4- Phenyl-2,6-heptanedione

This procedure represents a novel, convenient, and fairly general method for preparing y-aryl-/3-diketones. By this method the submitters have phenylated the dianion of 1-phenyl-1,3-butanedione (61%), 2,4-heptanedione (98%), 2,4-nonanedione (78%), 2,4-tridecanedione (53%), and 3,5-heptanedione (50%).6 Substituted diaryliodonium salts have also been used to produce l-(4-chlorophenyl)-2,4-pentadione (44%), 4-(4-methyl-phenyl)-l-phenyl-l,3-butanedione (44%), and l-(4-methyl-phenyl)-2,4-nonanedione (21%).6 Under these conditions no more than a trace, if any, of arylation at the a-position of the /3-diketones was observed by gas chromatography analysis. 

HEPTANEDIONE, 3-methyl-, 55, 127 Heptanenitrile, 2-ethenyl-2-phenyl, 55, 102 Heptanenitrile, 2-phenyl-, 55, 102 Heptanoic acid, 4-oxo-, ethyl ester... 

Four diarylheptanoids were isolated from the methanol ic extract of the rhizomes of 4. officinarum and identified on the basis of their spectral data and by chemical correlations as l,7-diphenylhept-4-en-3-one (40), 7-(4"-hydroxy-3"-methoxyphenyl)-l-phenylhept-4-en-3-one (41), 1,7-dipheny 1-5-hydroxy-3-heptanone (43) and 5-hydroxy-7-(4"-hydroxy-3"-methoxyphenyl)-l-phenyl-3-heptanone (44) [38]. From the chloroform-soluble fraction of the methanolic extract of the rhizomes of A. officinarum, three new diarylheptanoids, 5-methoxy-7-(4"-hydroxy-3"-methoxyphenyl)-l-phenyl-3-heptanone (46), 5-hydroxy-7-(4"-hydroxyphenyl)- -phenyl-3-heptanone (45) and 7-(4"-hydroxy-3"-methoxyphenyl)- -phenyl-3,5-heptanedione (49) were isolated together with 41, 43 and 44 [39]. Compound 44 was the major constituent of the chloroform-soluble fraction. Compounds 41, 43-46 and 49 showed inhibitory effect against PG synthetase and IC50 values of the compounds were reported [39]. In addition to compounds 43, 44 and 52, three new diarylheptanoids, 42,47 and 48 were isolated from the rhizomes of A. officinarum and the structures were elucidated on the basis of the spectroscopic data [40]. The configuration of C-5 of 43 and 52 was determined to be R and that of hexahydrocurcumin was S [40]. 

The universal synthetic method used to prepare an Ir(C N)2(LX)-type complex is shown in Fig. 5. Dimer complex [Ir(C N)2Cl]2 is readily prepared from reaction of the ligand precursor and IrCl3-nH20 [79], and chloro-ion ligands can be subsequently replaced with an LX chelate. The most studied ancillary ligand LX is acac, but it can be varied with other monoanionic bidentate ligands, such as picolinic acid, N-methylsalicylimine [23], 2-(5-phenyl-4//-[l,2,4]triazol-3-yl)-pyr-idine [28], 2,2,6,6-tetramethyl-3,5-heptanedionate, 1-phenyl-4,4-dimethyl-1,3-pen-tanedionate, l,3-diphenyl-l,3-propanedionate, pyrazolyl, pyrazolyl-borate [80], and (2-pyridyl) pyrazolate derivatives [81]. 

Diketones (XII-S4 R CHa.CeHs) condense with benzylideneaniline, but not with aliphatic Schiff bases, in the presence of potassium amide to give 2,3-dihydro-4-pyridones ( ff-a 6 Either directly (R = CH3) or by treatment of XII-8S (R = CfiHj) with sulfuric acid. Under these conditions 6-phenyl-2,4-hexanedione (XII-84, R = CHjCHjCeHs) gives l-anilino-l,7-diphenyl-3,5-heptanedione (MI-85, R = CHjCHjCeHs), which forms MI-86 (R = CHjCHjCeHs) on treatment with sulfuric acid. The isomeric dihydropyridone... 

Condensation reactions on nickel(II) matrices are sensitive to steric effects. X-Ray structm analysis showed [310, 320-328] that H2L263 and its metal complexes are saddle-like, rather than planar. The sources of structural nonplanarity are steric repulsions between methyl groups R, 4 and orr/K>-aromatic protons of the Schiff bases. The increase in the bulk of the groups in these positions hinders macrocyclisation. For example, 3,5-heptanedione, 4,6-nonanedione and 1-phenyl-2,4-pentanedione form cyclic products [Ni(L274)]-[Ni(L276)J, whereas dibenzoyl-methane, 2,6-dimethyl-3,5-heptanedione and 2,2,6,6-tetramethyl-2,5-heptanedione do not give macrocyclic compounds in the presence of nickel(II) and o-phda [300, 320]. In the case of dibenzoylmethane, the nickel(II) )ff-diketonate bis-diamine adduct is isolated (Eq. 2.164) [319]. 

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