The cyclodimerisation of 3-methyl-2-butenenitrile

3-Methyl-2-butenenitrile (1) cyclodimerised on treatment with lithium diisopropylamide in dimethoxyethane at temperatures between ?78°C and 0°C to 3-amino-4-cyano-1,5,5-trimethyl-1,3-cyclohexadiene (2) the structure of which was established by acid hydrolysis to the known 4-cyano-1,5,5-trimethyl-1-cyclohexene-3-one (3).     

Conical parametric scattering of a single extraordinary beam in BaTiO3 crystal

In this paper, the parametric scattering of a single extraordinary polarized beam of laser in BaTiO₃ photorefractive crystal has been investigated experimentally and theoretically. The resulting pattern consists of beam fanning, isotropic ring, and anisotropic one. Among all parts of scattering pattern, isotropic ring has not been studied as much as beam fanning and anisotropic ring, and there still are some differences in reports about it. Therefore, the study has mainly focused on this part. In this experimental configuration, isotropic ring is just visible in positive angles although the other parts of parametric scattering pattern can be visible from behind and in front of the crystal. In addition to steady state pattern in forward and backward directions, its transient behavior with the rotation of crystal has been studied. The results of experiments have been analyzed carefully, and their theoretical explanations have been presented based on the standard theory of parametric scattering in photorefractive crystals. It has been shown that this configuration corresponds to the so called parametric B-process scattering.     

The Preparation of a New Kind of Carbosilane Dendrimer with 4‐(Naphthalen‐1‐yl)phenyl Core‐An Application of Suzuki Coupling Reaction

Using the divergent method, carbosilane dendrimers with p‐bromophenyl core were synthesized by using alternating Grignard and hydrosilylation reactions. And then, α‐naphthalenyl was connected to the core by using Suzuki coupling reaction. This gave a new carbosilane dendrimer with a 4‐(naphthalen‐1‐yl)phenyl core. All the products were characterized by IR, ¹H NMR, ¹³C NMR, ²⁹Si NMR, and MS. The study shows that Suzuki Coupling reaction is an effective and powerful core‐functionalization method and a satisfactory result can be achieved through prolonging the reaction time.     

Modular construction of dendritic carbosilanes. Organization Of dendrimer connectivity around bifunctional precursors that are adapted for sequential convergent and divergent propagative steps

Regiospecific hydrosilylation of 1-bromo-4-(prop-2-enyl)benzene offers an efficient route to molecular building block precursors that can accommodate sequential divergent and convergent steps for dendritic extension, establishing a modular methodology for assembly and organization of connectivity used for synthesis of modified carbosilane dendrimers including 14.     

Self-chemical ionization of diethylzinc

The self-chemical ionization of diethylzinc is examined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and semiempirical molecular orbital calculations. Electron impact of diethylzinc neutral produces the radical cation, C(4)H(15)Zn(+) (m/z x 122), which reacts further with the neutral (C(2)H(5))(2)Zn to give the following product ions: Zn(+) (m/z x 64), C(2)H(5)Zn(+) (m/z x 93), C(4)H(9)Zn(+) (m/z x 121), C(4)H(11)Zn(2)(+) (m/z x 187), and C(6)H(15)Zn(2)(+) (m/z x 215). To determine the structure and pathways for production of these ions, monoisotopic (12)C(4)H(15)(64)Zn(+), (64)Zn(+) and (12)C(2)H(5)(64)Zn(+) were individually isolated and reacted with the neutral background. We also performed semiempirical molecular orbital calculations (ZINDO/1). The molecular orbital calculations and experimental data are consistent in predicting that the ethyl group on the diethylzinc cation carries the positive charge. Copyright 1999 John Wiley & Sons, Ltd.     

Pyrazolyl-bridged iridium dimers. 18.(1) influence of metal-metal bonding on the geometry of diiridium(II) adducts and hydrido-diiridium complexes formed from the diiridium(I) prototype [Ir(mu-pz)(PPh(3))(CO)](2) (pzH = Pyrazole) by dihydrogen addition or protonation

Slow uptake of molecular dihydrogen by the diiridium(I) prototype [Ir(mu-pz)(PPh(3))(CO)](2) (1: pzH = pyrazole) is accompanied by formation of a 1,2-dihydrido-diiridium(II) adduct [IrH(mu-pz)(PPh(3))(CO)](2) (2), for which an X-ray crystal structure determination reveals that (unlike in 1) the PPh(3) ligands are axial, with the hydrides occupying trans coequatorial positions across the Ir-Ir bond (2.672 A). Reaction with CCl(4) effects hydride replacement in 2, affording the monohydride Ir(2)H(Cl)(mu-pz)(2)(PPh(3))(2)(CO)(2) (3) in which Ir-Ir = 2.683 A. At one metal center, H is equatorial and PPh(3) is axial, while at the other, Cl is axial as is found in the symmetrically substituted product [Ir(mu-pz)(PPh(3))(CO)Cl](2) (4) (Ir-Ir = 2.754 A) that is formed by action of CCl(4) on 1. Treatment of 1 with I(2) yields the diiodo analogue 5 of 4, which reacts with LiAlH(4) to afford the isomorph Ir(2)H(I)(mu-pz)(2)(PPh(3))(2)(CO)(2) (6) of 3 (Ir-Ir = 2.684 A). Protonation (using HBF(4)) of 1 results in formation of the binuclear cation Ir(2)H(mu-pz)(2)(PPh(3))(2)(CO)(2)(+) (7: BF(4)(-) salt), which shows definitive evidence (from NMR) for a terminally bound hydride in solution (CH(2)Cl(2) or THF), but 7 crystallizes as an axially symmetric unit in which Ir-Ir = 2.834 A. Reaction of 7 with water or wet methanol leads to isolation of the cationic diiridium(III) products [Ir(2)H(2)(mu-OX)(mu-pz)(2)(PPh(3))(2)(CO)(2)]BF(4) (8, X = H; 9, X = Me).     

Ring‐Closing Metathesis on an Allyl‐Terminated Carbosilane Dendrimer

Grubbs' catalyst was used to prepare a series of carbosilane dendrimers with silacyclopentene peripheral groups, suitable for further elaboration to functional dendrimers. The efficiency of the ring closing metathesis reaction was found to be strongly dependent on the reaction temperature and the amount of catalyst used, as shown by ¹H NMR monitoring.     

怀孕期头发中一些元素含量的变化趋势

用同步辐射激发X射线荧光分析,对11个产妇怀孕期间头发内一些元素含量的变化趋势进行了测量,在各自对比的基础上,得到了一些结果。