2,6-dimethyl-4-pyrone complexes

Fig. 9. Normalized solubilities of l,2-dimethyl-3-hydroxy-4-pyridinone, dmppH, of its aluminum(III) and iron(III) complexes AKdmppla and Fe(dmpp)s, and of the 3-hydroxy-4-pyronate complexes Ga(malt)3 and In(etmalt)3 in methanol-water mixtures at 298.2 K (data from Refs. (114) and (234)).

By 0-acylation with 2-methyl-1,3-dioxolenium fluoroborate, which reacts as 0-acetyl ethylene oxide, 2,6-dimethyl-4-pyroiie is converted into 4-acetoxy-2,0-dimethylpyrylium fluoroborate (24, Y = 0, R = Ac, X=BT 4). The alleged compound with this structure which has been obtained from 8 and acetyl fluoroborate is, in fact, the BF3-complex of the pyrone. 

Alkoxy(carbene)iron(0) and amino(carbene)iron(0) complexes usually react with alkynes to give rj4-pyrone iron complexes and furans, respectively [54]. Nevertheless the chemoselective formation of naphthols was reported for alkoxy(carbene)iron(0) complexes with the electron-poor alkyne dimethyl... 

A series of Tc complexes with the monobasic ligands 2-methyl-3-oxy-4-pyronate (maltolate, Hma (78)) or l,2-dimethyl-3-oxy-pyridinonate, (Hdpp, (79)) were prepared in nonaqueous solution by chloride substitution in [TcOCU]. Stepwise substitution is observed. The substitution of one... 

Anionic [ReOBr3(L)] and neutral [ReOBr(L)2] complexes are formed by reactions of [NBu4][ReOBr4] with 2-methyl-3-oxy-4-pyrone or l,2-dimethyl-3-oxy-4-pyridinone which act as monobasic ligands. The monoligand complex can be regarded as an intermediate in the formation of the bis-chelate complex. 

Among seven-coordinate structures, many involve dike-tonate complexes Ln(diket)3 L these generally have either capped-octahedral or capped trigonal prismatic geometry. A considerable number of complexes with neutral donors (e g. thf) of the type LnX3L4 (X = halide, NCS), however, have structures closest to pentagonal bipyramidal, similarly found in the erbium perchlorate complex with 2,6-dimethyl-4-pyrone (Section 3.7.4). 

Pyrone synthesis by cycloaddition of CO2 to terminal alkynes (1-hexyne, 1-propyne) has also been investigated. This process can be catalytically promoted, albeit with low yield and selectivity, by Co [74] and Rh [75] complexes. Rh(dppe) (Ti -BPh4), in acetonitrile, at 390 K, catalyzed the formation of 4,6-dimethyl-2-pyrone from 1-propyne and CO2 (1 MPa) with a TON of 50 [75]. The Rh-catalyzed reaction has been proposed to proceed through a mechanism (Scheme 5.15) not involving an oxametallacycle intermediate species. The CO2 insertion into the Rh-C(sp )-o-bond of a Rh-alkenyl intermediate, obtained upon propyne dimerization, affords a linear unsaturated carboxylate which is converted into the pyrone. 

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