CO group

Champmartin D and Rubini P 1996 Determination of the 0-17 quadrupolar coupling constant and of the C-13 chemical shielding tensor anisotropy of the CO groups of pentane-2,4-dione and beta-diketonate complexes in solution. NMR relaxation study/norg. Chem. 35 179-83... 

Selenium dioxide, SeO, is ery poisonous (cf. p. I47), but is valuable particu larly for the oxidation of methylene ( CHs) groups to carbonyl ( CO) groups. 

TTie true ketones, in which the >CO group is in the side chain, the most common examples being acetophenone or methyl phenyl ketone, C HjCOCH, and benzophenone or diphenyl ketone, C HjCOC(Hj. These ketones are usually prepared by a modification of the Friedel-Crafts reaction, an aromatic hydrocarbon being treated with an acyl chloride (either aliphatic or aromatic) in the presence of aluminium chloride. Thus benzene reacts with acetyl chloride... 

The student should note that ketones in class (1), t.c., those having the >CO group in the side chain, will form additive compounds with sodium bisulphite only if this >CO group is not directly joined to the benzene ring acetophenone therefore will not form such compounds, whereas benzyl methyl ketone, CaHsCHjCOCH, will do so. Many quinones, particularly ortho quinones such as phenanthraquinone, form additive compounds with sodium bisulphite. 

These coloration changes are given by most compounds which possess the -CHj-CO— group for further examples, see Tests 4 (a) and (b) for Ketones, p. 344. 

The term Knoevenagel Condensation was originally applied to the base-catalysed condensation of the carbonyl ( CO) group of aldehydes and ketones with the reactive methylene group of malonic acid, with loss of w ater ... 

Bisulphite addition compound. Shake 1 ml. of acetone with 0 5 ml. of a saturated solution of NaHS03. A white precipitate is formed, the mixture becoming warm and then, on cooling, almost solid. Acetophenone and benzophenone, having the >CO group directly joined to tlie benzene ring, do not respond to the test (p- 257). 

The general theory behind the process is that the hypohalite will convert the amide to a haloamide. This then spontaneously changes to the isocyanate when heated and decomposes to the amine from the water present. In effect, all that happens is that a Carbonyl (CO) group is stripped off the starting amide to yield the corresponding amine. Yields pre- purification are around 80%, post-purification average around 65%. Certain uses of the result-... 

In 1877, Maly (45) discussing formula 34 applied to thiohydantoine found it unable to explain the basic properties of the compound. He preferred a structure in which the -CH2-CO- group would be bonded to only one nitrogen atom. Meyer (46) prepared a monophenyl thiohydantoin (m.p. 178°C) by condensing diloroacetanilide with thiourea and proposed 42 for its structure. 

An a helix can in theory be either right-handed or left-handed depending on the screw direction of the chain. A left-handed a helix is not, however, allowed for L-amino acids due to the close approach of the side chains and the CO group. Thus the a helix that is observed in proteins is almost always right-handed. Short regions of left-handed a helices (3-5 residues) occur only occasionally. 

The methylene grou]) (CbL) standing between two CO groups, such as occurs in acetoacctic ester, is characterised by cerltiin pro]icrties, which are shared hy all compounds of similar strurUire, vi/., by their behaviour towards nitrous acid, diazo-ben/.ene s.alts, and met.allic sodium or sodium alcohokate. 

It should be noted that the action of phenylhydrazine on the ketone group, and of diazobenzene salts on the methylene group situated between two CO groups, are analogous to that of hydrovylaniine and nitrous acid upon these two groups, of which the following are examples —... 

M ,(CO) Metal carbonyl clusters with bridging CO groups M-C(0) M... 

Figure 19.29 The structure of [Cr( ) -C6H6)(CO)3] showing the three CO groups in staggered configuration with respect to the benzene ring the Cr-O distance is 295 pm and the plane of the 3 O atoms is parallel to the plane of the ring.

Numerous carbonyl halides, of which the best known are octahedral compounds of the type [M(C0)4X2] are obtained by the action of halogen on Fe(CO)5, or CO on MX3 (M = Ru, Os). Stepwise substitution of the remaining CO groups is possible by X or other ligands such as N, P and As donors. 

This could account for the paramagnetism, but esr evidence shows that the 2 cobalt atoms are actually equivalent, and X-ray evidence shows the central Co-O-O-Co group to be planar with an 0-0 distance of l3l pm, which is very close to the 128 pm of the superoxide, 02, ion. A more satisfactory formulation therefore is that of 2 Co atoms joined by a superoxide bridge. Molecular orbital theory predicts that the unpaired electron is situated in a rr orbital extending over all 4 atoms. If this is the case, then the jr orbital is evidently concentrated very largely on the bridging oxygen atoms. 

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