A diketones

Anlhraquinone is a very stable compound which more closely resembles a diketone than a quinone it yields a monoxide with difficulty. 

CgHeNj. Brown-yellow crystals m.p. 103-104 C, b.p. 256 258°C. Its solutions reduce Ag ions and it is used as a photographic developer. It is also used as a dye-precursor, for the synthesis of phenazine derivatives and for characterizing inter alia) a-diketones. 

The secondary alcohol group, -CH(OH) in benzoin is readily oxidised to a ketone group, and thus benzil, a diketone, is obtained. 

The synthesis will therefore normally produce a 2,4-substituted pyrrole, with in addition an ester group or an acyl group at the 3-position, if a keto ster or a diketone respectively has been employed, and an ester group or an alkyl (aryl) group at the 5-position, according to the nature of the amino-ketone. 

Benzil (and other a-diketones Ar—CO—CO—Ar) upon refluxing with aqueous-alcoholic potassium hydroxide undergo the beozilic acid rearrangement. Thus benzil is converted into a salt of benzilic acid ... 

Ortho quinones (and also aromatic a-diketones, o-phenylenediamine to yield quinoxalines as follows. 

CgHjCOCHj + SeOa —> CgHgCOCHO + Se + H O This is one example of the oxidation by selenium dioxide of compounds containing a methylene group adjacent to a carbonyl group to thecorresponding a-ketoaldehyde or a-diketone (see also Section VII,23). 

The mechanism of the formation of an acyloin from an ester may involve the initial formation of a diketone the latter is reduced by the metal to give the sodium salt of the enediol form of the acyloin ... 

Synthesis Only cyclohexanone can enolise, but the a-diketone is more electrophilic no control needed ... 

In an intramolecular aldol condensation of a diketone many products are conceivable, since four different ends can be made. Five- and six-membered rings, however, wUl be formed preferentially. Kinetic or thermodynamic control or different acid-base catalysts may also induce selectivity. In the Lewis acid-catalyzed aldol condensation given below, the more substituted enol is formed preferentially (E.J. Corey, 1963 B, 1965B). 

The carbonylation of aryl iodides in the presence of alkyl iodides and Zn Cu couple affords aryl alkyl ketones via the formation of alkylzinc species from alkyl iodides followed by transmetallation and reductive elimination[380]. The Pd-catalyzed carbonylation of the diaryliodonium salts 516 under mild conditions in the presence of Zn affords ketones 517 via phenylzinc. The a-diketone 518 is formed as a byproduct[381],... 

The acylstannanes 874 and 875 are prepared by the reaction of acyl chlorides with (MciSnl - The symmetrical 1,2-diketones 877 can be prepared by the reaction of an excess of benzoyl chloride with (EtjSn) . Half of the benzoyl chloride is converted into the benzoyltin reagent 876, which is then coupled with the remaining benzoyl chloride under a CO atmosphere to afford the a-diketone 877[748], Triethyl phosphite is used as a ligand. 

Double. silylation of the a-diketone 120 with (Me3Si)2 is catalyzed by PdCl2(Me3P)2 to give the l,2-bis(siloxy)ethylene 121 in a good yield[ll7], Hydro.silylation of phenyl isocyanate (122) catalyzed by PdCN affords the /V-... 

Synthesis and Properties. A number of monomers have been used to prepare PQs and PPQs, including aromatic bis((9-diamines) and tetramines, aromatic bis(a-dicarbonyl) monomers (bisglyoxals), bis(phenyl-a-diketones) and a-ketones, bis(phenyl-a-diketones) containing amide, imide, and ester groups between the a-diketones. Significant problems encountered are that the tetraamines are carcinogenic, difficult to purify, and have poor stabihty, and the bisglyoxals require an arduous synthesis. 

Noncatalytic oxidation of propylene to propylene oxide is also possible. Use of a small amount of aldehyde in the gas-phase oxidation of propylene at 200—350°C and up to 6900 kPa (1000 psi) results in about 44% selectivity to propylene oxide. About 10% conversion of propylene results (214—215). Photochemical oxidation of propylene with oxygen to propylene oxide has been demonstrated in the presence of a-diketone sensitizers and an aprotic solvent (216). 

Monooximes of a-diketones have found applicability in the synthesis of 2-aminopyrazine 1-oxides by condensation with a-aminonitriles, and this reaction was used by White and coworkers in an approach to the synthesis of Cypridina etioluciferamine (Scheme 66 R = 3-indoloyl) (73T3761). In this instance, the use of TiCU as a catalyst was essential, since the carbonyl group in 3-acylindoles is normally deactivated and the required amine/carbonyl condensation is impractically slow. Under normal circumstances the carbonyl group in simple alkyl-substituted monoximes of a-diketones is the more reactive site and the reaction is rapid, requiring no catalysis (69LA(726)loo). 

BREDERECK Imidazole synthesis Synthesis o( imidazoles Irom (ormamide (acetamide) and a-diketones, a-ketols, a-aminoketones, a-oziminoketones... 

Synthesis of ptendines from diaminopyrfmidines and a-diketones or a-ketoaldehydes. 

Toluenesulfonylhydrazide reacts with a-diketones to yield mono / -toluenesulfonylhydrazones which may be converted to a-diazoke tones. ... 

M()Lobinanidine. Little is known about this base beyond the data recorded in Table C, but it appears to be oxidised to a lelobanine which yields a diketone resembling that from lobinine in giving a violet colour with alkali. 

Though the dialdehyde-tropinone synthesis does not succeed when the dialdehyde is replaced by a diketone, Blount and Robinson have shown that 1-methyltropinone (XXXV) can be obtained by the interaction of the keto-aldehyde, laevulinaldehyde. Me. CO. CH. CH. CHO, with methylamine and calcium acetonedicarboxylate, and from this by reduction to 1-methyl- -tropine and benzoylation, 1-methyl tropacocaine (b.p. 210°/15 mm. picrate, m.p. 163-4°) has been prepared. 

The benzilic acid rearrangement of steroid a-diketones is often the preferred method for ring contraction. Yields are generally excellent, and in several instances the reaction has been shown to be stereospecific. Preparation of the starting a-diketones is discussed below and illustrated with several excellent experimental procedures. 

In practice, the scope of the benzilic rearrangement as a tool for the ring contraction of steroids is defined by the availability of a-diketones, or the corresponding diosphenols. 

Ring contraction by benzilic acid rearrangement of a-diketones... 

Ring contraction by oxidative rearrangements of A-ring a-diketones by manganese dioxide... 

Fluonnated alkenes with one fluonne atom attached to the double bond are converted to a-hydroxyketones by potassium permanganate [30] (equation 22) a-Diketones are formed by permanganate hydroxylation of double bonds flanked by fluonne atoms [31] (equation 23)... 

The reaction of (fluoroalkenyl)carboranes with potassium permanganate in acetone leads to formation of a-diketones [119. These compounds react by photochemical reaction in which the radical formation at boron is followed by addition to the double bond [120] (equation 92). 

Polyfluorinated a-diketones react with 1,2-diainino compounds, such as ortlio-phenylenediamine, to give 2,3-substituted quinoxalmes [103] Furthermore, the carboxyl function of trifluoropyruvates offers an additional electrophilic center. Cyclic products are obtained with binucleophiles [13, 104] With aliphatic or aromatic 1,2-diamines, six-memhered heterocycles are formed Anilines and phenols undergo C-alkylation with trifluoropyruvates in the ortho position followed by ring closure to form y-lactams and y-lactones [11, 13, 52, 53, 54] (equation 23). 

Frequently, the decomposition of fluorine compounds results in a product with fewer carbon atoms through loss of carbon monoxide, carbon dioxide, or even an organic molecule Perfluonnated a-diketones undergo decarbonylanon with cesium fluoride in diglyme [90] (equation 57)... 

The coupling of enamines with aromatic diazonium salts has been used for the syntheses of monoarylhydrazones of a-diketones (370,488-492) and a-ketoaldehydes (488,493). Cleavage of the initial enamine double bond and formation of the phenylhydrazone of acetone and acetophenone has been reported with the enamines of isobutyraldehyde and 2-phenylpropionalde-hyde. Rearrangement of the initial coupling product to the hydrazone tautomer is not possible in these examples. 

---