铜催化苯硼酸与苯并呋咱-1-氧化物的胺化反应

C-N键普遍存在于药物和有机功能分子中,传统构建C-N键的方法包括Goldberg反应、Buchwald-Hartwig偶联、Chan-Lam偶联和C-H键活化胺化.虽然这些方法都可以高效构建C-N键,但它们需要使用官能化的芳基底物、官能化的胺化试剂或在氧化条件下进行.理想的胺化反应应在氧化还原中性条件下进行,更为理想的则是在引入氨基的同时引入另外一个官能团.实现这个目标最直接的策略就是使用氮杂环,通过N-E(E=N或O)键的断裂,N原子和E原子可同时被引入.最近我们课题组利用氨茴内酐和氮杂苯并降冰片烯的C-H键活化反应成功实现了这种双官能团化.尽管该法很有吸引力,但是要通过氮杂环的断裂实现双官能团化,需要发生非张力环的开环,这在热力学上是非常不利的.苯并呋咱-1-氧化物可以开环得到邻二硝基苯中间体.基于对胺化反应的兴趣,我们推测苯并呋咱1-氧化物可以作为一个胺化试剂实现苯硼酸的胺化.尽管亚硝基苯对芳基硼酸进行简单的胺化已经被报道,但需要化学计量的铜盐,或是引入还原剂.因此本文报道铜催化的苯硼酸的胺化反应,该反应以苯并呋咱1-氧化物为胺化试剂,在温和及氧化还原中性条件下成功实现了双官能团化.本文共完成了31个不同官能团取代的硝基苯胺骨架结构的合成,反应均以中等到良好的收率得到目标产物,最高收率可达99%.为了增加反应的实用性,我们还进行了放大实验,实验表明,当苯并呋咱-1-氧化物的量由0.2 mmol放大至4 mmol时,反应仍能以较高的收率得到目标产物.此外,目标产物通过进一步的衍生化反应还可方便地转化为其他杂环类化合物.例如,在PPh3作用下,通过还原环化作用可生成吩嗪.在钯催化下可发生分子内碳氢键氧化反应得到咔唑类化合物.通过还原及重氮化反应还可方便地转化为苯并三唑.总之,我们以苯并呋咱-1-氧化物为胺化试剂,在铜催化下成功实现了苯硼酸的胺化反应,合成了一系列双官能团化产物.该催化体系反应条件温和,底物适用范围广,对各种官能团具有很好的兼容性.     

一价铜催化的N-对甲基苯磺酰腙与3-丁炔-1-醇的串联反应:一种四氢呋喃类化合物的新合成方法

最近几年来,利用稳定的重氮类化合物和N-对甲基苯磺酰腙类化合物作为金属卡宾前体,在过渡金属催化下通过形成金属卡宾的偶联反应引起了人们广泛的兴趣.金属卡宾前体与有机金属物种反应,可以生成金属卡宾中间体,并发生金属上基团的转移插入过程,得到新的有机金属物种,从而实现丰富的偶联反应.这类经由金属卡宾转移插入过程的交叉偶联反应为构建C?C键,C?N键以及许多环状化合物和不饱和有机分子结构提供了可靠而强有力的工具.本课题组一直致力于研究该类经由金属卡宾中间体的催化转化和偶联反应,报道了在铜催化下,对甲苯磺酰腙以及重氮类化合物可以与端炔反应,通过所形成的炔基铜卡宾中间体的转移插入过程,可高效得到联烯类化合物.该类反应条件相对温和,并且有很好的底物普适性.不仅各种多取代的联烯类化合物,而且苯并呋喃,菲以及呋喃等结构都可由这类铜催化的腙和炔烃的偶联反应来得到.在这些反应中,通过炔基铜卡宾中间体上炔基的转移插入过程,在形成了C(Sp3)-Cu键以后,通过铜的1,3-迁移过程,可以得到联烯结构,随后发生分子内杂原子的亲核进攻或者6π电子环化过程来实现苯并呋喃,菲等杂环类结构的构建.另一方面,该类反应进一步拓展和研究,可望得到其他有价值的有机分子骨架.环状的醚类结构,如四氢呋喃结构,也是有机化合物中常见的结构类型,我们希望从目前已经发展成熟的卡宾前体与炔烃生成联烯的偶联反应出发,通过分子内的串联过程来高效地构建取代的环状醚类结构.我们设想,在炔烃上引入氧原子作为亲核试剂,在形成联烯化合物以后,通过分子内氧原子对联烯基的亲核进攻,来实现串联的分子内关环反应,从而构建环状醚类结构.本文以CuI为催化剂,3-丁炔-1-醇为炔烃偶联组分,采用二芳基对甲苯磺酰腙作为金属卡宾前体,实现了取代四氢呋喃的合成.在对甲苯磺酰腙与3-丁炔-1-醇类化合物发生偶联反应生成二芳基联烯基化合物以后,采用一锅法实现分子内的关环反应,从而生成亚烯基取代的四氢呋喃化合物.该串联反应不仅具有原料易得和操作较为简便等优点,而且底物普适性和官能团耐受性都较好,多种取代的二芳基腙类化合物都能以较好的收率得到目标产物,从而为四氢呋喃类化合物的合成提供了一种新的方法.该反应进一步展示了经由金属卡宾中间体的交叉偶联反应的普遍性,将在有机化学和有机合成领域具有广泛的研究和应用价值.     

Progress in thermal-mechantical effects induced by laser

对激光辐照诱导的热与力学问题研究进展进行了综述,包括材料在高温、高升温速率下的本构关系,典型薄板和柱壳等结构在激光辐照下的热力破坏效应,多层材料体系的激光破坏行为等几个方面,并着重介绍了包含相变与烧蚀过程的激光破坏分析模型与机制研究,激光辐照效应的流-热-固耦合数值模拟方法,以及短脉冲激光引起的冲击与破坏机理等方面的研究新进展.     

Structural modeling of beams on elastic foundations with elasticity couplings

A new simplified structural model and its governing equations for beams on elastic foundations with elastic coupling are proposed. This modeling system is simple but appropriate for the initial structural design of large-scale submerged floating-beam structures moored by tension legs spaced at uniform interval along the beam. The model is actually for beam on discrete elastic supports rather than on continuous elastic foundations. Therefore, the governing equations are based on finite difference calculus and solutions for beams on discrete elastic supports with elasticity coupling are also proposed. To clarify the applicability limit of the proposed model, the equivalence between a beam on discrete elastic supports and that on continuous elastic foundation is investigated by comparisons of characteristic solutions.     

Coupled modeling of damage growth and permeability variation in brittle rocks

This paper presents a coupled model for anisotropic damage and permeability evolution by using a micro–macro approach. The damage state is represented by a second order tensor. The evolution of damage is determined from a crack propagation criterion. The free enthalpy function of cracked material is obtained by using micromechanical considerations. It is assumed that cracks exhibit normal aperture which is coupled with the crack growth due to asperities of crack faces. By using Darcy’s law for macroscopic fluid flow and assuming laminar flow in microcracks, the overall permeability of the RVE is obtained by a volume averaging procedure taking into account crack aperture in each orientation.     

A coupled zigzag theory for the dynamics of piezoelectric hybrid cross-ply plates

A recently developed coupled third-order zigzag theory for the statics of piezoelectric hybrid cross-ply plates is extended to dynamics. The theory combines a third-order zigzag approximation for the in-plane displacements and a sub-layerwise linear approximation for the electric potential, considering all components of the electric field. The nonuniform variation of the transverse displacement due to the piezoelectric field is accounted for. The conditions for the absence of shear traction at the top and bottom surfaces and continuity of transverse shear stresses in the presence of electromechanical loading are satisfied exactly, thereby reducing the number of displacement variables to five, which is the same as in a first- or third-order equivalent single-layer theory. The governing equations of motion are derived from the extended Hamilton's principle. The theory is assessed by comparing the Navier solutions for the free and forced harmonic vibration response of simply supported plates with the exact three-dimensional piezoelasticity solutions. Comparisons for hybrid test, composite and sandwich plates establish that the present theory is quite accurate for the dynamic response of moderately thick plates.     

Continuum thermodynamic formulation of models for electromagnetic thermoinelastic solids with application in electromagnetic metal forming

The purpose of this work is the formulation and application of a continuum thermodynamic approach to the phenomenological modeling of a class of engineering materials which can be dynamically formed using strong magnetic fields. This is carried out in the framework of a thermodynamic, internal-variable-based formulation in which the deformation, temperature and magnetic fields are in general coupled. This coupling takes the form of the Lorentz force as an additional supply of momentum, and the electromotive power as an additional supply of energy, in the material. In the current approach, the basic thermomechanical field relations for mass, momentum and moment of momentum are obtained from the total energy balance via invariance, and completed by Maxwells field equations. The constitutive formulation is based on the exploitation of the Müller-Liu entropy principle, here for the case of isotropic thermoelastic, viscoplastic material behaviour. The resulting reduced constitutive and field relations and restrictions are then applied to the modeling and simulation of high-speed electromagnetic forming of metal tubes and sheet metal. In this context, scaling arguments show that, over the relevant length- and timescales of engineering interest, the evolution of the magnetic field is diffusive in nature, and thermal conduction is negligible. Comparison of the simulation and experimental results for the final sheet metal form shows very good agreement.Received: 16 March 2004, Accepted: 6 May 2004, Published online: 17 September 2004PACS: 46.05. + b, 46.25.Hf, 46.35 + z Correspondence to: B. Svendsen     

单裂隙流-固耦合渗流的试验研究

通过对较大尺寸的单裂隙岩体试块进行不同侧面加载的渗流试验,在实验室里开展了单裂隙流 固耦合渗流研究,模拟核废料贮藏库的围岩自由面的最危险部位的渗流量 应力耦合状态。分析了裂隙岩体渗流与应力的耦合机理,获得了几种典型情况下的试验数据,并拟合出不同应力条件下单裂隙岩体渗流量与应力间数学经验公式。从而说明并非任一方向的应力增加都能使渗流量减小,而是裂隙岩体的渗流量随着双向压应力的增加而减少,随着平行于裂隙面方向的单向压应力的增加而增加。缝隙开度虽然随着法向应力的增加而逐渐减小,但最终不可能完全闭合,所以,此时流量不可能为零。同时,在试验过程中还通过闭环控制来实现被加载面的均匀受力,这为大尺寸岩体试验提供了一种很好的加载方法。     

三维非线性有限元与弹性边界元耦合数值方法

本文系统地讨论了以下三个问题:(1) 有限元与边界元耦合中的几个数值问题,其中包括:边界积分方程的凝聚、等效刚度矩阵的对称化及面力不连续的处理;(2) 弹塑性有限元与弹性边界元的耦合;(3) 弹粘塑性有限元与弹性边界元的耦合及数值计算稳定性条件。     

Experimental and theoretical study of the nonlinear response of agiant magnetostrictive rod

In this paper, a magnetomechanical coupling constitutive relation of the giant magnetostrictive material was investigated experimentally and theoretically. A grain-oriented magnetostrictive rod of iron and rare earth was tested under a combined magnetomechanical loading. Two types of experimental curves were obtained, i.e., the magnetostrictive curve of the extensional strain vs the magnetic field, and the curve of the magnetic polarization intensity vs the pre-stress. A new theoretical constitutive model, based on the density of domain switching, is developed. Comparison of the theoretical predictions with the experimental results indicates that this model can capture the main characteristics of the magnetoelastic coupling deformation of a giant magnetostrictive rod. The project supported by the National Natural Science Foundation of China (10025209, 10132010, 10102007)