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141.
A continuous flow, microwave-assisted, parallel-capillary microreactor has been developed. Libraries of drug candidates were prepared on the milligram scale with this reactor by injecting plugs of reagents from separate syringes into common reaction capillaries, thereby producing discrete compounds in excellent yield and purity. Microwave irradiation provides the necessary energy that existing room-temperature microreactor technology lacks for higher activation barrier transformations, producing the required amounts of desired compounds in minutes or less. 相似文献
142.
Quantum equations of motion describing the energy transfer dynamics via intramolecular anharmonic coupling are presented and solved numerically. Dynamical features of the average excitations of a homogeneous system (SF6) and a heterogeneous system (H/W) are quantitatively discussed in terms of the intramolecular vibrational relaxation (IVR) rates. Possible mechanisms of surface-enhanced desorption via low-power laser radiation are proposed.This work was supported in part by the Office of Naval Research, the Air Force Office of Scientific Research (AFSC), United States Air Force, under Grant AFOSR-82-0046 and the National Science Foundation under Grant No. CHE-8022874Camille and Henry Dreyfus Teacher-Scholar (1975–82) 相似文献
143.
Robert Kolodziuk Mustapha Tollabi Catherine Goux-Henry Denis Sinou 《Journal of organometallic chemistry》2003,687(2):384-391
Carbohydrate-substituted phosphines are easily obtained in quite good yields by coupling of protected or non-protected d-glucosamine with the corresponding diphenylphosphino acid. These neutral ligands, in association with palladium acetate, are very active catalysts in the Suzuki cross-coupling reaction. The polyhydroxy phosphines are more active than the peracetylated phosphines. The process tolerates electron-rich as well as electron-poor substituents. Excellent turnovers, up to 97?000 are observed. 相似文献
144.
Stereochemistry of 7-aryl-1,7,8,8a-tetrahydro-3(2H)-indolizinones was studied by1H and13C NMR. Complete assignment of1H NMR signals and analysis of1H-1H coupling constants were performed using the iterative PANIC program. Values of3
J
6,7,3
J
7,8endo, and4
J
5,7 allow one to unambiguously identify the correspondingexo- andendo-stereoisomers. For stereoisomers with exo-orientation of H(7), complete assignment of13C NMR signals was performed on the basis of analysis of the13C-1H coupling constants using two dimensional heteronuclear shift-correlating spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 591–593, March, 1996. 相似文献
145.
Kaspar Bott 《Angewandte Chemie (International ed. in English)》1980,19(3):171-178
Numerous additions of carbocations to chloroolefins or acetylenes can be coupled with a solvolysis step when performed in a suitable acid; the products are variously substituted carboxylic acids, aldehydes, and ketones. Factors determining the success of these syntheses are the stability of the intermediate carbocations and suppression of the competing addition of protons to the unsaturated reaction component. Under the conditions of the Tscherniac-Einhorn reaction, amidomethylation of chloroolefins and acetylenes, i.e. the introduction of acylaminomethyl groups, is shown not to involve a trigonal α-chloro carbocation or a linear vinyl cation, but instead to proceed via a cyclic oxazinium ion intermediate. 相似文献
146.
J. C. Daran E. Gilbert M. Gouygou S. Halut B. Heim Y. Jeannin 《Journal of Cluster Science》1994,5(3):373-400
The diiron ynamine complex [Fe2(CO)7{-C(Ph)C(NEt2)}] (1) reacts with the diphenylbuta-1, 4-diyne, PhCC-CCPh, in refluxing hexane to yield three isomer complexes [Fe2(CO)6{C(Ph)C(NEt2)C(Ph)C(C2Ph}] (2a), [Fe2(CO)6{C(Ph)C(NEt2)C(C2Ph)C(Ph)}] (2b), and [Fe2(CO)6{NEt2)C(Ph)C(C2)C(Ph)}] (2c) All three compounds were identified by their1H NMR spectra. Compounds2a and2c were characterized by single crystal X-ray diffraction analyses. Crystal data: for2a: space group = P21/n,a = 17.873(1) Å, = 18.388(6) Å,c = 9.429(3) Å = 91.99(3)°,Z = 4.3751 reflections,R = 0.044; for2c: space group = P21/n,a = 40.58(2) å,b = 12.101(9) Å,c = 12.551(5) Å, = 94.29(7)°,Z = 8.4723 reflection,R = 0.076. Complexes2a and2b result from a [2 + 2] cycloaddition between one of the CC triple bonds of the diyne ligand and the FeC carbene bond, whereas2c results from insertion of one of the CC group into the bridging carbene. Addition of [Fe2(CO)9] on2a gave two major products, the tripledecker [Fe3(CO)8{C(Ph)C(NEt2)C(C2Ph)}], (3 and a tetrairon cluster [Fe4(CO)11{C(Ph)C(NEt2)C(Ph)C(C2Ph)}] (4). Both compounds were characterized by single crystal diffraction analyses. Crystal data: for3: space group = P21/n,a = 12.039(3) Å,b = 18.046(3) å,c = 15.270(2) Å, = 90.11(2)°,Z = 4, 1430 reflections,R = 0.067; for4 space group = C2/c,a = 18.633(3) Å,b = 21.467(1)_Å,c = 20.742(2) Å, = 115.03(8)°,Z = 8.992 reflections, R = 0.076. Complex4 is based on a spiked triangular cluster with the alkynyl triple bond attached in
3-parallel mode on the triangular grouping. 相似文献
147.
Kaupp M Patrakov A Reviakine R Malkina OL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(9):2773-2782
The characteristic dependence of J(31P,31P) spin-spin coupling constants of alkali metal tetraphosphane-1,4-diides on structure and composition has been analyzed by density functional methods. The computations confirm that the structure of the contact ion pairs is conserved in solution. Calculations on model systems M2P4H4, on naked P4H4(2-) anions, and on models including point charges, show that the role of the cations is mainly structural and to a smaller extent electrostatic. Three of the four J(P,P) coupling constants depend characteristically on the conformation of the anion, which in turn is determined by the substituents R and by cation-anion interactions. Several couplings exhibit a large through-space component and are thus strongly dependent on the relative orientation of nonbonding electron pairs on the phosphorus atoms involved. This is shown by visualization of coupling pathways using the recently introduced coupling energy density (CED), in combination with the electron localization function (ELF). 相似文献
148.
Manfred Schlosser 《Angewandte Chemie (International ed. in English)》1974,13(11):701-706
Merits and drawbacks of known carbon-carbon linking procedures are outlined. Two novel methods are discussed in some detail: the copper-catalyzed alkylation of Grignard reagents and reactions with allylpotassium compounds. Both methods provide a very efficient access to saturated, unsaturated, as well as functionally substituted hydrocarbons and moreover permit an astonishing degree of regio- and stereoselective control of olefin synthesis. 相似文献
149.
Alkylation of cyclohexenyl monoacetate 1 with R2Cu(CN)(MgCl)2 or RMgBr/CuCN (cat.) in Et2O produced trans 1,2-isomers 4, while arylation and alkenylation of 1 was accomplished with lithium borates 5 and a nickel cat. to afford trans 1,4-isomers 3 selectively. Furthermore, several transformations of the products were carried out to demonstrate synthetic advantages of the present reactions. 相似文献
150.
Nolde F Qu J Kohl C Pschirer NG Reuther E Müllen K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(13):3959-3967
Two new synthetic approaches to terrylenediimides, highly photostable fluorescent dyes, are described. For the first time terrylenediimide has been synthesised in a straightforward procedure that makes large quantities available. The second route includes an efficient cross-coupling reaction followed by a cyclodehydrogenation. Monofunctionalisation of the imide structure allows terrylenediimides now to be coupled with a variety of compounds, for example, by Suzuki cross-coupling, which can lead to an array of terrylenediimides with new functional groups such as hydroxy, amino, or carboxy groups needed to link up with other molecules. The functionalisation in the bay region is used to tune the properties of terrylenediimides and extend the range of applications, for example, by introducing water solubility. These tetrasubstituted terrylenediimides offer, depending on the substituents used, exciting features such as good solubility in common organic solvents, water solubility, or NIR absorption. 相似文献