Bis(trifluoromethyl)sulfene (CF3)2CSO2, Isolated as Adduct

Hartwig, Uwe; Pritzkow, Hans; Rall, Klaus; Sundermeyer, W.

doi:10.1002/anie.198902211

Cited by 25 publications

(5 citation statements)

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“…We ruled out a possible deamination approach from the correspondin aminobenzimidazole for the following reasons. Firstly, when we milled commerci aminobenzimidazole in the presence of NaOH, we did not see any change in the star Nevertheless, we cannot rule out a reaction mechanism based on the supposed carbenoid structure of TDO as well [89,[100][101][102] (Scheme 11b). In this case, the reaction mechanism initially follows a diverse pathway based on the minor charge separation between the two moieties of TDO (Scheme 11b, pathway 1) [90,103].…”

Section: Procedures Bmentioning

confidence: 90%

“…The resu 2-amino dehydrobenzimidazole then extrudes the NH2 moiety as ammonia for form the benzimidazole structure (Scheme 11a, pathway 3). Nevertheless, we cannot rule out a reaction mechanism based on the supposed benoid structure of TDO as well [89,[100][101][102] (Scheme 11b). In this case, the reac mechanism initially follows a diverse pathway based on the minor charge separation tween the two moieties of TDO (Scheme 11b, pathway 1) [90,103].…”

Section: Procedures Bmentioning

confidence: 97%

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Mechanochemistry Frees Thiourea Dioxide (TDO) from the ‘Veils’ of Solvent, Exposing All Its Reactivity

et al. 2023

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The synthesis of nitrogen-based heterocycles has always been considered essential in developing pharmaceuticals in medicine and agriculture. This explains why various synthetic approaches have been proposed in recent decades. However performing as methods, they often imply harsh conditions or the employment of toxic solvents and dangerous reagents. Mechanochemistry is undoubtedly one of the most promising technologies currently used for reducing any possible environmental impact, addressing the worldwide interest in counteracting environmental pollution. Following this line, we propose a new mechanochemical protocol for synthesizing various heterocyclic classes by exploiting thiourea dioxide (TDO)’s reducing proprieties and electrophilic nature. Simultaneously exploiting the low cost of a component of the textile industry such as TDO and all the advantages brought by a green technique such as mechanochemistry, we plot a route towards a more sustainable and eco-friendly methodology for preparing heterocyclic moieties.

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Section: Procedures Bmentioning

confidence: 90%

Section: Procedures Bmentioning

confidence: 97%

Mechanochemistry Frees Thiourea Dioxide (TDO) from the ‘Veils’ of Solvent, Exposing All Its Reactivity

et al. 2023

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“…Nevertheless, we cannot rule out a reaction mechanism based on the supposed carbenoid structure of TDO as well [90,[101][102][103] (Scheme 10b). In this case, the reaction mechanism initially follows a diverse pathway based on the minor charge separation between the two moieties of TDO (Scheme 10b, pathway 1) [91,104].…”

Section: Procedures Bmentioning

confidence: 98%

Mechanochemistry Frees the Thiourea Dioxide (TDO) from the ‘Veils’ of the Solvent, Exposing All Its Reactivity

Basoccu¹,

Cuccu²,

Caboni³

et al. 2023

Preprint

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The synthesis of nitrogen-based heterocycles has always been considered essential in the development of pharmaceuticals in medicine and agriculture. This explains why various synthetic approaches have been proposed in recent decades. However, performing as methods often imply harsh conditions or the employment of toxic solvents and dangerous reagents. Mechanochemistry is undoubtedly one of the most promising technologies currently used for reducing any possible environmental impact due to the worldwide interest in developing solvent-free synthetic pathways. Following this line, we propose a renewed mechanochemical protocol for synthesizing various heterocyclic classes by exploiting the reducing proprieties and the electrophilic nature of thiourea dioxide (TDO). Simultaneously using the ready availability and low cost of a component of the textile industry such as TDO and all the advantages brought by a green technique such as mechanochemistry, we plotted the route towards a more sustainable and eco-friendly methodology for obtaining heterocyclic moieties.

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“…Hexafluorothioacetone does not readily form a hydrate, but dimerises readily, particularly in the presence of base; high temperatures are then required to reverse the process [258] (Figure 8.97). The dimer of hexafluorothioacetone may also be obtained from hexafluoropropene [259] and the former has now been used in a route to a sulphene [260] (Figure 8.98). Bistrifluoromethylthioketene has been obtained as a monomer; that is very unusual, since thioketenes generally dimerise [261] (Figure 8 The nickel-dithiolene complex (Figure 8.100) is considered as a potential means of recovering ethene, because it is capable of binding ethene reversibly by a redox-switch process [262].…”

Section: Thiocarbonyl Compoundsmentioning

confidence: 99%

Functional Compounds Containing Oxygen, Sulphur or Nitrogen and their Derivatives

Chambers

2004

Fluorine in Organic Chemistry

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This chapter contains only a brief survey of the chemistry of a range of derivatives that are of interest to the organic chemist; further aspects have been discussed in detail and may be referred to elsewhere [1,2]. Because of the extreme electronegativity of fluorine and fluorocarbon groups, the acidities of various functions are increased by introduction of these groups. Some examples are given in Table 8.1: it is clear that fluorocarbon groups have a dramatic effect on the acidities of alcohols and carboxylic acids. Moreover, the CF 3 SO 2 group is one of the most electron-withdrawing groups known [3] and consequently the carbon acid ðCF 3 SO 2 Þ 2 CH 2 is more acidic than trifluoroacetic acid. Also, the sulphonamide ðCF 3 SO 2 Þ 2 NH is a strong acid [4].Conversely, fluorine or fluorocarbon groups have a major effect in reducing the base strength of amines, ethers and carbonyl compounds; for example, 2,2,2-trifluoroethylamine (pK b ¼ 3:3) is ca. 10 5 times less basic than ethylamine. Also, pentafluoropyridine is only protonated in strong acid [6], whereas hexafluoroacetone is not protonated even in superacids [7-9] and perfluorinated tertiary amines and ethers are sufficiently non-basic for them to be used as inert fluids interchangeably with perfluorocarbons.

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Bis(trifluoromethyl)sulfene (CF₃)₂CSO₂, Isolated as Adduct

Abstract: R2 0 CH2OH l a , b 7 + 8a, b P 9 3a, b Received: October 12, 1988 [3006 IE] German version: Angew. Chem. 101 (1989) 224 CAS Registry numbers: 3, 795-31-3: 4, 118724-94-0; 5, 767-45-3: 6, 118724-95-1; quinuclidine, 100-76-5.

Cited by 25 publications

References 14 publications

Mechanochemistry Frees Thiourea Dioxide (TDO) from the ‘Veils’ of Solvent, Exposing All Its Reactivity

Mechanochemistry Frees Thiourea Dioxide (TDO) from the ‘Veils’ of Solvent, Exposing All Its Reactivity

Mechanochemistry Frees the Thiourea Dioxide (TDO) from the ‘Veils’ of the Solvent, Exposing All Its Reactivity

Functional Compounds Containing Oxygen, Sulphur or Nitrogen and their Derivatives

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