Potential anticonvulsants. IX. Some isatin hydrazones and related compounds

A number of hydrazines, hydrazides, and related compounds have been condensed with isatin and substituted isatins. The anticonvulsant activity of these compounds is reported.     

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.     

The condensation of 1-morpholinocyclohexene with mannich ketones

Summary By the reaction of 1-morpholinocyclohexene with 1-diethylaminobutanone-3 and 1-diethylaminopentanone-3, with subsequent treatment with hydrochloric acid, ^1,8a-octalone-2 and 1-methyl-^1,8a-octalone-2 were obtained in yields of 40 and 66%.     

N-alkylation of trimethylsilyl derivatives of isatin with halomethyl ketones

Trimethylsilyl derivative of isatin react with halomethyl ketones at the nitrogen atom in contrast to sodium salt of isatin, which reacts with these compounds at heterocyclic carbon atom. Institute for the Biological Protection of Vegetation, Academy of Sciences of Moldova, 2058, Moldova. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1345–1346, October, 1999.     

Synthesis of cross-conjugated polyketones by the crossed-aldol condensation of cyclic ketones with aromatic dialdehydes

Insoluble cross-conjugated polyketones were prepared from terephthalaldehyde and a variety of cycloaliphatic ketones by the crossed-aldol condensation. Elemental analyses and infrared spectra suggest that the polymeric aldol intermediates were not completely dehydrated. Evidence is also presented that suggests conjugate addition of the base to the α,β-unsaturated ketone may occur. Soluble cross-conjugated polyketones were prepared from terephthalaldehyde and 2-indanone, which contains no beta hydrogens, and from cycloaliphatic ketones and 1,2-bis(4-formylphenoxy)ethane, a dialdehyde containing isolated aldehyde groups. It is proposed, therefore, that the lack of solubility in the terephthalaldehyde-based polyketones arises from crosslinking via enolate anions formed at the beta position of the cyclic ketones, which are delocalized through the carbonyl groups of neighboring backbone repeating units. © 1995 John Wiley & Sons, Inc.     

Novel three-component tandem reactions of cyclic mono ketones, isatin and sarcosine: formation of dispiropyrrolidines

One-pot, three-component tandem reactions of cyclic mono ketones, isatin and sarcosine affording dispiropyrrolidines stereoselectively are reported for the first time.     

Microwave-assisted aldol condensation of benzil with ketones

Under microwave irradiation,the corresponding hydroxycyciopentenones were prepared in high yields by the cross-aldol reactions of benzil with various ketones.When the reactions were performed in vailOUS solvents under classical heating for a long time,they produced the products in relatively low yields.     

A versatile synthesis of retinoids via condensation of the side-chain to cyclic ketones

A simple synthesis of ethyl 3,7-dimethyl-2,4,6-nonatriene-8-ynoates and their corresponding alcohols is presented; codensation with various cyclic ketones can lead to retinoids having modified ring structures.     

Chichibabin-type condensation of cyclic ketones with 3-R-1,2,4-triazin-5(4H)-ones

Reactions between substituted 1,2,4-triazines and ketones were investigated. General procedures for one-pot synthesis of hydrogenated derivatives of such polycyclic systems as benzo[c][1,2,4]triazino[1,6-a][2]azecine, [1,2,4]triazino[1,6-f]phenantridine, and dicyclopenta[b,d]pyrido[1,2-f][1,2,4]triazine are described.     

Acetylenic ketones. Part III . Reaction of acetylenic ketones with nucleophilic sulfur compounds

Aroylphenylacetylenes reacted with ammonium dithiocarbamate and ammonium hydrogen sulfide in 60% dioxane-waler mixture at 15° to give mainly a mixture of the corresponding β-hydroxy-α-thiobenzoylstyrene derivatives (III) and (E,Z)-β,β'-di(α-aroylstyryl) sulfides (IV), whereas with sodium xanthate and sodium sulfide they gave only (III). However, when benzoyl-(Ia) or p-ehlorobenzoyl-(Id)phenylacetylenes was refluxed with ammonium dithiocarbamate in ethyl alcohol, it gave a mixture of (IIIa or d) and the (E,E)-β,β'-di(α-aroylstyryl) sulfide (VIa or d). β-Hydroxy-α-thiobenzoylstyrene derivatives (III), (E,Z)-(IV) and (E,E)-(VI)-β,β'-di(α-aroylstyryl) sulfides reacted with hydrazine hydrate and phenylhydrazine to give 3(5)-aryl-5(3)-phenyl-(IX)- and 5-aryl-1,3-diphenyl-(X)pyrazoles, respectively. The former compounds (III) reacted with guanidine and ethyl hydrazinecarboxylate to give the corresponding aminopyrimidines (XIII) and acetophenone-N-ethoxycarbonyl hydrazones (XI), respectively.     

Reaction of cyclic ketones with KOH-DMSO

Upon reaction of cycloalkanones with a KOH-DMSO system 2-methylenecycloal-kanols are formed, the yield (10–37%) of which decreases in the series: cyclohexanone > cycloheptanone > cyclooctanone > cyclododecanone.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1601–1605, July, 1990.     

Studies with dithizone--XII. Formation of thiadiazolines by condensation with aldehydes and ketones

The red colour that develops when mineral acids are added to solutions of dithizone (I; 3-mercapto-1,5-diphenylformazan) in certain samples of dioxan is mainly due to the formation of 2-methyl-3-phenyl-5-phenylazo-1,3,4-thiadiazoline (II) derived in part from adventitious traces of 2-methyldioxalane. A purple compound of molecular formula C(13)H(10)N(4)S is also formed from (I) by an independent and slower reaction. The thiadiazoline (II) is readily prepared from (I) and acetaldehyde, but analogous compounds from formaldehyde benzaldehyde, acetone and ethyl methyl ketone are obtained in better yield by starting from diphenylthiocarbazide. Di-p-tolyldithizone gives similar reactions. Reduction of the thiadiazoline (II) [which has spectra very closely resembling those of 1:1 complexes of (I) with arylmercury (II) cations] with ammonium hydrogen sulphide in ethanol yields diphenylthiocarbazide by opening of the hetero-ring and elimination of an alkyl residue from the intermediate 3-alkylmercapto-1,5-diphenylformazan. Other examples of nucleophilic displacements from the formazan group by SH(-) have been investigated.     

Rhodium(III) catalyzed oxidation of cyclic ketones by alkaline hexacyanoferrate(III)

The kinetics of the oxidation of 2-methyl cyclohexanone and cycloheptanone with Fe(CN)₆ ³⁻ catalyzed by RhCl₃ in alkaline medium was investigated at four temperatures. The rate follows direct proportionality with respect to lower concentrations of hexacyanoferrate(III) ion, but tends to become zero order at higher concentrations of the oxidant, while the reaction shows first-order kinetics with respect to hydroxide ion and cyclic ketone concentrations. The rate shows a peculiar nature with respect to RhCl₃ concentrations in that it increases with increase in catalyst at low catalyst concentrations but after reaching a maximum, further increase in concentration retards the rate. An increase in the ionic strength of the medium increases the rate, while increase in the Fe(CN)₆ ⁴⁻ concentration decreases the rate.     

Molybdenum hexacarbonyl-catalyzed condensation of malononitrile with ketones and aldehydes

Molybdenum hexacarbonyl activated with pyridine or morpholine catalyzes the condensation of malononitrile with ketones and aldehydes at 140 °C, which leads to alkylidenemalononitriles in 75–100% yield.     

Reaction of 2-acyloxiranes with cyclic ketones

Acyloxiranes react with cyclopentanone and cyclohexanone in the presence of catalytic amounts of boron trifluoride etherate to give the corresponding 2-acyl-1,4-dioxaspiro[4,4]-nonanes and 2-acyl-1,4-dioxaspiro[4,5]decanes. The corresponding cis-2,3-dimethyl-2 acetyl-1,4-dioxaspiroalkanes are formed from trans-2,3-dimethyl-2-acetyloxirane.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 885–888, July, 1974.