Styryl Ketones Research Articles

Préparation, réduction chimique et électrochimique d'α-nitrostyrylcétones — synthèse d'hétérocycles azotés

Nitration of styryl ketones with nitrogen peroxide leads to the corresponding α-nitroethylenic ketones in good yield. However, the presence of methoxy groups involves a nitration on the aromatic nucleus.LiAlH4 reduction of α-nitrostyrylketones yields the corresponding racemic erythro- and threo-aminoalcohols; after acylation and cyclisation a dihydro-quinoline or a 2-oxazoline is obtained.Electrochemical reduction of these nitrostyryl-ketones selectively provides the α-ketoximes, which are themselves reduced electrolytically to α-aminoketones. These latter compounds dimerise in neutral medium to dihydro-2,5-pyrazines which aromatise to the corresponding pyrazines. In acid medium an α-ketol is obtained.A mechanism for the reduction is proposed implicating an enaminol intermediate.

ChemInform Abstract: SYNTHESES AND EVALUATION OF KETALS, HEMITHIOKETALS, AND DITHIOKETALS OF CONJUGATED STYRYL KETONES PRINCIPALLY FOR ANTINEOPLASTIC ACTIVITY

AbstractAus den Vinylketonen (I) erhält man nach bereits bekannten Methoden mit den entsprechenden Hydroxy‐ bzw. Mercaptoverbindungen (II) und (IV) die Ketale (III) und (V).

The reaction of some nuclear substituted acyclic conjugated styryl ketones and related Mannich bases with ethanethiol

The second order rate constants for the reaction of ethanethiol with a number of conjugated nuclear-substituted styryl ketones and related Mannich bases in 50% aqueous acetonitrile was undertaken. Variation of the alkyl group adjacent to the carbonyl function was accompanied by altered avidity to ethanethiol which was explained as being due in part to the varying inductive effects of the alkyl groups which would, in turn, affect the stability of the reaction intermediates. The greatest disparity in reactivity between groups of compounds was between the ketones and analogous Mannich bases which was in accord with the marked difference in bioactivities between these two groups of compounds.

Syntheses and evaluation of ketals, hemithioketals, and dithioketals of conjugated styryl ketones principally for antineoplastic activity

Ketals, hemithioketals, and dithioketals of nuclear-substituted styryl ketones were prepared as latentiated forms of the ketones. This undertaking was based on the premise that there is increased acidity in tumors compared to normal tissue, and thus preferential regeneration of the ketone in neoplastic tissue may occur. Attempts to form 1,3-dioxolans of Mannich bases were unsuccessful. The prepared compounds did not possess significant anticancer properties, but analgesic, anti-inflammatory, antihistaminic, and antimicrobial activities were found in the prepared Mannich bases.

Studies on the mass spectrometry of some acyclic nuclear substituted styryl ketoximes and ketones with special reference to the ortho effect

The mass spectra of several ring substituted acyclic styryl ketoximes and analogous ketones have been determined at 70 eV and also at low ionization voltages. The major fragmentation pathways for the oximes are loss of the ortho substituent from the parent ion as well as loss of the hydroxyl and hydroxylamine radicals. Other fragmentation pathways include γ- and δ-cleavages as well as the McLafferty rearrangement. While there was a total absence of α-cleavage from the parent ions, the facility of loss of the ortho substituents from the oxime molecular ions was compared with the same process occurring in the corresponding acyclic ketones, as well as the related cyclic derivatives, namely the substituted 2-benzylidinecyclohexanones and oximes. Stabilization of the resultant cyclized ion as well as steric factors are considered as factors favouring the cyclization process.

Evaluation of 1-(3,4-dichlorophenyl)-4-dimethylaminomethyl-1-nonen-3-one Hydrochloride effect on Nucleic acid and protein syntheses using murine leukemia L-1210 cells

Several Mannich bases derived from conjugated styryl ketones were shown to have potent cytotoxicity toward murine leukemia L-1210 cells and Walker 256 carcinosarcoma cells in culture. The most cytotoxic derivative, (E)-1-(3,4-dichlorophenyl)-4-dimethylaminomethyl-1-nonen-3-one hydrochloride, profoundly inhibited the incorporation of tritiated leucine into protein(s) and tritiated deoxythymidine into DNA at concentrations of 0.79-1.32 μM in L-1210 cells. At higher concentrations, incorporation of tritiated undine into RNA and tritiated deoxyuridine into DNA was inhibited to a lesser degree. This compound failed to inhibit the enzymes thymidylate synthetase or dihydrofolate reductase up to a concentration of 10−4M and was ineffective in retarding the growth of the Walker 256 carcinosarcoma in rats.

Syntheses and Bioactivities of l-(Hydroxyphenyl)-l-Nonen-3-Ones and Related Ethers and Esters

A number of nuclear hydroxy styryl ketones and related compounds were prepared and evaluated for antineoplastic and antimicrobial activities as well as for analgesic, anti-inflammatory, and antianaphylactic properties. The second-order rate constants for the reaction of several esters with hydroxide ion in aqueous dioxane (50% v/v) at 36.9° were determined. The screening results showed that activity against P-388 lymphocytic leukemia was found solely with the ethers and that antimicrobial properties were obtained virtually exclusively with the phenolic derivatives. All compounds showed analgesic properties, except for four that were algesic. While little anti-inflammatory activity was found, several compounds showed some antianaphylaxis.

Nuclear‐Substituted Styryl Ketone Analogs: Effects on Neoplasms, Microorganisms, and Mitochondrial Respiration of Tumorous and Normal Cells

Analogs of some antineoplastic and cytotoxic Mannich bases derived from conjugated styryl ketones were prepared and evaluated for activity in the P‐388 lymphocytic leukemia screen. Most of the new compounds had lower antineoplastic and murine toxicity than the parent compounds. Antimicrobial evaluation of some oximes and alcohols related to the Mannich bases revealed activity against certain Gram‐positive bacteria and fungi. Primary pharmacological evaluation showed that some compounds containing a dimethylaminomethyl group displayed analgesic and antihistaminic properties. Five of the Mannich bases were evaluated as respiratory inhibitors in mitochondria derived from hepatic tumors, liver tissue from tumor‐bearing animals, and normal rat liver. No statistical difference between the sensitivity of the three tissues to the compounds was obtained.

Pyrimidines. 69. Syntheses based on acetylpyrimidines. Dipyrimidinyls and pyrimidine analogs of chalcone

Substituted pyrimidinyl styryl ketones were obtained by condensation of 4-methyl-2-phenyl-5-acetylpyrimidine with aromatic aldehydes, and their conformations in KBr and in solution in CHCl3 were examined. 4′,5-Dipyrimidinyl derivatives were obtained by cyclization of the pyrimidinyl styryl ketones with benzamine. The isomeric trioxo-4′,5- and -4,6′-dipyrimidinyls were obtained by reaction of 5- and 6-acetyluracils with benzalbisurea.

ChemInform Abstract: SYNTHESIS AND EVALUATION OF 1‐(HYDROXYPHENYL)‐1‐NONEN‐3‐ONES AND RELATED COMPOUNDS FOR ANTINEOPLASTIC AND ANTIMICROBIAL ACTIVITIES

AbstractAuf dem im Formelschema skizzierten Weg werden die Nonen‐3‐one (IV) synthetisiert.

Réduction catalytique de cétones α,β-éthyléniques à température modérée par

The use of the catalyst [Formula: see text] in the reduction of the ethylenic system of styryl ketones by 1-phenylethanol permits the hydrogenation reaction to proceed at 50 °C. Some substituent effects in the α,β-unsaturated ketones were demonstrated at this temperature. These showed an increase in the initial rate of reduction for electron-attracting groups and the inverse effect for electron-donating groups. The observation of a relation between the electrochemical reduction potential of these ketones and their rate of hydrogenation suggests a transfer of hydrogen to the ketone by a hydride ion intermediate. [Journal translation]

Effect of Antineoplastic and Cytotoxic Mannich Bases Derived from Conjugated Styryl Ketones on Mitochondrial Respiration in Rat Liver Cells

Five cytotoxic Mannich bases (5-dimethylamino-1-substituted phenyl- 1-penten-3-ones), three having antineoplastic activity, were evaluat,ed for respiratory-inhibiting properties in rat liver mitochondria in the presence of lour substrates: succinate, glutamate, 3-hydroxybutyrate, and palmitylcarnitine. Four compounds (Ib-Ie) showed significant inhibiting properties which, on occasion, were reversed partially by coenzyme Q10. Evaluation of the spectra of the mitochondria1 cytochromes indicated that Ib-Ie blocked the electron transport chain prior to the sequence of cytochromes. Since inhibition occurred when different substrates were used, a common site of action for Ib-Ie is likely; competition of lb-lc with coenzyme Q10 probably occurs. Compounds Ia-Ie inhibited RNA polymerase from Swiss muuse kidney cells but were virtually bereft of activity versus RNA polymerase from L-1210 leukemia cells. Polarography of the Mannich bases and the related styryl ketones showed that antineoplastic activity was associated with higher half-wave potentials.

Synthesis and Evaluation of 1 - (Hydroxyphenyl) -1 -nonen-3-ones and Related Compounds for Antineoplastic and Antimicrobial Activities

Some 1 (hydroxyphenyl)-l-nonen-3-ones, the corresponding Mannich bases, and O-benzoyl esters were synthesized. Evaluation of these derivatives against murine P-388 lymphocytic leukemia indicated that, while the hydroxyphenyl styryl ketones and related esters were devoid of significant anticancer activities, etherification of the nuclear hydroxyl group gave compounds with a discernible increase in mean survival time. The hydroxyphenyl styryl ketones showed marked potencies against two pathogenic fungi and one yeast, while the corresponding ethers had diminished activities and the related esters were virtually devoid of antimicrobial activities. Two Mannich bases showed similar spectra of antimicrobial activities as the phenols and, in particular, were active against Trichophyton tnentagrophytes and Saccharomyces uvarum.

Steric effects in the electroreduction of 9-anthryl styryl ketone and 9,10-anthryl bis(styryl ketone)

The electrochemical behavior of 9-anthryl styryl ketone (ASK) and 9,10-anthryl bis(styryl ketone) (ABSK) in acetonitrile and N,N-dimethylformamide at a Pt electrode was investigated by cyclic and rotating ring disk electrode (RRDE) voltammetry and controlled potential coulometry. ASK is reduced in a reversible one-electron step to form the radical anion which rapidly couples ( k 2 =10 5 M −1 s −1 ) to form the dimeric dianion. The dimer can be reoxidized to form ASK. ABSK is reversibly reduced to the stable dianion which shows no tendency to couple. The cyclic voltammogram wave shape suggests that the styryl-keto groups in the 9-and 10-positions are non-interacting so that the reduction occurs in two steps whose standard potentials differ by the statistically predicted 36 mV.

Steric effects in the electroreduction of 9-anthryl styryl ketone and 9,10-anthryl bis(styryl ketone)

The electrochemical behavior of 9-anthryl styryl ketone (ASK) and 9,10-anthryl bis(styryl ketone) (ABSK) in acetonitrile and N,N-dimethylformamide at a Pt electrode was investigated by cyclic and rotating ring disk electrode (RRDE) voltammetry and controlled potential coulometry. ASK is reduced in a reversible one-electron step to form the radical anion which rapidly couples ( k 2=10 5 M −1 s −1) to form the dimeric dianion. The dimer can be reoxidized to form ASK. ABSK is reversibly reduced to the stable dianion which shows no tendency to couple. The cyclic voltammogram wave shape suggests that the styryl-keto groups in the 9-and 10-positions are non-interacting so that the reduction occurs in two steps whose standard potentials differ by the statistically predicted 36 mV.

Syntheses of Organozinc Enolates and Their Reactivities in Polymerization Reactions

Syntheses and reactivities of organozinc enolates, having same structure as that of the chain end of growing poly(vinyl ketone) molecules, were studied. An addition reaction of ZnEt2 with ethyl styryl ketone gave an organozinc enolate, ethylzinc 5-phenyl-3-heptene-3-olate (ZE), fairly quantitatively. In the polymerization of ethyl isopropenyl ketone initiated with ethylzinc 1,3-diphenyl-1-pentene-1-olate (ZC), a second-order rate law with respect to ZC was established, suggesting a coordination-addition mechanism plausible for this reaction in a way similar to the previous result with phenyl styryl ketone. At the same time as the above studies, the chemical behavior of ZC and ZE toward carbon dioxide (CO2) was also examined. Through the measurements of time course of IR and NMR spectra of the reaction system, it was concluded that a polymeric form of organozinc enolates should be the final product formed in the reaction between ZC (or ZE) and CO2. This polymeric organozinc compound was able to catalyze the reaction of methyloxirane with CO2 to give rise to poly(propylene carbonate) and propylene carbonate.

ChemInform Abstract: EPOXYDATION OF ALKYL(ARYL) STYRYL KETONES

Chemischer InformationsdienstVolume 8, Issue 22 Preparative Organic Chemistry ChemInform Abstract: EPOXYDATION OF ALKYL(ARYL) STYRYL KETONES I. G. TISHCHENKO, I. G. TISHCHENKOSearch for more papers by this authorI. F. REVINSKII, I. F. REVINSKIISearch for more papers by this authorV. N. SYTIN, V. N. SYTINSearch for more papers by this author I. G. TISHCHENKO, I. G. TISHCHENKOSearch for more papers by this authorI. F. REVINSKII, I. F. REVINSKIISearch for more papers by this authorV. N. SYTIN, V. N. SYTINSearch for more papers by this author First published: May 31, 1977 https://doi.org/10.1002/chin.197722130Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume8, Issue22May 31, 1977 RelatedInformation

Photodegradable polymers. II. Preparation of styrene copolymers with alkyl and phenyl β‐styryl ketones and their photodegradability

AbstractPhotodegradable polymers having pendent carbonyl groups attached directly to the polymer chain were prepared by copolymerization of styrene (St) with alkyl and phenyl β‐styryl ketones (RCOCHCHC6H5), where R = CH3, C2H5, n‐C5H11, n‐C11H23, t‐C4H9, cyclo‐C6H11, and C6H5. The photodegradability of these copolymers was traced by viscometric and IR spectroscopic measurements. The degradability of St–benzalacetophenone (BAPh) copolymer is greater than that of St–alkyl styryl ketone copolymers under the irradiation of a high‐pressure Hg lamp. The photodecomposition behavior St–BAPh copolymer was investigated in detail by a spectoirradiation technique. The changes in molecular weight and its distribution by photodegradation were measured by gel permeation chromatography, and the quantum yield for bond scission along the main chains of the copolymer was estimated to be about 5 × 10−3 by 328 nm irradiation in a benzene solution. Examination of the effect of wavelength of the radiation on the bond scission showed that 328‐nm light is most effective. The photochemical degradation process was shown to occur chiefly via triplet state of carbonyl groups by the quenching technique using 1,3‐cyclohexadiene as a triplet quencher. The quantum yield of decarbonylation process was also estimated to be about 4.2 × 10 −2 in benzene.

Compounds Related to Acridine. XIII. Reactions of 9-Vinyl- and 9-Ethynylacridine with C,N-Diarylnitrones

Abstract The reaction of 9-vinylacridine (1) with C,N-diarylnitrones (3) in xylene under reflux afforded 5-(9-acridinyl)-2,3-diarylisoxazolidines (4) and/or 9-acridinyl styryl ketones (5). On heating isoxazolidines 4 were readily converted into the styryl ketones 5 with the elimination of anilines: this is a new type of thermal decomposition of isoxazolidine ring. However, thermal decomposition of 3-(9-acridinyl)-2,5-diarylisoxazolidines (9) which were prepared from N-(9-acridinylmethylene)aniline N-oxide (7) and styrene (8), did not observed. On the other hand, the reaction of 9-ethynylacridine (2) with nitrones 3 in ethanol under the influence of hydrochloric acid proceeded smoothly to give the reversed 4-(9-acridinyl)-4-isoxazolines (11), which on heating were converted into the corresponding 4-oxazolines 12.

The acidities of weak acids. Part IV. Some methyl styryl ketones

A series of ring-substituted methyl styryl ketones (XC6H4·CH:CH·CO·CH3) have been synthesised and their acidities measured at 298.2 K using solutions of tetramethylammonium hydroxide (0.011 M) in dimethyl sulphoxide–water mixtures. In most cases the rates of detritiation in aqueous hydroxide ion solutions have also been measured. The results show that these compounds obey the same pKa–lgkTOH– relationship as was established for the structurally similar acetophenones.