Synthesis and Analysis of Thio-, Thiono-, and Dithio-Derivatives of Whiskey Lactone
Cis- and trans-3-methyl-4-octanolide (1, whiskey lactones) were converted into their thio- (2), thiono- (3), and dithio- (4) derivatives by reaction with phosphorus pentasulfide. The reaction products were characterized by GC−mass spectrometry, 1H NMR spectroscopy, and GC−olfactometry. Two-dimension...
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| Veröffentlicht in: | Journal of agricultural and food chemistry 2001-12, Vol.49 (12), p.5923-5928 |
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| container_title | Journal of agricultural and food chemistry |
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| creator | Schmarr, Hans-Georg Eisenreich, Wolfgang Engel, Karl-Heinz |
| description | Cis- and trans-3-methyl-4-octanolide (1, whiskey lactones) were converted into their thio- (2), thiono- (3), and dithio- (4) derivatives by reaction with phosphorus pentasulfide. The reaction products were characterized by GC−mass spectrometry, 1H NMR spectroscopy, and GC−olfactometry. Two-dimensional NOESY spectra showed that sulfur is incorporated into the ring with reversal of the absolute configuration at C-4, whereas substitution of the keto-oxygen atom by sulfur occurs with retention of ring configuration. The cis- and trans-pairs of 2, 3, and 4 were separated into enantiomers by GC on heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin and heptakis(2,3-di-O-acetyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin as chiral stationary phases. GC−olfactometry revealed a sweet coconut-like odor for the cis-thio- and pleasant mushroom-like flavors for the cis-thiono- and trans-dithio-derivatives of whiskey lactone. Keywords: Whiskey lactone; thio-whiskey lactone; thiono-whiskey lactone; dithio-whiskey lactone; enantioselective GC; GC−MS; 1H NMR |
| doi_str_mv | 10.1021/jf0107961 |
| format | Article |
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The reaction products were characterized by GC−mass spectrometry, 1H NMR spectroscopy, and GC−olfactometry. Two-dimensional NOESY spectra showed that sulfur is incorporated into the ring with reversal of the absolute configuration at C-4, whereas substitution of the keto-oxygen atom by sulfur occurs with retention of ring configuration. The cis- and trans-pairs of 2, 3, and 4 were separated into enantiomers by GC on heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin and heptakis(2,3-di-O-acetyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin as chiral stationary phases. GC−olfactometry revealed a sweet coconut-like odor for the cis-thio- and pleasant mushroom-like flavors for the cis-thiono- and trans-dithio-derivatives of whiskey lactone. Keywords: Whiskey lactone; thio-whiskey lactone; thiono-whiskey lactone; dithio-whiskey lactone; enantioselective GC; GC−MS; 1H NMR</description><identifier>ISSN: 0021-8561</identifier><identifier>EISSN: 1520-5118</identifier><identifier>DOI: 10.1021/jf0107961</identifier><identifier>PMID: 11743786</identifier><identifier>CODEN: JAFCAU</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Alcoholic Beverages - analysis ; Aroma and flavouring agent industries ; Biological and medical sciences ; Chromatography, Gas ; Food industries ; Fundamental and applied biological sciences. Psychology ; Lactones - analysis ; Lactones - chemical synthesis ; Lactones - chemistry ; Odorants - analysis ; Stereoisomerism ; Sulfhydryl Compounds - analysis ; Sulfhydryl Compounds - chemical synthesis ; Sulfhydryl Compounds - chemistry</subject><ispartof>Journal of agricultural and food chemistry, 2001-12, Vol.49 (12), p.5923-5928</ispartof><rights>Copyright © 2001 American Chemical Society</rights><rights>2002 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a410t-3cfb86f85f836738e301493580ec0d83b67634b6e2b7a9f097ead51e28b9e443</citedby><cites>FETCH-LOGICAL-a410t-3cfb86f85f836738e301493580ec0d83b67634b6e2b7a9f097ead51e28b9e443</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jf0107961$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jf0107961$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=13393566$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/11743786$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Schmarr, Hans-Georg</creatorcontrib><creatorcontrib>Eisenreich, Wolfgang</creatorcontrib><creatorcontrib>Engel, Karl-Heinz</creatorcontrib><title>Synthesis and Analysis of Thio-, Thiono-, and Dithio-Derivatives of Whiskey Lactone</title><title>Journal of agricultural and food chemistry</title><addtitle>J. Agric. Food Chem</addtitle><description>Cis- and trans-3-methyl-4-octanolide (1, whiskey lactones) were converted into their thio- (2), thiono- (3), and dithio- (4) derivatives by reaction with phosphorus pentasulfide. The reaction products were characterized by GC−mass spectrometry, 1H NMR spectroscopy, and GC−olfactometry. Two-dimensional NOESY spectra showed that sulfur is incorporated into the ring with reversal of the absolute configuration at C-4, whereas substitution of the keto-oxygen atom by sulfur occurs with retention of ring configuration. The cis- and trans-pairs of 2, 3, and 4 were separated into enantiomers by GC on heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin and heptakis(2,3-di-O-acetyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin as chiral stationary phases. GC−olfactometry revealed a sweet coconut-like odor for the cis-thio- and pleasant mushroom-like flavors for the cis-thiono- and trans-dithio-derivatives of whiskey lactone. Keywords: Whiskey lactone; thio-whiskey lactone; thiono-whiskey lactone; dithio-whiskey lactone; enantioselective GC; GC−MS; 1H NMR</description><subject>Alcoholic Beverages - analysis</subject><subject>Aroma and flavouring agent industries</subject><subject>Biological and medical sciences</subject><subject>Chromatography, Gas</subject><subject>Food industries</subject><subject>Fundamental and applied biological sciences. Psychology</subject><subject>Lactones - analysis</subject><subject>Lactones - chemical synthesis</subject><subject>Lactones - chemistry</subject><subject>Odorants - analysis</subject><subject>Stereoisomerism</subject><subject>Sulfhydryl Compounds - analysis</subject><subject>Sulfhydryl Compounds - chemical synthesis</subject><subject>Sulfhydryl Compounds - chemistry</subject><issn>0021-8561</issn><issn>1520-5118</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2001</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqF0d9P2zAQB3ALMY0Ce-AfmPoC0qQF7uL4Rx4RHdukok00Eo-Wk55VlzQBO0X0vyehFX2ZtKezfR-d7K8ZO0O4REjxaukAQeUSD9gIRQqJQNSHbAR9M9FC4hE7jnEJAFoo-MyOEFXGlZYjNpttmm5B0cexbebj68bWm2HTunGx8G3y_b00w2LoT3w3nE4o-Bfb-Rd6lw8LHx9pM57aqmsbOmWfnK0jfdnVE1bc_ihufiXTPz9_31xPE5shdAmvXKml08JpLhXXxAGznAsNVMFc81IqybNSUloqmzvIFdm5QEp1mVOW8RN2sR37FNrnNcXOrHysqK5tQ-06GpVyoVLA_0LUQosMZA-_bWEV2hgDOfMU_MqGjUEwQ9LmI-neft0NXZcrmu_lLtoenO-AjZWtXbBN5ePecd6_VQ4u2TofO3r96NvwaPpUlDDF35mZFPf53W2aG76fa6tolu069F8W_3HBNy0OngM</recordid><startdate>20011201</startdate><enddate>20011201</enddate><creator>Schmarr, Hans-Georg</creator><creator>Eisenreich, Wolfgang</creator><creator>Engel, Karl-Heinz</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QR</scope><scope>8FD</scope><scope>FR3</scope><scope>P64</scope><scope>7X8</scope></search><sort><creationdate>20011201</creationdate><title>Synthesis and Analysis of Thio-, Thiono-, and Dithio-Derivatives of Whiskey Lactone</title><author>Schmarr, Hans-Georg ; Eisenreich, Wolfgang ; Engel, Karl-Heinz</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a410t-3cfb86f85f836738e301493580ec0d83b67634b6e2b7a9f097ead51e28b9e443</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2001</creationdate><topic>Alcoholic Beverages - analysis</topic><topic>Aroma and flavouring agent industries</topic><topic>Biological and medical sciences</topic><topic>Chromatography, Gas</topic><topic>Food industries</topic><topic>Fundamental and applied biological sciences. Psychology</topic><topic>Lactones - analysis</topic><topic>Lactones - chemical synthesis</topic><topic>Lactones - chemistry</topic><topic>Odorants - analysis</topic><topic>Stereoisomerism</topic><topic>Sulfhydryl Compounds - analysis</topic><topic>Sulfhydryl Compounds - chemical synthesis</topic><topic>Sulfhydryl Compounds - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Schmarr, Hans-Georg</creatorcontrib><creatorcontrib>Eisenreich, Wolfgang</creatorcontrib><creatorcontrib>Engel, Karl-Heinz</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Chemoreception Abstracts</collection><collection>Technology Research Database</collection><collection>Engineering Research Database</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of agricultural and food chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Schmarr, Hans-Georg</au><au>Eisenreich, Wolfgang</au><au>Engel, Karl-Heinz</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis and Analysis of Thio-, Thiono-, and Dithio-Derivatives of Whiskey Lactone</atitle><jtitle>Journal of agricultural and food chemistry</jtitle><addtitle>J. Agric. Food Chem</addtitle><date>2001-12-01</date><risdate>2001</risdate><volume>49</volume><issue>12</issue><spage>5923</spage><epage>5928</epage><pages>5923-5928</pages><issn>0021-8561</issn><eissn>1520-5118</eissn><coden>JAFCAU</coden><abstract>Cis- and trans-3-methyl-4-octanolide (1, whiskey lactones) were converted into their thio- (2), thiono- (3), and dithio- (4) derivatives by reaction with phosphorus pentasulfide. The reaction products were characterized by GC−mass spectrometry, 1H NMR spectroscopy, and GC−olfactometry. Two-dimensional NOESY spectra showed that sulfur is incorporated into the ring with reversal of the absolute configuration at C-4, whereas substitution of the keto-oxygen atom by sulfur occurs with retention of ring configuration. The cis- and trans-pairs of 2, 3, and 4 were separated into enantiomers by GC on heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin and heptakis(2,3-di-O-acetyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin as chiral stationary phases. GC−olfactometry revealed a sweet coconut-like odor for the cis-thio- and pleasant mushroom-like flavors for the cis-thiono- and trans-dithio-derivatives of whiskey lactone. Keywords: Whiskey lactone; thio-whiskey lactone; thiono-whiskey lactone; dithio-whiskey lactone; enantioselective GC; GC−MS; 1H NMR</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>11743786</pmid><doi>10.1021/jf0107961</doi><tpages>6</tpages></addata></record> |
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| ispartof | Journal of agricultural and food chemistry, 2001-12, Vol.49 (12), p.5923-5928 |
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| language | eng |
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| source | ACS Publications; MEDLINE |
| subjects | Alcoholic Beverages - analysis Aroma and flavouring agent industries Biological and medical sciences Chromatography, Gas Food industries Fundamental and applied biological sciences. Psychology Lactones - analysis Lactones - chemical synthesis Lactones - chemistry Odorants - analysis Stereoisomerism Sulfhydryl Compounds - analysis Sulfhydryl Compounds - chemical synthesis Sulfhydryl Compounds - chemistry |
| title | Synthesis and Analysis of Thio-, Thiono-, and Dithio-Derivatives of Whiskey Lactone |
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