Topic
Thioacetone
About: Thioacetone is a research topic. Over the lifetime, 40 publications have been published within this topic receiving 522 citations. The topic is also known as: propanethione.
Papers
TL;DR: A number of complementary synthetic approaches to the β-thiolactone intermediate were described in this article for elaboration to the novel 1,3-dioxo-1,2-dithiolane moiety 6 found in the antitumour antibiotic substance leinamycin.
Abstract: A number of complementary synthetic approaches to the β-thiolactone intermediate 9 for elaboration to the novel 1,3-dioxo-1,2-dithiolane moiety 6 found in the antitumour antibiotic substance leinamycin 1 are described.Thus, deprotection of the benzylthio ether produced from 3-methylbut-2-enoic acid and toluene-α-thiol, leads to the mercapto acid 12 which on cyclisation produces the thiolactone 13. α-Methylation of the thiolactone 13, followed by α-oxygenation then gives rise to the substituted β-thiolactone 9. The β-thiolactone 9 is also produced when: (i) the sodium glycidate 17 is stirred with sodium sulfide leading to 18, followed by thiolactonisation; (ii) thioacetone is treated with the ketene derived from 2-acetoxypropanoyl chloride; and (iii) by irradiation of 3-methyl-2-trimethylsilyloxybut-2-ene 22 with thiophosgene leading to 23, followed by hydrolysis.The β-thiolactone 9 is then converted in three steps into the 1,3-dioxo-1,2-dithiolane 6 by: (i) ring opening to the thioic acid 15, using hydrogen sulfide–triethylamine; (ii) ring closure of 15 to 8 in the presence of aqueous ferric chloride; and finally (iii) oxidation using dimethyldioxirane.Treatment of the ethyl glycidate 19 with disodium disulfide in hot ethanol for 3 days provides the 1,2-dithiolane 8 directly, but in low yields (11–15%).When the aforementioned reaction sequences are translated to the glycidate 24, derived from 4-methylcyclohex-3-enone and α-chloropropanoic acid, the syntheses of the key intermediates 25, 27 and 26en route to the spiro-fused 1,3-dioxo-1,2-dithiolane 7 and leinamycin 1(see Scheme 1) were secured.
49 citations
TL;DR: A series of thioketone complexes of the type M(CO) 5 (S=CR 2 ), where M = Cr, Mo or W, and R = Me, Et or Ph, have been prepared by the reaction of M( CO) 5 I − with Ag + in the presence of the ketone (O = CR 2 ) and H 2 S. Infrared and 13 C NMR spectra of the compounds are consistent with the ligands being coordinated through the sulfur atom as discussed by the authors.
38 citations
TL;DR: In this paper, a Rydberg-valence interaction mixes the n, 4s and π,π* states of thioacetaldehyde, leading to a broad absorption of mixed character between 200 and 220 nm.
31 citations
TL;DR: The regiochemistry of 1,3-dithiolanes obtained from thiocarbonyl ylides 9 and thiones 10 shows a striking dependence on substituents, but the paucity of experimental criteria is troubling.
Abstract: The regiochemistry of 1,3-di-thiolanes obtained from thiocarbonyl ylides 9 and thiones 10 shows a striking dependence on substituents. Previously and newly performed experiments indicate that sterically hindered cycloalkanethione S-methylides and dialkyl-thioketone S-methylides react with alicyclic and aliphatic thiones to give the 2,2,4,4-tetrasubstituted 1,3-dithiolanes 11 exclusively. Aryl groups in one or both reactants lead to a preference for, or even complete formation of, 4,4,5,5-tetrasubstituted 1,3-dithiolanes 12. Several mechanisms appear to be involved, but the paucity of experimental criteria is troubling. Quantum-chemical calculations (see preceding paper) on the cycloaddition between thioacetone S-methylide and thioacetone furnish lower activation energies for the concerted process than for the two-step pathways via C,S- or C,C-biradicals; the favoring of the 2,4-substituted 1,3-dithiolanes over the 4,5-substituted type would be expected to increase with growing bulk of substituents. Aryl groups stabilize intermediate biradicals. Experimental criteria for the differentiation of regioisomeric dithiolanes are discussed. Thiocarbonyl ylides 9 are prepared by 1,3-cycloadditions between diazomethane and thioketones and subsequent N 2 elimination from the usually isolable 2,5-dihydro-1,3,4-thiadiazoles 17; different ratios of the two rate constants lead to divergent product formation scenarios.
29 citations
TL;DR: In this paper, a pyrolysis jet spectroscopic technique has been used to record the T1←S0, a 3A←A‘←X 1A1, which results from an n→π* electron promotion and gives rise to a pattern of vibronic bands that were attributed to activity of the methyl torsion and the sulphur out-of-plane wagging modes.
Abstract: Jet‐cooled, laser‐induced phosphorescence excitation spectra (LIP) of thioacetone (CH3)2CS/(CD3)2CS have been recorded over the region 16 800–18 500 cm−1 using the pyrolysis jet spectroscopic technique The responsible electronic transition, T1←S0, a 3A‘←X 1A1, results from an n→π* electron promotion and gives rise to a pattern of vibronic bands that were attributed to activity of the methyl torsion and the sulphur out‐of‐plane wagging modes The intensities of the torsional and wagging progressions in the excitation spectra were interpreted in terms of a C2v–Cs molecular distortion of the triplet molecule from its singlet ground state equilibrium structure A complete unrestricted Hartree–Fock (UHF) ab initio molecular orbital (MO) structural optimization of the T1 state predicted that the sulphur was displaced by 2736° from the molecular plane and the methyl groups were rotated by 1093° in clockwise–counterclockwise directions Restricted Hartree–Fock (RHF) calculations were used to generate the V(θ
29 citations
Related Topics (5)
Performance Metrics
| Year | Papers |
|---|---|
| 2020 | 3 |
| 2017 | 1 |
| 2016 | 1 |
| 2012 | 1 |
| 2011 | 1 |
| 2008 | 1 |