Heterocyclic analogs of pleiadiene

In most cases 2-R-2,3-dihydroperimidines are smoothly dehydrogenated by sulfur in refluxing xylene to give 2-substituted perimidines in high yields. 2-(5-Halo-2-furyl)-2,3-dihydroperimidines, which form IV and 2-(5-halo-2-furyl)perimidines when they are heated with sulfur, constitute an exception.See [1] for communication XXVIII.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, p, 986–988, July, 1977.     

Synthesis of Some Benzotriazole-Substituted Perimidines

2-substituted perimidines 3(a–g) were prepared from an acid-catalyzed reaction of 1,8-diaminonaphthalene with carboxylic acids using microwave irradiation. Addition of these perimidines to 1-chloromethyl benzotriazole in the presence of the sodium amide under reflux conditions gave benzotriazole-substituted perimidines 5(a–f). Yields of these products following recrystallization from water were of the order of 60–65%. IR and ¹HNMR spectra and elemental analysis were used for identification of these compounds.     

Heterocyclic analogs of pleiadiene. 50. Sulfonation of perimidines,perimidones, and 2,3-dihydroperimidines

The action of concentrated sulfuric acid on perimidine and 2-substituted perimidines, 1,3-dimethylperimidinium perchlorate, and the 1,3-dimethyl derivatives of perimidone and 2,3-dihydroperimidine gave the 6(7)-sulfonic acids of these compounds.See [1] for communication 49.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 691–696, May, 1980.     

Synthesis and special features of the structure of 6(7)-aminoperimidine derivatives

A method of synthesizing 6(7)-aminoperimidines has been developed based on the electrophilic amination of perimidines with sodium azide in PPA. The corresponding amides were synthesized by acylation and were also obtained by the Schmidt reaction from 6(7)-acetyl(or benzoyl)perimidines. A special feature of the structure of the 2-substituted amines and amides is the presence of annular tautomerism slow in NMR time.     

Unexpected reaction pathways in the reaction of alkoxyalkynylchromium(0) carbenes with aromatic dinucleophiles

Thermal- or SiO(2)-induced reactions of the Michael adducts of 1,2-aromatic dinucleophiles and alkynylchromium(0) carbene complexes, compounds 7-10, form different products in good yields depending on the nature of the aromatic dinucleophile used. Thus, 1,2-diaminobenzene derivatives 7 and 8 rearrange to pentacarbonylchromium(0) isocyanide complexes 11, 12, 14, and 15 in a process that occurs through bicyclic intermediates 24. Adducts 9 derived from o-aminophenol give 2,3-dihydro-1,5-benzoxazepine derivatives 17 by intramolecular 1,2-addition, followed by protonation at the chromium center and reductive elimination. In contrast, base-promoted addition of the phenolic hydroxy group in compound 9 a affords 3-ethoxy-5-phenyl-5,6-dihydro-2H-1,6-benzoxazocin-2-one (18), together with the expected adduct 17 a. Compound 18 is formed by a nucleophilic addition to a CO ligand in a preformed carbene complex. This is a new example of the rare attack of a nucleophile on a CO ligand in a Fischer carbene complex. Adducts 10 form seven-membered-ring carbene complexes 19 and 20 by intramolecular aminolysis. In contrast, reaction of alkynyl carbene complexes with 1,8-diaminonaphthalene under very mild conditions leads to 2-substituted perimidines 33 together with the corresponding ethoxymethylmetal carbene complex 32 through an unprecedented fragmentation process in a formal retro-Aumann reaction.     

Novel approach to the synthesis of 1,3-diazapyrenes

Methods have been developed for the synthesis of 1,3-diazapyrenes based on the reactions of perimidines with ethoxymethylene-1,3-dicarbonyl compounds and also 6(7)-benzoyl(acetyl, formyl)perimidines with carbonyl compounds in PPA. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 79–82, January, 2009.     

Lewis acid catalyzed reactions of donor-acceptor cyclopropanes with 1- and 2-pyrazolines: formation of substituted 2-pyrazolines and 1,2-diazabicyclo[3.3.0]octanes

The reaction of 2-substituted cyclopropane-1,1-dicarboxylates with 1- and 2-pyrazolines is efficiently catalyzed by scandium or ytterbium triflates to give N-substituted 2-pyrazolines or 1,2-diazabicyclo[3.3.0]octanes. The reactions of 2-pyrazolines give diazabicyclooctanes as the major products. In contrast, the reactions starting from 1-pyrazolines predominantly give N-substituted 2-pyrazolines, which become the major compounds obtained if an equimolar amount of GaCl₃ is used. A possible reaction mechanism is suggested.     

Efficient Synthesis of Functionalized Benzimidazoles and Perimidines: Ytterbium Chloride Catalyzed C?C Bond Cleavage

An efficient method is developed for the synthesis of functionalized benzimidazoles and perimidines by the condensation of aryl diamines with β‐carbonyl compounds catalyzed by ytterbium chloride. The reactions give good yields under mild conditions. A mechanism involving a lanthanide activated C C bond cleavage is proposed.     

Zirconium-catalyzed reaction of terminal alkenes with triethylindium

Terminal alkenes (undec-1-ene, oct-1-ene, and allylbenzene) reacted with triethylindium in the presence of a catalytic amount of Cp₂ZrCl₂ in hexane to give mixtures of three organoindium compounds whose hydrolysis in D₂O afforded 2-substituted 1,4-dideuterobutane containing minor amounts of 2-substituted 1- and 4-deuterobutanes.     

4-phenyl-4H-pyrazolo[3,4-c] furazans. The reactions of 3,4-dacylfuroxans with phenylhydrazine and with aniline

Three different 3,4-diaeylfuroxans (1) are shown to give 3-substituted-l-phenyl-4,5-dioximino-2-pyrazolines (2) upon reaction with phenylhydrazine. The compounds 2 were dehydrated to 6-sul)stituted-4-phenyl-4H-pyrazolo[3,4-c]furazans. ( 3 ) and thermally converted to 3-substituted 5-imino-4-oximino-1-phenyl-2-pyrazolines ( 6 ). The compounds 1 react with aniline to give 3-anilino-4-acylfurazans ( 10 ).     

Heterocyclic analogs of pleiadiene. XV. Direct acylation of perimidines in the naphthalene ring. Synthesis of 4 (9)- and 6 (7)-acylperimidines

It is shown that perimidines and aceperimidines are acylated by carboxylic acid or their anhydrides in polyphosphoric acid to give 6(7)-acylperimidines at 70–80° (kinetic control) and 4(9)-acylperimidines at 120–150° (thermodynamic control). Acetylation of the perimidines with acetic anhydride also takes place in the presence of perchloric acid.     

Synthesis of indoloand pyrroloquinazolones

2-Quinazolone reacts with various π-surplus systems (indoles and pyrroles) to give 3,4-dihydro-4-substituted 2-quinazolones. These compounds are capable of oxidation to 4-substituted 2-quinazolones. o-Carbamidobenzylideneurea gives identical products in these reactions.     

2-取代的6-溴甲基-4(3H)-喹唑啉酮的合成

2-取代的6-溴甲基-4(3H)-喹唑啉酮的合成;4(3H)-喹唑啉酮;苯并噁嗪酮;N-溴代琥珀酰亚胺; 合成     

A study of the synthesis and some reactions of perimidines

A study of the preparation of perimidines from 1,8-diaminonaphthalene and carbonyl compounds is presented. The optimum conditions for the reaction of the above diamine with carboxylic acids and esters, acid chlorides, anhydrides and aldehydes are defined. The chemical behavior and a number of previously unreported reactions of perimidines are presented. The latter include N-alkylations, reductions, oxidations and acylations.     

Methoxychlorination and dimethoxylation of alkenes the reactions of substituted styrenes with phenylselenenyl chloride in methanol

The addition of PhSeCl to α- and β-substituted styrenes in methanol is regio- and stereospecific and affords the products of methoxyselenenylation. These compounds further react with PhSeCl to give the deselenenylation products. In the case of α-substituted styrenes, 1-methoxy, 2-chloroalkanes are produced, whereas with β-substituted styrenes the major reaction products are the 1,2-dimethoxyalkanes and the 2,2-dimethoxyalkanes in which phenyl migration has occurred. It is shown that these reactions proceed through the intermediate formation of the alkyi phenylselenium dichlorides, PhCR(OMe)CHR₁SeCl₂Ph, which evolve with different mechanisms depending on the structure of the starting alkenes.     

Site‐ and Regioselectivity of the Reaction of Hydrazonoyl Chlorides with Perimidine Ketene Aminal. Antimicrobial Evaluation of the Products

Reaction of hydrazonoyl chlorides with perimidine ketene aminal derivative in dioxane in the presence of triethylamine afforded either pyrrolo[1,2‐a]perimidines or pyrazolyl perimidines depending on the type of hydrazonoyl chloride used. The reaction was found to be site‐ and regioselective according to the suggested mechanism. The structure of the newly synthesized compounds was established on the basis of spectral data and elemental analyses. In addition, the antimicrobial activity of the newly synthesized compounds was evaluated, and the results showed moderate activity of all compounds against the bacterial species.     

Intramolecular Friedel-Crafts-type reactions involving N-acyliminium ions derived from glycine templates

Enantiomerically pure 4-substituted 2-aralkyl-2,4-dihydro-1H-pyrazino[2,1-b]quinazoline-3,6-diones (1b-m) in which the alkyl chain is (CH(2))(n), n = 1-3, behave as glycine templates giving by treatment with [hydroxy(tosyloxy)iodo]benzene in ethyl acetate cis-1-tosyloxy derivatives. When these compounds contain electron-rich aryl substituents with n = 2, they spontaneously cyclize through intramolecular Friedel-Crafts-type diastereoselective reactions to give penta- or hexacyclic compounds. Otherwise, they give by solvolysis cis-1-alkoxy derivatives, which in a second step, may be cyclized in acid if n = 2, 3. All these reactions must occur through N-acyliminium species in S(N)1-like mechanisms. 1-Alkoxy-2-arylmethyl derivatives are reluctant to cyclize, giving trans-1-hydroxy compounds as the only isolated reaction products.     

Synthesis and biological activities of 1-[2-(dimethylamino)ethyl]- and 1-[3-(dimethylamino)propyl]-substituted 3-methyl-1,8-dihydrocycloheptapyrazol-8-ones and related compounds.

3-Methyl-1,8-dihydrocycloheptapyrazol-8-ones (2a-c), prepared from 3-acetyltropolones (1a-c), were treated with diazomethane, methyl iodide, dimethyl sulfate, and diethyl sulfate to give 1- and 2-alkylated compounds. The 1,8-dihydrocycloheptapyrazol-8-one (2a) also reacted with 2-(dimethylamino)ethyl, 2-(diethylamino)ethyl, 3-(dimethylamino)propyl, and 2,3-dihydroxypropyl chloride to afford the corresponding 1-substituted products. A preliminary study was made of the biological activities of some of the obtained compounds.     

The action of organolithium compounds on phthalazine and I (2H)-phthalazinone

Phthalazine and 1(2H)-phthalazinone undergo 1,2-addition of organolithium compounds to C = N to give, following hydrolysis, 1 - substituted - 1,2 - dihydrophthalazines and 4-substituted-3,4-dihydro-1(2H)-phthalazinones respectively. These dihydro-derivatives may be easily autoxidized to the corresponding 1-substituted phthalazines and 4-substituted-1(2H)-phthalazinones.     

Potential anticonvulsants. V. The condensation of isatins with C-acetyl heterocyclic compounds

A number of C-acetyl heterocyclic compounds were condensed with isatin and substituted isatins to give a series of 3-hydroxy-3-substituted oxindoles. The products from 2-acetylfuran and isatin, 2-acetylthiophene and isatin, and 2-acetylpyridine and 1-methylisatin were active at 100 mg/Kg in the maximal electroshock seizure test.