丙基联苯酯型液晶的合成:不饱和端基及氧原子对介晶性的影响

本文以对溴苯甲醚为原料制备成格氏试剂,与4-丙基环己酮亲核加成,脱水,Pd/C催化脱氢芳基化,L iPPh2脱甲基得到了4-正丙基-4’-羟基联苯。该联苯与酰氯酯化反应合成了系列丙基联苯酯类液晶化合物C3H7-C6H4-C6H4-OC(O)R。通过差示扫描量热法和热台偏光显微镜对其介晶性研究发现,当R=CnH2n 1(n=3,4)时,化合物无液晶性;但n=5-7、10,C8H16CH=CH2,C8H16C≡CH时,化合物具有SA相;当R=CH2OCmH2m 1(m=2-5),CH2OCH2CH2OCH3时,化合物呈有序度较较高的SB相。这类化合物的液晶相较窄,多在25℃-100℃范围内。TGA测试的化合物热分解温度都高于200℃。     

3-三氯化锡基丙烯酸乙酯与水杨醛缩m-溴-苯胺席夫碱配合物的室温固相合成及晶体结构

用室温固相合成法研究了酯基锡EtO2CCH2CH2SnCl3 1 与Schiff碱2-HOC6H4- CH=NC6H4Br-3 2 合成标题化合物(3-EtO2CCH2CH2SnCl3)?2-HOC6H4CH= N-C6H4Br-3) 3的配位反应。利用元素分析, UV-VIS, IR, 1H NMR等方法对配合物的结构进行了表征, 采用单晶X-射线衍射方法测定了3的晶体结构。3的分子式为C18H19BrCl3NO3Sn, Mr = 602.29。晶体属三斜晶系, P空间群, a = 7.75(2), b = 10.578(2), c = 13.936(3) , = 83.663(3), = 75.909(3), = 76.691(3), V = 1077(4) 3, Z=2, Dc = 1.858 g/cm3, F(000) = 588, = 3.433 mm-1, R = 0.0547, wR = 0.1341。Schiff碱是以酚羟基上的O原子与中心Sn原子配位, Schiff碱分子中的分子内氢键, 形成配合物后得到加强, 提出了3的2种共振式。与中心Sn原子配位的3个Cl原子、2个O原子和1个C原子形成畸变的八面体结构。     

含有长烷氧链混合醚-酯类苯并菲盘状液晶的合成及其介晶性研究

本文合成了含有不同柔链的对称和非对称苯并菲盘状液晶:sym-C18H6(OC11H23)3(O2CR)3和asym-C18H6(OC11H23)3(O2CR)3,R=(CH2OC2H5),CH2OC3H7,CH2OC4H9,CH2OC5H11,C3H7,C4H9,C5H11,C6H13,C7H15。通过偏光显微镜(POM)和差视扫描量热法(DSC)对它们的热致液晶性性进行了研究,结果显示:非对称性化合物比它们相应的对称性化合物有更高的熔点和清亮点。对于同一系列的化合物G18H6(OC11H23)3(OOCR)3,随取代基R的增长,其熔点下降,清高点反而升高。无论对称和非对称苯并菲衍生物G18H6(OC11H23)3(O2CR)3,(R=CH2OC2H5,CH2OC3H7,CH2OC4H9,CH2OC5H11),与有同样软链长度的苯并菲衍生物G18H6(OC11H23)3(O2CR)3,(R=C4H9,CK5H11,C6H13,C7H15)相比较,大都有更高的熔点和清亮点。另外,有足够长度软链的苯并菲衍生物在室温下就显示介晶相。     

1,3-双[4-(4'-甲基)-氧化偶氮苯基-苯氧羰基]苯氧甲基-1,1,3,3- 四甲基二硅 氧烷的合成、晶体结构和液晶性能

合成了[CH3(C6H4)N2O(C6H4)COO(C6H4)OCH2Si(CH3)2]2O,经IR,1^HNMR和元素分析表征,并测定其单晶结构。结果表明,晶体属单斜晶系,空间群为P21/c,晶胞参数a=1.7557(1),b=1.0938(9),c=2.3300(1)nm,β=105.6(6)°,V=4.3116nm^3,Mr=855.07,Z=4,Dc=1.317g/cm^3,μ(CuKα)=6.335cm^-1,F(000)=900,最终的偏离因子R=0.0837,Rw=0.0913。该分子中,柔性的四甲基二硅氧烷嵌段与氧化偶介晶基团形成ABA结构齐聚物。两条刚性的介晶基链节的轴向几乎平行向上伸出。径长比(L/D)为4.23.该液晶化合物的要变温度K174.4N226.8Ⅰ.通过结构分析,讨论了该类化合物的结构对液晶相变行为的影响。     

3-(四氯化锡)-丙酸甲酯阴离子的合成及晶体结构

在用酯基锡MeO2CCH2CH2SnCl3合成配合物MeO2CCH2CH2SnCl3·(2-OHC6H4CH=NC6H5)时,其配合物的甲苯溶液放置培养单晶时(放置十天以上)会发生分解生成配合物MeO2CCH2CH2SnCl4—·H+。研究了标题化合物的合成反应,用元素分析、IR、NMR对配合物进行了表征,并测定了晶体结构。为正交晶系,空间群为P2cn, a=7.852(2), b=12.236(1), c=16.952(4) ? V=1628.7?, Z=4, Dc=1.79g/cm3, F(000)= 860,m=22.2cm—1(Mo),R=0.0449, Rw=0.0382。标题化合物的空间构型为畸变的八面体构型,中心锡原子的配位数为6。     

烃基取代茚基钌羰基化合物的合成及晶体结构(英文)

配体C9H7R(R=CH2CH2CH3(1),CH(CH3)2(2),C5H9(3),CH2C6H5(4),CH2CH=CH2(5))分别与Ru3(CO)12在二甲苯或庚烷中加热回流,得到了6个双核配合物[(η5-C9H6R)Ru(CO)(μ-CO)]2(R=CH2CH2CH3(6),CH(CH3)2(7),C5H9(8),CH2C6H5(9),CH2CH=CH2(10))和[(η5-C9H6)(H3CH2C)CHCH(CH2CH3)(η5-C9H6)][Ru(CO)(μ-CO)]2(11)。通过元素分析、红外光谱、核磁共振氢谱对配合物的结构进行了表征,并用X-射线单晶衍射法测定了配合物6,9,10和11的结构。     

新型硅基桥连双(环戊二烯基)四羰基二铁类配合物的合成

以六甲基二硅烷为原料,经氯代、格式反应和锂化反应制得双(环戊二烯基)配体(C5H5)2MeSiSiMe2R(3a^3c),将该配体分别与五羰基铁在对二甲苯中回流反应,合成了3种新型的硅基桥连双(环戊二烯基)四羰基二铁类配合物[η^5,η^5-C5H4MeSi(SiMe2R)C5H4]Fe2(CO)2(μ-CO)2[R=p-C6H4CH3(4a),R=p-C6H4OCH3(4b),R=CH2C6H5(4c)],其结构经1H NMR,13C NMR,IR和元素分析表征。并用X-射线单晶衍射法确定了配合物4b的分子结构。结果表明:4b(CCDC:1942618)属单斜晶系,Cc空间群,晶胞参数a=18.591(3)A,b=10.3080(10)A,c=14.136(2)A,α=90°,β=117.262(6)°,γ=90°,V=2408.1(6)A^3,Z=4,F(000)=1152,Dc=1.546 g·cm^-3,μ=1.338 mm^-1,R1=0.0351,wR2=0.0754。     

三有机锡(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸酯的合成、结构和体外抗癌活性

利用三有机锡氢氧化物和手性配体(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸(HL)反应合成了3个三有机锡(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸酯R3SnL[1,R=c-C6H11(a),C6H5(b),C6H5C(CH3)2CH2(c)],通过元素分析、IR、1H NMR和X-射线单晶衍射表征了其结构。化合物1a属正交晶系,P212121空间群;化合物1b属单斜晶系,P21空间群。二者均为由羧基氧和内酰胺羰基氧桥联配位形成的右螺旋链状有机锡配位聚合物,锡原子具有五配位[SnC3O2]畸变三角双锥构型。化合物1a和1b对体外2种人癌细胞Colo205和Bcap37增殖均有强的抑制作用,其活性为1b1a。     

2,2-二甲基-1-[5-二茂铁基-3-(三氟甲基)-1H-吡唑-1-基]丙-1-酮的合成及其电化学性质

以乙酰基二茂铁为原料,经3步反应合成了一个新型的二茂铁衍生物——2,2-二甲基-1-[5-二茂铁基-3-(三氟甲基)-1H-吡唑-1-基]丙-1-酮(4),其结构经1H NMR,ESI-MS,元素分析和X-射线单晶衍射表征。4属单斜晶系,P2(1)/c空间群,晶胞参数a=7.805 6(4),b=20.906 1(11),c=11.124 6(6),β=93.820(2)°,V=1 811.33(17)3,Z=4,Dc=1.482 g·cm-3,μ=0.872 mm-1,R1=0.034 8,wR2=0.089 2。采用循环伏安法研究了4的电化学性质。结果表明:4有一对可逆的氧化还原峰,Epa=0.640 V,Epc=0.482 V,ΔE=153 m V。     

5-(2-芳氧甲基苯并咪唑-1一亚甲基)-1,3,4-噁二唑-2-硫酮的合成、晶体结构及生物活性研究

以2-芳氧甲基苯并咪唑-1-乙酰肼类化合物为原料在微波辐射条件下合成了10种尚未见文献报道的5-(2-芳氧甲基苯并咪唑-1-亚甲基)-1,3,4-噁二唑-2-硫酮衍生物,化合物结构经IR 1H NMR,13C NMR和元素分析进行了表征,6a晶体结构表明,该化合物通过分子间氢键自组装成了沿b轴无限延伸的一维链状超分子结构,属于单斜晶系,P21/c空间群,a=11.5484(13)A,6=16.5319(19)A,c=11.3595(14)A,β=108.755(2)°,Z=2,V=2053.6(4)A3,Dx=1.328 g/cm3,F(000)=860,μ=0.19 mm-1,R=0.060,wR=0.196.初步生物活性试验结果表明该系列部分化合物对油菜幼苗的生长具有明显的生长调节作用,并对枯草杆菌具有一定的抑制作用.     

1-烃基-1-硅杂环丁烷的合成及其Si—H键伸缩振动频率与结构关系的研究

硅杂环丁烷在有机硅化学中是一类非常重要的小分子环系化合物。由于硅杂环丁烷和环丁烷的环张力相似,因而显示出较高的反应活性。例如能与某些试剂作用,生成开环产物;在光解或热解条件下,产生具有Si=C结构的高活性中间体,可用以合成多种有机硅化合物。     

Preparation and substitution chemistry of [Bu4N]2[W6Cl8(p-OSO2C6H4CH3)6]. A useful precursor for pseudohalide, acetate, and organometallic complexes containing the [W6Cl8](4+) core

The tosylate (p-toluenesulfonate) cluster [Bu4N]2[W6Cl8(p-OSO2C6H4CH3)6] (1) has been prepared and characterized by IR and NMR spectroscopy, elemental analysis, and an X-ray crystal structure. This cluster complex is shown to be a useful starting material for the preparation of pseudohalide clusters, [Bu4N]2[W6Cl8(NCQ)6] (Q = O (2), S (3), and Se (4)), in high yields. Cluster 1 also serves as a precursor to the new cluster compounds: [Bu4N]2[W6Cl8(O2CCH3)6] (5), [Bu4N]2[W6Cl8((mu-NC)Mn(CO)2(C5H5))6] (6), [W6Cl8((mu-NC)Ru(PPh3)2(C5H5))6][ p-OSO2C6H4CH3]4 (7), and [W6Cl8((mu-NC)Os(PPh3)2(C5H5))6][ p-OSO2C6H4CH3]4 (8). X-ray crystal structures are reported for 1, 4, and 5.     

大取代茂钼化合物的合成与结构分析

利用芳基锂与6,6-二烷基富烯发生加成反应,制得大取代环戊二烯基负离子.用六羰基钼配位,合成出13个钼-钼双核及5个钼-卤素单核羰基化合物.研究了其IR、^1HNMR、^95MoNMR.测定了[(CH~3)~2C(m-CH~3C~6H~4]Mo(CO)~3Br(1)的晶体结构.该晶体属于单余晶系,晶胞参数为a=1.175(3),b=1.4196(2),c=1.1894(4)nm,β=118.03(2)°,Ⅴ=1.75134nm^3.Z=4,D~0=1.733g/cm^3,F(000)=904,μ=30.0cm^-1,R=0.039,R~W=0.050,空间群为P2~1/α.     

New structural features in triphenylphosphinesilver(I) sulfanylcarboxylates

We investigated the reactions of 1.5 : 1 : 1 mole ratio mixtures of triphenylphosphine, silver nitrate and 3-(aryl)-2-sulfanylpropenoic acids H(2)xspa in chloroform/water, where in the acid nomenclature, spa = 2-sulfanylpropenoato and x = p, Clp, mp, diBr-o-hp or f with p = 3-phenyl-, Clp = 3-(2-chlorophenyl)-, mp = 3-methoxyphenyl-, diBr-o-hp = 3-(3,5-dibromo-2-hydroxyphenyl)- and f = 3-(2-furyl)-. The compounds [Ag(PPh(3))(Hpspa)](1), [(AgPPh3)2(xspa)][x = Clp (2), o-mp (3), p-mp (4), diBr-o-hp (5) and f (6)] and [Ag(PPh3)3(Hfspa)](7) were isolated and all except 7 were characterized by IR, Raman and FAB mass spectrometry and by 1H, 13C and 31P NMR spectroscopy. Compound 6 was also characterized by (13)C CP/MAS, and compounds 1 and 6 by (109)Ag NMR spectroscopy. The crystal structures of 1, 2, 3, 4.(CH3)2CO, 5, 6.(CH3)2CO and 7 were determined by X-ray diffraction. has a supramolecular structure based on hydrogen bonding between dinuclear units, and all the other complexes adopt discrete structures. 2, 3, 4.(CH3)2CO, 5, and 6.(CH3)2CO are tetranuclear, and 7 mononuclear. The tetranuclear complexes contain the eight-membered coordination ring Ag4S2O2 (2, 3, 4.(CH3)2CO, 6.(CH3)2CO) or the twelve-membered ring Ag4(CO2)2S2 (5).     

Reactions of tris(amino)phosphines with arylsulfonyl azides: product dependency on tris(amino)phosphine structure

The Staudinger reaction of N(CH2CH2NR)3P [R = Me (1), Pr (2)] with 1 equiv of N3SO2C6H4Me-4 gave the ionic phosphazides [N(CH2CH2NR)3PN][SO2C6H4Me-4] [R = Me (3), R = Pr (5a)], and the same reaction of 2 with N3SO2C6H2Me3-2,4,6 gave the corresponding aryl sulfinite 5b. On the other hand, the reaction of 1 with 0.5 equiv of N3SO2Ar (Ar = C6H4Me-4) furnished the novel ionic phosphazide [[N(CH2CH2NMe)3P]2(mu-N3)][SO2Ar] (6). Data that shed light on the mechanistic pathway leading to 3 were obtained by low temperature 31P NMR spectroscopy. A crystal and molecular structure analysis of the phosphazide sulfonate [N(CH2CH2NMe)3PN3][SO3C6H4Me-4] (4), obtained by atmospheric oxidation of 3, indicated an ionic structure, the cationic part of which is stabilized by a transannular P-N bond. A crystal and molecular structure analysis of 6 also indicated an ionic structure in which the cation features two untransannulated N(CH2CH2NMe)3P cages bridged by an azido group in an eta 1: mu: eta 1 fashion. The reaction of P(NMe2)3 with N3SO2Ar (Ar = C6H4Me-4) in a 1:0.5 molar ratio furnished [[(Me2N)3P]2(mu-N3)][SO2-Ar] (11) in quantitative yield. On the other hand, the same reaction involving a 1:1 molar ratio of P(NMe2)3 and N3SO2Ar produced a mixture of 11, [(Me2N)3PN3][SO2Ar] (12), and the iminophosphorane (Me2N)3P=NSO2Ar (10). In contrast, the bicyclic tris(amino)phosphines MeC(CH2NMe)3P (7) and O=P(CH2NMe)3P (8) reacted with N3SO2-Ar (Ar = C6H4Me-4) to give the iminophosphorane MeC(CH2NMe)3P=NSO2Ar (14) (structured by X-ray means) and O=P(CH2NMe)3P=NSO2Ar (16) via the intermediate phosphazides MeC(CH2NMe)3PN3SO2Ar (13) and O=P(CH2NMe)3PN3SO2Ar (15), respectively. The variety of products obtained from the reactions of arylsulfonyl azides with proazaphosphatranes (1 and 2), acyclic P(NMe2)3, bicyclic tris(amino)phosphines 7 and 8 are rationalized in terms of steric and basicity variations among the phosphorus reagents.     

β- 丁氧酯基三氯化锡与席夫碱配合物的合成、结构与酯交换反应

合成了标题化合物n-BuO2CCH2CH2SnCl3.(2-HOC6H4CH=NC6H4-OMe-4'),通过元素分析,UV-Vis,IR和^1HNMR进行了表征。其晶体结构分析表明,该晶体属单斜晶系,空间群P21/c;a=1.4661(3),b=0.9307(2),c=1.7888(4)nm,β=94.04(3)°,Mr=579.45,Z=4;V=2.4348(8)nm^3,DC=1.581mg/m^3,μ=1.405mm^-^1,F(000)=1160,R=0.0354,Rw=0.0486。该化合物为含有分子内羰基氧配位,Schiff碱以酚羟基上的氧原子配位,中心锡原子为六配位,空间构型为畸变八面体构型的单分子有机锡化合物。研究了标题化合物在醇中的酯交换反应,合成了8个配合物(CH3CH2)2CHCH2-),并对它们进行了表征,提出了酯交换反应的机理     

Spectral, structural, and electrochemical properties of ruthenium porphyrin diaryl and aryl(alkoxycarbonyl) carbene complexes: influence of carbene substituents, porphyrin substituents, and trans-axial ligands

A wide variety of ruthenium porphyrin carbene complexes, including [Ru(tpfpp)(CR(1)R(2))] (CR(1)R(2) = C(p-C(6)H(4)Cl)(2) 1 b, C(p-C(6)H(4)Me)(2) 1 c, C(p-C(6)H(4)OMe)(2) 1 d, C(CO(2)Me)(2) 1 e, C(p-C(6)H(4)NO(2))CO(2)Me 1 f, C(p-C(6)H(4)OMe)CO(2)Me 1 g, C(CH==CHPh)CO(2)CH(2)(CH==CH)(2)CH(3) 1 h), [Ru(por)(CPh(2))] (por=tdcpp 2 a, 4-Br-tpp 2 b, 4-Cl-tpp 2 c, 4-F-tpp 2 d, tpp 2 e, ttp 2 f, 4-MeO-tpp 2 g, tmp 2 h, 3,4,5-MeO-tpp 2 i), [Ru(por)[C(Ph)CO(2)Et]] (por=tdcpp 2 j, tmp 2 k), [Ru(tpfpp)(CPh(2))(L)] (L = MeOH 3 a, EtSH 3 b, Et(2)S 3 c, MeIm 3 d, OPPh(3) 3 e, py 3 f), and [Ru(tpfpp)[C(Ph)CO(2)R](MeOH)] (R = CH(2)CH==CH(2) 4 a, Me 4 b, Et 4 c), were prepared from the reactions of [Ru(por)(CO)] with diazo compounds N(2)CR(1)R(2) in dichloromethane and, for 3 and 4, by further treatment with reagents L. A similar reaction of [Os(tpfpp)(CO)] with N(2)CPh(2) in dichloromethane followed by treatment with MeIm gave [Os(tpfpp)(CPh(2))(MeIm)] (3 d-Os). All these complexes were characterized by (1)H NMR, (13)C NMR, and UV/Vis spectroscopy, mass spectrometry, and elemental analyses. X-ray crystal structure determinations of 1 d, 2 a,i, 3 a, b, d, e, 4 a-c, and 3 d-Os revealed Ru==C distances of 1.806(3)-1.876(3) A and an Os==C distance of 1.902(3) A. The structure of 1 d in the solid state features a unique "bridging" carbene ligand, which results in the formation of a one-dimensional coordination polymer. Cyclic voltammograms of 1 a-c, g, 2 a-d, g-k, 3 b-d, 4 a, b, and 3 d-Os show a reversible oxidation couple with E(1/2) values in the range of 0.06-0.65 V (vs Cp(2)Fe(+/0)) that is attributable to a metal-centered oxidation. The influence of carbene substituents, porphyrin substituents, and trans-ligands on the Ru==C bond was examined through comparison of the chemical shifts of the pyrrolic protons in the porphyrin macrocycles ((1)H NMR) and the M==C carbon atoms ((13)C NMR), the potentials of the metal-centered oxidation couples, and the Ru==C distances among the various ruthenium porphyrin carbene complexes. A direct comparison among iron, ruthenium, and osmium porphyrin carbene complexes is made.     

二氯四(苯丙酮-1, 2, 4-三唑)合钴六水配合物晶体结构

0IntroductionRecently,thecompoundscontaining1H-1,2,4-tr-iazolegrouphaveattractedmuchinterestbecauseoftheirexhibitingsomefungicidalactivityandplantgrowthregulatingactivity犤1犦,andshowingantibacterialactivityagainstPucciniareconditeandrootsgrowthregulationforcucumber犤2犦.Also,suchcompoundsareincreasinglybeingstudiedbecauseofthecoordinationchemistryofazolesactingasligandsintransitionmetalcompounds.Asamatteroffact,thetriazolederivativeshavebeenextensivelyusedasterminalandbridgingligands,andthey…