Über die oxidationsprodukte von thiocarbon-säureamiden

Walter, Wolfgang; Holst, Joachim; Eck, Joachim

doi:10.1016/0022-2860(71)85015-9

Cited by 14 publications

(4 citation statements)

References 17 publications

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“…The oxidation of nitrogen substituted thiocarbonyl compounds has been studied in detail by Walter's group utilizing mostly hydrogen peroxide as the oxidant. Starting with the isolation of thioacetamide S ‐oxide (Figure 2a), A , R=CH 3 ), Walter conclusively demonstrated that the reaction product exhibits the structure of an S ‐oxide and does not correspond to its sulfenic acid tautomer [23,30] . Thioacetamide oxide is rather stable and can be stored at 0 °C for many months with little to no signs of decomposition, however, the compound disintegrates upon melting at 136–137 °C [23] .…”

Section: Introductionmentioning

confidence: 96%

“…Starting with the isolation of thioacetamide S ‐oxide (Figure 2a ), A , R=CH 3 ), Walter conclusively demonstrated that the reaction product exhibits the structure of an S ‐oxide and does not correspond to its sulfenic acid tautomer. [ 23 , 30 ] Thioacetamide oxide is rather stable and can be stored at 0 °C for many months with little to no signs of decomposition, however, the compound disintegrates upon melting at 136–137 °C. [23] While the oxidation protocol can easily be extended to primary thioamides independent of the nature of the substituent on carbon, [31] difficulties to isolate pure products emerge for secondary, B , and even more so for tertiary thioamide S ‐oxides, C (Figure 2a ).…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Sterically Encumbered Thiourea S‐Oxides through Direct Thiourea Oxidation

Medvedko

Ströbele

Wagner

2022

Chemistry A European J

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Thiourea S‐oxides can be viewed as formal analogs of the currently unknown diamino‐substituted Criegee intermediates (urea O‐oxides). However, the preparation of such S‐oxides is rather challenging, and the direct oxidation of thioureas typically only leads to formation of desulfurized products. Employing the accurate revDSD‐PBEP86‐D4 double hybrid density functional, it was found that the peracid mediated oxidation of thiourea S‐oxides exhibits a lower reaction barrier than the oxidation of the corresponding thiourea itself in contrast to most other ordinary thioketones. The undesired overoxidation reactivity, which is associated with strong π‐donation from the thiourea's nitrogen atoms, can be partially suppressed by introduction of bulky substituents and the utilization of protic solvents. In this regard, we managed to prepare two sterically encumbered thiourea S‐oxides in isolated yields of 35–40 %. The S‐oxides are stable in the solid state and in alcoholic solutions at room temperature for extended periods of time, but swiftly decompose in aprotic solvents by disproportionation. A dimesityl‐substituted thiourea S‐oxide complexed with residual mCBA could be characterized by means of X‐ray crystallography, confirming the importance of hydrogen bonding in the stabilization of the amino‐substituted C=S+−O− moiety.

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Section: Introductionmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Synthesis of Sterically Encumbered Thiourea S‐Oxides through Direct Thiourea Oxidation

Medvedko

Ströbele

Wagner

2022

Chemistry A European J

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“…Das in der vorliegenden Arbeit untersuchte Material wurde yon Wohlers (1970) (Jarchow, 1969) und Thioacetamid-S-Oxid (Walter, Holst & Eck, 1971) auf der N-Seite liegen, nicht aber auf der S-bzw. O-Seite wie bei 2-Phenyl-4-acetylphenoxy-2,6-dimethylimino-methansulfens~iure (Kato, 1972), so dass intramolekulare Wasserstoffbrficken N(n01)-H(nlT)... O(n01) mit n = 1,2 nahegelegt werden.…”

Section: Einfiihrungunclassified

Die Kristall- und Molekülstruktur des Primär-Oxydationsproduktes von S-(2-Methoxyphenyl)-N-(2,6-dimethylphenyl)-dithiourethan

Kato¹

1972

Acta Crystallogr Sect B

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“…All types of physical methods, i.e. UV/VIS [18], IR [19,20] Raman [20] 1H [15,21] and 13C NMR spectroscopy [22], X-ray crystallography [16,23] as well as dipole moment [24] and MS measurements [25] were applied in his group. This series of publications ended in 1979 with its 42nd communication [26].…”

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confidence: 99%