine or naphthalene- 1,5-diamine with substituted benzaldehydes and cyclopentane-1,3-dione in one step through intermediate formation of unstable arylaminoketoenol.     

Synthesis of benzo[<Emphasis Type="Italic">f</Emphasis>]quinoline derivatives by three-component condensation of tetronic acid with naphthalen-2-amine and formaldehyde

New derivatives of benzo[f]furo[3,4-b]quinoline, spiro[benzo[f]quinoline-2,3′-furan], and benzo[f]-quinoline-2-carboxylic acid were synthesized with high selectivity by three-component condensation of tetronic acid with naphthalen-2-amine and formaldehyde.     

Synthesis of <Emphasis Type="Italic">N</Emphasis>-substituted 1-hydroxypyrrolo[3,4-<Emphasis Type="Italic">f</Emphasis>]indol-5,7-diones

General methods were developed of the synthesis of N-substituted 1-hydroxypyrrolo[3,4-f]indole-5,7-diones using as initial compounds substituted 6-nitroisoindole-1,3-diones and 5-nitro-4-phenacylphtalic acids.     

Synthesis and functionalization of 7-hydroxyanthra[2,1-<Emphasis Type="Italic">b</Emphasis>]benzo[<Emphasis Type="Italic">d</Emphasis>]furan-8,13-diones

The diazotization of 1-amino-2-aryloxy-4-hydroxy-9,10-anthraquinones in various solvents and subsequent heating of the diazotization products lead to 7-hydroxyanthra[2,1-b]benzo[d]furan-8,13-diones. When consecutively treated with benzenesulfonyl chloride and amines, the products form 7-aminoanthra[2,1-b]benzo[d]furan-8,13-diones.     

Synthesis of <Emphasis Type="Italic">m</Emphasis>-carborane-C-carboxylic acid hexahydrobenzo[<Emphasis Type="Italic">a</Emphasis>]acridine esters

The possibility was demonstrated of selective preparation of m-carborane-C-carboxylic acid hexahydrobenzo[a]acridine esters both by the reaction of 1,3-diketones with azomethines obtained by condensation of m-carborane-C-carboxylic acid vanillin and vanillal esters with 1- or 2-naphthylamine and by the cascade heterocyclization of 1- or 2-naphthylamine, m-carborane-C-carboxylic acid vanillin and vanillal esters, and CH-acids.     

Synthesis and oxidation of vinyl derivatives of <Emphasis Type="Italic">N</Emphasis>-methyl[60]fullereno[<Emphasis Type="Italic">c</Emphasis>]pyrrolidine

Novel organometallic derivatives of N-methyl[60]fullereno[c]pyrrolidine bearing the vinyl fragment at the position 2 of the pyrrolidine ring were synthesized. Their oxidation with 3-chloroperoxybenzoic acid to give N-oxides and epoxides was studied in detail.     

Synthesis of substituted dibenz[<Emphasis Type="Italic">b,f</Emphasis>]oxepines from 2,4,6-trinitrotoluene

1,3-Dinitro[b,f]dibenzoxepine undergoes nucleophilic substitution with O-and S-nucleophiles, the nitro group at position 1 (peri-nitro group) being selectively replaced. The factors responsible for the selectivity of the reaction are discussed.     

Synthesis of 2,2-dimethyl-1,2-dihydrobenzo[<Emphasis Type="Italic">f</Emphasis>]-isoquinolines displaying antifungal activity

The reaction of 2,2-dimethyl-1,2-dihydrobenzo[f]isoquinoline with malonic acid gave (2,2-dimethyl-1,2,3,4-tetrahydrobenzo[f]isoquinolin-4-yl)acetic acid, the acid chloride of which readily forms esters with alcohols and phenols. Reaction of the same azomethine with thioglycolic acid leads to (2,2-di-methyl-1,2,3,4-tetrahydro-benzo[f]isoquinolin-4-yl)thioacetic acid. Activation of the initial azomethine by iodomethylation enables reaction with 1,3-indanedione to be carried out. The obtained substances display antifungal action.     

Synthesis of oxo derivatives of <Emphasis Type="Italic">N</Emphasis>-(<Emphasis Type="Italic">p</Emphasis>-tolysulfonyl)hexahydrocycloalka[<Emphasis Type="Italic">b</Emphasis>]indoles

Hydroxymercuration-demercuration of N-p-tolysulfonyl-4,4a,9,9a-tetrahydro-3H-carbazoles and N-p-tolyl(or methyl)sulfonyl-1,3a,4,8b-tetrahydrocyclopenta[b]indoles leads to the formation of the corresponding N-p-tolylsulfonyl-2,3,4,4a,9,9a-hexahydro-1H-carbazol-2-ols and N-p-tolyl(or methyl)sulfonyl-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indol-2-ols. The latter are oxidized to 2-oxo derivatives with potassium dichromate. The oxidation of 2-methoxy-8-methyl-N-p-tolylsulfonyl-2,3,4,4a,9,9a-hexahydro-1H-carbazol-1-ol under analogous conditions gives 2-methoxy-8-methyl-N-p-tolysulfonyl-2,3,4,4a,9,9a-hexahydro-1H-carbazol-1-one.     

Synthesis of 6-methyl-8<Emphasis Type="Italic">H</Emphasis>-dibenzo[<Emphasis Type="Italic">a</Emphasis>,<Emphasis Type="Italic">g</Emphasis>]quinolizin-8-imines <Emphasis Type="Italic">via Reissert</Emphasis> compounds

Alkylation of Reissert compounds derived from 3-methylisoquinolines with several 2-cyanobenzylbromides followed by hydrolytic cleavage provided the corresponding 1-benzyl-3-methylisoquinolines. Treatment of the latter with methylmagnesiumiodide caused cyclization to the title compounds rather than formation of 2-acetylbenzylisoquinolines.     

Synthesis and X-ray study of 6<Emphasis Type="Italic">H</Emphasis>-chromeno[3,4-<Emphasis Type="Italic">e</Emphasis>][1,3,4]triazolo[2,3-<Emphasis Type="Italic">a</Emphasis>]pyrimidine

2-Dimethylamino methylenechromanone 1 reacted with 4H-1,2,4-triazol-3-amine in acetic acid to give only one isolated product which was identified by X-ray study as 6H-chromeno[3,4-e][1,3,4]triazolo[2,3-a]-pyrimidine. The molecular structure of 3, C₁₂H₈N₄O, was determined to be monoclinic, P2₁/c, a = 16.3875(5), b = 8.8378(3), c = 13.8392(5) Å, β = 101.190(1)°, V = 1966.22(11) ų, Z = 8.     

<Emphasis Type="Italic">Z</Emphasis>-and <Emphasis Type="Italic">E</Emphasis>-conformers of <Emphasis Type="Italic">N</Emphasis>-chloroacetylcytisine

N-Chloroacetylcytisine was synthesized by acylation of (–)-cytisine. Stable Z- and E-conformers with respect to rotational isomerism around the N-12–CO bond were found in PMR spectra at room temperature. The point at which PMR resonances of the Z- and E-conformers coalesced upon heating was measured. The transition barrier between the conformers was estimated.     

Mononuclear and heterodinuclear phenanthrolinedione complexes of <Emphasis Type="Italic">d</Emphasis>- and <Emphasis Type="Italic">f</Emphasis>-block elements

1,10-Phenanthroline-5,6-dione (Phd) complexes of group 3 and lanthanide elements having formulae Ln(hfac)₃(Phd) (Ln = Y, Eu, Yb; hfac = hexafluoroacetylacetonate) were synthesised and characterised. Complexes of d-block elements of the type [MCl(Phd)(p-cymene)]⁺ (M = Ru, Os) were also prepared. In all these species, coordination of the polydentate ligand occurs by the N-donor moieties, as indicated by DFT calculations. The novel compounds were tested, together with fac-ReBr(Phd)(CO)₃, as precursors for the preparation of heterobimetallic d/f derivatives. The reaction of the rhenium complex with yttrium or lanthanide anhydrous triflate salts led to the formation of the complexes ReBr(CO)₃(N,N′-Phd-O,O′)Ln(OTf)₃(THF) (Ln = Y, Eu, Yb), where the trivalent ions interacted with the quinonoid moiety. The redox properties of the rhenium centre were strongly affected by the coordination of Ln(OTf)₃, as observed by comparing the cyclic voltammetry measurements carried out on fac-ReBr(Phd)(CO)₃ and on ReBr(CO)₃(N,N′-Phd-O,O′)Y(OTf)₃.