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).

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.

The Mechanism for Hydrolysis of Primary Alkyl Chlorosulfates in Water. The Kinetic Solvent Isotope Effect and the Secondary Deuterium Isotope Effect

1972 ◽  
Vol 50 (3) ◽  
pp. 434-437 ◽  
Author(s):  
E. C. F. Ko ◽  
R. E. Robertson
Keyword(s):  
Isotope Effect ◽  
Sulfonyl Chloride ◽  
Alkyl Halides ◽  
Activation Process ◽  
Deuterium Isotope Effect ◽  
Solvent Isotope Effect ◽  
Temperature Coefficients ◽  
Enthalpy Of Activation ◽  
Solvent Isotope ◽  
Hydrolysis Of

The temperature coefficients of the enthalpy of activation [Formula: see text] for the hydrolysis of the three chlorosulfates, methyl, ethyl, and β-chloro, are shown to have values of −50,−55, and −60 cal deg−1 mol−1; values in the same range as previously reported for the hydrolysis of the sulfonyl chlorides. The corresponding value for the β-methoxy isomer was −40 cal deg−1 mol−1, about the same as found for the p-methoxybenzenesulfonyl chloride. The kinetic solvent isotope effect, however, was significantly lower than reported for the sulfonyl chloride series, being about the same as found for the hydrolysis of the alkyl halides. While some degree of nucleophilic overlap is probably required in the activation process, the requirement here is reduced to about the same level as that for the primary halides, and there is no need to postulate a different mechanism on passing from the methyl to the ethyl member of the series, confirming the earlier conclusion of Buncel and Millington.

scholarly journals Amino acid sulfonamides based on 4-(1-oxo-1H-isochromen-3-yl)benzenesulfonyl chloride

2020 ◽  
Vol 15 (2) ◽  
pp. 27-32
Author(s):  
Anastasiia Riabchenko ◽  
Olga Shablykina ◽  
Serhiy Shilin ◽  
Svitlana Chumachenko ◽  
Volodymyr Khilya
Keyword(s):  
Amino Acid ◽  
Methyl Esters ◽  
Sulfonyl Chloride ◽  
Benzenesulfonyl Chloride ◽  
Acid Methyl ◽  
Similar Product ◽  
Alkali Hydrolysis ◽  
Hydrolysis Of ◽  
Derivatives Of ◽  
Amino Acid Methyl Esters

The creation of new amino acid derivatives of 4-(1-oxo-1H-isochromen-3-yl)benzenesulfonyl chloride 1 was investigated. The interaction of the sulfonyl chloride 1 with amino acid methyl esters (hydrochlorides) in 1,4-dioxane in the presence of triethylamine led to the corresponding amino acid sulfonamide derivatives of isocoumarin. The reaction of the sulfonyl chloride 1 with phenylalanine in the basic aqueous solution was complicated by the lactone system disclosure and led to 2'-carboxydeoxybenzoin ultimately (namely, 2-(2-(4-(N-(1-carboxy-2-phenylethyl)sulfamoyl)phenyl)-2-oxoethyl)benzoic acid). Similar product was obtained by the alkali hydrolysis of methyl ((4-(1-oxo-1H-isochromen-3-yl)phenyl)sulfonyl)leucinate.

Catalysis by α-substituted pyridines in the hydrolysis of aryl acetates and acetic anhydride

1983 ◽  
Vol 36 (10) ◽  
pp. 1951 ◽  
Author(s):  
LW Deady ◽  
WL Finlayson
Keyword(s):  
Acetic Anhydride ◽  
Nucleophilic Catalysis ◽  
Substituted Pyridines ◽  
Hydrolysis Of

Results for the hydrolysis of p-nitrophenyl acetate, 2,4-dinitrophenyl acetate and acetic anhydride, catalysed by various substituted 2-amino- and 2-methyl-pyridines, are reported. The results seem consistent with nucleophilic catalysis throughout, contrary to some literature reports.

Neutral Solvolysis of Acyl Carbon and the Temperature Dependence of the Kinetic Solvent Isotope Effect

1975 ◽  
Vol 53 (6) ◽  
pp. 869-877 ◽  
Author(s):  
B. Rossall ◽  
R. E. Robertson
Keyword(s):  
Temperature Dependence ◽  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Acyl Carbon ◽  
Rate Of Hydrolysis ◽  
Solvent Isotope ◽  
Neutral Conditions ◽  
Hydrolysis Of

The temperature dependence of the rate of hydrolysis of benzoic, phthalic, and succinic anhydrides have been determined in H2O and D2O under "neutral" conditions. Corresponding data have been obtained for methyl trifluoroacetate. While both series supposedly react by the same BAc2 mechanism, remarkable differences are made obvious by this investigation. Possible sources of such differences are proposed.

scholarly journals One-proton catalysis by the α-l-arabinofuranosidase III of Monilinia fructigena

1988 ◽  
Vol 254 (3) ◽  
pp. 899-901 ◽  
Author(s):  
T Selwood ◽  
M L Sinnott
Keyword(s):  
Isotopic Composition ◽  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Monilinia Fructigena ◽  
Single Proton ◽  
Solvent Isotope ◽  
Hydrolysis Of

1. Michaelis-Menten parameters for the hydrolysis of p-nitrophenyl alpha-L-arabinofuranoside were measured as a function of pL (pH or pD) in both 1H2O and 2H2O. 2. The variation of both Vmax. and Vmax./Km with pL is sigmoid, the pK governing Vmax. shifting from 6.34 +/- 0.05 in 1H2O to 6.84 +/- 0.07 in 2H2O, and that governing Vmax./Km from 5.89 +/- 0.03 in 1H2O to 6.38 +/- 0.05 in 2H2O. 3. In the plateau regions there is a small inverse solvent isotope effect on Vmax./Km (0.92), and one of 1.45 on Vmax. 4. The variation of Vmax. with isotopic composition is strictly linear, indicating that the isotope effect arises from the transfer of a single proton.

Nucleophilic catalysis of the hydrolysis of phenyl acetates by the succinimide anion in aqueous solution

1982 ◽  
Vol 47 (19) ◽  
pp. 3687-3691 ◽  
Author(s):  
Robert W. Huffman
Keyword(s):  
Aqueous Solution ◽  
Nucleophilic Catalysis ◽  
Hydrolysis Of

scholarly journals Research Article Product Composition Analysis and Process Research of Oligosaccharides Produced from Enzymatic Hydrolysis of High-Concentration Konjac Flour

ACS Omega ◽  
2020 ◽  
Vol 5 (5) ◽  
pp. 2480-2487
Author(s):  
Xianghua Tang ◽  
Xuan Zhu ◽  
Yunjuan Yang ◽  
Zhenxiong Qi ◽  
YueLin Mu ◽  
...  
Keyword(s):  
Enzymatic Hydrolysis ◽  
Process Research ◽  
Composition Analysis ◽  
High Concentration ◽  
Research Article ◽  
Product Composition ◽  
Konjac Flour ◽  
Hydrolysis Of
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