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Generation and trapping of ketenes in flow

Generation and trapping of ketenes in flow
Generation and trapping of ketenes in flow
Ketenes were generated by the thermolysis of alkoxyalkynes under flow conditions, and then trapped with amines and alcohols to cleanly give amides and esters. For a 10 min reaction time, temperatures of 180, 160, and 140 °C were required for >95?% conversion of EtO, iPrO, and tBuO alkoxyalkynes, respectively. Variation of the temperature and flow rate with inline monitoring of the output by IR spectroscopy allowed the kinetic parameters for the conversion of 1-ethoxy-1-octyne to be easily estimated (Ea = 105.4 kJ/mol). Trapping of the in-situ-generated ketenes by alcohols to give esters required the addition of a tertiary amine catalyst to prevent competitive [2+2] addition of the ketene to the alkoxyalkyne precursor
1434-193X
1491-1499
Henry, Cyril
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Bolien, David
5714a236-3f98-4069-9f96-a920c7a2966c
Ibanescu, Bogdan
f7ef4483-39f7-477e-ab85-b5e0bad2f7bc
Bloodworth, Sally
943160fc-1b70-4c29-b2e3-b7785cee8a0c
Harrowven, David C.
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Zhang, Xunli
d7cf1181-3276-4da1-9150-e212b333abb1
Craven, Andy
168347a1-62dc-4e3e-ac44-c1b91ab3de0b
Sneddon, Helen F.
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Whitby, Richard J.
45632236-ab00-4ad0-a02d-6209043e818b
Henry, Cyril
eaaacffd-d2a8-4c17-94b3-ffa2baed89ba
Bolien, David
5714a236-3f98-4069-9f96-a920c7a2966c
Ibanescu, Bogdan
f7ef4483-39f7-477e-ab85-b5e0bad2f7bc
Bloodworth, Sally
943160fc-1b70-4c29-b2e3-b7785cee8a0c
Harrowven, David C.
bddcfab6-dbde-49df-aec2-42abbcf5d10b
Zhang, Xunli
d7cf1181-3276-4da1-9150-e212b333abb1
Craven, Andy
168347a1-62dc-4e3e-ac44-c1b91ab3de0b
Sneddon, Helen F.
33850179-8489-433a-b8c9-09536a4e2b18
Whitby, Richard J.
45632236-ab00-4ad0-a02d-6209043e818b

Henry, Cyril, Bolien, David, Ibanescu, Bogdan, Bloodworth, Sally, Harrowven, David C., Zhang, Xunli, Craven, Andy, Sneddon, Helen F. and Whitby, Richard J. (2015) Generation and trapping of ketenes in flow. European Journal of Organic Chemistry, 2015 (7), 1491-1499. (doi:10.1002/ejoc.201403603).

Record type: Article

Abstract

Ketenes were generated by the thermolysis of alkoxyalkynes under flow conditions, and then trapped with amines and alcohols to cleanly give amides and esters. For a 10 min reaction time, temperatures of 180, 160, and 140 °C were required for >95?% conversion of EtO, iPrO, and tBuO alkoxyalkynes, respectively. Variation of the temperature and flow rate with inline monitoring of the output by IR spectroscopy allowed the kinetic parameters for the conversion of 1-ethoxy-1-octyne to be easily estimated (Ea = 105.4 kJ/mol). Trapping of the in-situ-generated ketenes by alcohols to give esters required the addition of a tertiary amine catalyst to prevent competitive [2+2] addition of the ketene to the alkoxyalkyne precursor

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Published date: February 2015
Organisations: Chemistry, Faculty of Engineering and the Environment

Identifiers

Local EPrints ID: 374790
URI: http://eprints.soton.ac.uk/id/eprint/374790
ISSN: 1434-193X
PURE UUID: 47f24f57-5549-427b-83ed-cb18c12c29f5
ORCID for Sally Bloodworth: ORCID iD orcid.org/0000-0003-2219-3635
ORCID for David C. Harrowven: ORCID iD orcid.org/0000-0001-6730-3573
ORCID for Xunli Zhang: ORCID iD orcid.org/0000-0002-4375-1571
ORCID for Richard J. Whitby: ORCID iD orcid.org/0000-0002-9891-5502

Catalogue record

Date deposited: 02 Mar 2015 11:17
Last modified: 18 Feb 2021 16:58

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Contributors

Author: Cyril Henry
Author: David Bolien
Author: Bogdan Ibanescu
Author: Xunli Zhang ORCID iD
Author: Andy Craven
Author: Helen F. Sneddon

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