Kondesationen mit hydrazin-N,N′-dicarbonsäurediamidin,XXIII [1] fluorierte β-diketone als reaktionspartner

Application of a 30% aqueous potassium carbonate solution for the condensation of 1,2-hydrazinedicaboxamidine with 1,1,1-trifluoro-2,4-pentanedione leads to the formation of 4,4′-dimethyl-6,6′-bis(trifluoromethyl)-2,2′-hydrazopyrimidine, with 1,1,1-trifluoro-2,4-hexanedione to 4,4′-diethyl-6,6′-bis-(trifluoromethyl)-2,2′-hydrazopyrimidine. 2-Guanidinoamino-4-methyl-6-trifluoromethylpyridine formed as an intermediate in this reacton may be isolated, while 4-ethyl-2-guanidinoamino-6-trifluoromethylpyrimidine undergoes cyclization to yield 2-amino-5-ethyl-7-trifluoromethyl-s-triazolo[1,5-a]pyrimidine.     

Studies on the synthesis of heterocyclic compounds. Part IV. Further investigation of the pschorr reaction with some pyrazole derivatives

Thermal decomposition of the diazonium sulfate derived from N-methyl-(1-phenyl-3-methylpyrazol-5-yl)-2-aminobenzamide afforded products formulated as 1-phenyl-3-methyl[2]benzopyrano[4,3-c]pyrazol-5-one (yield 10%), 1,4-dimethyl-3-phenylpyrazolo[3,4-c]isoquinolin-5-one (yield 10%), N-methyl-(1-phenyl-3-methylpyrazol-5-yl)-2-hydroxybenzamide (yield 8%) and 4′-hydroxy-2,3′-dimethyl-1′-phenylspiro[isoindoline-1,5′-[2]-pyrazolin]-3-one (yield 20%). Decomposition of the diazonium sulfate derived from N-methyl-(1,3-diphenylpyrazol-5-yl)-2-aminobenzamide gave products formulated as 7,9-dimethyldibenzo[e,g]pyrazolo[1,5-a][1,3]-diazocin-10-(9H)one (yield 8%), 4-methyl-1,3-diphenylpyrazolo[3,4-c]isoquinolin-5-one (yield 7%) and 4′-hydroxy-2-methyl-1′,3′-diphenylspiro[isoindoline-1,5′-[2]pyrazolin]3-one (yield 10%). The spiro compounds 6a,b underwent thermal and acid-catalysed conversion into the hitherto unknown 2-benzopyrano[4,3-c]pyrazole ring system 7a,b in good yield. Analytical and spectral data are presented which supported the structures proposed.     

N-二氯乙酰基-3,6-二甲基-3-乙基-9-氧代-1,5-二氮杂二环[4.3.0]壬烷的合成及生物活性研究

合成了新型除草剂安全剂N-二氯乙酰基-3,6-二甲基-3-乙基-9-氧代-1,5-二氮杂二环[4.3.0]壬烷.以丁酮为原料,与硝基甲烷作用,制得二硝基化合物,然后将其还原,还原产物与乙酰丙酸成环,再与二氯乙酰氯反应,即得到标题化合物.采用红外光谱、核磁共振谱和元素分析对产物进行了结构表征,并利用土培法对其进行了初步的生物活性测定.结果表明:化合物能够减轻绿磺隆对玉米的伤害.     

Pheromones ofColeoptera

Racemic 2,6-dimethyioctyl formate (1), a synthetic analog of the aggregation pheromone of two species ofTribolium beetles, has been obtained in six steps and in 28 % overall yield starting from methyl ethyl ketone, vinyl bromide, and 2-methylpropenal. The key step of the synthesis is the sigmatropic [3,3]-rearrangement of 4-ethyl-2,4-dimethyl-1,5-hexadien-3-ol (5) to 2,6-dimethyl-5-octenal (6).For Part 11 see Ref.1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 773–775, April, 1993.     

4(3H)-Quinazolinones containing heterocyclic group in position 3

The corresponding 2,3-substituted 4(3H)-quinazolinones were obtained in the reactions of 2-methyl- and 2-phenyl-4-oxo-3,1-benzoxazines with 1-amino-1,2,4-triazole, 4-amino-2,3-dimethyl-1-phenyl-5-pyrazolone, 2-amino-5-ethyl-1,3,4-thiadiazole, 3-amino-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazole, 1-amino-3-cyano-4,6-dimethyl-2-pyridone, and 1-amino-3-cyano-6-phenyl-4-trifluoromethyl-2-pyridone. The formation of N-benzolyanthranilamides in the reactions of 2-phenyl-4-oxo-3,1-benzoxazine with 2-amino-5-ethyl-1,3,4-thiadiazole and 1-amino-3-cyano-6-phenyl-4-trifluoromethyl-2-pyridones was exceptional. The structures of two of the products have been confirmed by X-ray crystallography.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 936–943, July, 2000.     

Isolation and properties of the products of the covalent hydration of 4H-imidazoles

The neutralization of 5-hydroxy-4,4-dimethyl-2-imidazolinium chlorides yields in the free state the products of the covalent hydration of the corresponding 4H-imidazoles — 5-hydroxy-4, 4-dimethyl-2-imidazolines. On being heated, the compounds obtained undergo various transformations, depending on the presence and position of oxygen-containing functions: 5-hydroxy-2-imidazoline gives 2-acetylamino-2-methyl-1-phenylpropan-1-ol; 3,5-dihydroxy-2-imidazoline dehydrates to 4H-imidazole 3-oxide; and 1,5-dihydroxy-2-imidazolines are converted into 2,3-dihydro-4H-1,2,5-oxadiazines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1087–1092, August, 1973.     

Synthesis and properties of homomologated and contracted dipyrrinone analogs of xanthobilirubic acid

Dipyrrinone analogs of xanthobilirubic acid, 5-[1,5-didehydro-3-ethyl-4-methyl-5-oxo-2H-pyrrol-2-ylidene)-methyl]-2,4-dimethyl-1H-pyrrol-3-propanoic acid, with alkanoic acid chain lengths varying from formic to caproic have been synthesized as their methyl esters and characterized spectroscopically. All of the dipyrrinones studied exhibit intermolecular hydrogen bonding in chloroform, as detected by ¹H-nmr, and the influence of the carboxyl group on the uv-visible spectrum decreases with increasing chain length.     

2-methyl-3-ethoxycarbonyl-4-hydroxythiophene in the vilsmeier reaction

Continuing our investigation of the properties of 2-methyl-3-ethoxycarbonyl-4-hydroxythiophene (I) [1], we found that it readily undergoes electrophilic substitution reactions. We studied the behavior of I under the conditions of the Vilsmeier reaction. The structures of the reaction products depend on the temperature conditions: at 30–35°C, 2-methyl-3-ethoxycarbonyl-4-hydroxy-5-formylthiophene (H) is formed in 74% yield while 2-methyl-3-ethoxycarbonyl-4-chloro-5-formylthiophene (III) is formed in 50% yield at 100°. The reaction of I with dimethylbenzamide and phosphorus oxychloride gives 2-methyl-3-ethoxycarbonyl-4-hydroxy-5-benzoylthiophene (IV) in 41% yield.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, p. 427, March, 1972.     

Skeletal transformations of perfluoro-1-ethyl-1-phenylbenzocyclobutene in the reaction with antimony pentafluoride

Interaction of perfluoro-1-ethyl-1-phenylbenzocyclobutene with SbF₅ at room temperature gives, after treatment of the reaction mixture with H₂O, perfluoro-4-[1-(2-methylphenyl)propylidene]cyclohexa-2,5-dienone as a main product. The reaction at 90-95 °C leads, after treatment with H₂O, to a mixture of perfluorinated 9-ethyl-9-methyl-1,2,3,4-tetrahydro-9H-fluorene, 9-ethyl-4a-methyl-4,4a-dihydrofluoren-1-one, 3-ethyl-3-phenylphthalide, 1-hydroxy-2-methyl-1-phenylindan, 3-methyl-2-phenylindenone and small amounts of other products.     

Synthesis of 2,5-dialkylpyrrolidines by conjugated catalytic hydrogenolysis of furan amines

Conclusions In hydrogenation in the vapor phase on a skeletal nickel-aluminum catalyst at 210–220°, 1-furyl-3-aminoalkanes undergo conjugated hydrogenolysis of the furan series at the 1,5-, 1,5- and 4,5-, as well as 1,5- and 3,4-bonds, forming 2-methyl-, 2-ethyl-, and 2-n-propyl-5-alkylpyrrolidines in yields of 38, 19, and 43%, respectively.Translated from Izvestiya Akademii Nauk SSSR, Setiya Khimicheskaya, No. 6, pp. 1120–1123, June, 1964     

Stereoselective Synthesis of 1,5-Diionic Organophosphorus Compounds

The reactive 1:1 intermediate produced in the reaction between triphenylphosphine and alkyl propiolates or ethynyl phenyl ketone was trapped by isopropylidene Meldrum's acid (5-isopropylidene-2,2-dimethyl-1,3-dioxane-4,6-dione) to produce alkyl 3-(isopropylidenemalonate-5-yl-5-ylid)-3-methyl-2-triphenylphosphoniomethylidene-butanoates or 3-(isopropylidenemalonate-5-yl-5-ylid)-3-methyl-2-triphenylphosphoniomethylidene-butanone in 75-86% yield. These 1,5-diionic phosphorus betaines exist as (Z) geometrical isomer in CDCl 3 solution.     

On the catalytic transformation of furan amines to 2,4-dialkylpyrroles

Conclusions In hydrogenation in the vapor phase on a skeletal nickel-aluminum catalyst at 290–300°, 1 -furyl-2-alkyl-3-aminopropanes are convened as a result of conjugated hydrogenolysis of the furan ring at the 1,5-1,5- and 4,5-, as well as 1,5- and 3,4-bonds, to 2-methyl-, 2-ethyl-, and 2-n-propyl-4-alkylpyrroles, in yields of 30, 25, and 45%, respectively.Translated from Izvestiya Akademii Nauk SSSR, Setiya Khimicheskaya, No. 6, pp. 1118–1120, June, 1964     

Formation of the benzo[f]pyrazolo[3,4-c][1,2,5]-triazepine system in the template reaction of o-amino-o′-halophenylazopyrazoles

The substance isolated from the template cyclization of 4-(2-bromo-4-methyl-1-phenylazo)-5-amino-3-methyl-1-propylpyrazole was identified by spectroscopic methods as 5-(2-bromo-4-methylphenyl)-3,7-dimethyl-1-propyl-1,5-dihydrobenzo[f]-pyrazolo[3,4-c][1,2,5]triazepine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 802–804, June, 1979.     

Regioselectivity in the diels-alder reactions of α-pyrones with alkynes

4-Ethyl-5-methyl-6-methylthio-2(H)-pyranone (4) undergoes Diels-Alder reactions with ethyl hexynoate (5), 3-heptyn-2-one (6), ethyl propiolate (7), and 3-butyn-2-one (8) to afford substituted benzenes with high regioselectivity upon extrusion of CO₂. 4-Ethyl-5,6-dimethyl-(1), 4-ethyl-3,6-dimethyl-(2) and 4-ethyl-5-methyl-(2H)-pyranone (3) gave excellant to good regioselectivity with internal alkynes 5 and 6 and poor regioselectivity with terminal alkynes 7 and 8. MNDO calculations have been carried out on the pyrones and alkynes and qualitative FMO analysis correctly predicts the major products.     

Synthesis of Some New Thiazoles and Pyrazolo[1,5-a]pyrimidines Containing an Antipyrine Moiety

Ethyl 2-{2-[4-(2,3-dimethyl-5-oxo-1-phenyl-3-(pyrazolin-4-yl)]-2-cyano-1-(phenylamino)vinylthio}-acetate, 2-[4-(2,3-dimethyl-5-oxo-1-phenyl-(3-pyrazolin-4-yl))(1,3-thiazol-2-yl)]2-(4-oxo-3-phenyl-(1,3-thiazoilidin-2-ylidene))ethanenitrile, 2-[4-(2,3-dimethyl-5-oxo-1-phenyl(3-pyrazolin-4-yl))(1,3-thiazol-2-yl)]-2-(4-methyl-3-phenyl(1,3-thiazolin-2-ylidene))ethanenitrile, 2-(5-acetyl-4-methyl-3-phenyl(1,3-thiazolin-2-ylidene))-2-[4-(2,3-dimethyl-5-oxo-1-phenyl(3-pyrazolin-4-yl))(1,3-thiazol-2-yl)]ethanenitrile, and ethyl 2-(cyano(4-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl)thiazol-2-yl)methylene)-2,3-dihydro-4-methyl-3-phenylthiazole-5-carboxylate were synthesized by treatment of 2-(4-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl)thiazol-2-yl)-3-mercapto-3-(phenylamino)-acrylonitrile with appropriate halo ketones or halo esters. Also, 4-{2-[5,7-dimethyl-2-(phenylamino)(7a-hydropyrazolo[1,5-a]pyrimidin-3-yl](1,-thiazol-4-yl)}-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one derivatives were synthesized via reaction of 4-{2-[5-amino-3-(phenylamino)pyrazolin-4-yl](1,3-thiazol-2-yl)}-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one with β-diketone or β-keto ester. All synthesized compound were established by elemental analysis, spectral data, and alternative synthesis whenever possible.     

Synthesis of 3-amino-4-nitropyrazoles

3-Bromo-1,5-dimethyl-4-nitropyrazole does not react upon heating with aqueous ammonia, while 1,5-dimethyl-3,4-dinitropyrazole under the same conditions yields 3-amino-1,5-dimethyl-4-nitropyrazole, which is formed from 3-bromo-1,5-dimethyl-4-nitropyrazole in the presence of a copper catalyst. The amination of 1-methyl-3,4-dinitropyrazole-5-carboxylic acid is accompanied by decarboxylation, which is characteristic for 4-substituted 1-methylpyrazole-5-carboxylic acids upon heating in aqueous ammonia or water.     

Reactions of diazaphospholes with phenyldiazomethane

Conclusions The action of 2-acetyl-5-methyl-1, 2, 3-diazaphosphole on phenyldiazomethane at –15°C in hexane leads to 2-acetyl-4-methyl-8-phenyl-1-phospha-2,3,7,8-tetraazabicyclo[3.3.0]octa-3,7-diene. The inverse action of phenyldiazomethane on 2-acetyl-5-methyl-1,2, 3-diazaphosphole at 0°C in ether gives 4, 11-diacetyl-6,7-dimethyl-2-phenyl-4,5,10,11-tetraaza-1,3-diphosphatricyclo[6.3.0.0^3,7]undeca-5, 9-diene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 412–418, February, 1986.     

Xanthobilirubic acid and its amides. Synthesis,spectroscopy, and solution structures

Xanthobilirubic acid, 5-[1,5-didehydro-3-ethyl-4-methyl-5-oxo-2H-pyrrol-2-ylidene)methyl]-2,4-dimethyl-1H-pyrrol-3-propanoic acid, its methyl ester, amide, N-methylamide and dimethylamide, and kryptopyrromethenone have been synthesized and characterized spectroscopically. In d₆-DMSO solution all pyrromethenones were monomeric, with lactam and pyrrole N-Hs H-bonded to solvent. In deuteriochloroform, the pyrromethenones preferred a dimeric form, with intramolecular H-bonding between the lactam C = 0 of one unit and the lactam and pyrrole N-Hs of the second.     

Synthesis,characterization, and antioxidant activity of heterocyclic Schiff bases

Schiff base derivatives have gained great importance due to revealing a great number of biological properties. Schiff bases were synthesized by treatment of 4-amino-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one ( 1 ) with various aldehydes in methanol at reflux. In addition, diamine was reacted with an aldehyde to yield the corresponding Schiff bases. The structures of synthesized Schiff bases were elucidated by spectroscopic methods such as microanalysis, ¹H-NMR, ¹³C-NMR, and FTIR. Antioxidant activities of synthesized Schiff bases were carried out using different antioxidant assays such as 1,1-diphenyl-2-picryl-hydrazyl free radical (DPPH^•) scavenging, 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) radical scavenging, and reducing power activity. (E)-4-((1H-indol-3-yl)methyleneamino)-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one ( 3 ), (E)-1,5-dimethyl-4-((2-methyl-1H-indol-3-yl)methyleneamino)-2-phenyl-1H-pyrazol-3(2H)-one ( 5 ), (E)-1,5-dimethyl-2-phenyl-4-(thiophen-2-ylmethyleneamino)-1H-pyrazol-3(2H)-one ( 7 ), (E)-1,5-dimethyl-2-phenyl-4-(quinolin-2-ylmethyleneamino)-1H-pyrazol-3(2H)-one ( 9 ), (1S,2S,N1,N2)-N1,N2-bis((1H-indol-3-yl)methylene)cyclohexane-1,2-diamine ( 11 ), and (1S,2S,N1,N2)-N1,N2-bis((2-methyl-1H-indol-3-yl)methylene)cyclohexane-1,2-diamine ( 12 ) were synthesized in high yields. Compound 5 displayed a good ABTS^•+ activity. Compound 3 revealed the outstanding activity in all assays. Compound 7 has the best-reducing power ability in comparison to other synthesized compounds. Although compounds 5, 11, 12 are new, compounds 3, 7, 9 are known. Due to revealing a good antioxidant activity, the synthesized compounds ( 3, 5, 7 ) have the potential to be used as synthetic antioxidant agents.     

Characteristic features of the reaction of 3(5)amino-5(3)-methylpyrazole with 1-nitroanthraquinone-2-carboxylic acid

In the reaction of 3(5)-amino-5(3)-methylpyrazole with 1-nitroanthraquinone-2-carboxylic acid in sulfolane at 150°C, 2-methyl-pyrazolo[5,1-b]naphtho[2,3-h]quinazoline-5,10,13-trione is formed with an admixture of 1-aminoanthraquinone-2-carboxylic acid and 1-aminoanthraquinone. Under similar conditions, from 4-amino-1,5-dimethylpyrazole, only 1-(1,5-dimethyl-4-pyrazolylamino)anthraquinone-1-carboxylic acid is formed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1191–1192, September, 1992.