Utilizing Mor‐DalPhos/Palladium‐Catalyzed Monoarylation in the Multicomponent One‐Pot Synthesis of Indoles

The application of a Mor‐DalPhos/palladium catalyst system in the one‐pot, multicomponent assembly of substituted indoles from ortho‐chlorohaloarenes, alkyl ketones (including acetone), and primary amines is reported. The described protocols offer improved substrate scope in all three reaction components, under more mild conditions and without the need for an additional drying agent. Also reported are the first examples of such multicomponent reactions where all reactants are combined at the start of the reaction, without the need for inert atmosphere reaction conditions.

     

固体碱催化合成3-甲胺基-1,2-丙二醇

以3-氯-1,2-丙二醇和一甲胺为原料,选用载有三乙胺的固体碱作催化剂合成3-甲胺基-1,2-丙二醇。采用正交实验和单因素分析探讨了反应的影响因素,得到最佳工艺条件为:3-氯-1,2-丙二醇与一甲胺(折算成100%)物质的量之比为1∶8,反应温度60℃,反应压力0.20 MPa,反应时间3.5 h,在该条件下3-甲胺基-1,2-丙二醇合成收率可达91.9%。通过元素分析、气相色谱、红外光谱对产物进行表征,结果证实得到了目标产物,且纯度可达99.5%以上。     

微孔聚丙烯膜表面胺基化修饰

发展了一种氨基接枝密度和分布可控的微孔聚丙烯膜(MPPM)表面修饰方法。首先通过紫外光接枝聚合法,在MPPM上接枝聚丙烯酸甲酯(PMA);然后通过丙烯酸甲酯和乙二胺的酰胺化缩合和Michael加成交替反应,将氨基可控地引入到MPPM表面。采用FTIR、XPS和ESEM对氨基化膜表面的化学组成及物理形态进行了表征;考察了氨基化膜的表面亲水性及渗透性能。结果表明,氨基化膜表面亲水性显著改善,吸水量可达(1 311.29±97.56)μg/cm2,为未修饰MPPM的145倍;制得的氨基化膜具有良好的水通量和金属离子渗透性能。     

聚醚多元醇胺化催化剂的制备和表征

以聚醚多元醇为原料,钌催化剂作用下催化胺化合成了端氨基聚醚。通过SEM、H2-TPR、BET等分析仪器对催化剂进行了表征。考察了铝镁比、活性组分含量、还原温度、助剂等条件对催化活性的影响。研究显示,以铝镁复合载体制备的催化剂在下列实验条件下表现出有效的催化活性:铝镁比为5%、活性组分含量为1.5%、还原温度为600℃,以硝酸钾为助剂。     

Stoichiometric Reductive C?N Bond Formation of Arylgold(III) Complexes with N‐Nucleophiles

The reductive formation of substituted anilines from amines and three well‐defined aryl‐ gold(III) complexes, i.e., dichloro(2,6‐lutidine)phen‐ ylgold(III) ( 2 ), dichloro(2,6‐lutidine)‐p‐tolylgold(III) ( 3 ), and chlorobis(triphenylphosphine)phenylgold(III) chloride ( 4 ) was studied. The reaction is stoichiometric in gold and represents a key step of a potential gold‐catalyzed intermolecular amination reaction of arenes. It proceeds smoothly with a broad range of N‐nucleophiles in the presence of sodium acetate (NaOAc) and enables the selective formation of N‐substituted anilines in good yields. A mechanistic pathway is proposed and discussed as well.     

2,6-二异丙基苯酚气相胺化反应过程的研究

对2,6-二异丙基苯酚气相胺化反应的液相产品进行了气相色谱-质谱分析,确定了产物组成。通过产物中的主副产物分析,对该反应的主副反应过程进行了初步研究。并在研究基础上优化了反应条件,提高了主产物2,6-二异丙基苯胺的选择性。     

Post-synthesis amination of polymer of intrinsic microporosity membranes for CO2 separation

Membrane separation is an energy-saving technology for carbon capture. However, it is subjected to permeability-selectivity trade-off limitation. Although chemical functionalization is proposed to boost separation efficiency, controlling sorption–diffusion process remains extremely challenging. In this study, a facile, controllable, and versatile chemical vapor amination strategy is reported to simultaneously tune gas sorption and diffusion in polymer of intrinsic microporosity (PIM)-based membranes for improving carbon capture performance. Through simple exposure in amine vapors under mild conditions, nucleophilic substitution of amines toward ether and halogen groups induce grafting, ring-opening, terminal replacement, chain-scission, and crosslinking of PIM-1, thereby underpinning CO₂-philicity and tailoring passageway. The prepared CO₂-philic membranes exhibit substantially improved CO₂/N₂ selectivity over 30.8, about 226% as that of original one, accompanied by high CO₂ permeability of 2590 Barrer, which can surpass the trade-off upper bound of polymer membranes. Our results reveal that post-synthesis amination is an effective route to obtain high-performance membranes.     

端氨基聚醚的合成

研究了以改性雷尼镍为催化剂、聚醚和液氨为原料,临氢高压催化氨化制备端氨基聚醚的工艺路线,考察了反应温度、催化剂用量、氨醇比、氢醇比对反应的影响.结果表明,温度220℃、氨醇摩尔比10 ～ 12、氢醇摩尔比0.6～0.8、催化剂质量分数为7％～11％、反应时间4～5h时,聚醚氨化制备端氨基聚醚的转化率大于97％.     

2,6-二甲基苯酚气相胺化催化剂的研制

研制了2,6-二甲基苯酚气相胺化合成2,6-二甲基苯胺催化剂Pd/尖晶石，考察了不同γ-Al₂O₃载体和尖晶石的组成对催化剂催化活性的影响，同时研究了反应温度对催化反应的影响。