The Role of Sulfene Intermediates in the Alcoholysis of Sulfonyl Halides in the Presence of Triethylamine<sup>1</sup>

Truce, William E.; Campbell, Robert W.

doi:10.1021/ja00967a024

Cited by 32 publications

(10 citation statements)

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“…Truce and Campbell (13) noted that reaction of 3 with triethylamine and methyl and ethyl alcohols gave both the rearranged and unrearranged esters and suggested that the former arose from vinylsulfene (CH2=CHCH=S02) and the latter from the sulfonylammonium ion (CH,CH= CHS02NtEt3). Remarkably, however, the products of simple hydrolysis of neither 1 nor 3 seem to have been described.…”

Section: C=c-a-nu+mentioning

confidence: 99%

“…There are two accepted general mechanisms for hydrolysis of alkanesulfonyl chlorides, or, more generally, for reactions of the following type RSO'Z + Nu1-' + RSO2Nu + Z'-' wherein Z is a leaving group (nucleofuge), and Nu1-' a nucleophile: (i) a dkect displacement on the sulfur atom (DDS mechanism) ( addition process going by way of an intermediate sulfene (R1R"C=S02) (12)(13)(14)(15)(16). Direct displacement, which may be a single reaction or involve two consecutive direct displacements in a nucleophilic catalysis mechanism, is observed in reactions of arenesulfonyl chlorides (2-7) and related species (lo, 1 1 ), and presumably with derivatives of alkanesulfonic acids lacking an &-hydrogen.…”

Section: Introductionmentioning

confidence: 99%

“…Direct displacement, which may be a single reaction or involve two consecutive direct displacements in a nucleophilic catalysis mechanism, is observed in reactions of arenesulfonyl chlorides (2-7) and related species (lo, 1 1 ), and presumably with derivatives of alkanesulfonic acids lacking an &-hydrogen. Elimination-addition, on the other hand, is the usual pathway for reactions of alkanesulfonyl chlorides and the like that have an &-hydrogen, in such common preparative reactions as the formation of alkanesulfonate esters by reaction of the alkanesulfonyl chloride with an alcohol and a tertiary amine (12)(13)(14); the direct displacement is observed, however, in the simple uncatalyzed hydrolysis and alcoholysis Can. J. Chem.…”

Section: Introductionmentioning

confidence: 99%

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Vinylogous nucleophilic catalysis. Tertiary amine promoted hydrolysis of 1-alkene-1-sulfonyl chlorides

King¹,

Hillhouse²,

Skonieczny³

1984

Can. J. Chem.

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This paper is dedicated to Professor Paul de Mayo on the occasion of his 60th birthday JAMES FREDERICK KING, JOHN HENRY HILLHOUSE, and STANISLAW SKONIECZNY. Can. J. Chem. 62, 1977Chem. 62, (1984. We present evidence that the reactions of ethenesulfonyl chloride ( I ) and trcrt~s-l -propene-l -sulfonyl chloride (3) with water in the presence of pyridine, trimethylamine, and a number of other tertiary amines proceed primarily by way of an initial + vinylogous substitution reaction to form the cationic sulFne, R.;NCHRCH=SOZ. which subsequently reacts with water either by addition (and deprotonation) to form the betaine R.;NCHRCHZSOI, or by vinylogous substitution (and deprotonation) to give the alkenesulfonate anion. CHR=CHSO, (R = H or CH3). Formation of,the latter represents the first well-supported example of vinylogous nucleophilic catalysis. These conclusions are drawn from kinetic and product composition observations, including ( ( I ) a-monodeuteration in the betaine and lack of deuteration of the ethenesulfonate (CHZ=CHSO,) from the reaction in DZO, fb) rate lowerings of up to 2000-fold for 2-(and 6-) substituted pyridines from those expected from Bronsted-type relationships shown by "unhindered" pyridine bases, (c) lack of a kinetic solvent isotope effect in the reaction of 1 with 3-cyanopyridine, (d) a lower rate of reaction of 3 vs. 1 not directly correlated with product composition, and (e) formation of similar product mixtures from either 1 or Pyr'CHZCHZSOZCI CI- (180) with aqueous pyridine. For the initial + formation of the sulfene, R3NCHZCH=SOZ, the available evidence does not distinguish between a two-step mechanism via an intermediate zwitterion and a closely related concerted reaction, but for the further reaction of the sulfene a process involving a zwitterionic intermediate common to both products is favoured. For the reaction of 1 or 3 in the absence of tertiary amines evidence is presented for a direct displacement on sulfur mechanism leading to the alkenesulfonate anion, plus a small proportion (up to 15%) of formation of the 2-hydroxy-I-alkanesulfonate anion by way of the sulfene HOCHRCH=SOZ (R = H or CH3).JAMES FREDERICK KING, JOHN HENRY HILLHOUSE et STANISLAW SKONIECZNY. Can. J . Chem. 62, 1977Chem. 62, (1984. On rapporte des donnCes qui suggkrent que la rCaction du chlorure d'6thknesulfonyle ( I ) et du chlorure de propkne-l sulfonyle-l trans (3) avec de I'eau, en prCsence de pyridine, de trimkthylamine et d'un certain nombre d'autres amines tertiaires, se produit principalement par le biais d'une rkaction initiale de substitution vinylogue conduisant i la formation du sulfkne cationique R;NCHRCH=SOZ, qui rkagit ensuite avec de I'eau soit par une addition (et une dCprotonation) pour former la bCtaYne R;NCHRCHZSO, soit par une substitution vinylogue (et une dCprotonation) pour donner I'anion alcknesulfonate, CHR=CHSO, (R = H ou CH3). La formation de ce dernier compose represente le premier exemple bien document6 d'une catalyse nuclCophile vinylogue. On tire ces conclusions en se basan...

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Section: C=c-a-nu+mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Vinylogous nucleophilic catalysis. Tertiary amine promoted hydrolysis of 1-alkene-1-sulfonyl chlorides

King¹,

Hillhouse²,

Skonieczny³

1984

Can. J. Chem.

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“…These esters had been prepared, however, under similar conditions from 2-chloroethanesulfonyl chloride (14,15), which is known to yield 1 on treatment with 2,6-lutidine (16). In addition, Truce and Campbell (8) had looked at the action of triethylamine and alcohols on 1 -propene-1 -sulfonyl chloride and had noted the formation of both the 1 -propene-and 2-propenesulfonate esters, CH3CH=CHS020R and CH2= CHCH2S020R. In our first experiments (13), simple mixing of 1 with 2-propanol in the presence of pyridine or trimethylamine followed by conventional work-up gave the ethenesulfonate ester (5, R = Pri) in mediocre (40-50%) yield.…”

Section: Initial Experiments and Related Workmentioning

confidence: 99%

“…With the esterifications, however, it is evident that although the principal reaction mode corresponds to that in water, some interconversion of 1 and 9 may occur. Consideration of how this latter reaction might take place leads to a circumstantial case for the detailed mechanism of the formation of the sulfene (8) in this system, as described in the next section.…”

Section: Initial Experiments and Related Workmentioning

confidence: 99%

Vinylogous nucleophilic catalysis. The tertiary amine promoted reaction of ethenesulfonyl chloride with alcohols

King¹,

Loosmore²,

Hillhouse³

et al. 1989

Can. J. Chem.

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Can. J. Chem. 67,330 (1989).Ethenesulfonyl chloride (1) reacts with alcohols in the presence of tertiary amines to give amixture of the alkyl ethenesulfonate (5) and the alkyl betylate ( R~' N ' C H~C H~S O~O R C1-). With pyridine and neopentyl alcohol the product composition from the reaction of 1 is identical to that from the pyridinio-sulfonyl chloride (9). These results, when taken with experiments with deuterium labelled reagents, lead to the conclusion that the major (-80%) reaction pathway involves conversion of 1 or 9 to the sulfene 8, which reacts with the alcohol to form 5 or the betylate, and hence vinylogous nucleophilic catalysis is the majorprocess leading to 5. The labelling experiments disclosed a minor pathway, evidently involving interconversion of 1 and 9. Examination of possible mechanisms leads to the suggestion that the sulfene is formed from 1 or 9 by way of the carbanion (14), i.e., that 9 reacts by an ElcB process, and that the minor pathway is simply the result of side reactions of the carbanion (14).Key words: sulfenes, sulfonyl transfer mechanisms, vinylogous nucleophilic catalysis.JAMES FREDERICK KING, SHEENA MAY LOOSMORE, JOHN HENRY HILLHOUSE et KISHAN CHAND KHEMANI. Can. J. Chem. 67,330 (1989).Le chlorure d1Cthknesulfony1e (1) rkagit avec les alcools, en prCsence d'amines tertiaires, pour conduire a un mClange d'ethknesulfonate d'alkyle (5) et de bCtylate d'alkyle (R3'N+CH2CH2SO2OR C1-). La rtaction du compost 1 avec I'alcool nCopentylique en presence de pyridine conduit a un melange dont la composition est identique a celle obtenue a partir du chlorure de pyridinio-sulfonyle (9). Lorsqu'on considkre ces rCsultats de concert avec les experiences effectutes a I'aide de rCactifs marques au deutCrium, on arrive a la conclusion que la principale voie rCactionnelle (-80%) implique la transformation des composts 1 ou 9 en sulfkne 8 qui reagit avec I'alcool pour former le composC 5 ou le bttylate; on en dCduit que la catalyse nuclCophile vinylogue est le processus principal conduisant au produit 5. Les expCriences de marquage ont mis en evidence l'existence d'une voie secondaire impliquant Cvidemment une interconversion des composCs 1 et 9. Un examen des divers mkcanismes possibles conduit a suggCrer que le sulfkne se forme a partir des composCs 1 ou 9 par le biais du carbanion 14, c'est-a-dire que le composC 9 rCagit par un processus ElcB et que le produit mineur n'est que le resultat de rCactions secondaires du carbanion 14.Mots clPs : sulfknes, mkcanismes de transfert sulfonyle, catalyse nuclCophile vinylogue.[Traduit par la revue]

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

Opitz

1967

Angewandte Chemie

106

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The Role of Sulfene Intermediates in the Alcoholysis of Sulfonyl Halides in the Presence of Triethylamine¹

Cited by 32 publications

References 5 publications

Vinylogous nucleophilic catalysis. Tertiary amine promoted hydrolysis of 1-alkene-1-sulfonyl chlorides

Vinylogous nucleophilic catalysis. Tertiary amine promoted hydrolysis of 1-alkene-1-sulfonyl chlorides

Vinylogous nucleophilic catalysis. The tertiary amine promoted reaction of ethenesulfonyl chloride with alcohols

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

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The Role of Sulfene Intermediates in the Alcoholysis of Sulfonyl Halides in the Presence of Triethylamine1

Cited by 32 publications

References 5 publications

Vinylogous nucleophilic catalysis. Tertiary amine promoted hydrolysis of 1-alkene-1-sulfonyl chlorides

Vinylogous nucleophilic catalysis. Tertiary amine promoted hydrolysis of 1-alkene-1-sulfonyl chlorides

Vinylogous nucleophilic catalysis. The tertiary amine promoted reaction of ethenesulfonyl chloride with alcohols

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

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The Role of Sulfene Intermediates in the Alcoholysis of Sulfonyl Halides in the Presence of Triethylamine¹