.beta.-Thioxo ketones. 2. Preparation and structure of some five- and six-membered 2-acylcycloalkanethiones and 2-thioacylcycloalkanones

Duus, Fritz

doi:10.1021/jo00439a004

Cited by 33 publications

(10 citation statements)

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“…The syntheses of the compounds 3-6 have been described previously. 10,11 Purities were checked by 'H NMR spectroscopy before recording the PE spectra. The PE spectra were recorded on a PS-18 spectrometer (Perkin-Elmer) with a He I source and calibrated with a mixture of argon and xenon introduced into the target chamber simultaneously with the sample.…”

Section: Methodsmentioning

confidence: 99%

“…The PE spectrum of S-methylated thioacetylacetone 6 containes three well-resolved bands below 11 eV with maxima at 8.54, 9.03, and 10.57 eV (Figure 1). The corrected areas are nearly identical, reflecting undoubtedly single ionizations.21,23 The highest lying 7r orbital in methyl vinyl sulfide 7, mainly localized on the sulfur atom, has been observed at 8.45 eV,24,25 for which reason we assign the 8.54-eV ionization as arising from a rr-type orbital, ir3 (cf.…”

Section: Qualitative Molecular Orbital Considerationsmentioning

confidence: 99%

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The electronic structure of .beta.-thioxoketones. A photoelectron spectroscopic study of the enol-enethiol tautomerism of thioacetylacetone and related compounds

Joergensen¹,

Carlsen²,

Duus³

1981

J. Am. Chem. Soc.

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Section: Methodsmentioning

confidence: 99%

Section: Qualitative Molecular Orbital Considerationsmentioning

confidence: 99%

The electronic structure of .beta.-thioxoketones. A photoelectron spectroscopic study of the enol-enethiol tautomerism of thioacetylacetone and related compounds

Joergensen¹,

Carlsen²,

Duus³

1981

J. Am. Chem. Soc.

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“…Thioacetylacetone was prepared and purified according to the procedures described earlier 10. 15–17 [D 8 ]Thioacetylacetone was synthesized by tert ‐butyllithium promoted Claisen condensation of [D 6 ]acetone (Aldrich) with ethyl [D 3 ]thionoacetate (D 3 CCSOCH 2 CH 3 ) according to a previously described procedure,17, 18 all working‐up operations were performed with fully deuterated solvents and reagents (D 2 O, DCl). Ethyl [D 3 ]thionoacetate was obtained from [D 3 ]acetonitrile (Aldrich) under Pinner reaction conditions 19.…”

Section: Experimental and Computational Detailsmentioning

confidence: 99%

Thioacetylacetone: Structural and Vibrational Assignments

et al. 2004

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Thioacetylacetone and its variously deuterated isotopomers have been investigated using electronic and vibrational spectroscopy combined with quantum chemical calculations. Thioacetylacetone is known for its photochromic properties, but the structures of the initial and final forms have been the subject of a long debate. Analysis of the IR spectra recorded in low-temperature argon and xenon matrices, room-temperature solutions, and in the gas phase has allowed us to establish the nature of the photochromic species and of its precursor. Similar to the case of another beta-thioxoketone, monothiodibenzoylmethane, the photo-product has been assigned to the nonchelated SH exo-rotamer of the (Z)-enethiol tautomeric form, whereas the dominant ground-state species corresponds to the chelated (Z)-enol tautomeric form. Detailed vibrational assignments have been proposed for both forms based on quantum chemical calculations and polarization experiments. In the case of the chelated (Z)-enol species prevailing in the ground state, a second-order perturbative anharmonic analysis at the B3LYP/cc-pVTZ level indicated strong anharmonic effects associated with the intramolecular hydrogen bond, leading to a shift of more than 600 cm-1 of the wavenumber of the OH-stretching vibration. A small fraction of the SH endo-rotameric chelated (Z)-enethiol form was also detected under unperturbed conditions. The (Z)-enethiol form can be converted into the (Z)-enol form by irradiation at 290 nm.

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“…Compound MTPO is known to exist as a tautomeric mixture with the thioketo–enol form (1) ( Scheme 1 ) dominating at ambient temperature. 16 Upon cooling the thioketo–enol form ( Fig. 4 ) becomes more dominant and at a temperature below 200 K, the “OH” resonance (chelated proton) broadens.…”

Section: Resultsmentioning

confidence: 99%

“…Compounds and solvents MTPO was synthesized as described in ref. 16. CH 2 Cl 2 , CD 2 Cl 2 , or CHCl 2 F were used as solvents.…”

Section: Experimental and Computational Detailsmentioning

confidence: 99%

Photoinduced and ground state conversions in a cyclic β-thioxoketone

et al. 2022

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.beta.-Thioxo ketones. 2. Preparation and structure of some five- and six-membered 2-acylcycloalkanethiones and 2-thioacylcycloalkanones

Cited by 33 publications

References 4 publications

The electronic structure of .beta.-thioxoketones. A photoelectron spectroscopic study of the enol-enethiol tautomerism of thioacetylacetone and related compounds

The electronic structure of .beta.-thioxoketones. A photoelectron spectroscopic study of the enol-enethiol tautomerism of thioacetylacetone and related compounds

Thioacetylacetone: Structural and Vibrational Assignments

Photoinduced and ground state conversions in a cyclic β-thioxoketone

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