2006AN ANGULAR INDEX TO INDICATE SURFACE HETEROGENEOUS

2006年9月27日在郑州市高考（理综-化学）质量分析会上的发言2006年高考理综试卷分析（化学）及复习建议郑州市教育局教学研究室曹淑玲一．试卷评价1．总况概述：(1)坚持“3＋X”高考改革的方向，体现了新课程方案的基本要求;(2)遵循“相对稳定”、“稳中求变”的命题原则, 体现了试题的持续性和稳定性；(3)采取“拼盘”的形式，实现了“同一学科试题相对集中”，每一个试题都有明显的学科分类;(4)实现了全卷“有较高的信度、效度，必要的区分度，适当的难度”；(5)紧扣“教纲”和“考纲”，以考查主干知识为主，体现了考试大纲中对各学科所提出的能力要求，有助于中学实施素质教育。

（6）全卷化学试题共12题，试题陌生度不大、层次分明、难度适中，基础题、中等题、难题分配较合理，区分度较好，适合各层次考生。

在重点考查基础知识的同时，侧重对考生能力的考查。

2．化学试题命题思想：（1）重视学科思想和化学用语的考查，突出学科特点。

今年试题中增加了物质结构等相关内容的考查比例，突出了“结构决定性质”的学科思想；同时全卷要求考生书写的化学方程式达11个，化学式5个（另隐有2个-同分异构），总计38分（+3），所占比重创历史新高。

（2）体现学科内知识的融合。

第10题有关定量反应中设计到钠、镁、钡、铝、氨及氯离子、氢氧根离子、碳酸根离子、硫酸根离子等第一至第七主族元素知识，第27题是化学反应原理、元素化合物知识与元素周期表知识的结合，第28题是化学实验知识与元素化合物知识的结合，第29题在考核有机化学的基础知识时，有效地将化学计算、实验设计方案的考核有机地融合在其中。

（3）注重考查考生的思维严密性。

如第II卷的26题关于氮、氧、硫元素的推断，考生必须对题给Y、Z和W三种元素在元素周期表中可能的四种情况有一个整体的认识。

再如第27题，要求学生由置换反应的原理结合元素化合物知识列举有关化学方程式，然后根据题给的限制条件加以选择确定。

a r X i v :c o n d -m a t /0310589v 1 [c o n d -m a t .s t a t -m e c h ] 24 O c t 2003Diffusion on a solid surface:Anomalous is normalJ.M.Sancho 1,casta 2,K.Lindenberg 3,I.M.Sokolov 4and A.H.Romero 5(1)Departament d’Estructura i Constituents de la Mat`e ria,Facultat de F´ısica,Universitat de Barcelona,Diagonal 647,E-08028Barcelona,Spain (2)Departament de F´ısica Aplicada,Universitat Polit`e cnica de Catalunya Avinguda Dr.Mara˜n on 44,E-08028Barcelona,Spain.(3)Department of Chemistry and Biochemistry 0340,and Institute for Nonlinear Science,University of California,San Diego,La Jolla,California A.(4)Institut f¨u r Physik,Humboldt Universitæt zu Berlin,Newtonstr.15,12489Berlin,Germany.(5)Advanced Materials Department,IPICyT,Camino a la presa San Jos´e 2055,CP 78216,San Luis Potos´ı,SLP,M´e xico.(Dated:February 2,2008)We present a numerical study of classical particles diffusing on a solid surface.The particles’motion is modeled by an underdamped Langevin equation with ordinary thermal noise.The particle-surface interaction is described by a periodic or a random two dimensional potential.The model leads to a rich variety of different transport regimes,some of which correspond to anomalous diffusion such as has recently been observed in experiments and Monte Carlo simulations.We show that this anomalous behavior is controlled by the friction coefficient,and stress that it emerges naturally in a system described by ordinary canonical Maxwell-Boltzmann statistics.PACS:05.40-a,68.43.Jk,68.35.FxDiffusion of atoms,molecules,and clusters on solid surfaces occurs in a number of modern technologies in-volving self-assembled molecular film growth,catalysis,and surface-bound nanostructures [1].The study of the motion of small and large organic molecules [2,3],and of adsorbed metal clusters composed of tens and even hundreds of atoms [4,5],has led to the unexpected ob-servation that,as with single atoms [6],long jumps may play a dominant role in these motions.Theoretical,numerical,and phenomenological discus-sions of surface diffusion have led to the clear understand-ing that jumps beyond nearest neighbors are ubiquitous in some parameter regimes [7].However,these studies focus on the fact that the motion is necessarily diffusive (which is the case at very long time scales).The possi-bility that jumps can be so long as to lead to superdiffu-sive motion over appreciable intermediate time scales is recognized as an interesting problem,but one in which L´e vy walks or flights [8]are invoked as a model input.AlthoughL´e vy-walk-like behavior is clearly observed in Hamiltonian systems [9,10]and in microcanonical sim-ulations [10,11],it is generally believed that such a fine signature of chaos is fully smeared away by thermal fluc-tuations.In the present work we show that L´e vy-like statistics appear quite naturally over long time scales within the usual Langevin framework for underdamped motion in a periodic or a random potential.While a detailed analysis of surface diffusion requires extensive calculations (e.g.,ab initio ,or molecular dy-namics),even the most powerful currently available com-puters can not carry such calculations to anywhere near experimentally relevant time scales [12].Moreover,cur-rent experimental probes of the topography of surfaces,scanning tunneling microscopy and atomic force mi-croscopy,are usually carried out at relatively high tem-peratures,which leads to additional difficulties for first-principles calculations.Therefore,simpler approaches are essential and valuable [7].We consider a generic model of classical particles mov-ing in a two-dimensional potential,under the action of thermal fluctuations and dissipation,the important con-trol parameter being the friction coefficient.In spite of the simplicity of the model,we find that it is able to reproduce the entire range of experimentally and compu-tationally observed phenomena,from superdiffusion all the way to subdiffusion.The equation of motion of a particle of mass m on the surface ism ¨x=−∇V (x /λ)−µ˙x +ξ(t )(1)where λis the characteristic length scale of the poten-tial.The parameter µis the coefficient of friction,andthe ξi (t )are mutually uncorrelated white noises that obey the fluctuation-dissipation relation ξi (t )ξj (t ′) =2µk B T δij δ(t −t ′).We first consider the nonseparable pe-riodic potentialV (x,y )=V 0cos πx λ cos πx λ,(2)where V 0is the barrier height at the saddle points.Equation (1)can be rewritten in scaled dimensionless variables,r x =x/λ,r y =y/λ,and s =mV 0.(3)We study four properties of the motion of the particle:the mean square displacement,the dependence of the diffusion coefficient on friction,the probability density function of displacements,and the velocity power spec-trum.Normal diffusive behavior is characterized by a lin-ear time dependence of the mean square displacement,2−2020406080100−20020406080100−20−1010203040−40−30−20−1001020FIG.1:Left:A trajectory for γ=1over t =20,000time units.Right:A trajectory for γ=0.04over t =15,000time units.The period of the potential is λ=4.Note the different scales in the two panels.r 2(s ) ∼s .Non-diffusive behavior shows a different time dependence, r 2(s ) ∼s α,with α>1(<1)for superdiffusive (subdiffusive)motion.In Fig.1we show typical trajectories obtained for two friction coefficients upon numerical simulation of the equations of motion with T =0.2(we use this value throughout).One (left panel)is for a large friction coefficient,and the particle follows typical diffusive motion characterized by short steps of length ∼λand frequent changes in direction.The other (right panel)corresponds to a small friction coefficient and clearly shows the preponderance of long (≫λ)tracks along cartesian coordinates.The evolution of r 2 averaged over 1000particles is shown in Fig.2for several friction coefficients.For very long times the motion is diffusive,as expected,but for small γand at intermediate times there is clear superdif-fusive ballistic (α=2)behavior over several decades in time.This is reflective of the long straight stretches seen in the low-γtrajectory in Fig.1.We stress that this behavior has emerged naturally and has not required ex-plicit insertion of any but ordinary thermal fluctuations in the model.Eventhough the motion of the particle may include long superdiffusive stretches,at long times the motion is necessarily diffusive.The dependence of the diffusion coefficient on the friction for small and for large γcan be obtained analytically using the approximate relation D ≈ l 2 /2τ,where l 2 is the mean square size of a jump out of one well and into another,and τ−1is the mean jump rate (related to the familiar “mean escape rate”).In the overdamped regime,jumps typically occur from one well to a neighboring well,so l 2 ≈1.Familiar Kramers formulas can be used to obtain the mean escape rate [13],with the resultD ∼1γ22e −1γe −14γe −1long time asymptotic dynamics.The interesting inter-mediate dynamics in the low friction regime that gives rise to long stretches of ballistic motion is reflected in the probability distribution function(pdf)of particle dis-placements r.This pdf is shown in Fig.3forγ=0.0004 and tree different time intervalsτs.For comparison,we also show a typical pdf for high damping(γ=1)at the intermediate time interval.In the high-γcurve the high-est maximum corresponds to no jumps(by far the most likely event at short times).The next is associated with jumps to a nearest neighbor well,and so on.In con-trast,the low-γcurves show a very different behavior, with features strongly resembling those of a L´e vy-walk model[9,15]:a peak at small displacements,a power-law intermediate regime,and a side hump at high displace-ments.Each of these is a distinct signature of L´e vy-walk-like dynamics,but one must be cautious in the detailed interpretation of these components.The persistent small displacement peak is associated with long trapping peri-ods during which a particle does not move at all because its energy is not sufficient to overcome the barrier.The high displacement peak,which moves outward with ve-locity of order unity,is associated with ballistic motion of those particles that acquire enough energy to move (and lose it very slowly).Genuine L´e vy-walk dynamics also exhibit a low displacement peak and a superdiffu-sive peak separated by a power law behavior,but there are some important differences.First,our distribution reflects ballistic transport in the intermediate regime(in the language of Ref.[15],ballistic transport occurs when 0<α<1in the L´e vy model),whereas the regime where the L´e vy model shows the features we have described is associated with sub-ballistic(but still superdiffusive)be-havior(again,in the language of Ref.[15],the behavior when1<α<2).Second,the slope in our power law regime(approximately0.7)is not related to the expo-nentαin the mean square displacement as it is for the L´e vy walk(where the slope is4−α).Third,our side hump is strongly broadened whereas the side hump in the L´e vy-walk model is associated with motion at a single constant velocity.In our case the velocity varies accord-ing to the equilibrium Maxwell-Boltzmann distribution. Nevertheless,the qualitative features of our distribution track those of the L´e vy walk.Note that the existence of the pronounced side hump reflects the fact that the particles performing long steps(“flights”)are those with a velocity in the tail of the Maxwellian distribution. Long ballistic excursions imply velocity correlations over considerable time intervals.The velocity power spectrum S(ω)= v(ω)v(−ω) for different values ofγ√is shown in Fig.4.The pronounced peak atω0=πs10−410−310−210−110101<r 2>/4sFIG.6: r 2 /4s for a particle in the random potential for γ=0.0004(solid),0.008(dotted),0.04(dashed)and 0.8(dot-dashed).The straight-line segment has unit slope as a guide to the eye.Inset:Exponents αversus friction coefficient γ.overdamped case [19],further theoretical and numerical support are needed to assess whether superdiffusion is the asymptotic behavior in the underdamped case.We summarize our findings.We have explored the be-havior of a particle in a two-dimensional potential de-scribed by ordinary Langevin dynamics under conditions of thermal equilibrium.In a periodic potential,in the underdamped regime,the motion of the particle includesa ballistic range that can extend over many decades of time.The pdf of the particle’s displacements under these conditions shows a structure strongly resembling one for L´e vy walks.This may explain a number of observations involving superdiffusive motion of organic molecules [3]and atomic clusters [5]on surfaces without the need to invoke extraordinary fluctuations beyond the usual ther-mal description.The long-time behavior is diffusive in all cases,and we have been able to predict theoretically the dependence of the diffusion coefficient on friction over essentially the entire range of values of the friction pa-rameter with no adjustable parameters .The situation in a random potential is even more complex,and exhibits a wide range of subdiffusive to superdiffusive regimes.Fur-ther analysis of the random potential case,and a more extensive presentation of the periodic problem,will be detailed elsewhere [20].This work was supported by the MCyT (Spain)under project BFM2003-07850,by the Engineering Research Program of the Office of Basic Energy Sciences at the U.S.Department of Energy under Grant No.DE-FG03-86ER13606,and by a grant from the University of California Institute for M´e xico and the United States (UC MEXUS)and the Consejo Nacional de Ciencia y Tecnolog´ıa de M´e xico (CoNaCyT).A.H.R.acknowledges support from Millennium Initiative,Conacyt-Mexico,under Grant W-8001.I.M.S.acknowledges the hospi-tality of the University of Barcelona under the CEPBA grant,as well as partial financial support by the Fonds der Chemischen Industrie.[1]G.E.Poirier and E.D.Plyant,Science 272,1145(1996);T.Yokoyama et al.,Nature (London)413,619(2001);K.Ho,J.Chem.Phys.117,11033(2002);R.M.Tromp and J.B.Jannon,Surf.Rev.Lett.9,1565(2002).T.Ala-Nissila,R.Ferrando,and S.C.Ying,Adv.Phys.51,949(2002).[2]J.Wecksesser et al.,Surf.Sci.431168(1999);J.Weckesser,PhD Thesis,Swiss Federal Institute of Tech-nology,Laussane (2000).[3]M.Schunack et al.,Phys.Rev.Lett.88,156102(2002).[4]G.Ertl and H.-J.Freund,Phys.Today 52,32(1999).[5]W.D.Luedtke and ndman,Phys.Rev.Lett.82,3835(1999).[6]D.Cowell Senft and G.Ehrlich,Phys.Rev.Lett.74,294(1995);T.R.Linderoth et al.,Phys.Rev.Lett.78,4978(1997); A.P.Graham et al.,Phys.Rev.B 56,10567(1997);S-M Oh et al.,Phys.Rev.Lett.88,236102(2002).[7]K.D.Dobbs and D.J.Doren,J.Chem.Phys.97,3722(1992);R.Ferrando,R.Spadacini,and G.E.Tommei,Phys.Rev.E 48,2437(1993);L.Y.Chen,M.R.Baldan,and S.C.Ying,Phys.Rev.B 54,8856(1996);J.L Vega,R.Guantes,and S.Miret-Art´e s,Phys.Cem.Chem.Phys.4,4985(2002);R.Guantes et al.,J.Chem.Phys.119,2780(2003).[8]M.F.Shlesinger,G.M.Zaslavsky,and J.Klafter,Nature363,31(1993).[9]J.Klafter and G.Zumofen,Phys.Rev E 49,4873(1994).[10]J.L.Vega,R.Guantes,and S.Miret-Art´e s,J.Phys.Condens.Matter 14,6193(2002).[11]R.Guantes,J.L.Vega,and S.Miret-Art´e s,Phys.Rev.B 64,245415(2001).[12]A.Gross,Surf.Sci.Rep.31,235(1998).[13]P.H¨a nggi,P.Talkner,and M.Berkovec,Rev.Mod.Phys.62,251(1990).[14]J.M.Sancho,A.H.Romero and K.Lindenberg,J.Chem.Phys.109,9888,(1998).[15]J.Klafter and G.Zumofen,Physica A 196,102(1993).[16]J.Garc ´ıa-Ojalvo and J.M.Sancho,Noise in Spatially Ex-tended Systems (Springer,New York,1999).[17]H.A.Makse,S.Havlin,M.Schwartz,and H.E.Stanley,Phys.Rev.E 53,5445(1996);E.Koscielny-Bunde,A.Bunde,S.Havlin,E.Roman,Y.Goldreich,and H.J.Schellnhuber,Phys.Rev.Lett.81,729(1998).[18]A.H.Romero and J.M.Sancho,p.Phys.156,1(1999);A.H.Romero,J.M.Sancho,and K.Lindenberg,Fluct.and Noise Lett.2,L79(2002).[19]A.H.Romero and J.M.Sancho,Phys.Rev.E 58,2833(1998).[20]casta et al.,in preparation.。

Lesson 58Depending on the nature of the coal sample involved, the mineral matter present may be derived from a number of different sources. Bulk samples taken from the coal as mined, for example, normally contain mineralogical contaminants due to the presence of intra-seam bands of non-coal material, as well as possibly debris from the adjacent roof and floor strata. However,individually, selected specimens, or plies and seam composites free of these materials, usually contain a distinctive suite of minerals.根据所涉煤样品的性质，矿物质本可能来自许多不同来源。

例如，批量从样本煤为雷区，通常包含矿物学污染物由于内煤层波段的非煤的材料，以及可能的相邻的屋顶和地板地层中的碎屑的存在。

但是，单独地，选定的标本，或层和煤层复合材料免费的这些材料，通常包含一整套独特的矿物。

QuartzQuartz is common in most coals, but seldom as a major constituent. It often occurs as angular grains in clay-rich bands, suggesting a detrital origin. However, it may also occur as a chemical precipitate possibly originally in the form of chalcedony, infilling cell cavities in the coal macerals or as veins cutting across the coal structure.石英在大多数煤是常见的，但很少作为主要成分。

An efficient electrophilic N-amination utilizing in situ generatedchloramine under phase transfer conditionsApurba Bhattacharya,a,*Nitin C.Patel,a Robert Erik Plata,a Michael Peddicord,b Qingmei Ye,b Luca Parlanti,b Venkatapuram A.Palaniswamy b and John A.Grosso baDepartment of Chemistry,Texas A&M University-Kingsville,Kingsville,TX 78363,United StatesbBristol-Myers Squibb Company,Process Research and Development Department,PO Box 191,New Brunswick,NJ 08903-0191,United StatesReceived 22December 2005;accepted 18May 2006Available online 13June 2006Abstract—An efficient,one-pot,phase transfer N-amination technology was developed.The protocol utilizes chloramine,an inex-pensive and safe electrophilic aminating agent potentially viable for commercial manufacturing.Ó2006Elsevier Ltd.All rights reserved.As part of our ongoing industry-university collaborative research program established between Texas A&M Uni-versity-Kingsville and Bristol-Myers Squibb Co.,we needed an expeditious entry into a diverse spectrum of N-aminated pyrroles.1Although a number of electro-philic amination methodologies are well known,their utility is often limited by poor yields,prohibitive costs,and serious safety issues,making them unsuitable for large scale application.2An alternative N-amination of pyrroles and indoles utilizing chloramine (NH 2Cl)was recently reported by researchers at Bristol-Myers Squibb.3This N-amination protocol involves initial gen-eration of NH 2Cl from aqueous NH 4OH,NH 4Cl and bleach,followed by extraction of NH 2Cl with methyl tert -butyl ether (MTBE)from the aqueous mixture.The chloramine solution is dried with anhydrous CaCl 2and then reacted in a separate vessel with the pyrrole an-ion generated from NaH in DMF,to produce the corre-sponding N-aminated pyrroles.While this technology was invaluable during our early development efforts and provided us with multi-gram supplies of N-amino-pyrroles,we sought improvements that would allow for greater safety,efficiency and operational simplicity.In the above procedure,because of the high solubility of chloramine in water and its limited solubility in MTBE (0.09M),large solvent volumes are required for efficient,extractive removal of chloramine from theaqueous reaction mixture.4This reduces the overall reaction throughput.In addition,chloramine is not suf-ficiently stable for storage.On standing,chloramine dis-proportionates to NHCl 2and NCl 3,a shock-sensitive compound constituting a potential safety concern.5Devising a technology where chloramine would be instantaneously consumed as soon as it is generated could potentially circumvent these problems by avoiding any undesirable accumulation during the process.Based on this premise,we devised a cost effective and practical one-pot,two phase (H 2O–MTBE)N-amination proto-col.The process can be accomplished in good yields and efficiency and offers significant advantages over the existing technologies in terms of throughput,safety,and operational simplicity.In the optimal procedure,chloramine is generated in the aqueous layer through oxidation of ammonia by NaOCl.At the same time,the substrate is deprotonated in the organic phase with the aid of a small amount of Aliquat-336(methyltrioctylammonium chloride)and promptly reacts with the small portion of chloramine present in the organic layer,affording the desired N–NH 2derivative in high yield.An excess of base (aq NaOH)is necessary to efficiently achieve the pyrrole deprotonation.After reaction completion,the organic layer is separated and can be utilized directly in the next step without further purification (Scheme 1).This process avoids accumulation of unreacted chlor-amine at any given time,thereby rendering this approach0040-4039/$-see front matter Ó2006Elsevier Ltd.All rights reserved.doi:10.1016/j.tetlet.2006.05.102*Corresponding author.Tel.:+13615932664;fax:+13615933597;e-mail:kfab002@Tetrahedron Letters 47(2006)5341–5343safe and viable for on-scale implementation.As opposed to the previously published chloramine N-amination protocol,this new procedure does not require the prepa-ration of the pyrrole anion under anhydrous conditions in a separate vessel or the drying of the diluted organic chloramine solution after the extractions.The low solu-bility of chloramine in organic solvents is no longer a limiting factor to the reaction throughput.The presence of the quaternary ammonium salt,Aliquat-336,is imper-ative;reactions conducted without Aliquat-336showed only trace amounts of the desired N-aminated product under otherwise identical conditions.Attempts to re-place Aliquat-336with several other surface active poly-ethylene glycol(PEG)type phase transfer agents such as Triton-X,were unsuccessful.6These conditions were also successfully applied to prepare a series of N-aminated heterocycles(pyrroles and indoles)in consistently high yield(Table1).A typical experimental procedure is as follows:aqueous sodium hypochlorite (58.76ml of ca.9%solution)was added over a period of20min,at room temperature,to a vigorously stirred mixture of3-methyl-1H-pyrrole-2,4-dicarboxylic acid diethyl ester(2g,8.9mmol)in MTBE(24ml,ammo-nium chloride(2.9g,53.2mmol),Aliquat-336(0.1g), aqueous NaOH(25.6ml of28.4%solution)and aqueous NH4OH(8.28ml of28%solution).The resulting reac-tion mixture was stirred at room temperature for an additional2–4h at the end of which time the complete disappearance of starting material and formation of product is observed by capillary GC and HPLC.The upper product-rich organic layer was separated from the spent aqueous layer and washed with aqueous Na2S2O3(40ml).The organic layer was then dried over anhydrous Na2SO4and evaporated in vacuo to produce 2.01g of1-amino-3-methyl-1H-pyrrole-2,4-dicarboxylic acid diethyl ester(94%yield).In summary,we have demonstrated an efficient,one-pot,phase transfer catalyzed N-amination process utiliz-ing chloramine as an inexpensive electrophilic aminating agent which proved to be superior to the existing tech-nologies.This protocol is practical and safe and is potentially viable for on-scale manufacturing.Studies aimed at extending the scope of this technology are in progress in our laboratories.AcknowledgementsFinancial support provided by Bristol-Myers Squibb Company,the Petroleum Research Fund(PRF),The National Institute of Health(NIH)and The Welch Foundation is gratefully acknowledged.References and notes1.The program was aimed at giving BS/MS level studentsexposure to pharmaceutical process R&D in an academic setting.Chem.Eng.News2001,41.Table 1.Phase transfer catalyzed electrophilic N-amination of heterocycles with chloramine7Entry Substrate N-Aminated substrate Yield(%)1NHOEtOEtOCH3NOOEtOEtOCH32942NHOEtOEtOHNOOEtOEtOH2923NHOEtOEtONOOEtOEtO2964NHOEtOEtOPhNOOEtOEtOPh2945NH OOEtOEtONOOEtOEtO290629372915342 A.Bhattacharya et al./Tetrahedron Letters47(2006)5341–53432.For O-(2,4-dinitrophenyl)hydroxylamine see:(a)Salem-nick,G.;Nir,Z.Tetrahedron1972,28,3833;A detonation has been reported while using this reagent.See:Radha-krishna,A.S.;Loudon,G.M.;Miller,.Chem.1979,44,4836;For safety studies of substituted(nitro-phenyl)hydroxylamines see:Boyles,D.C.;Curran,T.T.;Parlett,.Proc.Res.Dev.2002,6,230;(b) Sheradsky,T.Tetrahedron Lett.1968,16,1909;For a review on electrophilic amination see:(c)Tamura,Y.;Minamikawa,J.;Ikeda,M.Synthesis1977,1.3.Hynes,J.,Jr.;Doubleday,W.W.;Dyckman, A.J.;Godfrey,J.D.,Jr.;Grosso,J.A.;Kiau,S.;Leftheris,K..Chem.2004,69,1368,and references cited therein.4.The concentration of NH2Cl was determined by iodometrictitration.5.Goehring,R.R.In Encyclopedia of Reagents for OrganicSynthesis;Paquette,L.A.,Ed.;Wiley:New York,1995;Vol.2,pp1052–1053.6.Bhattacharya,A.;Purohit,V.;Rinaldi,.Proc.Res.Dev.2003,7,254.7.NMR data for all the compounds synthesized are consistentwith their expected structures,as for instance:1-Amino-3-methyl-1H-pyrrole-2,4-dicarboxylic acid diethyl ester(entry1):1H NMR(400-MHz,DMSO-d6):d1.26(t,J=7.3,3H),1.32(t,J=7.3,3H),2.47(s,3H),4.18(q,J=7.3,2H),4.28(q,J=7.3,2H),6.41(s,2H,NH2),7.43(s,1H);13C NMR (100-MHz,DMSO-d6):d11.9,14.4,14.5,59.4,60.2,110.4, 119.9,128.4,130.9,161.5,163.7;HRMS(ESI+)calcd for (M+H+)C11H17N2O4241.1188,found241.1189.1-Amino-1H-pyrrole-2,4-dicarboxylic acid diethyl ester(entry2):1H NMR(400-MHz,DMSO-d6):d1.24(t,J=7.3,3H),1.27 (t,J=7.3,3H),4.16(q,J=7.3,2H),4.22(q,J=7.3,2H),6.50(s,2H,NH2),7.01(s,1H),7.50(s,1H);13C NMR(100-MHz,DMSO-d6):d15.0,15.1,60.4,60.9,112.4,115.8, 122.1,131.5,161.0,163.7;HRMS(ESI+)calcd for(M+H+) C10H15N2O4227.1032,found227.1034.1-Amino-3-ethyl-1H-pyrrole-2,4-dicarboxylic acid diethyl ester(entry3):1H NMR(400-MHz,DMSO-d6):d1.06(t,J=7.3,3H), 1.23(t,J=7.3,3H),1.29(t,J=7.3,3H),2.96(q,J=7.3, 2H),4.15(q,J=7.3,2H),4.25(q,J=7.3,2H),6.39(s,2H, NH2),7.40(s,1H);13C NMR(100-MHz,DMSO-d6):d 14.9,15.1,16.4,19.3,59.9,60.8,110.2,119.9,131.5,135.6, 161.8,164.0;HRMS(ESI+)calcd for(M+H+)C12H19N2O4 255.1345,found255.1336.1-Amino-3-phenyl-1H-pyrrole-2,4-dicarboxylic acid diethyl ester(entry4):):1H NMR(400-MHz,DMSO-d6):d0.85 (t,J=7.3,3H),1.03(t,J=7.3,3H),3.95(q,J=7.3,2H), 3.99(q,J=7.3,2H),6.50(s,2H,NH2),7.29(m,5H),7.55 (s,1H);13C NMR(100-MHz,DMSO-d6):d11.8,12.3,57.5, 58.2,108.3,124.9,125.2,128.4,128.9,133.0,159.1,161.7; HRMS(ESI+)calcd for(M+H+)C16H19N2O4303.1331, found303.1345.1-Amino-3-propyl-1H-pyrrole-2,4-dicarb-oxylic acid diethyl ester(entry5):1H NMR(400-MHz, DMSO-d6):d0.89(t,J=7.3,3H),1.25(t,J=7.1,3H), 1.31(t,J=7.1,3H),1.48(m,2H),2.95(t,J=7.8,2H), 4.16(q,J=7.1,2H),4.26(q,J=7.1,2H),6.43(s,2H, NH2),7.43(s,1H);13C NMR(100-MHz,DMSO-d6):d 14.2,14.3,14.5,24.5,27.4,59.4,60.2,109.9,119.6,131.0, 132.3,161.4,163.6;HRMS(ESI+)calcd for(M+H+) C13H21N2O4269.1501,found269.1488.1-Amino-5-chloro-1H-indole-2-carboxylic acid ethyl ester(entry6):1H NMR (400-MHz,DMSO-d6):d 1.35(t,J=7.3,3H), 4.36(q, J=7.3,2H),6.09(s,2H,NH2),7.11,(s,1H)7.32(dd, J=9.2,2.2,1H),7.60(d,J=9.2,1H),7.71(d,J=2.2, 1H);13C NMR(100-MHz,DMSO-d6):d14.5,60.8,106.3, 113.0,121.3,123.7,125.1,125.2,128.2,137.7,161.2;HRMS (ESI+)calcd for(M+H+)C11H12ClN2O2239.0587,found 239.0581.1-Amino-1H-indole-2-carboxylic acid ethyl ester (entry7):1H NMR(400-MHz,CD3OD):d1.41(t,J=7.3, 3H),4.39(q,J=7.3,2H),7.09(apparent t,J=8.1,1H), 7.14(s,1H),7.30(apparent t,J=8.1,1H),7.60(two overlapping d,J=9.9,2H);13C NMR(100-MHz, CD3OD):d15.1,62.1,108.9,112.2,122.0,123.6,124.9, 126.5,128.3,141.1,163.9;HRMS(ESI+)calcd for(M+H+) C11H13N2O2205.0977,found205.0974.A.Bhattacharya et al./Tetrahedron Letters47(2006)5341–53435343。