磷氯化物（PCI3，PCI5，POCl3）作为氯化试剂在有机合成中应用的研究进展

综述了近十几年来磷氯化物(PCI3，PCI5，POCl3)作为氯化试剂在有机合成中应用的新进展，主要包括磷氯化物与羟基化合物、羧酸、羰基化合物、烯烃、古孤对电子基固化合物、磺酸及其盐、硅化合物、磷化合物的氯化反应，以及氢氯交换反应。     

环链转移反应及其在合成杂环化合物中的应用

概括了环链转移反应的类型、机理,同时综述了环链转移反应在合成取代杂环化合物中的应用。     

制备trans-Fe(CO)_3(PR_3)_2的新的取代过程

报道了用H_2Fe(CO)_4制备trans-Fe(CO)_3(PR_3)_2的新的羰基取代反应。在 过量质子存在下，H_2Fe(CO)_4中的羰基被活化，中心铁原子对膦的亲核进攻更为 敏感。在这种条件下H_2Fe(CO)_4与膦反应时，首先失去氢生成Fe(CO)_4(PR_3), Fe(CO)_4-(PR_3)再与第二个膦反应可高产率的得到trans-Fe(CO)_3(PR_3)_2。用 PPh_3与Fe(CO)_4(PPh_3)在过量质子存在下反应生成trans-Fe(CO)_3(PR_3)_2，证 实了上述过程。     

酸性沸石分子筛催化Knoevenagel综合反应

在高硅／铝比的酸性沸石分子筛HY上实现了Knoevenagel缩合反应，Bronsted酸和Lewis酸均可催化Knoevenagel缩合反应。考察了羰基化合物和活泼亚甲基化合物的反应活性顺序。结果表明，羰基化合物的羰基极化程度越高，反应越容易进程,示同于碱催化时的Knoevenagel缩合反应，活泼亚甲基化合物的活泼氢的酸性并不是影响其反应活性的重要因素。     

有机锑化合物在交叉偶联反应中的应用研究进展

近年来,有机锑化合物在交叉偶联反应中的应用引起了人们的广泛关注。本文主要对有机锑化合物在交叉偶联反应中的应用作了综述,重点介绍了其在Suzuki交叉偶联反应、Heck偶联反应以及Sonogashira偶联反应中的应用,并展望了其未来的发展方向。     

氮杂Wittig反应的最近进展

综述了最近几年氮杂Wittig反应的研究进展,包括分子间氮杂Wittig反应、分子内氮杂wittig反应及串联的氮杂Wittig反应。讨论了氮杂Wittig反应在一些含氮杂环、稠杂环及天然产物合成中的应用。     

GC－MS在苯基环氧化合物选择重排反应中的应用

首次使用气相色谱-质谱联用仪(GC-MS)对有机化合物重排反应进行了研究。苯基环氧化合物和α-氯代苯乙醇在气相色谱中发生重排反应，用质谱仪鉴定为其相应的羟基化合物。这种用GC-MS研究重排反应的方法在国内尚未见报道。此方法操作简便、反应迅速、产率高，为研究有机化合物的重排反应提供了一种新的方法。     

原位反应合成Mo-Si化合物系复合材料

采用反应烧结法原位合成了Mo Si系化合物复合材料，利用X射线衍射仪、扫描电镜和电子探针等考察了材料的显微结构和相组成.结果表明，随原料粉中Mo含量的增加， Mo Si系反应生成物依次向MoSi2→Mo5Si3→Mo3Si变化；各相分布较为均匀，组织致密，晶粒细小.     

钯类催化剂在形成碳－碳单键反应中的应用

钯催化反应是广泛被用于有机合成的简单而又重要的反应。主要综述钯类催化剂在形成碳－碳单键反应中的应用，着重阐述了卤代烃与有机金属化合物、烯烃、炔烃的交联反应。     

聚合物支载合成杂环化合物的研究进展

聚合物支载的反应与传统的经典液相反应相比，具有独特的优点，广泛应用于 杂环化合物的合成。综述了近年来杂环化合物的固相和液相合成研究。     

Double transacetalization of diacylium ions

A novel gas-phase reaction of diacylium ions of the O=C=X(+)=C=O type (X = N, CH) is reported: double transacetalization with cyclic acetals or ketals. The reaction is exothermic and highly efficient, and forms members of a new class of highly charged-delocalized ions: cyclic ionic diketals. Pentaquadrupole double- and triple-stage mass spectrometric (MS(2) and MS(3)) experiments reveal the high double transacetalization reactivity of O=C=N(+)=C=O and O=C=CH(+)=C=O, whereas the synthesis of differently substituted cyclic ionic diketals is performed in MS(3) experiments via sequential mono- and double transacetalization of O=C=N(+)=C=O and O=C=CH(+)=C=O with different acetals. With cyclic acetals, the acylium-thioacylium ion O=C=N(+)=C=S reacts promptly and selectively by mono-transacetalization at its acylium site, but the free thiacylium site of its cyclic ionic ketal is nearly unreactive by double transacetalization. Therefore, only the acylium site of O=C=N(+)=C=S can be efficiently protected by transacetalization. Low-energy MS(3) collision-induced dissociation of the cyclic ionic diketals of O=C=N(+)=C=O and O=C=CH(+)=C=O sequentially frees each of the protected acylium site to form the mono-derivatized ion, and then the fully deprotected diacylium ion.     

C7 and C9 carbon-rich bridges in diruthenium systems: synthesis, spectroscopic, and theoretical investigations of different oxidation States

Two methodologies of C-C bond formation to achieve organometallic complexes with 7 or 9 conjugated carbon atoms are described. A C7 annelated trans-[Cl(dppe)2Ru=C=C=C-CH=C(CH2)-C[triple bond]C-Ru(dppe)2Cl][X] (X = PF6, OTf) complex is obtained from the diyne trans-[Cl(dppe)2Ru-(C[triple bond]C)2-R] (R = H, SiMe3) in the presence of [FeCp2][PF6] or HOTf, and C7 or C9 complexes trans-[Cl(dppe)2Ru-(C[triple bond]C)n-C(CH3)=C(R1)-C(R2)=C=C=Ru(dppe)2Cl][X] (n = 1, 2; R1 = Me, Ph, R2 = H, Me; X = BF4, OTf) are formed in the presence of a polyyne trans-[Cl(dppe)2Ru-(C[triple bond]C)n-R] (n = 2, 3; R = H, SiMe3) with a ruthenium allenylidene trans-[Cl(dppe)2Ru=C=C=C(CH2R1)R2][X]. These reactions proceed under mild conditions and involve cumulenic intermediates [M+]=(C=)nCHR (n = 3, 5), including a hexapentaenylidene. A combination of chemical, electrochemical, spectroscopic (UV-vis, IR, NIR, EPR), and theoretical (DFT) techniques is used to show the influence of the nature and conformation of the bridge on the properties of the complexes and to give a picture of the electron delocalization in the reduced and oxidized states. These studies demonstrate that the C7 bridging ligand spanning the metal centers by almost 12 angstroms is implicated in both redox processes and serves as a molecular wire to convey the unpaired electron with no tendency for spin localization on one of the halves of the molecules. The reactivity of the C7 complexes toward protonation and deprotonation led to original bis(acetylides), vinylidene-allenylidene, or carbyne-vinylidene species such as trans-[Cl(dppe)2Ru[triple bond]C-CH=C(CH3)-CH=C(CH3)-HC=C=Ru(dppe)2Cl][BF4]3.     

Synthesis and Crystal Structure of 2-Amino-3-cyano- 4-（3,4-dimethoxyphenyl）-4H-benzo[h]chromenes

1INTRODUCTION4H-Chromeneisaconstructionunitofsomenaturalproducts.4H-Chromeneswithaminoandcyanogroupsarealsosynthonofsomespecialnaturalproducts[1,2].Thesubstituted4H-chromenespossessawiderangeofpharmacologicalactivi-ties[3～5].Inordertoinvestigatetheactivi…     

Molecular structure of vinylphosphine derivatives. Electron diffraction study of Cl2P−CH=CR2 (R=H,Me)

Internal rotation about the P?C bonds in the Cl₂PCH=CH₂ and Cl₂PCH=CMe₂ molecules is diseussed. It is shown that the cis (with eclipsed C=C bonds and lone electron pair of the phosphorus atom) and eclipsed conformers of the Cl₂PCH=CH₂ molecule are in equilibrium. The geometrical parameters and conformation compositions are refined. The content of the cis conformer is 40%. The Cl?P?C=C torsion angles are ±128.5° for the cis conformer and ?29.6 and ?132.6° for the eclipsed conformer. The Cl₂PCH=CMe₂ molecule occurs only in the cis form. For Cl₂PCH=CMe₂, the geometrical parameters are as follows: bond lengths C?H=1.124(11), C=C=1.322(8), P?C=1.789(3), and P?Cl=2.042(2) Å; bong angles (deg) C?P?Cl=99.1(4), Cl?P?Cl=99.6(6), C=C?CH₃=120.1 and 125.7, and P?C=C=122.3(9); torsion angles Cl?P?C=C=±129.3(3).     

Microwave spectrum of cyclohexanecarbonitrile

The microwave rotational spectrum of cyclohexanecarbonitrile was investigated in the frequency region 8–40 GHz. From the measured transition frequencies the rotational constants of the two molecular were derived (equatorial isomer: A = 4238.77, B = 1399.172, C = 1128.845 MHz; axial isomer: A = 3005.58, B = 1763.483, C = 1558.615 MHz). Assuming the values of 1.531, 1.096 and 1.159 Å, respectively, for the CC, CH and CN distances, and supposing that the ring structure has the same symmetry as in cyclohexane, the following structural parameters were also obtained: equatorial isomer CCC (carbon ring) = 111.40°, r(CCN) = 1.489 Å, HCCN = 107.42°; axial isomer CCC (carbon ring) = 111.65°, r(CCN) = 1.489 Å, HCCN = 105.53°.     

Synthesis and Crystal Structure of Ethyl （2-Amino-4-（2-chlorophenyl）-4H-benzo-[h]-chromene-2-yl） Formate

1 INTRODUCTION 2-Aminochromene is an important class of compounds as the main compounds of many natu- rally occurring products which can be used as cos- metics and pigments[1] and potential biodegradable agrochemicals[2～4]. Inorganic solid supports as c…     

A multinuclear NMR study of [Pt0(PPh3)2(alkene)] compounds containing asymmetric olefins

The 1H, 13C, 31P, and 195Pt NMR spectra of [Pt0(PPh3)2(eta-ABC(1) = C(2)XY)] compounds (ABC(1)= C(2)XY (1) A = B = X = Y = H; (3) A = B = X = H, Y = CN; (4) A = H, B = p-NO2-Ph, X = COOCH3, Y = CN; (5) A = H, B = Ph, X = COOCH3, Y = CN; (6) A = H, B = Ph, X = Y = CN; (7) A = H, B = OEt, X = Y = CN), where X and Y are electronacceptor substituents, and the 1H spectrum of [Pt0(PPh3)2(eta2-C60)] (2) are reported together with extended analyses and assignments, based also on the ring current effect of the olefin phenyl in (4-6). Deviations from first order in the 13C spectra allowed the determination of the relative signs of the coupling constants J(P(1), C) and J(P(2), C) of the alkene and of the triphenylphosphine carbons. Best fit simulation of the phosphine C ipso spectrum provided also the 13C isotopic shift on phosphorus for (1). These compounds are characterised by strong differences between the two platinum-phosphorus coupling constants in the case of asymmetric olefins (3-7). The chemical shifts of alkene C(1) and C(2) indicate notable polarisation of the olefin after complexation, while the 1J(Pt, C(1)) and 1J(Pt, C(2)) values are in agreement with a stronger interaction of Pt with C(1) than with C(2). These findings together with the trend of 195Pt chemical shifts confirm the important role played by back-donation in the bonding of platinum(0)-olefin compounds.     

2-氨基-3-氰基-4-(4-氟苯基)-4H-苯并[h]苯并吡喃的合成和晶体结构

标题化合物与N,N-二甲基甲酰胺(DMF)形成的1:1混合结晶物C20H23FN2OC3H7NO由对氟苯甲醛、丙二腈、-萘酚在六氢吡啶存在下合成并经DMF与水的混合溶剂重结晶而得, 其结构通过元素分析、IR 和1H NMR对化合物进行了表征,用X-射线单晶衍射法测定了该化合物的晶体结构。结果表明,晶体属于单斜晶系,P21/n空间群,a = 6.365(1), b = 10.620(2), c = 29.122(6) ? b = 92.00(1), V = 1967.3(6) ?, Mr = 389.42, Z = 4, Dc = 1.315 g/cm3, m (MoKa) = 0.092 mm-1, F(000) = 816。晶体结构用直接法解出,经全矩阵最小二乘法修正,最终偏离因子R = 0.047, wR = 0.1053。化合物分子中,原子C(1), C(2), C(3), C(4), C(5) 和O(1)形成1个六员环,该六员环中C(1)C(2)键长为1.346(3) 牛砻魑肆被肺焦瓜蟆?     

Synthesis and Crystal Structure of 1,7,7-Trimethyl- 4-（4-methoxyphenyl）-4,6,7,8-tetrahydroquinoline- 2,5（1H,3H）-diones under Microwave Irradiation

1 INTRODUCTION Various quinolone derivatives are known to dis- play interesting biological properties ranging from microbial activity to cytotoxicity[1]. They have been reported as antiviral (HIV-1)[2] and antitumor agents[3] as well as used as tubulin[4], topoisomerase[5] and thrombocyte inhibitors[6]. As a member of the quino- lone family, substituted N-phenyl-2-quinolones re-present the structural basis of many biologically active compounds, such as protein kinase inhibitors, immunodu…     

Synthesis and reactions of group 6 metal half-sandwich complexes of 2,2-dicyanoethylene-1,1-dichalcogenolates [(Cp*)M[E(2)C=C(CN)(2)](2)]-(M = Mo,W; E = S,Se)

A series of group 6 transition metal half-sandwich complexes with 1,1-dichalcogenide ligands have been prepared by the reactions of Cp*MCl(4)(Cp* = eta(5)-C(5)Me(5); M = Mo, W) with the potassium salt of 2,2-dicyanoethylene-1,1-dithiolate, (KS)(2)C=C(CN)(2) (K(2)-i-mnt), or the analogous seleno compound, (KSe)(2)C=C(CN)(2) (K(2)-i-mns). The reaction of Cp*MCl(4) with (KS)(2)C=C(CN)(2) in a 1:3 molar ratio in CH(3)CN gave rise to K[Cp*M(S(2)C=C(CN)(2))(2)] (M = Mo, 1a, 74%; M = W, 2a, 46%). Under the same conditions, the reaction of Cp*MoCl(4) with 3 equiv of (KSe)(2)C=C(CN)(2) afforded K[Cp*Mo(Se(2)C=C(CN)(2))(2)] (3a) and K[Cp*Mo(Se(2)C=C(CN)(2))(Se(Se(2))C=C(CN)(2))] (4) in respective yields of 45% and 25%. Cation exchange reactions of 1a, 2a, and 3a with Et(4)NBr resulted in isolation of (Et(4)N)[Cp*Mo(S(2)C=C(CN)(2))(2)] (1b), (Et(4)N)[Cp*W(S(2)C=C(CN)(2))(2)] (2b), and (Et(4)N)[Cp*Mo(Se(2)C=C(CN)(2))(2)] (3b), respectively. Complex 4 crystallized with one THF and one CH(3)CN molecule as a three-dimensional network structure. Inspection of the reaction of Cp*WCl(4) with (KSe)(2)C=C(CN)(2) by ESI-MS revealed the existence of three species in CH(3)CN, [Cp*W(Se(2)C=C(CN)(2))(2)]-, [Cp*W(Se(2)C=C(CN)(2))(Se(Se(2))C=C(CN)(2))]-, and [Cp*W(Se(Se(2))C=C(CN)(2))(2)]-, of which [Cp*W(Se(2)C=C(CN)(2))(Se(Se(2))C=C(CN)(2))]-(5) was isolated as the main product. Treatment of 2a with 1/4 equiv of S(8) in refluxing THF resulted in sulfur insertion and gave rise to K[Cp*W(S(2)C=C(CN)(2))(S(S(2))C=C(CN)(2))](6), which crystallized with two THF molecules forming a three-dimensional network structure. 6 can also be prepared by refluxing 2a with 1/4 equiv of S(8) in THF. 3a readily added one Se atom upon treatment with 1 mol of Se powder in THF to give 4 in high yield, while the treatment of 3a or 4 with 2 equiv of Na(2)Se in THF led to formation of a dinuclear complex [(Cp*Mo)(2)(mu-Se)(mu-Se(Se(3))C=C(CN)(2))] (7). The structure of 7 consists of two Cp*Mo units bridged by a Se(2-) and a [Se(Se(3))C=C(CN)(2)](2-) ligand in which the triselenido group is arranged in a nearly linear way (163 degrees). The reaction of 2a with 2 equiv of CuBr in CH(3)CN yielded a trinuclear complex [Cp*WCu(2)(mu-Br)(mu(3)-S(2)C=C(CN)(2))(2)] (8), which crystallized with one CH(3)CN and generated a one-dimensional chain polymer through bonding of Cu to the N of the cyano groups.