Synthesis, characterization and spectroscopic properties of some 2-substituted 1,3-indandiones and their metal complexes

New 2-acyl-1,3-indandione derivatives, compounds 1–4, were obtained by condensation of 2-acetyl-1,3-indandione with benzaldehyde, thiophene-2-aldehyde, thiophene-3-aldehyde and furane-2-aldehyde, respectively. The structures of the newly synthesized 2-substituted 1,3-indandiones were characterized by means of spectroscopic methods (FT-IR, ¹H and ¹³C NMR, UV-Vis and MS). Based on the obtained results it is suggested that the compounds exist in the exocyclic enolic form. Mass spectral fragmentation paths are also proposed. In order to verify the possibility for tautomerization processes of the newly synthesized compounds their absorption spectra were recorded in various solvents. Furthermore, the complexation properties of the compounds with metal(II) ions were also studied. A series of non-charged complexes with Cu(II), Cd(II), Zn(II), Co(II) and Ni(II) was isolated and analyzed by elemental analyses and IR. The paramagnetic Cu(II) complexes were studied by EPR and distorted, flattened tetrahedral structures are predicted. The other metal complexes show the presence of water molecules, most probably coordinated to the metal ion, thus forming octahedral geometry. Ultimately, the studied properties of the newly synthesized compounds, 1–4, suggest that they may find application as extracting agents for metal ions, rather than as optical sensors.      

2-N-Imidazolyl- and 2-N-pyrazolyl-1,3-indandiones

It was shown by spectroscopic methods that 2-N-imidazolyl-, 2-N-(N-methylimidazolyl)-, and 2-N-(N-methylpyrazolyl)-1,3-indandiones exist in the form of inner salts, whereas 2-N-pyrazolyl-1,3-indandione exists in the form of an enol with an intramolecular hydrogen bond.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1082–1085, August, 1982.     

Reactions of 2-acyl-1,3-indandiones

2-Pivaloyl-1,3-indandione reacts with thiosemicarbazide in aqueous base, through two successive retro-Claisen reactions, to yield 1-hydroxy-4-methylphthalazine. The mechanism of this reaction is described. Under similar conditions, 2-benzoyl and 2-acetyl-1,3-indandione, did not undergo the same reaction, a steric factor is considered.     

Asymmetric synthesis of multicyclic spiro-1,3-indandiones via a cascade Michael/Michael reaction of curcumins and 2-arylidene-1,3-indandiones

An organocatalytic cascade Michael/Michael reaction between curcumins and 2-arylidene-1,3-indandiones has been studied. Prolinol, chiral thiourea-tertiary amines, and cinchona alkaloids were evaluated as catalysts. Quinine was identified as the best catalyst for the transformation. Multicyclic spiro-1,3-indandiones were prepared in moderate to excellent yields, diastereoselectivities, and enantioselectivities.     

Diphthalolylpyrkolidines from 2-arylidene-1,3-indandiones and phenyl azide

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 269–270, February, 1989.     

A method for C2 acylation of 1,3-indandiones

The 1,3-indandione scaffold is an important structural motif used in the preparation of a large number of industrial chemical and pharmaceutical compounds. However, few approaches allow for the direct C2 acylation on these building blocks. A method was developed using DMAP and EDCI, which is mild in reactivity, covers a diverse range of carboxylic acid acylating agents, is compatible with electron releasing and withdrawing substituents on the 1,3-indandione partner, and performs well in a polar aprotic solvent (for solubility reasons) This method cleanly afforded twenty five different products in yields of 32–96%.     

Reactions of 2-acyl-1,3-indandiones with monosubstituted hydrazines and hydrazides

Methyl- and phenylhydrazines react with 2-(diphenylacetyl)-1,3-indandione ( 1 ) to yield respectively the 1-(methylhydrazone) and the 1-(phenylhydrazone) of 2-(diphenylacetyl)-1,3-indandione ( 2a and 2b ). In comparison, acetic and benzoic acid hydrazides react with 1 to give respectively the α-(acetylhydrazone) and the α-(benzoylhydrazone) of 2-(diphenylacetyl)-1,3-indandione ( 3a and 3b ). Cyclization of 2a and 2b gives 2,3-disubstituted indeno[1,2-c]pyrazol-4(2H)-ones ( 7a and 7b ). Cyclization of 3a and 3b , followed by methylation, gives 1-methyl- and 2-methyl-3-(diphenylmethyl)indeno[1,2-c]pyrazol-4(1 and 2H)-ones ( 9a and 9b ). 2-Isovaleryl-1,3-indandione reacts with phenylhydrazine to give directly 3-isobutyl-1-phenylindeno[1,2-c]-pyrazol-4(1H)-one ( 10 ).     

Isomeric solid enols on ring- and amide-carbonyls of substituted 2-carbanilido-1,3-indandiones

Both isomeric enols on ring carbonyl (5b) and on amide carbonyl (6b) derived from N-p-methoxyphenyl-2-carbamido-1,3-indandione (4b) were isolated, and their X-ray structures were determined. X-ray diffraction of the N-o,p-dimethoxy analogue indicated a disorder ascribed to the presence of a 6:4 mixture of 5c and 6c. Calculation (B3LYP/6-31+G*) gave good agreement with observed geometries. The calculated energies indicated that enols 6 are more stable by <1 kcal/mol than enols 5 and much more stable than amides 4.     

Synthesis of spiroindene-1,3-dione isothiazolines via a cascade michael/1,3-dipolar cycloaddition reaction of 1,3,4-oxathiazol-2-one and 2-arylidene-1,3-indandiones

The reaction of 1,3,4-oxathiazol-2-one derivative with 2-arylidene-1,3-indandione to furnish novel spiroindene-1,3-dione isothiazoline derivatives by Michael/1,3-dipolar [3+2]-cycloaddition reaction was investigated. The key 1,3-dipolar cycloaddition reaction step was examined in toluene solvent at reflux temperature to obtain mixture of two regioisomers (6a and 6b – 14a and 14b) and single isomers (15–20). The scope of this new reaction was demonstrated with many examples with high reactivity and yields.     

Synthesis and properties of a series of porphyrin-nicacid dyads and their Mn and Zn complexes

In this article, a series of porphyrin-nicacid dyads and their Mn and Zn complexes were synthesized and characterized by elemental analysis, UV–Vis, IR, MS, and ¹H NMR spectroscopies. Fluorescence studies show that for increasing length of alkoxy chains the fluorescence intensity and quantum yield of the porphyrin ligands is C₂ > C₃ > C₄ > C₅ > C₆ > C₁₀. Electrochemical results indicate that the length of side chain has little effect on the redox potential.     

Macroheterocyclic Compounds Based on Nitro- and Chloro-1,3-indandiones

Macroheterocyclic compounds of symmetrical structure were prepared by reactions of 4- and 5-nitro-1,3-indandions and 4-chloro-1,3-indandione with m-phenylenediamine.     

Transition metal complexes with 1,3-bis-(2-hydroxyphenyl)-1,3-propanedione—I : Mononuclear complexes

Reaction of 1,3-(2-hydroxyphenyl)-1,3-propanedione (BhPPH₃), a ligand with three possible sites of coordination acting as a chelating agent, with metal acetates results in the formation of mononuclear species M(BhPPH₂)₂S,S′ (M=Mn, Fe, Co, Ni, Zn; S,S′=CH₃OH, C₂H₅OH or H₂O); M′(BhPPH₂)₂ (M′=Cu, Pd), and M″(BhPPH₂)₃S,S′ (M″= Fe, Al). The complexes have been studied by ¹H-NMR when possible, and IR spectra. The position of the methine proton (=CH-) at 6.88 ppm in Zn(BhPPH₂)₂S,S′ indicates that BhPPH₃ behaves in mononuclear complexes as a common β-diketone. Most of the complexes lose S,S′ molecules on heating but a crystal structure of Zn(BhPPH₂)₂ · 2C₂H₅)OH indicates that the C₂H₅OH molecules are oxygen bonded to the metal centre.     

Synthesis and properties of hyperbranched polyester polyacrylic acids and their metal complexes

New polydentate ligands based on the hyperbranched third generation polyesters containing terminal acrylic acid fragments were synthesized. The ionization and complexation parameters of new compounds in solution were estimated by spectrophotometry and pH-metric titration followed by experimental data processing using mathematical simulation by the CPESSP program. The procedure for the synthesis was proposed. The polynuclear cobalt(II), nickel(II), and copper(II) complexes with polyester polycarboxylates were synthesized.     

Vibrational and electronic properties of polyaza chain molecules and their metal complexes

The polyaza chain molecules exhibit a quasi planar backbone with all-trans geometry. The chelation of several metallic ions such as copper (II) and zinc (II) constrains different conformations of the chain molecules. The vibrational and electronic properties are typical of the conformation of the polyaza backbone as well as the spin spin exchange between the metallic ions through the azine bonds.     

1,3-Diphosphapropenes for novel chemistry of metal complexes

2-Methyl-3,3-diphenyl-1-(2,4,6-tri-t-butylphenyl)-1,3-diphosphapropene was obtained as a chelate ligand for palladium(II) and platinum(II) complexes. Sulfurization of 2-methyl-1,3-diphosphapropene mainly gave 3-thioxo-1,3-diphosphapropene which bears a PC-PS skeleton and was used as a ligand of transition-metal complexes. A doubly-sulfurized product of the 1,3-diphosphapropene, 1,3-dithioxo-1,3-diphosphapropene, was isolated and characterized. The palladium(II) complexes containing the ligated 1,3-diphosphapropenes were used for catalytic reactions such as cross-couplings and direct conversion of allyl alcohol to allylaniline.     

Structure, spectroscopic properties, and reversible solid-to-solid reactions of metal complexes of 5-nitro-pyrimidin-2-olate

In searching for coordination polymers containing the highly polarized 5-nitro-pyrimidin-2-olate ligand (NP), a number of species containing 3d transition metals have been prepared and characterized, namely Co(NP)2(H2O)4, [Co(NP)2]n, Ni(NP)2(H2O)4, [Ni(NP)2]x, and [Zn(NP)2]n. Their structures have been determined by X-ray powder diffraction methods. The hydrated compounds contain mononuclear M(NP)2(H2O)4 units interconnected by means of a three-dimensional (3D) network of hydrogen bonds. The homoleptic species, at variance from the already known metal(II) pyrimidin-2-olate ones, crystallize as two-dimensional (2D) slabs, where the metal coordination is of the MN3O kind. The electron-withdrawing nitro group, never bound to the metal ion, is likely to influence the observed stereochemistry through steric and dipolar effects within the crystal lattice. The thermal, spectroscopic, and magnetic properties of these species are presented. The M(NP)2(H2O)4/[M(NP)2]x,n systems interconvert reversibly upon dehydration/rehydration processes.