Isopropylation of naphthalene with propene resulted in a variety of isomers having different alkylation levels.The most important isomer is 2,6-DIPN,which is the precursor of important monomer 2,6-naphthalene di- carb...Isopropylation of naphthalene with propene resulted in a variety of isomers having different alkylation levels.The most important isomer is 2,6-DIPN,which is the precursor of important monomer 2,6-naphthalene di- carboxylic acid used for making liquid crystal polymers.In order to increase the yield of 2,6-DIPN,the intermo- lecular transalkylation with naphthalene was applied to the mixture of other DIPNs and PIPN to obtain MIPN en- riched product,which underwent isopropylation with propene to produce 2,6-DIPN in a higher yield.The experi- mental study showed that the preferable conditions for transalkylation were reaction temperature of 325℃,the mo- lar ratio of isopropyl group to naphthyl group(IP/N)of 0.8︰1—0.9︰1,reaction time of 4h and 5%of amorphous silica-alumina by mass.The conversions of DIPN and PIPN in its mixture were 62%—69%and 87%—88%respec- tively and the yield of MIPN was greater than 40%.The mixture of MIPN enriched product and recovered MIPN from rectification was subject to isopropylation with propene at 275℃over a shape-selective catalyst to produce 2,6-DIPN in a yield up to 38%.A recycled process of recovered components was established,through one cycle the yield of 2,6-DIPN based on naphthalene may be 2.8 times higher than before,and the utilization ratio of raw naph- thalene was increased by 46%.展开更多
We report herein that a commercially available CeO2 is an active and reusable catalyst for the C3-selective alkenylation of oxindole with aldehydes under solvent-free conditions. This catalytic method is generally app...We report herein that a commercially available CeO2 is an active and reusable catalyst for the C3-selective alkenylation of oxindole with aldehydes under solvent-free conditions. This catalytic method is generally applicable to different aromatic and aliphatic aldehydes, giving 3-alkyledene-oxindoles in high yields(87%–99%) and high stereoselectivities(79%–93% to E-isomers). This is the first example of the catalytic synthesis of 3-alkenyl-oxindoles from oxindole and various aliphatic aldehydes. The Lewis acid-base interaction between Lewis acid sites on CeO2 and benzaldehyde was studied by in situ IR. The structure-activity relationship study using CeO2 catalysts with different sizes suggests that defect-free CeO2 surface is the active site for this reaction.展开更多
Starting from the oxygenated piperidine building block 20,two synthetic approaches to new building blocks (8R,8aS)-and (8R,8aR)-8-hydroxy-5-indolizidinones 19a/19b and 15a/15b have been developed,respectively. The fir...Starting from the oxygenated piperidine building block 20,two synthetic approaches to new building blocks (8R,8aS)-and (8R,8aR)-8-hydroxy-5-indolizidinones 19a/19b and 15a/15b have been developed,respectively. The first one is based on the trans-diastereoselective reductive alkylation (dr = 93:7),followed by a four-step procedure; and the second one called for the RCM reaction on the N,O-acetal derived from a vinylation,which was followed by a pyrrole formation,and a stereocontrolled cis-selective (dr = 91:9) catalytic hydrogenation. Reduction of the diastereomer 15a produced (8R,8aR)-8-indolizidinol (18).展开更多
基金Supported by the Northeast Rejuvenation Strategy Foundation of Anshan City,China(032042).
文摘Isopropylation of naphthalene with propene resulted in a variety of isomers having different alkylation levels.The most important isomer is 2,6-DIPN,which is the precursor of important monomer 2,6-naphthalene di- carboxylic acid used for making liquid crystal polymers.In order to increase the yield of 2,6-DIPN,the intermo- lecular transalkylation with naphthalene was applied to the mixture of other DIPNs and PIPN to obtain MIPN en- riched product,which underwent isopropylation with propene to produce 2,6-DIPN in a higher yield.The experi- mental study showed that the preferable conditions for transalkylation were reaction temperature of 325℃,the mo- lar ratio of isopropyl group to naphthyl group(IP/N)of 0.8︰1—0.9︰1,reaction time of 4h and 5%of amorphous silica-alumina by mass.The conversions of DIPN and PIPN in its mixture were 62%—69%and 87%—88%respec- tively and the yield of MIPN was greater than 40%.The mixture of MIPN enriched product and recovered MIPN from rectification was subject to isopropylation with propene at 275℃over a shape-selective catalyst to produce 2,6-DIPN in a yield up to 38%.A recycled process of recovered components was established,through one cycle the yield of 2,6-DIPN based on naphthalene may be 2.8 times higher than before,and the utilization ratio of raw naph- thalene was increased by 46%.
基金supported financially by a series of JSPS KAKENHI grants:17H01341,18K14051,18K14057,and 19K05556 from the Japan Society for the Promotion of Science(JSPS)by the Japanese Ministry of Education,Culture,Sports,Science,and Technology(MEXT)within the projects"Integrated Research Consortium on Chemical Sciences(IRCCS)"and"Elements Strategy Initiative to Form Core Research Center"by the JST-CREST project JPMJCR17J3。
文摘We report herein that a commercially available CeO2 is an active and reusable catalyst for the C3-selective alkenylation of oxindole with aldehydes under solvent-free conditions. This catalytic method is generally applicable to different aromatic and aliphatic aldehydes, giving 3-alkyledene-oxindoles in high yields(87%–99%) and high stereoselectivities(79%–93% to E-isomers). This is the first example of the catalytic synthesis of 3-alkenyl-oxindoles from oxindole and various aliphatic aldehydes. The Lewis acid-base interaction between Lewis acid sites on CeO2 and benzaldehyde was studied by in situ IR. The structure-activity relationship study using CeO2 catalysts with different sizes suggests that defect-free CeO2 surface is the active site for this reaction.
基金the NSF of China (20672089, 20832005)the NFFTBS (J1030415)the National Basic Research Program of China (973 Program, 2010CB833200)
文摘Starting from the oxygenated piperidine building block 20,two synthetic approaches to new building blocks (8R,8aS)-and (8R,8aR)-8-hydroxy-5-indolizidinones 19a/19b and 15a/15b have been developed,respectively. The first one is based on the trans-diastereoselective reductive alkylation (dr = 93:7),followed by a four-step procedure; and the second one called for the RCM reaction on the N,O-acetal derived from a vinylation,which was followed by a pyrrole formation,and a stereocontrolled cis-selective (dr = 91:9) catalytic hydrogenation. Reduction of the diastereomer 15a produced (8R,8aR)-8-indolizidinol (18).
