33424-83-8Relevant articles and documents
Synthesis of rodlike dispiro hydrocarbon skeletons for new liquid crystal compounds
Feuerbacher, Nina,Voegtle, Fritz,Windscheidt, Jens,Poetsch, Eike,Nieger, Martin
, p. 117 - 120 (1999)
A simple synthesis of the dispiro[5.2.5.2]hexadecane skeleton was developed. Starting from the cyclohexanedicarbaldehyde 6 the dispirane was prepared in one step. The synthesised dispirodiketone 4 is a key compound for the preparation of a number of new l
Highly efficient transformation of alcohol to carbonyl compounds under a hybrid bifunctional catalyst originated from metalloporphyrins and hydrotalcite
Zhou, Wei-You,Tian, Peng,Sun, Fu'An,He, Ming-Yang,Chen, Qun
, p. 105 - 116 (2016/01/26)
The development of a highly active and selective catalytic system that is economical, environmentally benign, and easily recoverable is highly desirable. Bifunctional hybrid catalysts originated from metalloporphyrins (MTSPP; M = Co, Fe, and Mn), and hydrotalcite have been synthesized, characterized, and investigated in the aerobic oxidation of alcohols in the presence of isobutyraldehyde. The designed catalysts exhibited excellent activity, broad applicable scope, and good stability in the oxidation. The effect of surface basicity on the catalytic performance has been studied in detail. The research results showed that as well as protecting the metalloporphyrin molecule, the surface basicity of hydrotalcite also contributed to improving the catalytic activity and the selectivity of aldehyde, and a synergistic effect was observed in the catalytic system. A proposed mechanism for the reaction involving the formation of high-valence cobalt-oxo porphyrin intermediate was postulated based on catalytic results and Hammett and H218O experiments.
The competitive and non-competitive hydroformylation of conjugated dienes starting with tetrarhodium dodecacarbonyl. An in-situ high-pressure infrared spectroscopic study
Liu, Guowei,Garland, Marc
, p. 76 - 85 (2007/10/03)
It is well known that the liquid-phase homogeneous unmodified rhodium catalysed hydroformylation of alkenes is poisoned by the presence of trace quantities of conjugated dienes. Nevertheless, some hydroformylation of conjugated dienes is possible with unmodified rhodium, and this reaction is in general slower than alkene hydroformylations at comparable reaction conditions. In the present contribution, we examined (A) the catalytic behaviour of alkenes in the presence of trace conjugated diene impurities and (B) the catalytic behaviour of a variety of dienes using Rh4(CO)12 in n-hexane solvent at 293 K under 1.0-4.0 MPa CO and 0.5-2.0 MPa H2. The analytic method was in-situ high-pressure infrared spectroscopy. It was observed that (I) in the hydroformylation of poisoned alkenes, most of the rhodium reacts with the trace quantity of conjugated dienes and not the alkenes in this competitive situation and (II) the metal carbonyl spectra of the hydroformylation of a variety of dienes are very similar. The primary absorbance maxima observed in the hydroformylations of conjugated dienes occur at circa 2109, 2091, 2087, 2064, 2049, 2037, 2030, 2020, 2012, 1999, and 1990 cm-1. Given the known chemistry Of Rh4(CO)12 under syngas, and the very well documented chemistry of Rh4(CO)12 under alkene hydroformylation conditions, the lack of bridging carbonyls in the present experiments strongly suggested that the new infrared vibrations are due to mononuclear rhodium species. Preliminary analysis suggests the presence of at least three new species. In particular, the formation of observable η3 allyl rhodium tricarbonyl species, σ allyl rhodium tetracarbonyl species and even acyl rhodium tetracarbonyl species RCORh(CO)4 (R = alkenyl and/or formylalkyl) seems probable. Characteristic wavenumbers of 2108, 2064, 2037, 2020 and 1700 cm-1 are tentatively assigned to the latter. The reduced hydroformylation activity in the competitive hydroformylation of alkenes arises due to the much higher affinity of rhodium complexes for conjugated dienes than for alkenes under otherwise similar reaction conditions.