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

1989 ◽  
Vol 67 (2) ◽  
pp. 330-334
Author(s):  
James Frederick King ◽  
Sheena May Loosmore ◽  
John Henry Hillhouse ◽  
Kishan Chand Khemani
Keyword(s):  
Tertiary Amine ◽  
Reaction Pathway ◽  
Sulfonyl Chloride ◽  
Side Reactions ◽  
Tertiary Amines ◽  
Nucleophilic Catalysis ◽  
Product Composition ◽  
Major Process ◽  
A Minor ◽  
Transfer Mechanisms

Ethenesulfonyl chloride (1) reacts with alcohols in the presence of tertiary amines to give a mixture of the alkyl ethenesulfonate (5) and the alkyl betylate (R3′N+CH2CH2SO2OR Cl−). 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 major process 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 E1cB process, and that the minor pathway is simply the result of side reactions of the carbanion (14). Keywords: sulfenes, sulfonyl transfer mechanisms, vinylogous nucleophilic catalysis.

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

1984 ◽  
Vol 62 (10) ◽  
pp. 1977-1995 ◽  
Author(s):  
James Frederick King ◽  
John Henry Hillhouse ◽  
Stanisław Skonieczny
Keyword(s):  
Sulfonyl Chloride ◽  
Tertiary Amines ◽  
Nucleophilic Catalysis ◽  
Product Composition ◽  
Similar Product ◽  
Substituted Pyridines ◽  
Solvent Isotope ◽  
Zwitterionic Intermediate ◽  
Hydrolysis Of ◽  
Concerted Reaction

We present evidence that the reactions of ethenesulfonyl chloride (1) and trans-1-propene-1-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 sulfene, [Formula: see text], which subsequently reacts with water either by addition (and deprotonation) to form the betaine [Formula: see text], or by vinylogous substitution (and deprotonation) to give the alkenesulfonate anion, [Formula: see text] (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 (a) α-monodeuteration in the betaine and lack of deuteration of the ethenesulfonate [Formula: see text] from the reaction in D2O, (b) rate lowerings of up to 2000-fold for 2- (and 6-) substituted pyridines from those expected from Brønsted-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+CH2CH2SO2Cl Cl− (18a) with aqueous pyridine. For the initial formation of the sulfene, [Formula: see text], 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-1-alkanesulfonate anion by way of the sulfene HOCHRCH=SO2 (R = H or CH3).

Organic sulfur mechanisms. 24. Preparation and reactions of 2-hydroxyethanesulfonyl chloride, the first hydroxyalkanesulfonyl chloride

1983 ◽  
Vol 61 (7) ◽  
pp. 1583-1593 ◽  
Author(s):  
James Frederick King ◽  
John Henry Hillhouse
Keyword(s):  
Aqueous Solution ◽  
Hydroxy Group ◽  
Intramolecular Cyclization ◽  
Ring Opening ◽  
Sulfonyl Chloride ◽  
Tertiary Amines ◽  
Deuterium Labelling ◽  
Chlorination Process ◽  
Principal Reaction ◽  
A Minor

2-Hydroxyethanesulfonyl chloride (1a) is readily made by reaction of an aqueous solution of 2-mercaptoethanol (4a) with chlorine. This is the first clearly proved preparation of a compound which is both an alcohol and a sulfonyl chloride. Reactions of 1a with water and alcohols evidently proceed largely by intramolecular cyclization to the transient β-sultone (2a), which then undergoes nuclcophilic ring opening to form the products. In the presence of tertiary amines a minor but significant part of the reaction is shown by deuterium labelling to proceed via hydroxymethylsulfene (14). the principal reaction of which is simply to add the alcohol or water; only a small part, if any, of the sulfene (14) loses the hydroxy¡ group to give the ethenesulfonate derivatives (13 or 22). Aqueous chlorination of 3-mercapto-1-propanol gave 3-chloro-1-propanesulfonyl chloride (5a) and 1,3-propane sultone (2b) with no sign of any 3-hydroxy-1-propanesulfonyl chloride (1b). A mechanism for the aqueous chlorination process invoking a cyclic chlorooxasulfoxoniuin ion (27) is discussed.

scholarly journals CO2 Methanation over Rh/CeO2 Studied with Infrared Modulation Excitation Spectroscopy and Phase Sensitive Detection

Catalysts ◽  
2020 ◽  
Vol 10 (6) ◽  
pp. 601
Author(s):  
Felix Hemmingsson ◽  
Andreas Schaefer ◽  
Magnus Skoglundh ◽  
Per-Anders Carlsson
Keyword(s):  
Reaction Pathway ◽  
Sensitive Detection ◽  
Side Reactions ◽  
Co2 Methanation ◽  
Individual Contributions ◽  
Phase Sensitive ◽  
Phase Sensitive Detection ◽  
Modulation Excitation Spectroscopy ◽  
Modulation Excitation

Methane is a well-established fuel molecule whose production from CO 2 through methanation garners increasing interest as an energy storage solution. While often produced with Ni based catalysts, other metals are of interest thanks to higher robustness and activity-selectivity numbers. The Rh/CeO 2 catalyst has shown appreciable properties for CO 2 methanation and its structural dynamics has been studied in situ. However, the reaction pathway is unknown. Here, we present infrared modulation excitation spectroscopy measurements with phase sensitive detection of a Rh/CeO 2 catalyst adsorbate composition during H 2 pulsing (0–2 vol.%) to a constant CO 2 (0.5 vol.%) feed. Various carbonyl (CO) and carbonate (b-CO 3 /p-CO 3 ) ad-species clearly respond to the hydrogen stimulus, making them potential reaction intermediates. The different CO ad-species are likely intermediates for product CO and CH 4 but their individual contributions to the respective formations are not unambiguously ascertained. As for the carbonate dynamics, it might be linked to the reduction/oxidation of the CeO 2 surface upon H 2 pulsing. Formate (HCOO) ad-species are clearly visible but appear to be, if not spectators, linked to slow side reactions possibly also affected by CeO 2 redox processes.

Tertiary amine-catalyzed and direct synthesis of α-chloroalkanesulfonylhydrazines from azodicarboxylates and sulfonyl chlorides

2016 ◽  
Vol 14 (21) ◽  
pp. 4918-4926 ◽  
Author(s):  
Bingnan Zhou ◽  
Jiaxi Xu
Keyword(s):  
Tertiary Amine ◽  
Direct Synthesis ◽  
Tertiary Amines ◽  
Sulfonyl Chlorides

α-Chloroalkanesulfonylhydrazines were synthesized directly and efficiently from alkanesulfonyl chlorides and dialkyl azodicarboxylates under the catalysis of tertiary amines.

Oxidative reaction of 2-aminopyridine-3-sulfonyl chlorides with tertiary amines

2016 ◽  
Vol 22 (6) ◽  
Author(s):  
Huiping Wei ◽  
Gaigai Wang ◽  
Binbin Li ◽  
Jianjun Huang ◽  
Haiyan Li ◽  
...  
Keyword(s):  
Aerobic Oxidation ◽  
Sulfonyl Chloride ◽  
Dual Role ◽  
Tertiary Amines ◽  
Oxidative Reaction ◽  
Sulfonyl Chlorides

Abstract2-Aminopyridine-3-sulfonyl chlorides undergo a reaction with tertiary amines in the presence of air to produce sulfonylethenamines. The 2-aminopyridine-3-sulfonyl chloride apparently plays a dual role in the process promoting the aerobic oxidation of the amine and electrophilically trapping the resulting enamine.

Simulation of radical polymerization of methyl methacrylate at room temperature using a tertiary amine/BPO initiating system

2015 ◽  
Vol 6 (31) ◽  
pp. 5719-5727 ◽  
Author(s):  
Alexander Zoller ◽  
Didier Gigmes ◽  
Yohann Guillaneuf
Keyword(s):  
Methyl Methacrylate ◽  
Radical Polymerization ◽  
Free Volume ◽  
Tertiary Amine ◽  
Room Temperature ◽  
Empirical Models ◽  
Side Reactions ◽  
System P

A model was developed for the polymerization of methyl methacrylate at room temperature. The model used both free volume and empirical models for propagation, termination and several side reactions.

scholarly journals The α-tertiary amine motif drives remarkable selectivity for Pd-catalyzed carbonylation of β-methylene C–H bonds

2017 ◽  
Vol 8 (12) ◽  
pp. 8198-8203 ◽  
Author(s):  
Kirsten F. Hogg ◽  
Aaron Trowbridge ◽  
Andrea Alvarez-Pérez ◽  
Matthew J. Gaunt
Keyword(s):  
Tertiary Amine ◽  
Tertiary Amines

The selective C–H carbonylation of methylene bonds, in the presence of traditionally more reactive methyl C–H and C(sp2)–H bonds, in α-tertiary amines is reported.

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