Naphthomoles. 7. Synthesis of 4,11-dimethoxynaphtho[2,3-f]indole-5,10-dione and 4-methoxynaphtho[2,3-f]-indole-5,10-dione

4,11-Dimethoxynaphtho[2,3-f]indole-5,10-dione and 4-methoxynaphtho[2,3-f[indole-5,10-dione have been synthesized by the Leimgruber-Batcho reaction from 1,4-dimethoxy-2-methyl-3-nitroanthraquinone.Russian University of Chemical Technology, Moscow 125190. Center for Drug Chemistry, All-Russian Scientific Research Institute for Pharmaceutical Chemistry, Moscow 119815. Translated from Khimiya Geterotsklicheskikh Soedinenii, No. 8, pp. 1050–1054, August, 1996. Original article submitted March 20, 1996.     

Selective fluorination of dispiro[3.1.3.1]decan-5,10-dione by diethylaminosulfurtrifluoride to give 10,10-difluorodispiro[3.1.3.1]decan-5-one and 5,5,10,10-tetrafluorodispiro[3.1.3.1]decane

Dispiro[3.1.3.1]decan-5,10-dione was selectively difluorinated at room temperature by diethylaminosulfur trifluoride (DAST) to give 10,10-difluorodispiro[3.1.3.1]decan-5-one. The latter was reduced to 5,5-difluorodispiro[3.1.3.1]decane and also reacted with excess DAST to give 5,5,10,10-tetrafluorodispiro[3.1.3.1]decane. Proton and fluorine magnetic resonance studies on 5,5-difluorodispiro[3.1.3.1]decane did not show significant cross-ring coupling (< 0.5 Hz) between geminal fluorines on C-5 and geminal hydrogens on C-10. The fluorine magnetic resonance spectrum of 5,5,10,10-tetrafluorodispiro[3.1.3.1]decane was a single sharp line which establishes that through-space coupling between geminal fluorines at C-5 and C-10 and geminal hydrogens on other carbons does not exist. A study of the infrared and ultraviolet spectra of dispiro[3.1.3.1]-decane-5,10-dione indicate the cross-ring carbonyl groups interact significantly.     

Naphthoindoles. 8. Electrophilic substitution reactions of 4,11-dimethyxynaphtho[2,3-f]indole-5,10-dione

Some electrophilic substitution reactions characteristic of indole derivatives have been investigated for 4,11-dimethoxynaphtho[2,3-f]indole-5,10-dione. The corresponding 3 derivatives were obtained as a result of Vilsmeier, Mannich, and acylation reactions.See [1] for Part 7.Russian Chemico-Technological University, Moscow 125190. Center for Drug Chemistry, All-Russian Chemical and Pharmaceutical Research Institute, Moscow 119815. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 939–941, July, 1998.     

Synthesis of 5,8-dihydroxynaphtho[2,3-c][1,2,5]thiadiazole-6,9-dione and 6,9-dihydroxybenzo[g]quinoxaline-5,10-dione

The synthesis of 5,8-dihydroxynaphtho[2,3-c][1,2,5]thiadiazole-4,9-dione 3 , 6,9-dihydroxybenzo[g]quinoxaline-5,10-dione 4 , and their lesser oxygenated analogs via Friedel-Crafts and Diels-Alder synthesis is reported.     

Reactions of 3-acetyltropolone and its methyl ethers with hydroxylamine. Formation of 8H-cyclohept[d]isoxazol-8-one and 8H-cyclohept[c]isoxazol-8-one

The reaction of 3-acetyltropolone ( 1 ) with hydroxylamine under the acidic condition gave 3-methyl-8H-cyclohept[d]isoxazol-8-one ( 4 ) and its oxime ( 5 ), and under the neutral condition gave 4 and 3-acetyltropolone oxime ( 6 ). The reaction of 3-acetyl-2-methoxytropone ( 2a ) with hydroxylamine under the acidic condition gave 4, 5 , and 4-methyl-1H-2,3-benzoxazin-1-one ( 7 ), and under the neutral condition gave 4, 7 , 3-methyl-8H-cyclohept[c]isoxazol-8-one ( 8 ), and its oxime ( 9 ). The reaction of 7-acetyl-2-methoxytropone ( 2b ) with hydroxylamine under the acidic condition gave 4 and 5 , and under the neutral condition gave 5, 7 , and 9 .     

Polymerization of meta-naphthoquinone methide: 3,4-benzo-6-methylenebicyclo [3.1.0] hex-3-ene-2-one

Polymerization behavior of meta-naphthoquinone methide, 3,4-benzo-6-methylenebicyclo[3.1.0]hex-3-ene-2-one ( 1 ), was studied. Radical initiator 2,2′-azobis(isobutyronitrile) (AIBN) induced polymerization of 1 , but ionic initiators potassium tert-butoxide, butyllithium, and boron trifluoride etherate did not. Polymerization of 1 proceeded via ring-opening and aromatization to give a polymer with head-to-tail monomer unit placement. Compound 1 copolymerized with methyl methacrylate (MMA) in the presence of AIBN to obtain the monomer reactivity ratios r₁ ( 1 ) = 0.28 ± 0.07 and r₂(MMA) = 0.39 ± 0.02 at 60°C and Q and e values of Q = 1.04 and e = −1.03, indicating that 1 is a conjugative and electron-donating monomer. Ring-opening and aromatization of 1 also took place in the copolymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 741–746, 1997     

Condensed isoquinolines. 20. Characteristic features of thermal rearrangement of 7,12-dihydro-5H-isoquino[2,3-a]quinazolin-5-one to form 6,11-dihydro-13H-isoquino[3,2-b]quinazolin-13-one

We studied the dependence of the direction of conversions for salts of angular 7,12-dihydro-5H-isoquino[2,3-a]quinazolin-5-one on temperature and the nature of the anion: heating in high-boiling solvents leads either to aromatization of the heterosystem or to the rearrangement product, the linear 6,11-dihydro-13H-isoquino[3,2-b]quinazolin-13-one. When its hydrobromide is heated in high-boiling solvents, along with dimerization of the linear isomers, processes of oxidation at the positions 6 and 11 of the heterosystem occur. The dimer obtained in the reaction with morpholine is readily cleaved, with formation of a 6-(4-morpholyl)-substituted linear compound. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 430–439, March, 2007.     

Synthesis and photochemical properties of phenoxy derivatives of anthra[2,3-b]furan-5,10-dione

Nucleophilic replacement of the hydroxy groups in ethyl 4,11-dihydroxy-2-methyl-5,10-dioxo-5,10-dihydroanthra[2,3-b]furan-3-carboxylate by chlorine upon treatment with phosphorus acid chlorides gave the corresponding 4(11)-chloro derivatives which were converted into photochromic ethyl 4(11)-phenoxy-2-methyl-5,10-dioxo-5,10-dihydroanthra[2,3-b]furan-3-carboxylates. Photoinduced decomposition of the latter leads to the formation of phenol and fluorescent hydroxyanthra[2,3-b]furandiones.