Intramolecular nucleophilic participation by the thiol group during amide hydrolysis. Part 2. The imidazole catalysis dilemma

Catalysis by imidazole and N-methylimidazole buffers of the intramolecular thiolysis of N-n-propyl 2-mercaptomethylbenzamide (forming 2-thiophthalide) has been studied in aqueous solution at 40.0 °C, μ = 1.0. Unlike other buffers previously studied, imidazole and N-methylimidazole are able to cataly...

Full description

Saved in:
Bibliographic Details
Published in:Canadian journal of chemistry 1992-01, Vol.70 (1), p.62-67
Main Authors: McDonald, Robert S, Patterson, Patricia, Rodwell, June, Whalley, Ann
Format: Article
Language:English
Citations: Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
cited_by cdi_FETCH-LOGICAL-c1692-4b82152f04707de1a639506aed636a9ca2ce7b0f0b79ad525227da4ee010512d3
cites
container_end_page 67
container_issue 1
container_start_page 62
container_title Canadian journal of chemistry
container_volume 70
creator McDonald, Robert S
Patterson, Patricia
Rodwell, June
Whalley, Ann
description Catalysis by imidazole and N-methylimidazole buffers of the intramolecular thiolysis of N-n-propyl 2-mercaptomethylbenzamide (forming 2-thiophthalide) has been studied in aqueous solution at 40.0 °C, μ = 1.0. Unlike other buffers previously studied, imidazole and N-methylimidazole are able to catalyze, by a general base route, formation of neutral tetrahedral intermediate; this pathway is rate limiting at pH ≤ 7.5. At higher pH, the previously reported general acid-catalyzed breakdown of this intermediate is rate limiting. The relevance of these observations to the currently accepted pathway for the acylation of papain by amide substrates is discussed. Keywords: amide hydrolysis, intramolecular, thiol participation, imidazole, papain model.
doi_str_mv 10.1139/v92-012
format article
fullrecord <record><control><sourceid>crossref_nrcre</sourceid><recordid>TN_cdi_crossref_primary_10_1139_v92_012</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>10_1139_v92_012</sourcerecordid><originalsourceid>FETCH-LOGICAL-c1692-4b82152f04707de1a639506aed636a9ca2ce7b0f0b79ad525227da4ee010512d3</originalsourceid><addsrcrecordid>eNp9kE9LxDAQxYMouK7iV8hJQeg6Sf9tj7K4urCgh_Vcpkm6jaRNSVqhgt_d6O5VD8MwzO_NYx4h1wwWjMXF_UfBI2D8hMxYsoQo5gU7JTMAWEYJJPycXHj_HsYceDojX5tucNhao8Ro0NFuFEbZvtFGC9qjG7TQPQ7adrSa6NCoUNoaund27Kkcne72FFstFW0m6ayZvPYL-hqUlC_oLgh02OJncKACB_wFqNRGtS1ekrMajVdXxz4nb-vH3eo52r48bVYP20iwLLyTVEvOUl5DkkMuFcMsLlLIUMkszrAQyIXKK6ihyguUKU85zyUmSgGDlHEZz8nt4a5w1nun6rJ3ukU3lQzKn9TKkFoZUgvk3YHsnHDKK3Si-Qe--Rs-QmUv6_gbsl19Aw</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Intramolecular nucleophilic participation by the thiol group during amide hydrolysis. Part 2. The imidazole catalysis dilemma</title><source>EZB Electronic Journals Library</source><creator>McDonald, Robert S ; Patterson, Patricia ; Rodwell, June ; Whalley, Ann</creator><creatorcontrib>McDonald, Robert S ; Patterson, Patricia ; Rodwell, June ; Whalley, Ann</creatorcontrib><description>Catalysis by imidazole and N-methylimidazole buffers of the intramolecular thiolysis of N-n-propyl 2-mercaptomethylbenzamide (forming 2-thiophthalide) has been studied in aqueous solution at 40.0 °C, μ = 1.0. Unlike other buffers previously studied, imidazole and N-methylimidazole are able to catalyze, by a general base route, formation of neutral tetrahedral intermediate; this pathway is rate limiting at pH ≤ 7.5. At higher pH, the previously reported general acid-catalyzed breakdown of this intermediate is rate limiting. The relevance of these observations to the currently accepted pathway for the acylation of papain by amide substrates is discussed. Keywords: amide hydrolysis, intramolecular, thiol participation, imidazole, papain model.</description><identifier>ISSN: 0008-4042</identifier><identifier>EISSN: 1480-3291</identifier><identifier>DOI: 10.1139/v92-012</identifier><language>eng</language><publisher>Ottawa, Canada: NRC Research Press</publisher><ispartof>Canadian journal of chemistry, 1992-01, Vol.70 (1), p.62-67</ispartof><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c1692-4b82152f04707de1a639506aed636a9ca2ce7b0f0b79ad525227da4ee010512d3</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>McDonald, Robert S</creatorcontrib><creatorcontrib>Patterson, Patricia</creatorcontrib><creatorcontrib>Rodwell, June</creatorcontrib><creatorcontrib>Whalley, Ann</creatorcontrib><title>Intramolecular nucleophilic participation by the thiol group during amide hydrolysis. Part 2. The imidazole catalysis dilemma</title><title>Canadian journal of chemistry</title><addtitle>Revue canadienne de chimie</addtitle><description>Catalysis by imidazole and N-methylimidazole buffers of the intramolecular thiolysis of N-n-propyl 2-mercaptomethylbenzamide (forming 2-thiophthalide) has been studied in aqueous solution at 40.0 °C, μ = 1.0. Unlike other buffers previously studied, imidazole and N-methylimidazole are able to catalyze, by a general base route, formation of neutral tetrahedral intermediate; this pathway is rate limiting at pH ≤ 7.5. At higher pH, the previously reported general acid-catalyzed breakdown of this intermediate is rate limiting. The relevance of these observations to the currently accepted pathway for the acylation of papain by amide substrates is discussed. Keywords: amide hydrolysis, intramolecular, thiol participation, imidazole, papain model.</description><issn>0008-4042</issn><issn>1480-3291</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1992</creationdate><recordtype>article</recordtype><recordid>eNp9kE9LxDAQxYMouK7iV8hJQeg6Sf9tj7K4urCgh_Vcpkm6jaRNSVqhgt_d6O5VD8MwzO_NYx4h1wwWjMXF_UfBI2D8hMxYsoQo5gU7JTMAWEYJJPycXHj_HsYceDojX5tucNhao8Ro0NFuFEbZvtFGC9qjG7TQPQ7adrSa6NCoUNoaund27Kkcne72FFstFW0m6ayZvPYL-hqUlC_oLgh02OJncKACB_wFqNRGtS1ekrMajVdXxz4nb-vH3eo52r48bVYP20iwLLyTVEvOUl5DkkMuFcMsLlLIUMkszrAQyIXKK6ihyguUKU85zyUmSgGDlHEZz8nt4a5w1nun6rJ3ukU3lQzKn9TKkFoZUgvk3YHsnHDKK3Si-Qe--Rs-QmUv6_gbsl19Aw</recordid><startdate>19920101</startdate><enddate>19920101</enddate><creator>McDonald, Robert S</creator><creator>Patterson, Patricia</creator><creator>Rodwell, June</creator><creator>Whalley, Ann</creator><general>NRC Research Press</general><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>19920101</creationdate><title>Intramolecular nucleophilic participation by the thiol group during amide hydrolysis. Part 2. The imidazole catalysis dilemma</title><author>McDonald, Robert S ; Patterson, Patricia ; Rodwell, June ; Whalley, Ann</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c1692-4b82152f04707de1a639506aed636a9ca2ce7b0f0b79ad525227da4ee010512d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1992</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>McDonald, Robert S</creatorcontrib><creatorcontrib>Patterson, Patricia</creatorcontrib><creatorcontrib>Rodwell, June</creatorcontrib><creatorcontrib>Whalley, Ann</creatorcontrib><collection>CrossRef</collection><jtitle>Canadian journal of chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>McDonald, Robert S</au><au>Patterson, Patricia</au><au>Rodwell, June</au><au>Whalley, Ann</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Intramolecular nucleophilic participation by the thiol group during amide hydrolysis. Part 2. The imidazole catalysis dilemma</atitle><jtitle>Canadian journal of chemistry</jtitle><addtitle>Revue canadienne de chimie</addtitle><date>1992-01-01</date><risdate>1992</risdate><volume>70</volume><issue>1</issue><spage>62</spage><epage>67</epage><pages>62-67</pages><issn>0008-4042</issn><eissn>1480-3291</eissn><abstract>Catalysis by imidazole and N-methylimidazole buffers of the intramolecular thiolysis of N-n-propyl 2-mercaptomethylbenzamide (forming 2-thiophthalide) has been studied in aqueous solution at 40.0 °C, μ = 1.0. Unlike other buffers previously studied, imidazole and N-methylimidazole are able to catalyze, by a general base route, formation of neutral tetrahedral intermediate; this pathway is rate limiting at pH ≤ 7.5. At higher pH, the previously reported general acid-catalyzed breakdown of this intermediate is rate limiting. The relevance of these observations to the currently accepted pathway for the acylation of papain by amide substrates is discussed. Keywords: amide hydrolysis, intramolecular, thiol participation, imidazole, papain model.</abstract><cop>Ottawa, Canada</cop><pub>NRC Research Press</pub><doi>10.1139/v92-012</doi><tpages>6</tpages><oa>free_for_read</oa></addata></record>
fulltext fulltext
identifier ISSN: 0008-4042
ispartof Canadian journal of chemistry, 1992-01, Vol.70 (1), p.62-67
issn 0008-4042
1480-3291
language eng
recordid cdi_crossref_primary_10_1139_v92_012
source EZB Electronic Journals Library
title Intramolecular nucleophilic participation by the thiol group during amide hydrolysis. Part 2. The imidazole catalysis dilemma
url http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-28T19%3A18%3A07IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-crossref_nrcre&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Intramolecular%20nucleophilic%20participation%20by%20the%20thiol%20group%20during%20amide%20hydrolysis.%20Part%202.%20The%20imidazole%20catalysis%20dilemma&rft.jtitle=Canadian%20journal%20of%20chemistry&rft.au=McDonald,%20Robert%20S&rft.date=1992-01-01&rft.volume=70&rft.issue=1&rft.spage=62&rft.epage=67&rft.pages=62-67&rft.issn=0008-4042&rft.eissn=1480-3291&rft_id=info:doi/10.1139/v92-012&rft_dat=%3Ccrossref_nrcre%3E10_1139_v92_012%3C/crossref_nrcre%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-c1692-4b82152f04707de1a639506aed636a9ca2ce7b0f0b79ad525227da4ee010512d3%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true