The static O-H bond parameters including O-H bond length, O-H charge difference, O-H Mulliken population and O-H bond stretching force constant (k) for 17 phenols were calculated by ab initio method HF/6-31G**. In com...The static O-H bond parameters including O-H bond length, O-H charge difference, O-H Mulliken population and O-H bond stretching force constant (k) for 17 phenols were calculated by ab initio method HF/6-31G**. In combination with the O-H bond dissociation enthalpies (BDE) of the phenols determined by experiment, it was found that there were poor correlationships between the static O-H bond parameters and O-H BDE. Considering the good correlationship bt tween O-H BDE and logarithm of free radical scavenging rate constant for phenolic antioxidant, it is reasonable to believe that the ineffectiveness of static O-H bond parameters in characterizing antioxidant activity arises from the fact that they cannot measure the O-H BDE.展开更多
Visible-light-mediated O-H functionalization reactions of alcohols with diazo compounds have been fully developed in recent years.However,alkenyl and acetylenic alcohols were rarely examined in these reactions due to ...Visible-light-mediated O-H functionalization reactions of alcohols with diazo compounds have been fully developed in recent years.However,alkenyl and acetylenic alcohols were rarely examined in these reactions due to the inevitable side reactions involving cycloaddition.Herein,the visible-light-mediated O-H functionalization reactions of alkenyl alcohols with diazo compounds were developed.This process competed favorably with the cycloaddition reaction.A series of multifunctional ethers were provided in low to high yields with aryldiazoacetates or 3-diazooxindoles.Biologically relevant spirooxindole-fused oxacycle could be easily accessed from the O-H functionalization product of alkenyl alcohol and 3-diazooxindole.展开更多
An efficient TfOH-catalyzed O—H insertion reaction of α-aryl diazoesters with carboxylic acids is reported.This metal-free protocol provides an operationally simple method for a one-pot assembly of diverse α-acylox...An efficient TfOH-catalyzed O—H insertion reaction of α-aryl diazoesters with carboxylic acids is reported.This metal-free protocol provides an operationally simple method for a one-pot assembly of diverse α-acyloxy esters in moderate to high yields with a broad substrate scope.All starting materials are readily available,and the reactions can be conducted in the open air at room temperature.展开更多
滇西维西县铜厂箐铜矿床赋存于中侏罗统花开佐组二段粉砂质泥岩、粉砂岩夹泥灰岩中,受断裂构造控制呈脉状产出。本次通过研究与该矿床铜矿化关系密切的石英及方解石C-H-O同位素组成特征,揭示其成矿流体来源,进而探讨该矿床成因。研究发...滇西维西县铜厂箐铜矿床赋存于中侏罗统花开佐组二段粉砂质泥岩、粉砂岩夹泥灰岩中,受断裂构造控制呈脉状产出。本次通过研究与该矿床铜矿化关系密切的石英及方解石C-H-O同位素组成特征,揭示其成矿流体来源,进而探讨该矿床成因。研究发现,该矿床中主成矿阶段与铜矿共生的方解石样品的δ13 C V-PDB值变化于-6.93‰~-6.16‰,均值为-6.69‰,δ18 O V-SMOW值变化于10.88‰~13.07‰,均值为11.98‰;与铜矿共生的石英样品的δ18 O V-SMOW值变化于14.22‰~16.88‰,均值为15.93‰,δD V-SMOW值介于-87.0‰~-61.7‰,均值为-75.99‰,表明成矿流体主要源自岩浆水。结合区域地质背景,认为在喜马拉雅期印度-欧亚大陆碰撞背景下,由于澜沧江深大断裂和雪龙山断裂长期活动,伴有深部岩浆含矿热液沿构造裂隙充填,形成铜厂箐脉状铜矿床。展开更多
文摘The static O-H bond parameters including O-H bond length, O-H charge difference, O-H Mulliken population and O-H bond stretching force constant (k) for 17 phenols were calculated by ab initio method HF/6-31G**. In combination with the O-H bond dissociation enthalpies (BDE) of the phenols determined by experiment, it was found that there were poor correlationships between the static O-H bond parameters and O-H BDE. Considering the good correlationship bt tween O-H BDE and logarithm of free radical scavenging rate constant for phenolic antioxidant, it is reasonable to believe that the ineffectiveness of static O-H bond parameters in characterizing antioxidant activity arises from the fact that they cannot measure the O-H BDE.
文摘Visible-light-mediated O-H functionalization reactions of alcohols with diazo compounds have been fully developed in recent years.However,alkenyl and acetylenic alcohols were rarely examined in these reactions due to the inevitable side reactions involving cycloaddition.Herein,the visible-light-mediated O-H functionalization reactions of alkenyl alcohols with diazo compounds were developed.This process competed favorably with the cycloaddition reaction.A series of multifunctional ethers were provided in low to high yields with aryldiazoacetates or 3-diazooxindoles.Biologically relevant spirooxindole-fused oxacycle could be easily accessed from the O-H functionalization product of alkenyl alcohol and 3-diazooxindole.
文摘An efficient TfOH-catalyzed O—H insertion reaction of α-aryl diazoesters with carboxylic acids is reported.This metal-free protocol provides an operationally simple method for a one-pot assembly of diverse α-acyloxy esters in moderate to high yields with a broad substrate scope.All starting materials are readily available,and the reactions can be conducted in the open air at room temperature.
文摘滇西维西县铜厂箐铜矿床赋存于中侏罗统花开佐组二段粉砂质泥岩、粉砂岩夹泥灰岩中,受断裂构造控制呈脉状产出。本次通过研究与该矿床铜矿化关系密切的石英及方解石C-H-O同位素组成特征,揭示其成矿流体来源,进而探讨该矿床成因。研究发现,该矿床中主成矿阶段与铜矿共生的方解石样品的δ13 C V-PDB值变化于-6.93‰~-6.16‰,均值为-6.69‰,δ18 O V-SMOW值变化于10.88‰~13.07‰,均值为11.98‰;与铜矿共生的石英样品的δ18 O V-SMOW值变化于14.22‰~16.88‰,均值为15.93‰,δD V-SMOW值介于-87.0‰~-61.7‰,均值为-75.99‰,表明成矿流体主要源自岩浆水。结合区域地质背景,认为在喜马拉雅期印度-欧亚大陆碰撞背景下,由于澜沧江深大断裂和雪龙山断裂长期活动,伴有深部岩浆含矿热液沿构造裂隙充填,形成铜厂箐脉状铜矿床。
