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1.
顺-9-十四碳烯-1-醇乙酸酯(1)是鳞翅目许多昆虫的性信息素或其组分之一 [1]。已报道的化合物1的合成方法是采取C 10+C 4或C 9+C 5偶联原则 [2]。本文报道另一条合成路线(图1),采取C 8+C 6原则,以1,8-辛二醇(2)为原料,经过ω-氯代辛醇(3)得2-(8'-氯辛烷-1-氧基)四氢吡喃(4) [2d],卤代物4与己炔-1(5) [3]的锂盐缩合得炔化物6,然后以Lindlar催化剂 [4]进行部分氢化,粗产品7无需分离可直接去保护基并乙酞化得产物1,五步的总得率约40%. 相似文献
2.
Richard在1959年合成了第一个环戊二烯基(取代环戊二烯基)钛衍生物,(CH 3C 5H 4)(C 5H 5)T1Cl 2[1].我们曾报道了环戊二烯基(烯烃基环戊二烯基)二卤化钛的合成和反应 [2]。 相似文献
3.
鉴于富勒烯C 60所具有的缺电子烯烃的特性 1以及CpCo(PPh 3) 2可与烯或炔反应生成钴杂环有机化合物, 2,3 因此我们设想如果用C 60代替烯、炔,令其与η 5-RC 5H 4Co(PPh 3) 2( 1) 或η 5-RC 5H 4Co(PPh 3)(PhC≡CPh)( 2)反应,则应得到一类新型的富勒烯C 60有机钴杂环化合物。然而与这一设想不同的是,上述反应并未得到预期的C 60钴杂环有机物,所得到的却是另一类新型的有机钴C 60衍生物(η 2-C 60)(η 5-RC 5H 4)CoPPh 3( 3).此外,我们发现当 3或 2同I 2反应时,可生成C 60或PhC≡CPh配体被I 2置换产物η 5-RC 5H 4Co(PPh 3)I 2( 4)。 相似文献
4.
研究了4种不同电荷的Co(Ⅲ)金属配合物跨人红细胞膜的动力学,并测定了它们跨人红细胞膜的一级反应动力学速率常数,发现[Co(C 2O 4) 3] 3-的跨膜速率明显高于[Co(en) 3] 3+,[Co(en) 2(C 2O 4)] +和[Co(en)(C 2O 4) 2] -,后3种配合物的跨膜速率常数随正电荷的减少略有增加,跨膜机制为简单扩散.[Co(C 2O 4) 3] 3-的跨膜速率受阴离子通道抑制剂DIDS明显抑制,抑制率为51.95%,推测其跨膜机制为部分经阴离子通道协同简单扩散过膜.人红细胞摄入L-[Co(C 2O 4) 3] 3-的速率明显大于D-[Co(C 2O 4) 3] 3-,显示了一定的手性选择性. 相似文献
5.
为分析C 1~C 3正构醛、 醇化合物在质子转移反应飞行时间质谱(PTR-TOF MS)中的产物离子特征, 考察了不同E/N值(E: 电场强度, N: 气体分子数密度)下C 1~C 3正构醛、 醇的产物离子种类和强度的变化. 结果表明, 低分子量正构醇类(甲醇、 乙醇和丙醇)倾向于形成质子化聚合物[ nMH] +及其失水离子[ nMH-H 2O] +, 且随着E/N值升高, 醇类会产生较多裂解碎片和多聚体离子. 低分子量正构醛(甲醛、 乙醛和丙醛)主要产生质子化产物[MH] +和一水合质子化产物[M·H 3O] +, 高E/N值(>125 Td)会抑制甲醛质子化, 也会抑制其加合产物的生成. 乙醛倾向于形成水加合物, 且随着E/N值增高, 质子化乙醛与 一水合质子化乙醛的变化趋势相反. 另外, 丙醛在较高的E/N值下会产生一系列聚合物, 如[MH·C 2H 5] +和[2MH] +. 通过分析C 1~C 3正构醛、 醇的质子转移反应特征及产物离子形成过程, 获得了C 1~C 3正构醛、 醇的特征离子和对应的最佳E/N设置值, 为低分子量醛、 醇的定性分析提供了重要依据. 相似文献
6.
以富勒烯C 60, L-苏氨酸及对苯二甲醛为原料, 在氮气保护下反应得到含醛基官能团的2-(4-醛基苯基)-5-(1-羟乙基)富勒烯吡咯烷衍生物(C 60-CHO). 将该材料修饰于玻碳电极表面, 并利用醛基与氨基之间温和、高效的缩合反应, 将5-氨基修饰的寡聚核苷酸共价固定到了C 60-CHO修饰的玻碳电极表面, 构建了一种新型的电化学DNA传感器. 以[Fe(CN) 6] 3−/4−为电活性探针, 采用电化学阻抗法对转基因植物CaMV35S启动子基因特征片段进行检测. 实验结果表明, 杂交前后的电子传递电阻差值(D Ret)与目标序列浓度对数(lg CS2)在1.0×10 -13~1.0×10 -9 mol/L浓度范围内呈良好的线性关系, 线性回归方程为D Ret/(10 3 Ω)=3.471 lg ( CS2/mol/L)+50.425 ( r=0.9977), 检测限为1.5×10 −14 mol/L. 杂交特异性实验进一步表明该传感器对完全互补、碱基错配和非互补序列具有良好的识别能力. 相似文献
7.
三(2-甲基-2-苯基丙基)锡氧化物(Torque,苯丁锡,[(C 6H 5CMe 2CH 2) 3Sn] 2O)是-个已商品化的有机锡杀螨剂 [1]。为了研究三烃基锡衍生物中阴离子配体对生物活性的影响,本文用苯丁锡与酚或羧酸反应,合成了四个系列的含氧三(2-甲基-2-苯基丙基)锡衍生物。 相似文献
8.
在流动余辉装置上, 利用N 2空心阴极放电制备活性氮, 研究了活性氮与碘乙烷(C 2H 5I)反应的化学发光. 在620~820 nm波长范围内观察到了较强的发射光谱, 拟合得到的光谱常数表明它来源于NI(b 1Σ +→X 3Σ -)跃迁, 并对35个谱峰进行了振动归属. 最后讨论了活性氮中主要成分与C 2H 5I反应的可能过程, 结合辅助性实验分析表明, 活性氮中的N( 2P)与C 2H 5I直接反应很可能产生激发态NI(b 1Σ +)自由基. 这是利用化学反应直接产生激发态NI(b 1Σ +)的首次报道, 观察到的激发态最高振动能级为 v'=6. 相似文献
9.
羰基化反应是有机合成化学中常用的方法之一,但常规的羰基化反应大多要求高温(150~200℃)、高压(10~20 M Pa)或使用贵金属催化剂(如钌、铑、铱等),并且C 1源多用一氧化碳 [1].开发和利用CO 2这一丰富的C 1资源,并最大限度地降低其排放量具有挑战意义.但CO 2活化比较困难,在通常条件下难以转化成其它化学品 [2].在光促进下的羰基化反应可克服上述困难,使反应在温和条件及非贵金属催化下完成,同时可用CO 2代替CO作为C 1源,因此这是一个对环境友好的工艺 [3].本文报道烯烃在光促进常温常压和非贵金属钴配合物催化下与二氧化碳的羰基化反应,同时通过 13CO 2和 13CH 3OH同位素实验,对反应产物的结构进行了分析. 相似文献
10.
1991年Iijima [1]在研究C 60的同时,首次在高分辨透射电镜(HRTEM)下发现具有纳米尺寸的被称为纳米碳管(carbonnanotube)的中空的多层管状物。1992年Ebbesen等人 [2]发现了大量合成这种纳米管的方法。 相似文献
11.
The preparation and properties as well as some reactions of a series of arylcarbonylbis(triphenylphosphine)iridium(I) complexes [Ir(Ar)(CO)(PPh 3) 2] (Ar = C 6H 5, C 6F 5, 2-C 6H 4CH 3, 3-C 6H 4CH 3, 4-C 6H 4CH 3, 2-C 6H 4OCH 3, 2,6-C 6H 3-(OCH 3) 2, 4-C 6H 4N(CH 3) 2, 3-C 6H 4Cl, 4-C 6H 4Cl, 4-C 6H 4Cl, 3-C 6H 4CF 3, 4-C 6H 4CF 3) are described, and the most important IR data as well as the 31P NMR parameters of these, without exception trans-planar, compounds are given. Some of the complexes react with molecular oxygen to form well defined dioxygen adducts [Ir(Ar)(O2)(CO)(PPh3)2] (Ar = C6H5, 3-C6H4CH3, 4-C6H4CH3). Complexes with ortho-substituted aryl ligands are not oxygenated. This effect is referred to as a steric shielding of the metal center by the corresponding ortho-substituents. With SO2 the similar irreversible addition compound [Ir(4-C6H4CH3)-(SO2)(CO)(PPh3)2] is obtained. Sulfur dioxide insertion into the Ir---C bond cannot be observed. The first step of the reaction between [Ir(4-C6H4CH3)(CO)(PPh3)2] and hydrogen chloride involves an oxidative addition of HCl to give [Ir(H)(Cl)(4-C6-H4CH3)(CO)(PPh3)2]. Ir---C bond cleavage by reductive elimination of toluene from the primary adduct does not occur except at elevated temperature. 相似文献
12.
CpCo(CO) 2 is oxidised by [Cp 2Fe]BF 4 (Cp = C 5H 5) in the presence of neutral ligands L to give the dications [CpCoL 3] 2+ (L = SMe 2, S(n-C 4H 9) 2, PMe 3, C 5H 5N, MeCN; Me = CH 3). In [CpCo(SMe 2) 3] 2+, sulfane ligands are substituted by neutral ligands L, L---L and L---L---L, to give the complexes [CpCoL 3] 2+ (L = SeMe 2, TeMe 2, PMe 3, P(OMe) 3, AsMe 3, SbMe 3, t-C 4H 9NC, C 5H 5N, MeCN), [Cp-Co(L---L)SMe 2] 2+ (L---L = R 2P(CH 2) nPR 2, n = 1, 2, R = C 6H 5; bipyridine, o-phenanthroline, neocuproin) and [CpCo(L---L---L)] 2+ (L---L---L = RP(CH 2CH 2PR 2) 2, R = C 6H 5). The dications react with iodide resulting in the monocations [CpCoL 2I] + and [CpCo(L---L)I] +. Azacobaltocinium cations [CpCo(C 4R 2H 2N)] + (R = H, CH 3) are obtained by reaction of [CpCo(SMe 2) 3] 2+ with metal pyrrolides. 相似文献
13.
Liquid crystalline 4-XC 6H 4N=NC 6H 4X-4′ [X = C 4H 9 (1a), C 1OH 21 (1b), OC 4H 9 (1c), OC 8H 17(1d)] can be easily prepared in high yields from the corresponding anilines. In order to study the influence of metals on the thermal properties of these materials, we have obtained adducts [AuCl 3(4-C 4H 9OC 6H 4N=NC 6H 4OC 4H 9-4′)] (2) and [Ag(OC1O 3)L 2] [L = 4-XC 6H 4N=NC 6H 4X-4′; X = OC 4H, (3a), OC 8H 17 (3b)]. The silver adducts show themotropic behaviour. Mercuriation of dialkylazobenzenes 1a-b takes place with [Hg(OAc) 2] and LiCl to give [Hg(R)Cl] [R = C 6H 3(N=NC 6H 4X-4′)-2, X-5; X = C 4H 9 (bpap) (4a), C 10H 21 (dpap) (4b)] while dialkoxyazobenzenes 1c–d require [Hg (OOCCF 3) 2] to obtain [Hg(R)Cl] [R = C 6H 3(N---NC 6H 4X-4′)-2, X-5; X = OC 4H 9 (bxpap) (4c), OC 8H 17 (4d)]. 4a-c react with NaI to give [HgR 2] [R= bpap (5a), dpap (5b), bxpap (5c), oxpap (5d)l. Both chloroaryl-, 4a and 4c, and diaryl-mercurials, 5a and 5c, act readily as transmetailating agents towards [Me 4N] [AuCl 4] in the presence of [Me 4N]Cl to give [Au(η 2-R)Cl 2] [R = bpap (6a), bxpap (6b)]. After reaction of [AuCl 3(tht)] (tht = tetrahydrothiophene) with [Me 4N]Cl and 4b (1:2:1), [Me 4N][Au(dpap)Cl 3] (7) can be isolated. C---H activati bxpap (8b)]. None of the complexes 4–8 shows mesomorphic behaviour. 相似文献
14.
合成了4个新型NiBDT配位化合物,BDT为具有9个S原子的杂戊烯.元素分析、IR谱、UV谱确定这4个新配合物的化学式分别为[(CH 3) 4N] 2[Ni(C 5S 9) 2](1),[(C 2H 5) 4N] 2·[Ni(C 5S 9) 2](2),[(C 4H 9) 4N] 2[Ni(C 5S 9) 2](3),[(C 6H 5)(CH 3) 3N] 2[Ni(C 5S 9) 2](4).采用Ito法对配合物1的X射线粉末图进行了指标化,确定该晶体属单斜晶系,简单晶格,晶胞参数:a=0.680nm,b=0.714nm,c=2.302nm,γ=111.4°,Z=2. 相似文献
15.
早期合成的Keggin结构杂多酸均是同种齿顶原子,后来人们合成了一系列含两种齿顶原子的三元杂多酸~[1,2],我们曾制备了含3种齿顶原子的四元杂多酸~[3,4].随着齿顶原子种类的增多,杂多酸在水溶液中的稳定性降低.本文采用空缺杂多酸阴离子逐步与不同齿顶原子结合,最后用溶解度极小的(C_1H_9)_4N~+盐沉淀方法合成了未见报道的磷的四元杂多酸盐. 相似文献
16.
The dimethylphosphino substituted cyclopentadienyl precursor compounds [M(C 5Me 4CH 2PMe 2)], where M=Li + (1), Na + (2), or K + (3), and [Li(C 5H 4CR′ 2PMe 2)], where R′ 2=Me 2 (4), or (CH 2) 5 (5), [HC 5Me 4CH 2PMe 2H]X, where X −=Cl − (6) or PF 6− (7) and [HC 5Me 4CH 2PMe 2] (8), are described. They have been used to prepare new metallocene compounds, of which representative examples are [Fe(η-C 5R 4CR′ 2PMe 2) 2], where R=Me, R′=H (9); R=H and R′ 2=Me 2 (10), or (CH 2) 5 (11), [Fe(η-C 5H 4CMe 2PMe 3) 2]I 2 (12), [Fe{η-C 5Me 4CH 2P(O)Me 2} 2] (13), [Zr(η-C 5R 4CR′ 2PMe 2) 2Cl 2], where R=H, R′=Me (14), or R=Me, R′=H (15), [Hf(η-C 5H 4CMe 2PMe 2) 2]Cl 2] (16), [Zr(η-C 5H 4CMe 2PMe 2) 2Me 2] (17), {[Zr(η-C 5Me 4CH 2PMe 2) 2]Cl}{(C 6F 5) 3BClB(C 6F 5) 3} (18), [Zr{(η-C 5Me 4CH 2PMe 2) 2Cl 2}PtI 2] (19), [Mn(η-C 5Me 4CH 2PMe 2) 2] (20), [Mn{(η-C 5Me 4CH 2PMe 2B(C 6F 5) 3} 2] (21), [Pb(η-C 5H 4CMe 2PMe 2) 2] (23), [Sn(η-C 5H 4CMe 2PMe 2) 2] (24), [Pb{η-C 5H 4CMe 2PMe 2B(C 6F 5) 3} 2] (25), [Pb(η-C 5H 4CMe 2PMe 2) 2PtI 2] (26), [Rh(η-C 5Me 4CH 2PMe 2)(C 2H 4)] 29, [M(η,κ P-C 5Me 4CH 2PMe 2)I 2], where M=Rh (30), or Ir, (31). 相似文献
17.
采用密度泛函理论(DFT)计算了MgAl-LDHs层板与无机阴离子(F -、Cl -、NO 3-、CO 32-、SO 42-)和有机阴离子(水杨酸根离子([HO(C 6H 4)COO] -)、苯甲酸根离子([(C 6H 5)COO] -)、对二甲氨基苯甲酸根离子([p-(CH 3) 2N(C 6H 4)COO] -)、十二烷基磺酸根离子[C 12H 25SO 3] -、己烷基磺酸根离子[C 6H 13SO 3] -、丙烷基磺酸根离子[C 3H 7SO 3] -)间的相互作用,获得稳定超分子几何结构及相互作用能。层板主体与客体间存在较强的超分子作用,包括主客体间静电作用和氢键等。主、客体间相互作用能数值大小顺序为CO 32- > SO 42- > F -> Cl -> NO 3-;[p-(CH 3) 2N(C 6H 4)COO] -> [(C 6H 5)COO] -> [HO(C 6H 4)COO] -和[C 12H 25SO 3] -> [C 6H 13SO 3] - > [C 3H 7SO 3] -。另外,还采用自然键轨道(NBO)计算和分析了LDHs 层板与阴离子间作用机理,从二阶微扰理论计算得到的稳定化能变化趋势与相互作用能数据基本吻合。 相似文献
18.
The coordinatively unsaturated uranium(IV) complex U[N(C 6H 5) 2] 4 has been prepared via the stoichiometric reaction of diphenylamine with [(Me 3Si) 2N] 2
H 2. U[N(C 6H 5) 2] 4 coordinates Lewis bases such as Et 2O, THF, pyridine or (EtO) 3PO, based on electronic absorption spectroscopy and 1H NMR studies. Exchange between U[N(C 6H 5) 2] 4 and U[N(C 6H 5) 2] 4(L), where L is THF or pyridine, is rapid on the NMR time-scale between 307 and 323 K. Measurement of equilibrium constants for L = THF provides Δ H and Δ S values of −60 kJ mol −1 and −1.8 × 10 2 J K −1 mol −1, respectively. U[N(C 6H 5) 2] 4 coordinates and binds (EtO) 3PO much more tightly ( Keq = & > 10 4 M −1) than THF or pyridine with the exchange rate between U[N(C 6H 5) 2] 4 and U[N(C 6H 5) 2] 4[OP(OEt) 3] being close to the NMR time-scale. 相似文献
19.
From the reaction of MeReO 3 with the neutral arylamine C 6H 5CH 2NMe 2 and the aryldiamine C 6H 4(CH 2NMe 2) 2−1,3, have been isolated in good yields the 1/1 adduct complex [MeReO 3 · C 6H 5CH 2NMe 2], 1, and the 2/1 adduct complex [(MeReO 3) 2 · C 6H 4(CH 2NMe 2) 2− 1,3], 2, respectively. The X-ray molecular structure of 2 shows that both rhenium centres have a trigonal bipyramidal geometry and in the axial positions of each rhenium centre are one of the NMe 2 units of the aryldiamine ligand and a methyl group. The mono(ortho)-chelated arylaminorhenium trioxide complex [ReO 3(C 6H 4CH 2NMe 2−2], 3, can be synthesized by a transmetallation reaction of ClReO 3 with [ZnC 6H 4CH 2NMe 2−2 2] in a 2:1 molar ratio. In a similar way the bis(ortho)-chelated arylaminorhenium trioxide complex [ReO 3C 6H 3(CH 2NMe 2) 2−2,6], 4, can be synthesized by addition of a mixture of [Li 2C 6H 3(CH 2NMe 2) 2−2,6 2] and ZnCl 2 to ClReO 3. Complexes 3 and 4 have been isolated as white solids in 66% and 81% yields respectively. The rhenium centre in complex 4 has a bicapped tetrahedral geometry in which the monoanionic C 6H 3(CH 2NMe 2) 2−2,6 − ligand is pseudo-facially bonded with a characteristic N1-Re-N2 angle of 107.7(3)°, a Re-C ipso bond length of 2.112(11) Å and Re-N1 and Re-N2 bond lengths of 2.518(9) Å and 2.480(8) Å respectively. 相似文献
20.
The synthesis of cyclopentadienyl complexes containing polydentate C 5R 4(CH 2CH 2NMe 2) ligands (R = H, Me) and Group 13 elements (Al, Ga, In) is described. The compounds (C 5Me 4CH 2CH 2NMe 2) AlX 2 (X = Me, Cl, Br, I), (C 5Me 4CH 2CH 2NMe 2)MCl 2 (M = Ga, In), (C 5H 4CH 2CH 2NMe 2)AlX 2 (X = H, Me, Et, Cl), (C 5H 4CH 2- CH 2NMe 2)GaCl 2,and (C 5H 4CH 2CH 2NMe 2)InMe 2 are obtained by three different procedures. All compounds that have been characterized, so far, by X-ray diffraction studies show an additional intramolecular coordination of the nitrogen atom in the side chain. Monomeric structures and sufficient volatilities make them potential candidates for MOCVD processes. 相似文献
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