催化裂化条件下噻吩与改性Y分子筛的作用机制

以HY、NiY和稀土离子改性的Y分子筛(REY)为研究对象,采用固定床装置评价噻吩模拟油催化裂化性能;运用气相色谱-氢火焰离子发光检测器(GC-FID)、气相色谱-硫化学发光检测器(GC-SCD)和原位红外光谱技术分析产物,关联分子筛的酸性,研究催化裂化条件下噻吩与改性Y分子筛的作用机制。实验结果表明,催化裂化条件下,噻吩与分子筛的作用机制差异主要取决于与B酸或L酸相关的非骨架铝物种或金属离子物种的存在形式。其中,NiY分子筛中,噻吩主要是吸附在与NiOH⁺物种相关的L酸中心,而Ni₄AlO₄³⁺等物种减弱B酸性中心从而降低其裂化性能。对HY来说,噻吩易在与AlO⁺等物种相邻的B酸中心上聚合形成三联噻吩,并发生一定的氢转移和裂化反应;而对REY而言,分子筛中与RE物种相关的L酸位会促进噻吩在与非骨架铝羟基等物种(如Al(OH)₂⁺、Al(OH)²⁺等)相邻的B酸中心形成的二联噻吩发生氢转移和裂化反应。     

预裂化理论研究:基质表面酸性位类型及不同类型酸性位接触顺序对裂化过程小分子烯烃收率的影响

在区分氢负离子转移反应与氢转移反应、非选择性氢转移反应与总的氢转移反应的情况下,通过合成物性相近但酸性不同的氧化铝,用以作为裂化催化剂基质材料,在固定床反应器上考察了催化裂化过程,基质酸性位类型及基质表面Lewis及Brönsted酸性位接触顺序对小分子烯烃(丙烯、丁烯)收率的影响。结果表明,催化裂化生成小分子烯烃过程中,分子筛与基质所呈现出的反应特点存在较大的区别,前者活性虽高,但总的氢转移反应活性过强。基质材料裂化活性虽低但其表面以氢负离子转移反应为主,反应路径角度更有利于小分子烯烃收率的提高。另外,基质表面存在Brönsted酸性位,或原料油首先与基质表面Lewis酸性位相接触再与Brönsted酸性位反应的预裂化过程,会在促进裂化反应发生的同时抑制总的氢转移反应,更有利于小分子烯烃收率的提高。     

Mind the correct basis set: A case study for predicting gas phase acidities of small compounds using calculations from first principles

Some of the most popular computational methods have been utilized to determine a dependency of the acidity trend of the first‐row hydrides on a choice of basis set. For about three decades, methyl anion ( ) was known as the strongest base but after Tian et al. were able to produce the gas phase lithium monoxide anion (LiO–) they discovered it was a stronger base than (Tian et al., Proc Natl Acad Soc USA 2008, 105, 7647). Furthermore, the authors confirmed their experimental results using high‐level ab initio methods, namely W1 and W2C composite methods, as well as complete active space‐averaged quadratic coupled cluster and Brueckner Doubles with triple excitation contribution (BD(T)) within the aug‐cc‐pVQZ basis set. These methods are highly demanding in terms of the computational effort as well as a level of expertise needed from the user to correctly conduct such calculations. We have shown that the proper acidity trend, that is, , can be obtained with less expensive, ”black‐box” type methods if only the basis set is properly chosen. Our results prove that the diffuse augmented basis sets are absolutely necessary for appropriate predictions of acidities. Our calculations show that the correct order of is achieved by augmenting relatively small cc‐pVXZ (X = D,T) basis sets. A similar effect is observed for the family of Pople's basis sets. Our estimate for with CCSD(T)/aug‐cc‐pVTZ was 423.8 kcal/mol, which agrees very well with the experimental value 425.7 ± 6.1 kcal/mol. An important finding is that the proper acidity trend may be reversed if the basis sets are not correctly selected. © 2014 Wiley Periodicals, Inc.     

Catalytic Asymmetric Reactions of 4‐Substituted Indoles with Nitroethene: A Direct Entry to Ergot Alkaloid Structures

A domino Friedel–Crafts/nitro‐Michael reaction between 4‐substituted indoles and nitroethene is presented. The reaction is catalyzed by BINOL‐derived phosphoric acid catalysts, and delivers the corresponding 3,4‐ring‐fused indoles with very good results in terms of yields and diastereo‐ and enantioselectivities. The tricyclic benzo[cd]indole products bear a nitro group at the right position to serve as precursors of ergot alkaloids, as demonstrated by the formal synthesis of 6,7‐secoagroclavine from one of the adducts. DFT calculations suggest that the outcome of the reaction stems from the preferential evolution of a key nitronic acid intermediate through a nucleophilic addition pathway, rather than to the expected “quenching” through protonation.     

Synthesis,Characterization and Application of Some Axially Chiral Binaphthyl Phosphoric Acids in Asymmetric Mannich Reaction

Two novel chiral Br?nsted acids 3b and 3c were prepared without involving the complexity of Suzuki coupling. Catalyst 3c bearing two additional hydroxyl groups at 3 and 3′ positions of axially chiral 1,1‐binaphthalene‐2,2′‐diol phosphoric acid was applied in a model Mannich reaction to afford β‐amino ester in high yield (92%) and enantiomeric excess (91%) at low reacting temperature of ?40°C. In addition, those β‐amino ester derivatives with high yields and excellent enatioselectivities were obtained in the presence of catalyst 3c under the above condition.     

Supercritical carbon dioxide extraction and gas chromatography–mass spectrometry analysis of Gymnema sylvestre R.Br. roots

Supercritical fluid extraction (SFE) achieves a wide range of applications since the past decade as a sustainable green technology. The present study investigates the process for producing high yield by supercritical carbon dioxide (Sc-CO₂) extraction form Gymnema sylvestre R.Br. roots. The effect of temperature and pressure on the percentage of accumulative yield is demonstrated. It is found that the highest yield is obtained at the temperature of 60°C and the pressure of 10?MPa. A proper review showed that there is a lack in the study of Sc-CO₂ extraction of this plant especially for optimization of SFE process which makes this study useful and valuable. For more benefit, the extract which achieves highest percentage is subjected to gas chromatography–mass spectrometry to study its chemical composition and detect the active principle compounds which present with high concentration and expected to be responsible of the pharmaceutical properties of the extract.     

Brønsted Acid Catalysis in Visible‐Light‐Induced [2+2] Photocycloaddition Reactions of Enone Dithianes

1,3‐Dithiane‐protected enones (enone dithianes) were found to undergo an intramolecular [2+2] photocycloaddition under visible‐light irradiation (λ =405 nm) in the presence of a Brønsted acid (7.5–10 mol %). Key to the success of the reaction is presumably the formation of colored thionium ions, which are intermediates of the catalytic cycle. Cyclobutanes were thus obtained in very good yields (78–90 %). It is also shown that the dithiane moiety can be reductively or oxidatively removed without affecting the photochemically constructed ring skeleton.     

Acetic acid functionalized ionic liquid systems: An efficient and recyclable catalyst for the regioselective ring opening of epoxides with NaN3

In the present study, an environmentally benign, efficient, and solvent-free procedure was developed for the synthesis of 1,2-azidoalcohols by the regioselective ring opening of some epoxides with sodium azide (NaN₃) in the presence of an acetic acid functionalized imidazolium salt [Cmmim]BF₄ or [Cmmim]Br as a green and Brønsted acidic ionic liquid (BAIL) catalyst under mild and neutral reaction conditions at 60 °C. The remarkable features of this procedure are excellent regioselectivity, simple work-up procedure, high yields of products, short reaction times, and ease of recyclability of ionic liquids.