Formation of acrylic acid from lactic acid in supercritical water
Supercritical (SC) water is an unusual medium in which fast and specific heterolytic reactions can be conducted at temperatures as high as 400{degree}C. In supercritical water, lactic acid decomposes into gaseous and liquid products via three primary reaction pathways. Products of the acid-catalyzed...
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| Veröffentlicht in: | Journal of organic chemistry 1989-09, Vol.54 (19), p.4596-4602 |
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| container_end_page | 4602 |
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| container_issue | 19 |
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| container_title | Journal of organic chemistry |
| container_volume | 54 |
| creator | Mok, William Shu Lai Antal, Michael Jerry Jones, Maitland |
| description | Supercritical (SC) water is an unusual medium in which fast and specific heterolytic reactions can be conducted at temperatures as high as 400{degree}C. In supercritical water, lactic acid decomposes into gaseous and liquid products via three primary reaction pathways. Products of the acid-catalyzed heterolytic decarbonylation pathway are carbon monoxide, water, and acetaldehyde. Products of the homolytic, decarboxylation pathway are carbon dioxide, hydrogen, and acetaldehyde. Products of the heterolytic, dehydration pathway are acrylic acid and water. The intramolecular nucleophilic displacement of the {alpha}-hydroxyl by the carbonyl group of lactic acid, producing {alpha}-propiolactone as an unstable intermediate which subsequently rearranges to become the unsaturated acid, is a likely mechanism for acrylic acid formation, although an intramolecular E2 elimination initiated by attack of the carbonyl oxygen on a methyl hydrogen cannot be ruled out. Support for the former mechanism comes in part from the observed 100% relative yield of acrylic acid from {beta}-propiolactone in SC water. |
| doi_str_mv | 10.1021/jo00280a027 |
| format | Article |
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In supercritical water, lactic acid decomposes into gaseous and liquid products via three primary reaction pathways. Products of the acid-catalyzed heterolytic decarbonylation pathway are carbon monoxide, water, and acetaldehyde. Products of the homolytic, decarboxylation pathway are carbon dioxide, hydrogen, and acetaldehyde. Products of the heterolytic, dehydration pathway are acrylic acid and water. The intramolecular nucleophilic displacement of the {alpha}-hydroxyl by the carbonyl group of lactic acid, producing {alpha}-propiolactone as an unstable intermediate which subsequently rearranges to become the unsaturated acid, is a likely mechanism for acrylic acid formation, although an intramolecular E2 elimination initiated by attack of the carbonyl oxygen on a methyl hydrogen cannot be ruled out. Support for the former mechanism comes in part from the observed 100% relative yield of acrylic acid from {beta}-propiolactone in SC water.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/jo00280a027</identifier><identifier>CODEN: JOCEAH</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>400201 - Chemical & Physicochemical Properties ; ACRYLIC ACID ; CARBOXYLIC ACIDS ; Chemistry ; DATA ; DATA ANALYSIS ; Exact sciences and technology ; EXPERIMENTAL DATA ; HYDROGEN COMPOUNDS ; HYDROXY ACIDS ; INFORMATION ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; Kinetics and mechanisms ; LACTIC ACID ; MEASURING INSTRUMENTS ; MEASURING METHODS ; MONOCARBOXYLIC ACIDS ; NUMERICAL DATA ; ORGANIC ACIDS ; Organic chemistry ; ORGANIC COMPOUNDS ; OXYGEN COMPOUNDS ; PRODUCTION ; Reactivity and mechanisms ; SUPERCRITICAL STATE ; WATER</subject><ispartof>Journal of organic chemistry, 1989-09, Vol.54 (19), p.4596-4602</ispartof><rights>1990 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a423t-f2ac27735f14a9364f51db8e114d36011b8605052712d7139b044c977cd893063</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jo00280a027$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jo00280a027$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,314,780,784,885,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=6748348$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/7156258$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Mok, William Shu Lai</creatorcontrib><creatorcontrib>Antal, Michael Jerry</creatorcontrib><creatorcontrib>Jones, Maitland</creatorcontrib><title>Formation of acrylic acid from lactic acid in supercritical water</title><title>Journal of organic chemistry</title><addtitle>J. Org. Chem</addtitle><description>Supercritical (SC) water is an unusual medium in which fast and specific heterolytic reactions can be conducted at temperatures as high as 400{degree}C. In supercritical water, lactic acid decomposes into gaseous and liquid products via three primary reaction pathways. Products of the acid-catalyzed heterolytic decarbonylation pathway are carbon monoxide, water, and acetaldehyde. Products of the homolytic, decarboxylation pathway are carbon dioxide, hydrogen, and acetaldehyde. Products of the heterolytic, dehydration pathway are acrylic acid and water. The intramolecular nucleophilic displacement of the {alpha}-hydroxyl by the carbonyl group of lactic acid, producing {alpha}-propiolactone as an unstable intermediate which subsequently rearranges to become the unsaturated acid, is a likely mechanism for acrylic acid formation, although an intramolecular E2 elimination initiated by attack of the carbonyl oxygen on a methyl hydrogen cannot be ruled out. Support for the former mechanism comes in part from the observed 100% relative yield of acrylic acid from {beta}-propiolactone in SC water.</description><subject>400201 - Chemical & Physicochemical Properties</subject><subject>ACRYLIC ACID</subject><subject>CARBOXYLIC ACIDS</subject><subject>Chemistry</subject><subject>DATA</subject><subject>DATA ANALYSIS</subject><subject>Exact sciences and technology</subject><subject>EXPERIMENTAL DATA</subject><subject>HYDROGEN COMPOUNDS</subject><subject>HYDROXY ACIDS</subject><subject>INFORMATION</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>Kinetics and mechanisms</subject><subject>LACTIC ACID</subject><subject>MEASURING INSTRUMENTS</subject><subject>MEASURING METHODS</subject><subject>MONOCARBOXYLIC ACIDS</subject><subject>NUMERICAL DATA</subject><subject>ORGANIC ACIDS</subject><subject>Organic chemistry</subject><subject>ORGANIC COMPOUNDS</subject><subject>OXYGEN COMPOUNDS</subject><subject>PRODUCTION</subject><subject>Reactivity and mechanisms</subject><subject>SUPERCRITICAL STATE</subject><subject>WATER</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1989</creationdate><recordtype>article</recordtype><recordid>eNptkMtKAzEUhoMoWKsrX2AQwYWM5p6ZZWmtCgXFVnAX0kyCqe2kJCnatzdltLjwbA785zu3H4BzBG8QxOh24SHEFVQQiwPQQwzDkteQHoJe1nFJMCfH4CTGBczBGOuBwdiHlUrOt4W3hdJhu3Q6Z9cUNvhVsVQ6_QquLeJmbYIOLmtqWXyqZMIpOLJqGc3ZT-6D1_HdbPhQTp7uH4eDSakoJqm0WGksBGEWUVUTTi1DzbwyCNGGcIjQvOKQQYYFwo1ApJ5DSnUthG6qmkBO-uCim-tjcjJql4x-175tjU5SIMYxqzJ03UE6-BiDsXId3EqFrURQ7iySfyzK9GVHr1XM_9igWu3ivoULWhG6G1p2mIvJfO3LKnxkhAgmZ89TOR0hyMTLSL5l_qrjlY553ya02Zd_D_gGX0l-nQ</recordid><startdate>19890901</startdate><enddate>19890901</enddate><creator>Mok, William Shu Lai</creator><creator>Antal, Michael Jerry</creator><creator>Jones, Maitland</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>19890901</creationdate><title>Formation of acrylic acid from lactic acid in supercritical water</title><author>Mok, William Shu Lai ; Antal, Michael Jerry ; Jones, Maitland</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a423t-f2ac27735f14a9364f51db8e114d36011b8605052712d7139b044c977cd893063</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1989</creationdate><topic>400201 - Chemical & Physicochemical Properties</topic><topic>ACRYLIC ACID</topic><topic>CARBOXYLIC ACIDS</topic><topic>Chemistry</topic><topic>DATA</topic><topic>DATA ANALYSIS</topic><topic>Exact sciences and technology</topic><topic>EXPERIMENTAL DATA</topic><topic>HYDROGEN COMPOUNDS</topic><topic>HYDROXY ACIDS</topic><topic>INFORMATION</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>Kinetics and mechanisms</topic><topic>LACTIC ACID</topic><topic>MEASURING INSTRUMENTS</topic><topic>MEASURING METHODS</topic><topic>MONOCARBOXYLIC ACIDS</topic><topic>NUMERICAL DATA</topic><topic>ORGANIC ACIDS</topic><topic>Organic chemistry</topic><topic>ORGANIC COMPOUNDS</topic><topic>OXYGEN COMPOUNDS</topic><topic>PRODUCTION</topic><topic>Reactivity and mechanisms</topic><topic>SUPERCRITICAL STATE</topic><topic>WATER</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Mok, William Shu Lai</creatorcontrib><creatorcontrib>Antal, Michael Jerry</creatorcontrib><creatorcontrib>Jones, Maitland</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Mok, William Shu Lai</au><au>Antal, Michael Jerry</au><au>Jones, Maitland</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Formation of acrylic acid from lactic acid in supercritical water</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>1989-09-01</date><risdate>1989</risdate><volume>54</volume><issue>19</issue><spage>4596</spage><epage>4602</epage><pages>4596-4602</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><coden>JOCEAH</coden><abstract>Supercritical (SC) water is an unusual medium in which fast and specific heterolytic reactions can be conducted at temperatures as high as 400{degree}C. In supercritical water, lactic acid decomposes into gaseous and liquid products via three primary reaction pathways. Products of the acid-catalyzed heterolytic decarbonylation pathway are carbon monoxide, water, and acetaldehyde. Products of the homolytic, decarboxylation pathway are carbon dioxide, hydrogen, and acetaldehyde. Products of the heterolytic, dehydration pathway are acrylic acid and water. The intramolecular nucleophilic displacement of the {alpha}-hydroxyl by the carbonyl group of lactic acid, producing {alpha}-propiolactone as an unstable intermediate which subsequently rearranges to become the unsaturated acid, is a likely mechanism for acrylic acid formation, although an intramolecular E2 elimination initiated by attack of the carbonyl oxygen on a methyl hydrogen cannot be ruled out. Support for the former mechanism comes in part from the observed 100% relative yield of acrylic acid from {beta}-propiolactone in SC water.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/jo00280a027</doi><tpages>7</tpages></addata></record> |
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| ispartof | Journal of organic chemistry, 1989-09, Vol.54 (19), p.4596-4602 |
| issn | 0022-3263 1520-6904 |
| language | eng |
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| subjects | 400201 - Chemical & Physicochemical Properties ACRYLIC ACID CARBOXYLIC ACIDS Chemistry DATA DATA ANALYSIS Exact sciences and technology EXPERIMENTAL DATA HYDROGEN COMPOUNDS HYDROXY ACIDS INFORMATION INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY Kinetics and mechanisms LACTIC ACID MEASURING INSTRUMENTS MEASURING METHODS MONOCARBOXYLIC ACIDS NUMERICAL DATA ORGANIC ACIDS Organic chemistry ORGANIC COMPOUNDS OXYGEN COMPOUNDS PRODUCTION Reactivity and mechanisms SUPERCRITICAL STATE WATER |
| title | Formation of acrylic acid from lactic acid in supercritical water |
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