AlCl3-mediated cleavage of ethereal methyl–oxygen bond in aroylated 2,7-dimethoxynaphthalene compounds proceeds chemospecifically and regioselectively. The ethereal bond at the β(2)-position of 1-monoaroylated 2,7-d...AlCl3-mediated cleavage of ethereal methyl–oxygen bond in aroylated 2,7-dimethoxynaphthalene compounds proceeds chemospecifically and regioselectively. The ethereal bond at the β(2)-position of 1-monoaroylated 2,7-dimethoxynaphthalene is cleaved readily and predominantly against the β(7)-position, whereas scission of β-ethereal bonds of 1,8-diaroylated 2,7-dimethoxynaphthalene hardly undergoes like the non-aroylated mother frame compound of 2,7-dimethoxynaphthalene.展开更多
The direct aroylation of ArCOPdCl with potassium aryltrifluoroborates establishes a new cross-coupling synthetic tool for the synthesis of various fluorine substituted benzophenones. The new microwave irradiated proce...The direct aroylation of ArCOPdCl with potassium aryltrifluoroborates establishes a new cross-coupling synthetic tool for the synthesis of various fluorine substituted benzophenones. The new microwave irradiated process is very efficient and produce high yield benzophenone products within minutes.展开更多
The title compounds 3 and 4 condensed with aromatic aldehydes to give a--aroylsicinnamoyl ketene cyclic dithioacetals 5 and 6 with sodium ethoxide as the base. The stereochemistryofs and 6 was assigned as E-configurat...The title compounds 3 and 4 condensed with aromatic aldehydes to give a--aroylsicinnamoyl ketene cyclic dithioacetals 5 and 6 with sodium ethoxide as the base. The stereochemistryofs and 6 was assigned as E-configuration by 1H NMR.展开更多
An interesting regioselectivity is observed when the mixture of potassium crotyltrifluoroborate (1a) and aroyl chlorides having electron-deficient and electron-rich groups is microwaved in the presence of palladium-ca...An interesting regioselectivity is observed when the mixture of potassium crotyltrifluoroborate (1a) and aroyl chlorides having electron-deficient and electron-rich groups is microwaved in the presence of palladium-catalyst. In the case of electron withdrawing group with phenyl ring of aroyl chlorides, isomerized α,β-unsaturated compound 3 is the product whereas electron donating group with phenyl ring of aroyl chlorides furnishes α-adduct 4. Similar aroylation reaction is also established for potassium allyltrifluoroborate (1b). In this case, regioselectivity is unaffected with changing electron-rich or electron-deficient groups in phenyl ring of the aroyl chlorides. Reactions proceed with, essentially in same rate, affording the corresponding aryl propenyl ketones (crotonophenones) 5 in good to high yields.展开更多
New solid complexes derived from the reaction of aroyl hydrazones, 2-hydroxy-1-naphthaldehyde benzene sulphonyl hydrazone (HNB), and 2-hydroxy-1-naphthaldehyde p-toluene sulphonyl hydrazone (HNT), with Co<sup>2+...New solid complexes derived from the reaction of aroyl hydrazones, 2-hydroxy-1-naphthaldehyde benzene sulphonyl hydrazone (HNB), and 2-hydroxy-1-naphthaldehyde p-toluene sulphonyl hydrazone (HNT), with Co<sup>2+</sup>, Ni<sup>2+</sup>, and Cu<sup>2+</sup> salts have been isolated and characterized using elemental analyses, spectral (UV-vis., IR), molar conductivity and magnetic measurements. The modes of bonding as well as the stereochemistry of the isolated solid complexes were discussed. The results suggested that both HNB and HNT coordinated with the metal ions in a bidentate manner forming a polymeric chain in the case of HNB while monocular complexes were formed in the case of HNT. The amounts of solvent in the solid complexes were determined by TGA measurements. Also, spectral studies of HNT with Co<sup>2+</sup> and Fe<sup>3+</sup> ions in solution were carried and the ratio of complexes was determined by continuous variation, molar ratio, and slope ratio methods. Moreover, the results suggest the formation of 1:1 (M:L) for Co<sup>2+</sup> ions while three species with ratios of 1:1, 1:2, and 2:1 (M:L) have been observed in the case of Ni<sup>2+</sup> and Cu<sup>2+</sup>. Finally, conductance titration of HNB and HNT with Co<sup>2+</sup> ion elucidates the formation of two species with ratios 1:1 and 1:2 (M:L) in the case of the Co<sup>2+</sup>-HNB while 1:1 (M:L) belongs to the Co<sup>2+</sup>-HNT system.展开更多
The palladium-catalyzed late-stage aroylation of 4-methyl-1,5-diaryl-lH-pyrazole-3-carboxylates has been developed via direct and exclusive mono-Csp^2-H bond activation with broad substrate scope and good functional g...The palladium-catalyzed late-stage aroylation of 4-methyl-1,5-diaryl-lH-pyrazole-3-carboxylates has been developed via direct and exclusive mono-Csp^2-H bond activation with broad substrate scope and good functional group tolerance. A dual-core dimeric palladacycle is confirmed by X-ray single crystal crystallography, and probably serves as an active species in the catalytic cycle.展开更多
An unprecedented palladium/copper cocatalyzed coupling reaction of indoles with simple aroyl hydrazides has been developed under aerobic conditions. A range of aroyl hydrazides underwent palladium/copper cocatalyzed o...An unprecedented palladium/copper cocatalyzed coupling reaction of indoles with simple aroyl hydrazides has been developed under aerobic conditions. A range of aroyl hydrazides underwent palladium/copper cocatalyzed oxidative arylation with indoles open to air in a 1：1 mixture of dimethyl sulfoxide and nitromethane to give structurally diverse 2-arylindoles or 3-arylindoles in moderate to good yields. The reaction well tolerates a wide variety of functional groups such as alkoxy, halo, ester.展开更多
The deprotonative functionalization of toluenes,for their weak acidity,generally needs strong bases,thus leading to the requirement of harsh conditions and the generation of by-products.Direct nucleophilic acyl substi...The deprotonative functionalization of toluenes,for their weak acidity,generally needs strong bases,thus leading to the requirement of harsh conditions and the generation of by-products.Direct nucleophilic acyl substitution reaction of amides with organometallic reagents could provide an ideal solution for ketone synthesis.However,the inert amides and highly reactive organometallic reagents bring great challenges for an efficient and selective synthetic approach.Herein,we reported an lithium diisopropylamide(LDA)-promoted benzylic aroylation of toluenes with unactivated tertiary benzamides,providing a direct and efficient synthesis of various aryl benzyl ketones.This process features a kinetic deprotonative functionalization of toluenes with a readily available base LDA.Mechanism studies revealed that the directed ortho-lithiation of the tertiary benzamide with LDA promoted the benzylic kinetic deprotonation of toluene and triggered the nucleophilic acyl substitution reaction with the amide.展开更多
The dynamic kinetic resolution of 2-aroyl-l-tetralones was achieved via asymmetric transfer hydrogenation using （S,S）-RuCl（p-cymene）TsDPEN （TsDPEN=N-（tosyl）-1,2-diphenylethylenediamine） in formic acid/triethyl...The dynamic kinetic resolution of 2-aroyl-l-tetralones was achieved via asymmetric transfer hydrogenation using （S,S）-RuCl（p-cymene）TsDPEN （TsDPEN=N-（tosyl）-1,2-diphenylethylenediamine） in formic acid/triethylamine （5 ： 2, molar ratio）, afforded the desired products in good yields （up to 85%） with diastereomeric ratio up to 〉99 ： 1 and high enantiomeric excesses （up to 〉99%）. The absolute configuration of major the product was con- firmed by X-ray crystal structure analysis.展开更多
Eight N 5 (3 carboxy 1,2,4 triazolyl) N ′ aroyl ureas have been synthesized from 3 amino 1,2,4 triazolyl 5 carboxylic acid and substituted benzoylisocyanates in yields of 59 6%～55 9% with mp>300 ℃. The structure...Eight N 5 (3 carboxy 1,2,4 triazolyl) N ′ aroyl ureas have been synthesized from 3 amino 1,2,4 triazolyl 5 carboxylic acid and substituted benzoylisocyanates in yields of 59 6%～55 9% with mp>300 ℃. The structures of the title compounds were confirmed by IR, 1H NMR and elemental analysis. The room temperature biological activity tests showed that some target compounds have a good activity as plant growth regulator, the best of them appeared compounds Ⅱ b and Ⅱ c(for auxin).展开更多
To synthesize and evaluate antimicrobial activity of novel heterocyclic compounds, the corresponding title aroyl ureas have been synthesized by the reaction of 2-amino-5-(3-pyridyl)-1,3,4-thiadiazole with aroyl isocya...To synthesize and evaluate antimicrobial activity of novel heterocyclic compounds, the corresponding title aroyl ureas have been synthesized by the reaction of 2-amino-5-(3-pyridyl)-1,3,4-thiadiazole with aroyl isocyanates. Their antimicrobial activities in vitro were tested by disk diffusion methods and broth microdilution according to M-27A protocol recommended by NCCLS. Twelve new compounds were obtained, and their structures were confirmed by MS, IR, 1H NMR and elemental analysis. The biological screening tests showed that most of the compounds have some antifungal activities in vitro. Aroyl ureas incorporating pyridyl thiadiazole ring may be developed as novel antifungal candidate drugs and are worthwhile to be further studied.展开更多
文摘AlCl3-mediated cleavage of ethereal methyl–oxygen bond in aroylated 2,7-dimethoxynaphthalene compounds proceeds chemospecifically and regioselectively. The ethereal bond at the β(2)-position of 1-monoaroylated 2,7-dimethoxynaphthalene is cleaved readily and predominantly against the β(7)-position, whereas scission of β-ethereal bonds of 1,8-diaroylated 2,7-dimethoxynaphthalene hardly undergoes like the non-aroylated mother frame compound of 2,7-dimethoxynaphthalene.
文摘The direct aroylation of ArCOPdCl with potassium aryltrifluoroborates establishes a new cross-coupling synthetic tool for the synthesis of various fluorine substituted benzophenones. The new microwave irradiated process is very efficient and produce high yield benzophenone products within minutes.
文摘The title compounds 3 and 4 condensed with aromatic aldehydes to give a--aroylsicinnamoyl ketene cyclic dithioacetals 5 and 6 with sodium ethoxide as the base. The stereochemistryofs and 6 was assigned as E-configuration by 1H NMR.
文摘An interesting regioselectivity is observed when the mixture of potassium crotyltrifluoroborate (1a) and aroyl chlorides having electron-deficient and electron-rich groups is microwaved in the presence of palladium-catalyst. In the case of electron withdrawing group with phenyl ring of aroyl chlorides, isomerized α,β-unsaturated compound 3 is the product whereas electron donating group with phenyl ring of aroyl chlorides furnishes α-adduct 4. Similar aroylation reaction is also established for potassium allyltrifluoroborate (1b). In this case, regioselectivity is unaffected with changing electron-rich or electron-deficient groups in phenyl ring of the aroyl chlorides. Reactions proceed with, essentially in same rate, affording the corresponding aryl propenyl ketones (crotonophenones) 5 in good to high yields.
文摘New solid complexes derived from the reaction of aroyl hydrazones, 2-hydroxy-1-naphthaldehyde benzene sulphonyl hydrazone (HNB), and 2-hydroxy-1-naphthaldehyde p-toluene sulphonyl hydrazone (HNT), with Co<sup>2+</sup>, Ni<sup>2+</sup>, and Cu<sup>2+</sup> salts have been isolated and characterized using elemental analyses, spectral (UV-vis., IR), molar conductivity and magnetic measurements. The modes of bonding as well as the stereochemistry of the isolated solid complexes were discussed. The results suggested that both HNB and HNT coordinated with the metal ions in a bidentate manner forming a polymeric chain in the case of HNB while monocular complexes were formed in the case of HNT. The amounts of solvent in the solid complexes were determined by TGA measurements. Also, spectral studies of HNT with Co<sup>2+</sup> and Fe<sup>3+</sup> ions in solution were carried and the ratio of complexes was determined by continuous variation, molar ratio, and slope ratio methods. Moreover, the results suggest the formation of 1:1 (M:L) for Co<sup>2+</sup> ions while three species with ratios of 1:1, 1:2, and 2:1 (M:L) have been observed in the case of Ni<sup>2+</sup> and Cu<sup>2+</sup>. Finally, conductance titration of HNB and HNT with Co<sup>2+</sup> ion elucidates the formation of two species with ratios 1:1 and 1:2 (M:L) in the case of the Co<sup>2+</sup>-HNB while 1:1 (M:L) belongs to the Co<sup>2+</sup>-HNT system.
基金the National Natural Science Foundation of China(Nos. 21476074 and 21676088)for financial support
文摘The palladium-catalyzed late-stage aroylation of 4-methyl-1,5-diaryl-lH-pyrazole-3-carboxylates has been developed via direct and exclusive mono-Csp^2-H bond activation with broad substrate scope and good functional group tolerance. A dual-core dimeric palladacycle is confirmed by X-ray single crystal crystallography, and probably serves as an active species in the catalytic cycle.
文摘An unprecedented palladium/copper cocatalyzed coupling reaction of indoles with simple aroyl hydrazides has been developed under aerobic conditions. A range of aroyl hydrazides underwent palladium/copper cocatalyzed oxidative arylation with indoles open to air in a 1：1 mixture of dimethyl sulfoxide and nitromethane to give structurally diverse 2-arylindoles or 3-arylindoles in moderate to good yields. The reaction well tolerates a wide variety of functional groups such as alkoxy, halo, ester.
基金This work was supported by the Natural Science Foundation of Tianjin(19JCYBJC20100).
文摘The deprotonative functionalization of toluenes,for their weak acidity,generally needs strong bases,thus leading to the requirement of harsh conditions and the generation of by-products.Direct nucleophilic acyl substitution reaction of amides with organometallic reagents could provide an ideal solution for ketone synthesis.However,the inert amides and highly reactive organometallic reagents bring great challenges for an efficient and selective synthetic approach.Herein,we reported an lithium diisopropylamide(LDA)-promoted benzylic aroylation of toluenes with unactivated tertiary benzamides,providing a direct and efficient synthesis of various aryl benzyl ketones.This process features a kinetic deprotonative functionalization of toluenes with a readily available base LDA.Mechanism studies revealed that the directed ortho-lithiation of the tertiary benzamide with LDA promoted the benzylic kinetic deprotonation of toluene and triggered the nucleophilic acyl substitution reaction with the amide.
文摘The dynamic kinetic resolution of 2-aroyl-l-tetralones was achieved via asymmetric transfer hydrogenation using （S,S）-RuCl（p-cymene）TsDPEN （TsDPEN=N-（tosyl）-1,2-diphenylethylenediamine） in formic acid/triethylamine （5 ： 2, molar ratio）, afforded the desired products in good yields （up to 85%） with diastereomeric ratio up to 〉99 ： 1 and high enantiomeric excesses （up to 〉99%）. The absolute configuration of major the product was con- firmed by X-ray crystal structure analysis.
文摘Eight N 5 (3 carboxy 1,2,4 triazolyl) N ′ aroyl ureas have been synthesized from 3 amino 1,2,4 triazolyl 5 carboxylic acid and substituted benzoylisocyanates in yields of 59 6%～55 9% with mp>300 ℃. The structures of the title compounds were confirmed by IR, 1H NMR and elemental analysis. The room temperature biological activity tests showed that some target compounds have a good activity as plant growth regulator, the best of them appeared compounds Ⅱ b and Ⅱ c(for auxin).
文摘To synthesize and evaluate antimicrobial activity of novel heterocyclic compounds, the corresponding title aroyl ureas have been synthesized by the reaction of 2-amino-5-(3-pyridyl)-1,3,4-thiadiazole with aroyl isocyanates. Their antimicrobial activities in vitro were tested by disk diffusion methods and broth microdilution according to M-27A protocol recommended by NCCLS. Twelve new compounds were obtained, and their structures were confirmed by MS, IR, 1H NMR and elemental analysis. The biological screening tests showed that most of the compounds have some antifungal activities in vitro. Aroyl ureas incorporating pyridyl thiadiazole ring may be developed as novel antifungal candidate drugs and are worthwhile to be further studied.
