Phase carbonyl derivatives

Withers, H.P., Eliezer, K.F., and Mitchell, J.W. 1990. Slurry-phase Fischer-Tropsch synthesis and kinetic studies over supported cobalt carbonyl derived catalysts. Ind. Eng. Chem. Res. 29 1807-14. 

Thiocarbonyl compounds are converted into the corresponding carbonyl derivatives in good yield (70-99%) by their reaction with concentrated aqueous sodium hydroxide and dichloromethane in the presence of tetra-n-butyiammonium hydrogen sulphate [4], The reaction is general for thioeslers, thioamides, thioureas and thiones (Table 3.28), and no reaction occurs in the absence of the phase-transfer catalysts. The reaction is also aided by the initial 5-methylation of the thiocarbonyl group [5]. 

Aqueous NaOH (5M, 20 ml) and TBA-HS04 (0.17 g, 0.5 mmol) and CH2C12 (25 ml) are stirred at room temperature for 30 min. The thiocarbonyl compound (ca. 0.2 g) in CH2C12 (2 ml) is added and the mixture is stirred for a further period of time. The organic phase is separated, washed well with aqueous HC1 (2 M) and water, dried (MgS04), and evaporated to yield the carbonyl derivative. 

Table 4.1-6 Characteristic frequencies of carbonyl derivatives X-CO-Y in a condensed undiluted phase, in cm ...

Certain aromatic compounds containing alkyl groups have been converted to carbonyl derivatives by liquid-phase oxidation of these groups with air in the presence of chromium oxide catalysts. 

I n this chapter we include the first compilation of reported absolute intensity data for metal carbonyl species. We have attempted to refer this data to a common set of units but the literature contains ambiguities which it has not always proved possible to resolve. Absolute intensity data such as these provide an indication of the extent to which the vibrations of a metal carbonyl derivative are affected by the solvent in which they are studied. Present indications are that solvent-solute interactions are of prime importance and it would be most useful to have gas-phase absolute intensity data with which to compare solution measurements. 

Hydrogenation with homogeneous catalysis has received increasing attention over the last few decades. Hexarhodium hexadecacarbonyl (181 Scheme 35) under water gas shift conditions forms 1,2,3,4-tetrahydroquinoline (128) or N-formyl-1,2,3,4-tetrahydroisoquinoline (182) with the parent hete-roaromatic. When hydrogen is substituted for carbon monoxide, 4-methylquinoline is reduced to 4-methyl-5,6,7,8-tetrahydroquinoline (183) exclusively.Isoquinoline behaves similarly generating A/-formyl-l,2,3,4-tetrahydroisoquinoline (184). Similar reductions under water gas shift or synthesis gas conditions using transition metal carbonyls derived from Mn, Co and Fe, have been recorded.Promotion by phase transfer agents is observed in some cases. 

Adams, G. W., Bowie, J. H., Hayes, R. N. The complex anionic rearrangements of deprotonated a-oximino carbonyl derivatives in the gas phase. J. Chem. Soc, Perkin Trans. 21991,1809-1818. 

Benzyl- and phenylacetyl derivatives of tetracarbonylcobalt(I) are believed to be important intermediates in the cobalt-catalyzed carbonylation of benzyl halides to phenylacetic acidi2twi and to phenylpyruvic acid ", carried out under phase transfer catalysis in the presence of catalytic amounts of a cobalt-carbonyl derivative. The carbonylation to phenylacetic acid proceeds as follows ... 

Asymmetric alkylation of P-keto carbonyl derivatives under phase-transfer conditions is a very convenient and useful way to construct a chiral quaternary carbon center. In 2002, Dehmlow and coworkers reported the asymmetric benzylation of the cyclic (3-ketoester, 2-(tert-butoxycarbonyl)cyclopentanone (70) in the presence of the cinchoninium PTC 72 in excellent chemical yield with 46% ee (Scheme 6.21) [46]. 

Isomerisation of a-acetylenic alcohols into a,P-ethylenic carbonyl derivatives in vapor phase... 

The rearrangement of a-acetylenic alcohols into a-p ethylenic carbonyl derivates has been extensively studied. Different catalysts have been proposed acid catalysts such as sulfuric, hydrochloric or acetic acids which give rise to unselective rearrangements [1,2] and more recently, oxo derivatives of vanadium, molybdenum or tungsten in liquid phase [3]. 

General discussion of intra- and intermolecular interactions 3 van der Waals interactions 3 Coulombic interactions 5 Medium effects on conformational equilibria 5 Quantum mechanical interpretations of intramolecular interactions 7 Methods of study 8 Introduction 8 Nmr and esr spectroscopy 8 Microwave spectroscopy (MW) 12 Gas-phase electron diffraction (ED) 12 X-ray crystallographic methods 13 Circular-dichroism spectroscopy and optical rotation 14 Infrared and Raman spectroscopy 18 Supersonic molecular jet technique 20 Ultrasonic relaxation 22 Dipole moments and Kerr constants 22 Molecular mechanic calculations 23 Quantum mechanical calculations 25 Conformations with respect to rotation about sp —sp bonds 27 Carbon-carbon and carbon-silicon bonds 28 Carbon-nitrogen and carbon-phosphorus bonds 42 Carbon-oxygen and carbon-sulphur bonds 48 Conformations with respect to rotation about sp —sp bonds Alkenes and carbonyl derivatives 53 Aromatic and heteroaromatic compounds 60 Amides, thioamides and analogues 75 Conclusions 83 References 84... 

Commonly utilized starting transition metal materials are oxides, halides, salts of fatty acids, complexes containing sulfur, etc. The role of the reducing agents is to lower the oxidation state of a metal and not to reduce the compound to an active metallic phase because this would, in most cases, lead to the inhibition of the reaction as shown by thermodynamic calculations. This point is also indicated by the formation of carbonyl derivatives possessing CO and other coordinating ligands as intermediates. 

The benzoic acid derivative 457 is formed by the carbonylation of iodoben-zene in aqueous DMF (1 1) without using a phosphine ligand at room temperature and 1 atm[311]. As optimum conditions for the technical synthesis of the anthranilic acid derivative 458, it has been found that A-acetyl protection, which has a chelating effect, is important[312]. Phase-transfer catalysis is combined with the Pd-catalyzed carbonylation of halides[3l3]. Carbonylation of 1,1-dibromoalkenes in the presence of a phase-transfer catalyst gives the gem-inal dicarboxylic acid 459. Use of a polar solvent is important[314]. Interestingly, addition of trimethylsilyl chloride (2 equiv.) increased yield of the lactone 460 remarkabiy[3l5]. Formate esters as a CO source and NaOR are used for the carbonylation of aryl iodides under a nitrogen atmosphere without using CO[316]. Chlorobenzene coordinated by Cr(CO)j is carbonylated with ethyl formate[3l7]. 

The alkyl derivatives of thiazoles can be catalytically oxidized in the vapor phase at 250 to 400°C to afford the corresponding formyl derivatives (21). Molybdenum oxide, V2O5, and tin vanadate are used as catalysts either alone or with a support. The resulting carbonyl compounds can be selectively oxidized to the acids. 

The Diacel columns can be used for the separation of a wide variety of compounds, including aromatic hydrocarbons having hydroxyl groups, carbonyls and sulfoxides, barbiturates, and P-blockers (35,36). There are presendy nine different cellulose derivative-based columns produced by Diacel Chemical Industries. The different columns each demonstrate unique selectivities so that a choice of stationary phases is available to accomplish a separation. 

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