几种磺酰胺类萃取剂的合成

通过磺酰氯和伯胺的亲核取代反应合成并鉴定了5种新型高选择性的磺酰胺类萃取剂:8-(烷基苯磺酰胺)喹啉、2-(烷基苯磺酰胺)吡啶、2-(烷基苯磺酰胺甲基)噻吩、2-(烷基苯磺酰胺)苯并噻唑和2-(烷基苯磺酰胺)噻唑。     

二芳基甲胺类化合物的合成新方法

本文报道了通过水相氮杂1,6-共轭加成反应合成二芳基甲胺类衍生物的方法。以对甲苯磺酰胺为亲核试剂,对4-芳基亚甲基2,6-二叔丁基-2,5环己二烯-1-酮共轭体系进行反应,高效地合成了取代二芳基甲胺类衍生物。反应原料廉价易得,原子经济性高,无需使用金属试剂、有机溶剂、还原剂,操作简单,绿色环保。     

N-苯磺酰咔啉的合成

描述了碱性条件下咔啉类化合物的苯磺酰胺化反应。在Na H作用下,具有两亲结构的β-或γ-咔啉与N-氟代双苯磺酰胺反应生成不同种类的目标化合物,实现咔啉苯磺酰胺的简便合成,收率良好。机理研究表明,在反应中间体咔啉氮负离子的影响下,N-氟代双苯磺酰胺的N—S键断裂提供苯磺酰基,这是商品化试剂N-氟代双苯磺酰胺作为亲电氟化、自由基氟化和胺化试剂之后新的应用。     

过渡金属催化N-磺酰基取代的杂环化合物的合成研究进展

概述了不同过渡金属催化下通过炔基和磺酰胺基反应,形成N-磺酰基取代的杂环化合物。由于过渡金属催化合成N杂环类化合物的方法高效便捷,因而具有广泛的研究前景。     

治疗骨髓增殖性肿瘤药物TG101209的合成

本文研究了治疗骨髓增殖性肿瘤药物TG101209的合成工艺。以2,4-二羟基-5-甲基嘧啶为起始原料,与三氯氧磷、氨水发生氯化、取代反应生成2-氯-4-氨基-5-甲基嘧啶(B),B再与N-叔丁基-3-溴苯磺酰胺(C)发生Buchwald偶联反应得到3-[(2-氯-5-甲基-4-嘧啶基)胺基]-N-(叔丁基)苯磺酰胺(D)。以甲醇为溶剂,D与CH3OH-HCl反应得到3-[(2-氯-5-甲基-4-嘧啶基)胺基]-N-(叔丁基)苯磺酰胺盐酸盐(E),E与1-甲基-4-(4-氨基苯基)哌啶(G)发生亲核取代反应得到N-叔丁基-3-(5-甲基-2-[4-(4-甲基-1-哌嗪)苯胺基]-4-胺基嘧啶)-苯磺酰胺(TG101209)。总收率达到30.9%,HPLC测得纯度达到99.7%。     

N-烷基取代的4-氯-3-氨基苯磺酰胺类化合物的制备

N-烷基取代的4-氯-3-氨基苯磺酰胺类化合物是制备特殊领域酸性染料、分散染料的重要中间体.本文对4-氯-3-氨基苯磺酰胺以及N-烷基取代的系列化合物的合成路线及优缺点进行了评价.在制备磺酰氯时用氯化亚砜代替氯磺酸,大大减少了工业废酸.还原时通过催化加氢来取代铁粉或硫化钠,提高了收率,节能环保.     

氮杂环N-氧化物在有机合成和药物合成上的应用

笔者在本文中综述了氮杂环N-氧化物在氮杂环极性转换、亲核取代反应、酰胺的α、β-脱氢反应和药物合成中的应用。     

1-(1,3-噻唑啉-2-基)-3-巯基氮杂环丁烷盐酸盐的工艺研究

以2-巯基-2-噻唑啉为起始原料,经过甲基化、与3-羟基氮杂环丁烷盐酸盐发生亲核取代SN2、甲磺酰氯活化羟基、与硫代乙酸钾发生亲核取代SN2、碱性水解5个反应步骤,合成目标产物,总收率51.6％,HPLC纯度98.5％.各中间体及终产品通过熔点、IR、1HNMR、MS等手段进行了结构确证.该方法反应条件温和、操作简便、...     

取代苯磺酰氨基丙基杂氮硅三环化合物的合成

通过取代苯磺酰氯和γ-氨丙基杂氮硅三环的亲核取代反应，合成了苯磺酰氨基丙基杂氮硅三环、p-甲基苯磺酰氨基丙基杂氮硅三环、p-氯代苯磺酰氨基丙基杂氮硅三环、p-溴代苯磺酰氨基丙基杂氮硅三环、m-硝基苯磺酰氨基丙基杂氮硅三环5种取代苯磺酰氨基丙基杂氮硅三环类化合物；用IR和^1HNMR等方法对其结构进行了表征，并初步探讨了反应条件。     

苄磺酰基查尔酮类化合物的合成

一种苄磺酰基查尔酮类化合物被发现有较好的抗癌活性。以苯甲亚磺酸钠原料,与2-溴苯乙酮发生亲核取代反应,所得产物羰基砜再与取代苯甲醛发生缩合反应可以合成该类苄磺酰基查尔酮类化合物。该路线操作简单,步骤少,产率高。     

Enzymatic transition state poise and transition state analogues

The development of kinetic isotope effect methods for enzymatic reactions has resulted in the systematic determination of enzymatic transition state structure for several distinct chemical reaction mechanisms. Although it is early in the experimental development of the method, examples of concerted nucleophilic displacements (A(N)D(N) or S(N)2), aromatic nucleophilic displacements (A(N)D(N) or S(N)Ar), and both concerted and stepwise dissociative nucleophilic displacements (D(N)A(N) and D(N)A(N); S(N)1 reactions) have been exemplified. The transition state for each reaction exhibits a characteristic extent of bond-breaking and bond-making, defined here as transition state poise. Thus, concerted nucleophilic displacements (S(N)2 or D(N)A(N)) exhibit various extents of residual bond order to the leaving group and to the attacking nucleophile at the transition state. Aromatic nucleophilic displacements reach their rate-limiting transition states before or after formation of the tetrahedral intermediate. Several concerted, symmetric nucleophilic displacements at carbon have been described. Enzymatic transition state poise is summarized in a single diagram of bond orders using the terminology of Jencks. The analysis reveals enzymatic contributions to transition state poise, provides precedent for assignment of reaction types, and summarizes the current status of the experimental characterization of enzymatic transition states. Binding strengths of transition state analogues are readily correlated with transition state poise.     

Nucleophile Substitutionen an Kohlensäurederivaten. XX. Aminolyse des Bis(trichlormethyl)carbonates

Nucleophilic Substitutions at Carbonic Acid Derivatives. XX. Aminolysis of Bis(trichlormethyl)carbonate The rate constants for the two steps of the reaction of bis(trichlormethyl)carbonate with substituted anilines have been determinated by conductivity measurements. The first relatively fast step of the reaction is the nucleophilic attack of the amine to the bis(trichloromethyl)-carbonate leading to trichloromethylurethane through a six or four centers transition state in which the carbon-nitrogen bond is formed parallel with the transfer of the proton. In this reaction a phosgene molecule is also produced, which reacts very fast with amine to form a N,N′-diarylurea. The second, much slower step, is the nucleophilic attack of the amine to the trichloromethylurethane. Through a similar transition state in which the proton transfer has even a higher importance, a N,N′-disubstituted urea and an other molecule of phosgene are formed.     

助剂对煤基合成气甲烷化反应用镍基催化剂的促进作用

助剂促进的合成气甲烷化反应用镍基催化剂具有反应活性高、使用寿命长以及甲烷选择性高等优点,被广泛应用于煤基合成气甲烷化制替代天然气反应中。本文重点介绍了贵金属、碱土金属、稀土金属以及过渡金属助剂等对活性镍基催化剂的分散度、还原度、双金属合金协同效应、镍基催化剂结构稳定性及其对合成气甲烷化反应速率和产物选择性的影响。较系统地分析了这些助剂改性镍基催化剂的作用机制。提出了非贵金属助剂以及复合助剂将是合成气甲烷化用镍基催化剂助剂研发的发展方向,旨在为煤基合成气制替代天然气甲烷化催化剂的研发提供借鉴和参考。     

Electrochemical costripping models and mutual interferences of mutli-transition metal systems on the surface of boron-doped diamond

Electrochemical behaviors of electrodeposition stripping of some transition metals, such as Ag, Cu, Pb, Sn, and Cd were investigated on boron-doped diamond (BDD) film with differential pulse anodic stripping voltammetry (DPASV). The results show that the metal costripping process on the surface of BDD is influenced by deposition potential of transition metals, potential of hydrogen evolution reaction, mutual interferences between two transition metals, and so on. Electrochemical costripping models and mutual interferences of binary transition metals are proposed. (i) When the hydrogen evolution potential is higher or lower than the deposition potential of two transition metals, the metals do not form alloys and compound the cathode ions in the solution, and the costripping process conforms to metal 1 stripping-metal 2 stripping. (ii) When the hydrogen evolution potential is between the deposition potential of two transition metals, the metals do not form alloys and compound the cathode ions in the solution, and the costripping process conforms to metal 1 stripping-hydrogen evolution-metal 2 stripping. (iii) When two transition metals form alloys, the costripping process conforms to metal 1 stripping-alloy striping-metal 2 stripping. (iv) When the hydrogen evolution potential is between deposition potential of two transition metals, and transition metal 2 is complexed with one kind of cathode ion in the solution, the costripping process conforms to metal 1 stripping-hydrogen evolution-metal 2 complex formation-metal 2 stripping. Moreover, the electrochemical-costripping model of two transition metals in a solution with three or more transition metals, is similar to that in the binary system. It is also found that various metals electrodeposited on BDD film in the form of single metal or alloy can be completely stripped away by the constant-potential electrolysis technique at 2.8 V for 10 s.     

金属氧化物催化剂在消除柴油车排气颗粒物中的应用

介绍了用于柴油车排气颗粒物后处理的金属氧化物催化剂，包括过渡金属氧化物、主族金属氧化物和碱土金属氧化物。较详细地讨论了催化剂组成及性能、相关催化反应、控制因素和反应机理。     

Organogold reactivity with palladium, nickel, and rhodium: transmetalation, cross-coupling, and dual catalysis

Using two transition metals to simultaneously catalyze a reaction can offer distinct opportunities for reactivity and selectivity when compared to using single-metal catalyst systems. Creating dual transition metal catalytic systems is complicated, however, by challenges in predicting compatible reactivities and designing turnover pathways for both metals. In this Account, we describe our development of dual-metal catalysis reactions involving gold and a second transition metal. The unique rearrangement intermediates accessible through gold-only catalysis, which exploits the soft Lewis acidity of Au(I), make gold an attractive partner for dual-metal catalysis reactions. Because of the complexity of achieving simultaneous turnover of two catalysts and predicting compatibilities, our approach has been to first gain a fundamental understanding of the reactivity of the two metals with each other, both in stoichiometric and monocatalyzed reactions. To this end, we have investigated the combined reactivity of organogold compounds with palladium, nickel, and rhodium. We narrate the intricacies of turning over two catalysts simultaneously and thereby illuminate the valuable role of fundamental studies in identifying the optimal conditions to promote desirable two-metal reactivity and compatibility. Transmetalation, redox reactivity, and new mechanisms for dual-metal catalytic turnover were probed from this standpoint. We have applied the knowledge gained through these studies to the development of reactions that are dual-catalyzed by gold and palladium, as well as nickel- and rhodium-catalyzed reactions of organogold compounds. More broadly, these new reactions expand the reactivity available to catalytic organogold intermediates via trapping and functionalization reactions with other transition metals. Our investigations reveal strategies useful for designing dual-metal reactions with gold. First, the versatility of gold as a transmetalation partner suggests that many potential methods may exist to intercept catalytic organogold intermediates with a second transition metal. Second, ligands on both metals should be selected carefully in order to prevent catalyst deactivation. Finally, reactions must be designed such that any oxidative steps involving the second metal outcompete undesired reactions with redox-active organogold compounds. We believe that the application of these principles will allow for the design of a diverse set of dual-catalyzed functionalizations befitting the wide variety of gold-catalyzed transformations already established.     

Transition Metals Supported on Activated Carbon as Benzene Hydroxylation Catalysts

The direct conversion of benzene to phenol by hydroxylation with hydrogen peroxide was carried out over catalyst containing various transition metals impregnated on activated carbon. Iron and vanadium impregnated catalysts gave better yields of phenol compared to copper impregnated catalysts. The activity of transition metals supported on activated carbon catalyst in the production of phenol was V > Fe > Cu. In addition to the role of transition metals in catalyzing the hydroxylation reaction, the hydrophobic nature of the activated carbon surface and also the surface acidity and basicity seems to have enhanced the performance of these catalysts.     

过渡金属配合物催化烯烃的自由基反应进展

近年来，通过烯烃官能团化构建有机化合物成为有机合成领域的研究热点之一。当选择种类、晶体结构和性能多样的过渡金属配合物作为催化剂时，这类反应具有高效、高选择性且成本低的特点。本文总结了近五年来利用过渡金属盐及其配合物作为催化剂，经过自由基反应历程实现未活化烯烃官能团化的研究进展，其反应特点是在过渡金属催化下，烯烃生成自由基并与其它底物或试剂偶联成键，从而实现官能团化。其中，催化性能优异的催化剂除了贵重金属铑、钯和钌等的配合物之外，还有普通金属，如铁、镍、铜和钴的盐及其配合物。这些方法拓展了烯烃官能团化的研究领域，为有机合成工作者提供新方法和思路，还为将来的产业化生产提供新方案。     

COSMO‐based computer‐aided molecular/mixture design: A focus on reaction solvents

In this article, we investigate reaction solvent design using COSMO‐RS thermodynamics in conjunction with computer‐aided molecular design (CAMD) techniques. CAMD using COSMO‐RS has the distinct advantage of being a method based in quantum chemistry, which allows for the incorporation of quantum‐level information about transition states, reactive intermediates, and other important species directly into CAMD problems. This work encompasses three main additions to our previous framework for solvent design (Austin et al., Chem Eng Sci. 2017;159:93–105): (1) altering the group contribution method to estimate hydrogen‐bonding and non‐hydrogen‐bonding σ‐profiles; (2) ab initio modeling of strong solute/solvent interactions such as H‐bonding or coordinate bonding; and (3) solving mixture design problems limited to common laboratory and industrial solvents. We apply this methodology to three diverse case studies: accelerating the reaction rate of a Menschutkin reaction, controlling the chemoselectivity of a lithiation reaction, and controlling the chemoselectivity of a nucleophilic aromatic substitution reaction. We report improved solvents/mixtures in all cases. © 2017 American Institute of Chemical Engineers AIChE J, 63: 104–122, 2018     

催化在有机合成中的新进展

近年来,过渡金属催化的卤代芳烃与各种亲核试剂的偶联反应已成为构筑C―C或C―杂原子键的有效手段,例如著名的Suzuki、Kumada、Stille、Negishi等生成C―C键的偶联反应等。最近,C―H键的直接活化及功能化方面有了一些突破。介绍了这一领域的新进展。