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151.
Nitrosyl chloride is only chlorinating in darkness and above 100°. In the sun light and at room temperature it reacts as a chlorinating, nitrosating, nitrating and oxidizing agent. With trichlorethylene in fact pentachlorethane 1,1,1,2-tetrachloro-2-nitrosoethane, 1,1,1,2-tetrachloro-2-nitroethane, dichloracetic acid and a compound of empirical formula C4H2Cl5NO2 are obtained. Tetrachloroethylene carried to hexachlorethane, pentachloronitrosoethane and tetrachloro-2-(pentachlorethyl)-1,2-oxazetidine. Introduced nitrosyl chloride provided nitrogen monoxide prouved by gaz chromatography. This monoxide reacted afterwards to give nitrogen which is the single nitrogenous gazeous compound. Carbondioxide is a minor component of the gaz. 相似文献
152.
Half-sandwich complexes of the type [(RCOCp)M(CO)(3)] with M = Re and (99(m))Tc were synthesized from [M(OH(2))(3)(CO)(3)](+) in water. The R group can be an organic residue or a receptor binding biomolecule with a spacer to cyclopentadienyl (Cp). This provides a general route to Cp complexes of technetium without the need for starting from [TcBr(CO)(5)]. The X-ray structure of [(C(6)H(5)CH(2)COC(5)H(4))Tc(CO)(3)] has been elucidated. The compound crystallizes in the monoclinic space group P2(1)/c with a = 16.1454(9), b = 7.6300(6), and c = 12.3922(7) A and beta = 107.792(6) degrees. We have chosen a serotonergic receptor ligand (WAY) as an example for the derivatization of Cp with a bioactive molecule. WAY is linked to Cp by an aliphatic chain of variable length. The half-sandwich complexes were prepared from water and organic solvents. The structure of [(WAY4-Cp)Re(CO)(3)] could be elucidated. The compound crystallizes in the monoclinic space group P2(1)/c with a = 15.7112(6), b = 6.8775(3), and c = 25.5217(12) A and beta = 103.778(5) degrees. Quantification of inhibition constants gave a clear structure-activity relationship. A single methylene group between the receptor binding site and the half-sandwich complex gave an IC(50) of 217 nM for HT(1A), whereas a butylene linker resulted in retention of the inhibition constant with an IC(50) of 6 nM with respect to underivatized WAY. For use as radiopharmaceuticals, the compounds have also been prepared with (99m)Tc in quantitative yield. 相似文献
153.
Christian Roussel Alexandru T. Balaban Ulf Berg Michel Chanon Roger Gallo Gerd Klatte Joseph A. Memiaghe Jacques Metzger Daniela Oniciu Johanna Pierrot-Sanders 《Tetrahedron》1983,39(24):4209-4219
The effect of the shape of a methyl group on reactivity, which cannot be accounted for by considering a methyl group as a spherical substituent with the appropriate van der Waals radius, was considered in kinetics of alkylalion of substituted pyridines and barriers to rotation and ground state conformations of an isopropyl group attached to a planar framework. The perturbation of a methyl group by an o-methyl group is accounted for by a unique conformational explanation which involves the polyhedral shape of the methyl group. 相似文献
154.
Matthew R. Wood Thomas A. Brettell Roger A. Lalancette 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(2):m33-m35
The title salt, methyl (1R,2R,3S,5S,8S)‐3‐benzoyloxy‐8‐methyl‐8‐azabicyclo[3.2.1]octane‐2‐carboxylate tetrachloroaurate(III), (C17H22NO4)[AuCl4], has its protonated N atom intramolecularly hydrogen bonded to the O atom of the methoxycarbonyl group [N⋯O = 2.755 (6) Å and N—H⋯O = 136°]. Two close intermolecular C—H⋯O contacts exist, as well as five C—H⋯Cl close contacts. The [AuCl4]− anion was found to be distorted square planar. 相似文献
155.
Rate constants for the reactions of OH radicals and NO3 radicals with dimethyl phosphonate [DMHP, (CH3O)2P(O)H], dimethyl methylphosphonate [DMMP, (CH3O)2P(O)CH3], and dimethyl ethylphosphonate [DMEP, (CH3O)2P(O)C2H5] have been measured at 296 +/- 2 K and atmospheric pressure using relative rate methods. The rate constants obtained for the OH radical reactions (in units of 10(-12) cm3 molecule(-1) s(-1)) were as follows: DMHP, 4.83 +/- 0.25; DMMP, 10.4 +/- 0.6; and DMEP, 17.0 +/- 1.0, with a deuterium isotope effect of k(OH + DMMP)/k(OH + DMMP-d9) = 4.8 +/- 1.2. The rate constants obtained for the NO3 radical reactions (in units of 10(-16) cm3 molecule(-1) s(-1)) were as follows: DMHP, < 1.4; DMMP, 2.0 +/- 1.0; and DMEP, 3.4 +/- 1.4. Upper limits to the rate constants for the O3 reactions of < 8 x 10(-20) cm3 molecule(-1) s(-1) for DMHP and < 6 x 10(-20) cm3 molecule(-1) s(-1) for DMMP and DMEP were determined. Products of the reactions of OH radicals with DMHP, DMMP, and DMEP were investigated in situ using atmospheric pressure ionization mass spectrometry (API-MS) and, for the DMMP and DMEP reactions, Fourier transform infrared (FT-IR) spectroscopy. API-MS analyses showed the formation of products of molecular weight 96 and 126, attributed to CH3OP(O)(H)OH and (CH3O)2P(O)OH, respectively, from DMHP; of molecular weight 110, attributed to CH3OP(O)(CH3)OH, from DMMP; and of molecular weight 124 and 126, attributed to CH3OP(O)(C2H5)OH and (CH3O)2P(O)OH, respectively, from DMEP. FT-IR analyses showed formation (values given are % molar yields) of the following: from DMMP, CO, 54 +/- 6; CO2, 5 +/- 1 in dry air; HCHO, 3.9 +/- 0.7; HC(O)OH, < 1.4 in dry air; RONO2, approximately 4; and formate ester, approximately 8; and from DMEP, CO, 50 +/- 7; CO2, 11 +/- 4; CH3CHO, 18 +/- 8; HCHO, < 7; HC(O)OH, < 6; RONO2, < or = 5; and formate ester, 5.0 +/- 1.5. Possible reaction mechanisms are discussed. 相似文献
156.
157.
158.
A simple and efficient synthesis of the title compounds by modified Grignard methodology is described. 相似文献
159.
Nigel M. Groome Elghareeb E. Elboray Dr. Martyn W. Inman Prof. H. Ali Dondas Dr. Roger M. Phillips Colin Kilner Prof. Ronald Grigg 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(6):2180-2184
Naturally occurring indole‐3‐carbinol and 3,3‐diindolylmethane show bioactivity in a number of disparate disease areas, including cancer, prompting substantial synthetic analogue activity. We describe a new approach to highly functionalised derivatives that starts from allene gas and proceeds via the combination of a three‐component Pd0‐catalysed cascade with a one‐pot, three‐component carbophilic PtII cascade linked to a stereoselective acid‐catalysed Mannich–Michael reaction that generates complex cyclopropyl diindolylmethanes which show selective activity against prostate cancer cell lines. 相似文献
160.
Andrzej Chmura Sven Rustler Monica Paravidino Fred van Rantwijk Andreas Stolz Roger A. Sheldon 《Tetrahedron: Asymmetry》2013,24(19):1225-1232
Enantiomerically pure (S)-mandelic acid was synthesised from benzaldehyde by sequential hydrocyanation and hydrolysis in a bienzymatic cascade at starting concentrations up to 0.25 M. A cross-linked enzyme aggregate (CLEA) composed of the (S)-selective oxynitrilase from Manihot esculenta and the non-selective nitrilase from Pseudomonas fluorescens EBC 191 was employed as the biocatalyst. The nitrilase produces approx. equal amounts of (S)-mandelic acid and (S)-mandelic amide from (S)-mandelonitrile under standard conditions, but we surprisingly found that high (up to 0.5 M) concentrations of HCN induced a marked drift towards amide production. By including the amidase from Rhodococcus erythopolis in the CLEA we obtained (S)-mandelic acid as the sole product in 90% yield and >99% enantiomeric purity. 相似文献