Synthesis of aminoalkyl derivatives of 2-benzyl-5-hydroxyindole

Derivatives of 2-benzyl-5-methoxyindole-3-carboxylic acid are decarboxylated on heating and are converted to the corresponding 2-benzyl-5-methoxyindoles. 2-Benzyl-5-methoxygramine hydrochlorides were obtained from the latter and used to obtain (2-benzyl-5-methoxy-3-indolyl)acetonitriles. The nitriles were converted to 2-benzyl-5-methoxytryptamines by hydrogenation. A number of Mannich bases were obtained by aminomethylation of 2-benzyl-3-carbomethoxy-5-hydroxyindole derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 208–212, February, 1971.     

Synthesis of 1-benzyl-3,6-diazahomoadamantane

By condensation of 4-phenylbutan-2-one with tetramethylenediethylenetetramine 1-benzyl-3,6-diazahomoadamantan-9-one was synthesized. Further nitration of 1-benzyl-3,6-diazahomoadamantan-9-one yielded 1-(4-nitrobenzyl)-3,6-dia?ahomoadamantan-9-one. The modification of the nitro and carbonyl groups resulted in the formation of 1-benzyl-3,6-diazahomoadamantane and its derivatives with functional groups in the benzene ring and at the bridge carbon atom C⁹.     

1-Aroyl-2-benzyl-5-hydroxypyrazolidines

The PMR spectral data show that 1-aroyl-2-benzyl-5-hydroxypyrazolidines are preferentially present in cyclic form in solution, while the proportion of the linear form increases to 50% in the gaseous phase, according to mass spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1199–1203, September, 1990.     

Lactams—I The synthesis and acid hydrolysis of 4- and 5-substituted 1-benzyl-2-piperidone derivatives

In order to explain the difficulty in hydrolysing the lactam linkage of 1-benzyl-2-oxo-5-ethyl-4-piperidineacetic acid (XIV) under acid conditions, several model compounds such as 1-benzyl-2-piperidone (X), 1-benzyl-5-ethyl-2-piperidone (XI), 1-benzyl-4-ethyl-2-piperidone (XII) and 1-benzyl-2-oxo-4-piperidineacetic add (XIII) were prepared and their hydrolysis in boiling 6N HCl was studied. For each of the lactams, the hydrolysis was found to proceed to an equilibrium as shown in Table 1. Substituents at the 4- and 5-positions of the piperidone ring seemed to favour the ring form in the equilibrium between piperidones (X-XIV) and ω-amino acid hydrochlorides (type XV).     

Synthesis of 2-Acyl-1-benzyl-, 1-phenylethyl- and spirobenzyltetrahydroisoquinolines

N-Acyl-1-benzyl-, 1-phenylethyl-and 1-spirobenzyltetrahydro-isoquinolines are obtained from N-acyl-2-phenylethylamines and arylalkyl aldehydes or cyclic ketones in acidic media.     

Synthesis and characterization of novel 2-(1-benzyl-3-[4-fluorophenyl]-1H-pyrazol-4-yl)-7-fluoro-4H-chromen-4-one derivatives

Novel 1-benzyl-3-(4-fluorophenyl)-1H-pyrazole-4-carbaldehydes 3a to 3e were synthesized via Vilsmeier-Haack reaction of the appropriate 1-benzyl-2-(1-(4-fluorophenyl)ethylidene)hydrazines, derived from 4-fluoroacetophenone 1 with substituted 2-benzylhydrazines 2a to 2e . The base catalyzed condensation of 1-benzyl-3-(4-fluorophenyl)-1H-pyrazole-4-carbaldehydes 3a to 3e with 1-(4-fluoro-2-hydroxyphenyl)ethanone 4 gave (E)-3-(1-benzyl-3-(4-fluorophenyl)-1H-pyrazol-4-yl)-1-(4-fluoro-2-hydroxyphenyl)prop-2-en-1-ones 5a to 5e . On cyclization with dimethyl sulfoxide (DMSO)/I₂, compounds 5a to 5e gave 2-(1-benzyl-3-(4-fluorophenyl)-1H-pyrazol-4-yl)-7-fluoro-4H-chromen-4-ones 6a to 6e . Structures of all novel compounds were confirmed by infrared (IR), proton nuclear magnetic resonance (¹H NMR), carbon nuclear magnetic resonance (¹³C NMR), and mass spectral data. All the synthesized compounds were screened for their antibacterial activities.     

Some reactions of 5-benzyl-2,3,5-trichloro-4,4-dimethoxy-cyclopent-2-en-1-one and its derivatives

5-Benzyl-2,3,5-trichloro-4,4-dimethoxycyclopent-2-en-1-one and 2-benzyl-2,4,5-trichlorocyclopent-4-ene-1,3-dione were subjected to dehydrochlorination by the action of 1,4-diazabicyclo[2.2.2]octane, selective dechlorination at C⁵ by the action of CrCl₂, and Ad_NE replacement of the chlorine atom at C³ by the action of secondary amines. The reduction of 2-benzyl-2,4-dichloro-5-morpholinocyclopent-4-ene-1,3-dione with sodium tetrahydridoborate in methanol and ethanol gave different products.     

Synthesis of 4,6-diaryl-1-benzyl-6-hydroxy-5,5-dimethyl-2-oxopiperidine-3-carbonitriles and their analogs via a modified Reformatsky reaction

Organozinc compounds obtained from 1-aryl-2-bromo-2-methylpropanone and zinc react with N-benzyl-3-aryl-2-cyanoacrylamides or N-[6-(2-cyano-1-oxo-3-phenylprop-2-enylamino)hexyl]-2-cyano-3-phenylacrylamide to give 4,6-diaryl-1-benzyl-6-hydroxy-5,5-dimethyl-2-oxopiperidine-3-carbonitriles or 1,6-bis(6-aryl-3-cyano-6-hydroxy-5,5-dimethyl-2-oxo-4-phenylpiperidyl)hexanes as a single isomer with trans-located piperidine hydrogen atoms.     

Synthesis and reactions of 1-benzyl-3-haloalkyl-5-chloropyrazoles

Synthesized 1-benzyl-3-chloroalkyl-5-chloropyrazoles reacted with indole and pyrrole in DMSO in the presence of alkali to give 3-(heter-1-yl)alkyl-substituted 1-benzyl-5-chloropyrazoles. 1-[(1-Benzyl-5-chloropyrazol-3-yl)methyl]indole reacted regiospecifically with chloroal trifluoromethylsulfonyl- and 4-chlorophenylsulfonylimines providing the products of C-amidotrichloroethylation into the position 3 of the indole ring. {1-[(1-Benzyl-5-chloropyrazol-3-yl)methyl]indol-3-yl}sulfanylacetic acid was obtained by the reaction of 1-[(1-benzyl-5-chloropyrazol-3-yl)methyl]-indole with iodine, thiourea, and chloroacetic acid.     

Benzazoles and naphthazoles XXXV. Autooxidative coupling of 1-benzyl-2-hydrazinobenzmidazole with nitroformaldehyde arylhydrazones

1-Benzyl-2-hydrazinobenzimidazole undergoes autooxidative coupling with nitroformaldehyde arylhydrazones to give meso-carbon-unsubstituted 1-(1-benzyl-2-benzimidazolyl)-5-arylformazans (instead of the expected formazans with a nitro group in the meso position). Data on the structures and complexing abilities of the new unsymmetrical formazans of the benzimidazole series are presented.See [1] for communication XXXIV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 393–395, March, 1972.     

Iron(II) complexes of 1-benzyl-2-phenylbenzimidazole and 2-coumarinylbenzimidazole

Summary Iron(II) complexes of 1-benzyl-2-phenylbenzimidazole (BPBI) and 2-coumarinylbenzimidazole (CBI) have been prepared and characterised. The chloride, bromide, iodide and thiocyanate complexes have the general formula FeL₂X₂ (where L = BPBI or CBI) while the perchlorate complex of CBI has the composition [Fe(CBI)₃](CIO₄)₂. The perchlorate complex behaves as a 1 : 2 electrolyte in nitrobenzene and methanol; Fe(BPBI)₂I₂ shows considerable dissociation in nitrobenzene while the other complexes behave as nonelectrolytes. The i.r. spectra of the complexes suggest that N(3) of BPBI and N(3) together with the CO group of CBI are the coordination sites. The magnetic and spectral evidence suggests a regular octahedral geometry for the perchlorate complex and pseudotetrahedral configuration for the iodide and thiocyanate complexes. The other complexes appear to be distorted octahedral with halide bridging.Author to whom all correspondence should be addressed.     

Synthesis and properties of 2-imino-3-benzyl-5-phenyl-1, 3, 4-oxadiazoline

2-Imino-3-benzyl-5-phenyl-1, 3, 4-oxadiazoline (Ia) was synthesized by the reaction of benzyl chloride with 2-amino-5-phenyl-1, 3, 4-oxadiazole (II). A number of imino-group derivatives of Ia were prepared. The structure of the compounds prepared were confirmed by means of their IR spectra.     

Substituted pyridines 5-methyl-4-benzyl-2-styryl(phenylethynyl)pyridines

5-Methyl-4-benzyl-2-styrylpyridine (II), its p-dimethylaminostyryl analog IV, and 5-methyl-4-benzyl-2-(1,3-dioxo-2-hydrindenyl)pyridine (V) have been prepared. II has been converted into 5-methyl-4-benzyl-2-phenylethynylpyridine (VII), 5-methyl-4-benzylpyridine-2-carboxylic acid (VIII), and 3-styryl-6, 7-benzoisoquinoline (X).Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1228–1231, September, 1970.     

Synthesis and photochromic and fluorescence properties of 3-(1-benzyl-5-methoxy-2-methylindolyl)-4-thienyl-substituted furan(pyrrole)-2,5-diones

New nonsymmetrical dihetarylethenes, 3-(1-benzyl-5-methoxy-2-methyl-1H-indol-3-yl)-4-(3-thienyl)furan-2,5-dione and 1-alkyl- and (1-aryl)-3-(1-benzyl-5-methoxy-2-methyl-1H-indol-3-yl)-4-(3-thienyl)-1H-pyrrole-2,5-dione, exhibiting photochromic properties in solutions were synthesized. Noncyclic isomers of dihetarylethenes show fluorescence with quantum yields up to 0.13.     

Photochromism of 2-benzyl-3-benzoyl-4(1H)-quinolone derivatives

A series of 2-benzyl-3-benzoyl-4(1H)-quinolone derivatives was investigated. The UV–vis spectra of all photochromic derivatives and the corresponding colored photoenols are similar and almost solvent independent. In contrast, the stability of the photoenols depends strongly on the substituents at the quinolone moiety and solvent. We conclude that conversion of the photoinduced forms into the initial quinolones occurs through ionization rather than usual for photochromic compounds thermal relaxation or sigmatropic H-shift. The experimental observations are in good agreement with the results of quantum mechanical calculations.     

5-苄基-4-叔丁基-2-苄亚氨基噻唑的合成与杀菌活性

5-苄基-4-叔丁基-2-氨基噻唑与水杨醛衍生物反应制备了12种5-苄基-4-叔丁基-2-苄亚氨基噻唑类新化合物。初步测试了25种5-苄基-4-叔丁基-2-苄亚氨基噻唑的杀菌活性。结果表明,化合物1a(500mg/L)对水稻纹枯病菌抑制率为95%;化合物1i、1j、1l、1p、1q和1s(25mg/L)对小麦赤霉病菌的抑制率分别为55.1%、55.1%、51.3%、51.5%、51.5%和51.5%;化合物1i、1l和1s(25mg/L)对辣椒疫霉病菌抑制率分别为51.1%、51.9%和64.9%;化合物1h和1j(25mg/L)对黄瓜灰霉病菌抑制率为53.1%和61.2%;化合物1t、1o和1r(25mg/L)对油菜菌核病菌的抑制率分别为56.1%、56.1%和65.4%;化合物1w(25mg/L)对烟草赤星病菌的抑制率为52.6%。     

Regioselective photo-oxidation of 1-benzyl-4,9-dihydro-3H-beta-carbolines

The synthesis of a series of beta-carboline-based analogues of the natural product fascaplysin is presented; the compounds were produced using a novel photo-oxidation reaction of 1-benzyl-4,9-dihydro-3H-beta-carbolines as the key step.     

Crystal structure and quantum chemical calculations of (E)1-benzyl-3-((4-methoxyphenyl)imino)-5-methylindolin-2-one

The known Schiff base compound, (E)1-benzyl-3-((4-methoxyphenyl)imino)-5-methylindolin-2-one, was prepared as before by reacting 1-benzyl-5-methylindoline-2,3-dione with 4-methoxyaniline. The product was unambiguously characterized using elemental analysis, ¹H and ¹³C-NMR spectroscopy, and its new single-crystal X-ray structural analysis. Molecular orbital calculations were conducted in order to investigate the structures and relative stabilities of the (E) and (Z) isomers of 1-benzyl-3-([4 methoxyphenyl]-imino)-5-methylindolin-2-one. Specific attention was paid to the (E) isomer. The available crystallographic experimental data for the latter ensured also validation of the model structures computationally derived at the theoretical B3LYP/6-31G(d,p) level.     

Synthesis and crystal structure of ethyl 1-benzyl-2-hydroxy-5-methyl-3-oxo-2-phenacyl-2,3-dihydropyrrole-4-carboxylate

Reaction of 5-phenyl-2,3-dihydro-2,3-furandione with ethyl 3-benzylamino-2-butenoate, resulting in ethyl 1-benzyl-2-hydroxy-5-methyl-3-oxo-2-phenacyl-2,3-dihydropyrrole-4-carboxylate and benzylamide ofN-benzoylpyruvic acid, was studied. The structure of the pyrrole derivative was confirmed by X-ray analysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1552–1555, August, 1995.     

Polyfluoroalkylation and alkenylation of 1-benzyl-1H-indazol-3-ol

The polyfluoroalkylation and alkenylation of 1-benzyl-1H-indazol-3-ol by halopolyfluoroalkanes and fluorinated olefins has been studied. It was shown that only reactions proceeding with the participation of difluorocarbene lead to a mixture of N- and O-alkylation products. In all other cases, interaction with halopolyfluoroethanes and polyfluoroalkenes forms O-polyfluoroalkyl and alkenyl derivatives of indazolol.