Carbonyls lability

Fischer s carbyne complexes are thermally labile (facile loss of CO) and decompose bimolecularly with formation of alkynes. This carbonyl lability may be traced to the strong Tt-acidity of the carbyne ligand, which compromises retrodonation to the carbonyl ligands. On treatment with donor ligands, however, thermally stable substituted derivatives may be obtained (Figure 5.36). 

Active Raney nickel induces desulfurization of many sulfur-containing heterocycles thiazoles are fairly labile toward this ring cleavage agent. The reaction occurs apparently by two competing mechanisms (481) in the first, favored by alkaline conditions, ring fission occurs before desul-, furization, whereas in the second, favored by the use of neutral catalyst, the initial desulfurization is followed by fission of a C-N bond and formation of carbonyl derivatives by hydrolysis (Scheme 95). 

With palladium chloride catalyst, carbon monoxide, and an alcohol the labile hydroxyl is alkylated during carbonylation (199). 

Unlike ethynylation, in which acetylene adds across a carbonyl group and the triple bond is retained, in vinylation a labile hydrogen compound adds to acetylene, forming a double bond. 

Cross-linked PVP can also be obtained by cross-linking the preformed polymer chemically (with persulfates, hydrazine, or peroxides) or with actinic radiation (63). This approach requires a source of free radicals capable of hydrogen abstraction from one or another of the labile hydrogens attached alpha to the pyrrohdone carbonyl or lactam nitrogen. The subsequently formed PVP radical can combine with another such radical to form a cross-link or undergo side reactions such as scission or cyclization (64,65), thus ... 

The 9ai7-quinolizine structure (82) for the labile adduct from 3,5-dimethylpyridine was clearly established by the nuclear magnetic resonance studies of Richards and Higham, and subsequent work showed the labile adduct from 3-methylpyridine was analogous. As the labile adducts from all the pyridines and benzopyridines so far examined have very similar infrared absorption spectra in the 5-7 yn. (carbonyl and aromatic) region and within quite close limits very similar ultraviolet absorption spectra, it can be concluded that all are derivatives of 9aH-quinolizine,... 

Addition reactions of the a-seleno lithium reagent 26 to carbonyl compounds have been undertaken 27. The a-seleno lithium reagents are configurationally labile at — 78 °C 27 28 and, therefore, the diastereoselectivity observed with 26 ( 90 10) does not significantly depend on the nature of the electrophile but rather reflects the thermodynamic ratio of the diastereomeric lithium compounds. 

The limitations of the reaction have not been systematically investigated, but the inherent lability of the aziridines can be expected to become troublesome in the case of epoxyketones which are slow to form hydrazones. The use of acid catalysis is curtailed by the instability of the aziridines, particularly the diphcnylaziridine, in acidic media. Because of their solvolytic lability, the hydrazones are best formed in inert solvents. A procedure proven helpful in some cases is to mix the aziridine and the epoxyketone in anhydrous benzene, and then to remove the benzene on a rotary evaporator at room temperature. Water formed in the reaction is thus removed as the azeotrope. This process is repeated, if necessary, until no carbonyl band remains in the infrared spectrum of the residue. 

No comparative kinetic study has been made on the same alkyl carbonyl system for two members of a given transition metal triad. Qualitative data show that the middle member is more reactive than the heaviest one e.g., CpMo(CO)jR > CpW(CO)jR (Section VI,B), Rh(III) > Ir(III) (Section VI,E), and Pd(II) > Pt(II) (Section VI,F). However, the extreme unreactivity of CpW(CO)jR and a considerable difference in lability between most alkyls of Rh(III) and Ir(III), as well as those of Pd(II) and Pt(II), have prevented detailed investigations. Surprisingly, no kinetic studies have been conducted on insertion reactions of RRe(CO)5, which would seem readily amenable to such investigations. 

Poly (iminocarbonates) are little known polymers that, in a formal sense, are derived from polycarbonates by the replacement of the carbonyl oxygen by an imino group (Fig. 5). This backbone modification dramatically increases the hydrolytic lability of the backbone, without appreciably affecting the physicomechanical properties of the polymer the mechanical strength and toughness of thin,... 

In the case of replacement of CO from the group VI carbonyl compounds there is additional evidence to the effect that the type A ligands labilize CO whereas the type B do not, but rather promote a second-order reaction. For the group VII octahedral compounds there is no strong evidence in favour of an associative activation step, except when interpretation is obscured by subsequent or concurrent reaction (but see ref. 146). There is, however, good reason to believe that such an associative reaction does occur in certain of the group VI compounds. 

Silyl enol ethers are an elegant means to protect the reactive and hence labile enolate moiety [15]. At the time of reaction, the enolate group is generated as an intermediate and reacts with the carbonyl-carrying compound. 

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