Benzalacetone Research Articles

Vicinal di-functionalization of α,β-unsaturated ketones via manganese carbene intermediates: synthesis of γ-acyl-δ-lactones by cascade Michael addition/aldol/transesterification reactions

The carbene–enolate complexes generated upon reaction of the carbene anion [Cp′(CO) 2MnC(OEt)CH 2] − with benzylidene acetone and chalcone react with benzaldehyde to form the 6-membered oxacyclocarbene complexes Cp′(CO) 2MnCCH 2CH(Ph)CH(C{O}R)CH(Ph)O (R=Me, Ph). The latter, which can be regarded as the result of cascade Michael addition/aldol/transesterification reactions, are readily oxidized by air to release the corresponding γ-acyl-δ-lactones.

Synthesis and expansion reaction of ferrocenylacetylene dimetal carbonyl compounds. The molecular structures of μ-FcCCHCoMo(CO)5Cp and μ3-FcCHCFeCo2(CO)9

Two ferrocenylacetylene dimetal carbonyl clusters μ-FcCCHCo(CO)3M(CO)2Cp (2, M=Mo; 3, M=W) were obtained from the reactions of the precursor μ-FcCCHCo2(CO)61 with metal exchange reagents NaM(CO)3Cp in THF under reflux. The dimetal compounds 1, 2, and 3 can further react with Fe2(CO)9 in the presence of benzylideneacetone (BDA) to give the corresponding μ3-ferrocenylvinylidene bridged trimetal clusters μ3-FcCHCFeCo2(CO)94 and μ3-FcCHCFeCoM(CO)8Cp (5, M=Mo; 6, M=W), respectively, probably through the formation of the intermediate (BDA)Fe(CO)3 which acts as an Fe(CO)3 transfer-reagent. The new compounds 2–6 were characterized by C/H analysis, IR and 1H-NMR spectrocopies. The molecular structures of 2 and 4 were determined by X-ray structural analysis. 2 is triclinic with space group P1̄ (#2), a=8.733(2) Å, b=14.870(3) Å, c=8.200(2) Å, α=92.77(2)°, β=101.78(2)°, γ=78.41(2)°, V=1021.2(4) Å3, and Z=2; final R=0.025, Rw=0.034 for 2988 reflections. Cluster 4 is orthorhombic with space group P212121 (#19), a=12.186(5) Å, b=14.870(5) Å, c=7.800(6) Å, V=2340(2) Å3 and Z=4; final R=0.062, Rw=0.065 for 2401 reflections.

One-pot synthesis of 4-aminobicyclo[2.2.2]octan-2-ones

Dialkylammonium rhodanides and benzylidene acetone give racemic (6 RS,7 RS)-4-dialkylamino-bicyclo[2.2.2]octan-2-ones in a one-pot reaction in good yields. The mechanism of the reaction includes a Diels-Alder step. The structures are established by NMR spectra and a single crystal structure analysis. The compounds consist of cations of racemates of optically active (6 R,7 R)- and (6 S,7 S)-4-dialkylamino-6,7-diphenylbicyclo[2.2.2]octan-2-ones and isothiocyanate anions.

Hydrophobic Properties of Antimutagenic Benzalacetones and Related Compounds.

The π values of benzalacetones (BZ) and trans-1, 1, 1-trifluoro-4-phenyl-3-buten-2-ones (TF) with a substituent on the benzene ring were analyzed by the directional Hommett-type treatment. The correlation equation showed that πBZ and πTF values are altered from the π value of monosubstituted benzenes, πPhX, mainly by the change in the hydrogen bonding behavior of the variable substituent caused by the electron-withdrawing fixed substituent. The log k' values for BZ and TF derived from reversed-phase liquid chromatography (RPLC) were correlated with log P values determined by using different compositions of methanol-phosphate buffer (pH 7.4) as eluents. A good linear correlation was obtained at 50% methanol concentration.

Synthesis and spectral, thermal, and photocrosslinking studies of poly(benzylidene phosphoramide ester)s

A new class of poly(benzylidene phosphoramide ester)s containing a photoreactive benzylidene chromophore in the main chain were synthesized from bis(4-hydroxy-3-methoxy benzylidene) acetone with various substituted N-aryl phosphoramidic dichlorides by an interfacial polycondensation technique. The synthesized polymers were characterized by inherent viscosity, IR, and 1H-, 13C-, and 31P-NMR spectroscopy. The molecular weights of these polymers were determined by gel permeation chromatography. These polymers were studied for their thermal stability and photochemical properties. Thermal properties were evaluated by thermogravimetric analysis and differential scanning calorimetry. It was found that halogen-containing polymers show a higher thermal stability than that of nonhalogenated polymers. The photocrosslinking property of these polymers was studied by ultraviolet spectroscopy. The photoreactive benzylidene chromophore in the main chain dimerizes via 2π + 2π cycloaddition reaction to form a cyclobutane derivative and leads to crosslinking. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2151–2157, 1997

Behaviour of benzylidene acetone during zinc electrodeposition in weakly acid solution containing a nonionic surfactant and/or carboxylic acid

The transformation products of benzylidene acetone formed during zinc electrodeposition in solutions containing a nonionic surfactant and/or carboxylic acid were determined by IR and 1H NMR-spectra after extraction and chromatographic separation. 1-Phenylbutanone-3, 1-phenylbutanole-3 and 1-phenylbutane were cathodic reaction products. Benzaldehyde, acetone, benzyl alcohol and benzoic acid were chemical reaction products in the cathodic layer. The nonionic surfactant increased the solubility of benzylidene acetone and carboxylic acid. This effect is probably caused by hydrophobic interaction and formation of associates. The associates cover a larger area of the cathodic surface than unsaturated ketone and/or carboxylic acid alone. It is supposed that a synergistic effect of additive mixtures on zinc electrodeposition may be caused by the formation of associates.

Synthesis, Structure, and Reactivity of the Complexes Fe(η3-S2CPR3)(CO)3. Electronic Factors Affecting the Dichotomy between η2and η3Coordination Modes in Transition Metal Complexes of Dithiocarboxy Ligands

The reaction of Fe(BDA)(CO)3 (BDA = benzylidene acetone) (1) with the dithiocarboxy adduct S2CPR3 affords complexes of formula Fe(η3-S2CPR3)(CO)3 (2). The pseudoallylic coordination of the SCS grouping is ascertained by an X-ray determination on the cyclohexyl derivative, 2a. The primary geometry of the complexes 2 is also maintained upon the electrophilic attack of a methyl cation to one of the sulfur atoms. This piece of information was obtained by solving the structure of the complex [Fe{η3-CH3SC(S)PCy3}(CO)3]CF3SO3 (3a). Unfortunately, the complete set of X-ray data for the latter cannot be completed due to the high disorder affecting the CF3SO3 anion. Altogether, these and the other experimental data available for a variety of MLn(S2CX) complexes have prompted a general theoretical study (based on EHMO calculations) of the factors affecting the η3−η2 coordination dichotomy of the dithiocarboxy ligands, S2CX. The Fe(CO)3 fragment, also in view of one extra vacant coordination site, appears better suit...

Modellreaktionen zur umsetzung von ferrocen-1,1′-dithiol mit Diolefinen: II. Die Säuren- and basenkatalysierten reaktionen von ferrocenthiolen mit aktivierten olefinen

Both ferrocenethiol and ferrocene-1,1′-dithiol, Fe(C 5H 5)(C 5H 4SH) and Fe(C 5H 4SH) 2, add to activated olefins to give 1:1 and 1:2 adducts, respectively. The base-catalysed (NEt 3) reactions of the monofunctional ferrocenethiol with the mono-olefins methyl methacrylate, methyl vinyl sulfone and benzylidene acetone lead to the expected 1:1 adducts whereas 2:1 adducts are obtained with bifunctional olefins such as divinyl sulfone and dibenzylidene acetone. The corresponding bifunctional ferrocene-1,1′-dithiol gives 1:2 adducts with methyl methacrylate, methyl vinyl ketone and benzylidene acetone. For comparison, the aliphatic 2-ferrocenyl-ethanethiol, Fe(C 5H 5)(C 5H 4CH 2CH 2SH), was reacted with methyl vinyl sulfone and divinyl sulfone. In all cases, the disulfides Fc-SS-Fc and FcCH 2CH 2SSCH 2CH 2Fc, respectively, are also formed. The acid-catalysed (HCI) reactions of ferrocenethiol and ferrocene-1,1′-dithiol, Fe(C 5H 5)(C 5H 4SH) and Fe(C 5H 4SH) 2, with isobutyl vinyl ether produce the expected 1:1 and 1:2 adducts although the formation of dimercaptals is also possible. Thus the reaction of ferrocene1,1′-dithiol with isobutyl vinyl ether leads to both the 1:2 adduct and the 2-methyl 1,3-dithia-[3]ferrocenophane, Fe(C 5H 4S) 2CH(CH 3), and the HCI-catalysed addition of ferrocenethiol to 1,4-butanediol divinyl ether gives 1,1-di(ferrocenylmercapto) ethane, CH 3CH(SFc) 2. The new sulfur derivatives of ferrocene were characterized by 1H and 13C NMR spectroscopy.

Surface morphology and crystal orientation of electrodeposited tin from acid stannous sulphate solutions containing various additives

The changes in surface morphology and crystal orientation of electrodeposited tin from acid stannous sulphate solutions containing 1 mm N,N-bis(tetraoxyethylene)octadecylamine (TOGA) and various concentration (0.2–2 mm) of benzalacetone (BA) have been studied as functions of electrolysis time or BA concentration by electrochemical methods, scanning electron microscopy and X-ray diffractometry. The inhibitory effect on the reduction of the tin (II) ion became stronger with increasing concentration of BA. In the presence of both TOOA and BA, when electrolyses were carried out at the more negative potentials than the reduction potential of BA, the reduction product of BA induced reticular crystals (network structure) of tin over the whole surface. This structure appeared in the early stage of electrolysis and exhibited an intense (200) diffraction peak. On the other hand, the crystal grain size and the surface roughness of electrodeposited tin became smaller with increasing concentration of BA from 0.2 to 2 mm. Further, fine-grained and smooth electrodeposits of tin were obtained from acid stannous sulphate solutions containing TOOA and high concentration of BA due to the synergistic effect of these adsorbed species.

Synergistic effects of benzalacetone and benzophenone on the electrocrystallization of tin from acid stannous sulphate solutions

The synergistic effects of two kinds of aromatic ketones (benzalacetone (BA), benzophenone(BP)) and N,N-bis(polyoxyethylene)octadecylamines (POOA) on the surface morphology and the crystal orientation of electrodeposited tin from acid stannous sulphate solutions have been studied by electrochemical methods, scanning electron microscopy and X-ray diffractometry. BA itself had no effect on the reduction of tin (II) ions, but the reduction product of BA had a strong inhibitory effect on the reduction of tin (II) ions. However, the inhibitory effect of BP was stronger than that of the reduction product of BP. POOA induced a uniform deposition of tin over the whole surface, but the crystal grain size and the surface roughness of electrodeposited tin were relatively large. On the other hand, fine-grained and smooth electrodeposited tin, which had a preferred orientation with the (10 0) plane parallel to the surface, were obtained from acid stannous sulphate solutions containing POOA, BA and BP due to the synergistic effects of the three kinds of adsorbed species. It was found that BA has a levelling action and BP has a grain refinement action.

CHLOROSULFONATION OF αβ-UNSATURATED ARYLIDENE KETONES

Abstract 2-Thienylideneacetone (4), and the benzylidene derivatives of ethyl methyl ketone (19) and diethyl ketone (20) were reacted with excess chlorosulfonic acid to give the thienylidene 5,β-disulfonyl chloride (5) and the styrene disulfonyl chlorides (21 and 22). These were characterized by preparation of the sulfonamides (6-9, 23 and 24) required for screening as pest control agents. Benzylidene acetone (1) was condensed with aryl aldehydes to give the corresponding 1,5-diaryl-1,4-dien-3-ones (25-28), but the condensation failed with p-anisaldehyde and o-vanillin. Attempted chlorosulfonation of compounds (25 and 28) was unsuccessful and the products could not be characterised as sulfonamide derivatives. The 1H NMR spectra of selected compounds are briefly discussed.

Organomolybdän‐ und Organowolfram‐Reagenzien, V. über die additive, reduktive Carbonyldimerisierung (ARCD‐Reaktion)

Organomolybdenum and Organotungsten Reagents, V[1]. – On the Additive, Reductive Carbonyl Dimerization (ARCD Reaction)Reagents of the type R4(PrO)4(μ‐PrO)2W2 (3; R = Me, Et, Pr, Bu, sBu, iBu, Hex, Me3SiCH2, Ph) prepared in situ by the action of organolithium or Grignard compounds on (PrO)4(μ‐PrO)2‐W2Cl4 (2), react with aromatic aldehydes or ketones and with the α,β‐unsaturated ketone benzylidene acetone in a novel reaction, called the ARCD reaction, to give products 4 of the type RRRC—CRRR with mostly good yields. In the case of benzylidene acetone and furfural besides the ARCD products the rearranged products 27 and 29 are formed. With the reagent Ph4(PrO)4(μ‐PrO)2W2 (3b) ARCD reactions are also possible in moderate yields with aliphatic aldehydes and ketones. The more closely investigated reagent Me4(PrO)4(μ‐PrO)2W2 (3a; decomposition at about — 45C) tolerates the aromatic bound functional groups Cl, F, OH, OMe, and NMe2 in the substrates, but not the NO2 and CO2Et substituents. It reacts with PhCOX (X = OEt, Cl, OCOPh) via acetophenone to give PhCMe2—CMe2Ph. — For the ARCD reactions a radical mechanism (Scheme 7) is postulated.

Effects of aromatic carbonyl compounds on the electrocrystallization of zinc from acid sulfate solutions

The electrochemical characteristics of N,N-bis(decaoxyethylene)octadecylamine(DOOA) and the three kinds of aromatic carbonyl compounds [cinnamaldehyde(CA), benzalacetone(BA), 2-acetonaphthone(AN)] as well as the effects of such organic additives on the electrocrystallization of zinc from acid sulfate solutions have been studied by means of various electrochemical methods and scanning electron microscope observations. DOOA and three kinds of carbonyl compounds were adsorbed on the electrode. DOOA adsorbed on the electrode as a quaternary ammonium ion strongly inhibited the electrochemical reduction of the zinc ion. BA or AN had a stronger inhibitory effect on the reduction of zinc ions than CA. Large plate-like electrodeposits of zinc (sides 3–10 μm) were obtained from acid sulfate solutions in the absence of organic additives. On the other hand, needle-like or fibrous crystals were observed on the whole surface by adding DOOA alone. Small block-like or granular crystals (sides 1–2 μm) were observed on the whole surface by adding BA or AN alone. Further, fine-grained, smooth and compact electrodeposits of zinc were obtained from acid sulfate solutions containing DOOA and BA or DOOA and AN.

Effects of aromatic carbonyl compounds on the surface morphology and crystal orientation of electrodeposited tin from acid stannous sulfate solutions

The effects of three kinds of aromatic carbonyl compounds [cinnamaldehyde(CA), benzalacetone(BA), 2-acetonaphthone(AN)] and N,N-bis(tetraoxyethylene)octadecylamine(TOOA) on the surface morphology as well as crystal orientation of electrodeposited tin from acid stannous sulfate solutions have been studied by means of electrochemical methods, scanning electron microscopic observation and measurements of X-ray diffraction patterns. The inhibitory effects of the reduction of tin(II) ion became stronger in the order BA, CA and AN in the case of oxidant, and in the order CA, AN and BA in the case of reductant. The differences in the inhibitory effects between the oxidant and reductant became greater in the order of AN, CA and BA. Block-like crystals were observed on the whole surface by adding TOOA. Plate-like, needle-like or dendritic crystals were observed but compact electrodeposits could not be obtained by adding carbonyl compounds alone. On the other hand, compact and smooth electrodesposits of tin which had a preferred orientation with the (100) plane parallel to the surface were obtained from acid stannous sulfate solutions containing TOOA and BA.

Photo-degradable polystyrene Part II: styrene-co-vinyl ketones

Styrene was copolymerized with two commercially available ketone functional monomers; i.e., methyl vinyl ketone (MVK) and benzalacetone (BA). BA copolymerizes poorly with styrene. This, along with its low volatility, results in high residual BA monomer in the final polymer. 13C NMR characterization of SBA showed that the polystyryl radical adds to both carbons of the double bond and at similar rates. The SMVK copolymers were found to degrade twice as efficiently as SBA copolymers.

Synthesis of cycloheptenyldiphenylphosphine oxides from the reactions of a cyclic phosphonium salt with α,β-unsaturated carbonyl compounds

The reactions of the ylide from the five-membered cyclic phosphonium salt 1 with methyl vinyl ketone, chalcone, and benzylidene acetone afforded cycloheptenyldiphenylphosphine oxides via a Michael-type reaction followed by an intramolecular Wittig reaction.

On the way to chiral copper(I) arenethiolate catalysts for the enantioselective conjugate addition of methyl lithium and methyl magnesium iodide to benzylideneacetone

Selective conjugate addition (0 % enantiomeric excess (e.e.)) of organoarenethiolatocuprates (from methyl lithium and 2-[1-( R)-(dimethylamino)ethyl]phenylthiolatocopper(I), CuSAr*) to benzylideneacetone (BA) is found up to a LiMe/CuSAr* ratio of 2 1 indicating the potential of the chiral SAr*-anion as non-transferable group; at higher ratios only 1,2-addition occurs. Reactions of methyl magnesium iodide with BA in the presence of a catalytic amount of CuSAr* (9 mol%) result in exclusive conjugate addition with 57% e.e..

Photophysics of bis(p-N,N-dimethylamino)benzylidene acetone: Does photoinduced electron transfer occur from a twisted excited state?

Photoexcitation of the title compound (DMBA) in polar solvents leads to sequential formation of at least three excited species as detected by laser transient absorption spectroscopy: the lowest Franck–Condon singlet, a twisted singlet (P-state), and the lowest triplet states. Only the initially formed, localized singlet is emissive under our conditions. Interystem crossing to triplet occurs primarily from the twisted P-state in acetonitrile and in methanol. Photo-CIDNP and quantum yield measurements indicate that electron transfer occurs exclusively from the triplet in acetonitrile or methanol to sensitize decomposition of diphenyliodonium cation and to bleach DMBA. Analysis of the photochemistry is complicated by formation of a charge transfer complex of enhanced photolability. Using tris(trichloromethyl)-sym-triazine as the electron acceptor in hydrocarbon solvent, bleaching of DMBA again occurs, somewhat more efficiently than with the 'onium salt in polar solvent. We infer that under these conditions electron transfer occurs from the P-state. Keywords: photochemistry, fluorescence, electron transfer, TICT, chalcone.

ChemInform Abstract: Electroreduction of Benzalacetone in N,N‐Dimethylformamide

ChemInform Abstract: Electroreduction of Benzalacetone in N,N‐Dimethylformamide

Synergistic effects of adsorbed species on the surface morphology and crystal orientation of electrodeposited tin

The synergistic effects of adsorbed species (polyoxyethylenealkylamine (POAA), diphenylamine-crotonaldehyde reaction product (RP) and benzalacetone (BA)) on the surface morphology and crystal orientation of electrodeposited tin from acid stannous sulfate solutions have been studied by means of various electrochemical methods, scanning electron microscopic observation and measurements of X-ray diffraction patterns. Needle-like or columnar electrodeposits of tin were obtained from acid stannous sulfate solution in the absence of adsorbed species. On the other hand, fine-grained, smooth and compact electrodeposits of tin, which had a preferred orientation with the (200) plane parallel to the surface, were obtained from acid stannous sulfate solutions containing POAA, RP and BA due to the synergistic effect of the three kinds of adsorbed species. It was found that POAA acts to produce a uniform tin deposition over the whole surface, RP acts as a grain refiner and BA has a leveling action.