Sulfine und Sulfene — die S‐Oxide und S,S‐Dioxide der Thioaldehyde und Thioketone

Opitz, G.

doi:10.1002/ange.19670790402

Cited by 106 publications

(25 citation statements)

References 95 publications

(6 reference statements)

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“…We decided to investigate the usefulness of thiocitric acid 311 or thioisocitric acid 312 as a relatively hydrophilic ligand for gold(I) in what it was hoped would be orally active antiarthritic preparations. While attempts to prepare thiocitric acid 311 failed we were able to carry out an anti-Markovnikov addition of thioacetic acid to aconitic acid 313; see Scheme 37, equation (110). The adduct 314 could then in a straightforward manner be converted to 1-(aurothio)-1,2,3-propanetricarboxylic acid hydrate 315, a close analog of myocrisin.…”

Section: Potential Antiarthritic Agentsmentioning

confidence: 97%

“…Among these were methylsulfonylmethanesulfonic acid, MeSO 2 CH 2 SO 3 H, 184 and bis(methylsulfonyl)methanesulfonic acid, (MeSO 2 ) 2 CHSO 3 H, 187, both of which were unknown at that time. As shown in Scheme 21 we were able to obtain both compounds from Opitz's methylsulfonylsulfene, MeSO 2 CH¼SO 2 , 183 [110] as key intermediate [111]. The sulfonic acid 184 was formed by addition of water to 183 and isolated in the shape of its sodium and silver salt, respectively; cf.…”

Section: Methylsulfonylmethanesulfonic Acid and Bis(methylsulfonyl)mementioning

confidence: 99%

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Sulfur, An Important Element in my Life

Senning¹

2003

Sulfur Reports

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Section: Potential Antiarthritic Agentsmentioning

confidence: 97%

Section: Methylsulfonylmethanesulfonic Acid and Bis(methylsulfonyl)mementioning

confidence: 99%

Sulfur, An Important Element in my Life

Senning¹

2003

Sulfur Reports

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“…endo, exo-1, I I , 4,4', 5,5 ',6,6', 7.93,7.97,8.35,11.51,12.13,13.43,14.02,14.83,16.11 (CH,),52.50,57.53 (CH),58.45,61.14,(CJ,74.18,(CS02,Cq),134.44,137.76,138.56,141.76 (=C,Cq 11,395,349,331,305,299,269,259,241,227,197,195,185 c) To a solution of 4.08 g (30 mmol) of 6 and 3.03 g (30 mmol) of Et3N in 50 ml of EtCN, a solution of 1.43 g (10 mmol) of 2-propanesulfonyl chloride in 30 ml of EtCN was added dropwise at -70°C. After the mixture had been stirred at -70°C overnight, it was allowed to warm to room temp.…”

Section: N T I -7 -P E N T a M E T H Y L -2 -T H I Ubicyclo[22l/hepmentioning

confidence: 99%

Trapping reactions of sulfenes generated from sulfonic acid derivatives and bases, 2. [4 + 2] cycloadditions of 1,2,3,4,5‐pentamethylcyclopentadiene and 1,3‐diphenylbenzo[c]furan with sulfenes

et al. 1995

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Sulfenes 2a-0, generated in situ from sulfonyl chlorides and Et3N, are trapped by 1,2,3,4,5-pentamethylcyclopentadiene Sulfenes generated in situ from sulfonyl chlorides and triethylamine (Et3N) react with cyclopentadiene according to a [4 + 21 cycloaddition only if they bear either bulky or electron-attracting groups [']. We now found that 1,2,3,4,5-pentamethylcyclopentadiene (6) is a diene suitable for trapping simple sulfenes. It is easily does not dimerize, undergoes Diels-Alder reactions with dienophiles 100 times more rapidly than ~yclopentadiener~], and -due to its relatively low acidity (pKs = 26.1 as opposed to 18 for cycl~pentadiene [~]) -also allows the use of bases stronger than Et3N without giving rise to sulfonylations['l. Although 6 is slightly less reactive than strongly polar enamines such as N-(2-methyl-1 -propenyl)pyrrolidine, as a hydrocarbon it requires sulfene 2 itself and not sulfeneadducts like 3, 4, or Reaction of 1,2,3,4,5-Pentamethylcyclopentadiene (6) with Methanesulfonic Acid Derivatives l a and Bases B (Scheme 1 and Table 1) In tetrahydrofuran (THF), 6 readily traps the sulfene generated in situ from mesyl chloride or methanesulfonic acid anhydride/Et3N to afford [4 + 21 cycloadduct 8a (72 and 60%, respectively). In acetonitrile (MeCN) mesylsulfene (7) is formed additionally which surprisingly not only undergoes a [4 + 21 cycloaddition affording endolexo-9 (crystal structure analyses) but also, to a slight extent, a [2 + 21 cycloaddition furnishing 10 the configuration of which was as cycloaddition partners. also proven by a crystal structure analysis. This is the only example of a competing [2 + 21 cycloaddition.Mesyl chloride and Et3N were allowed to react completely at -40°C in MeCN to yield the mesylsulfene-Et3N-S,N adduct 5L61. 6 was subsequently added and only the cycloadducts 9 and 10 derived from mesylsulfene were obtained. When, however, in in-situ experiments, Et3N was replaced by the "proton sponge" (PS) N;N, ","-tetramethyl-1 ,s-naphthalenediamine which for sterical reasons cannot form amine adducts with sulfened51, only the sulfene cycloadduct 8a (66 and 6O%, respectively) was formed, even in MeCN. This proves that the sulfene-Et3N-S,N adduct 4, which cannot be directly detected, represents a precursor of the mesylsulfene-Et,N-S,N adduct 5, and that the sulfene itself undergoes a [4 + 21 cycloaddition affording 8a. This is even more clearly evident from the formation of 8a (48") from 6 and mesyl chloride in the presence of NaH as a base in THE The application of this novel method to the generation of amine-free sulfenes with the formation of hydrogen and poorly-soluble sodium halide prevents secondary reactions of sulfenes which proceed via 3 and 4.Furthermore, with mesyl fluoride, this method even affords 12% of 8a. On the other hand, the use of Et3N in boiling MeCN or THF was here unsuccessful. When an equimolar mixture of 6 and N-(2-methyl-l-propenyl)pyrrolidine was allowed to react with mesyl chloride/Et3N at 0°C in THF, the sulfene was trapped exclusively by the en...

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“…We decided to investigate the usefulness of thiocitric acid 311 or thioisocitric acid 312 as a relatively hydrophilic ligand for gold(1) in what it was hoped would be orally active antiarthritic preparations. While attempts to prepare thiocitric acid 311 failed we were able to carry out an anti-Markovnikov addition of thioacetic acid to aconitic acid 313; see Scheme 37, equation (110). The adduct 314 could then in a straightforward manner be converted to I -(aurothio)-1,2,3-propanetricarboxylic acid hydrate 315, a close analog of myocrisin.…”

Section: Potential Antiarthritic Agentsmentioning

confidence: 99%