Convenient Preparation of Allylic and Vinylic Ketones from Carboxylic Esters and Grignard Reagents. Synthesis of ar-Turmerone
A method was established for the synthesis of long chain ketones by reactions of 3, 4-unsaturated carboxylic esters with alkyl and alkenyl Grignard reagents. Grignard reaction of ethyl (E) -3-hexenoate (1b) with n-pentylmagnesium bromide (2a) gave 3-dodecen-6-one (3b) and 6-n-pentyl-3-dodecen-6-ol (...
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| Veröffentlicht in: | Journal of Japan Oil Chemists' Society 1999/11/20, Vol.48(11), pp.1257-1262,1320 |
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| container_end_page | 1262,1320 |
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| container_issue | 11 |
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| container_title | Journal of Japan Oil Chemists' Society |
| container_volume | 48 |
| creator | SUGAHARA, Kotoji INABA, Teruhiko FUJITA, Tsutomu SAKAMOTO, Masami MINO, Takashi UBUKATA, Yoshihito ABE, Taichi |
| description | A method was established for the synthesis of long chain ketones by reactions of 3, 4-unsaturated carboxylic esters with alkyl and alkenyl Grignard reagents. Grignard reaction of ethyl (E) -3-hexenoate (1b) with n-pentylmagnesium bromide (2a) gave 3-dodecen-6-one (3b) and 6-n-pentyl-3-dodecen-6-ol (5b). Subsequent to reactions in the presence of Et3N at 253K, greater ketone selectivity was noted. Reactions of other 3, 4-unsaturated carboxylic esters (1b-d) and acids (1a'-c') with Grignard reagents (2a-c) gave ketones (3b, c, d, f) in good yields under the same conditions. Dialkylmonohomoallyl alcohols (5b, f-i), produced as by-products, readily underwent conversion to symmetrical ketones (6b, f-i) by thermolysis. With trihomoallyl alcohols (5q, r, t), diallylic ketones (3q, r, t) were obtained. The ketones quickly underwent isomerization to conjugated ketones (7q, t) by treatment with acid catalysts. By these reactions, various unsaturated ketones including ar-turmerone (8h) could be prepared selectively from 1, 4-addition reaction of conjugated ketones with Grignard reagents. |
| doi_str_mv | 10.5650/jos1996.48.1257 |
| format | Article |
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Synthesis of ar-Turmerone</title><source>J-STAGE Free</source><source>EZB Electronic Journals Library</source><creator>SUGAHARA, Kotoji ; INABA, Teruhiko ; FUJITA, Tsutomu ; SAKAMOTO, Masami ; MINO, Takashi ; UBUKATA, Yoshihito ; ABE, Taichi</creator><creatorcontrib>SUGAHARA, Kotoji ; INABA, Teruhiko ; FUJITA, Tsutomu ; SAKAMOTO, Masami ; MINO, Takashi ; UBUKATA, Yoshihito ; ABE, Taichi ; Nippon Medical School ; Faculty of Engineering ; Department of Chemistry ; Takasago International. CO ; LTD ; Chiba University ; Department of Materials Technology</creatorcontrib><description>A method was established for the synthesis of long chain ketones by reactions of 3, 4-unsaturated carboxylic esters with alkyl and alkenyl Grignard reagents. Grignard reaction of ethyl (E) -3-hexenoate (1b) with n-pentylmagnesium bromide (2a) gave 3-dodecen-6-one (3b) and 6-n-pentyl-3-dodecen-6-ol (5b). Subsequent to reactions in the presence of Et3N at 253K, greater ketone selectivity was noted. Reactions of other 3, 4-unsaturated carboxylic esters (1b-d) and acids (1a'-c') with Grignard reagents (2a-c) gave ketones (3b, c, d, f) in good yields under the same conditions. Dialkylmonohomoallyl alcohols (5b, f-i), produced as by-products, readily underwent conversion to symmetrical ketones (6b, f-i) by thermolysis. With trihomoallyl alcohols (5q, r, t), diallylic ketones (3q, r, t) were obtained. The ketones quickly underwent isomerization to conjugated ketones (7q, t) by treatment with acid catalysts. By these reactions, various unsaturated ketones including ar-turmerone (8h) could be prepared selectively from 1, 4-addition reaction of conjugated ketones with Grignard reagents.</description><identifier>ISSN: 1341-8327</identifier><identifier>EISSN: 1884-1996</identifier><identifier>DOI: 10.5650/jos1996.48.1257</identifier><language>eng ; jpn</language><publisher>Japan Oil Chemists' Society</publisher><subject>allylic ketone ; ar-turmerone ; symmetrical ketone ; thermolysis ; vinyl ketone</subject><ispartof>Journal of Japan Oil Chemists' Society, 1999/11/20, Vol.48(11), pp.1257-1262,1320</ispartof><rights>Japan Oil Chemists' Society</rights><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,1877,4010,27900,27901,27902</link.rule.ids></links><search><creatorcontrib>SUGAHARA, Kotoji</creatorcontrib><creatorcontrib>INABA, Teruhiko</creatorcontrib><creatorcontrib>FUJITA, Tsutomu</creatorcontrib><creatorcontrib>SAKAMOTO, Masami</creatorcontrib><creatorcontrib>MINO, Takashi</creatorcontrib><creatorcontrib>UBUKATA, Yoshihito</creatorcontrib><creatorcontrib>ABE, Taichi</creatorcontrib><creatorcontrib>Nippon Medical School</creatorcontrib><creatorcontrib>Faculty of Engineering</creatorcontrib><creatorcontrib>Department of Chemistry</creatorcontrib><creatorcontrib>Takasago International. CO</creatorcontrib><creatorcontrib>LTD</creatorcontrib><creatorcontrib>Chiba University</creatorcontrib><creatorcontrib>Department of Materials Technology</creatorcontrib><title>Convenient Preparation of Allylic and Vinylic Ketones from Carboxylic Esters and Grignard Reagents. Synthesis of ar-Turmerone</title><title>Journal of Japan Oil Chemists' Society</title><addtitle>J. Jpn. Oil Chem. Soc.</addtitle><description>A method was established for the synthesis of long chain ketones by reactions of 3, 4-unsaturated carboxylic esters with alkyl and alkenyl Grignard reagents. Grignard reaction of ethyl (E) -3-hexenoate (1b) with n-pentylmagnesium bromide (2a) gave 3-dodecen-6-one (3b) and 6-n-pentyl-3-dodecen-6-ol (5b). Subsequent to reactions in the presence of Et3N at 253K, greater ketone selectivity was noted. Reactions of other 3, 4-unsaturated carboxylic esters (1b-d) and acids (1a'-c') with Grignard reagents (2a-c) gave ketones (3b, c, d, f) in good yields under the same conditions. Dialkylmonohomoallyl alcohols (5b, f-i), produced as by-products, readily underwent conversion to symmetrical ketones (6b, f-i) by thermolysis. With trihomoallyl alcohols (5q, r, t), diallylic ketones (3q, r, t) were obtained. The ketones quickly underwent isomerization to conjugated ketones (7q, t) by treatment with acid catalysts. By these reactions, various unsaturated ketones including ar-turmerone (8h) could be prepared selectively from 1, 4-addition reaction of conjugated ketones with Grignard reagents.</description><subject>allylic ketone</subject><subject>ar-turmerone</subject><subject>symmetrical ketone</subject><subject>thermolysis</subject><subject>vinyl ketone</subject><issn>1341-8327</issn><issn>1884-1996</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1999</creationdate><recordtype>article</recordtype><recordid>eNpVkE9r3DAQxU1poSHJuVd9AW_0x7KsY1iSbWmgJU17FWN5nNXilcLIKd1Dv3u13m2hl5lheO83w6uqD4KvdKv5zS5lYW27arqVkNq8qS5E1zX1cfe2zKoRdaekeV9d5xx6zrk1Ump5Uf1ep_gTY8A4s6-EL0AwhxRZGtntNB2m4BnEgf0IcZk_45wiZjZS2rM1UJ9-Lfu7PCPlRbqh8ByBBvaI8FywecW-HeK8xRzyEQtUP73SHqmArqp3I0wZr8_9svp-f_e0_lg_fNl8Wt8-1F622tSDbzoYQVsr2r5Xugc9IkDLOy2EH1GrdmxkD2ANSK658XIABVzZwdheN-qyujlxPaWcCUf3QmEPdHCCu2OA7hygazp3DLA4NifHHofgYUpxChGL7JVi-dQNO5PC5LeuuKzjvOmEKE0tbieU5EILqYwupPsTaZfnEsi_y0Bz8BP-d1mc6wL5K_BbIIdR_QGP2pVr</recordid><startdate>1999</startdate><enddate>1999</enddate><creator>SUGAHARA, Kotoji</creator><creator>INABA, Teruhiko</creator><creator>FUJITA, Tsutomu</creator><creator>SAKAMOTO, Masami</creator><creator>MINO, Takashi</creator><creator>UBUKATA, Yoshihito</creator><creator>ABE, Taichi</creator><general>Japan Oil Chemists' Society</general><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>1999</creationdate><title>Convenient Preparation of Allylic and Vinylic Ketones from Carboxylic Esters and Grignard Reagents. Synthesis of ar-Turmerone</title><author>SUGAHARA, Kotoji ; INABA, Teruhiko ; FUJITA, Tsutomu ; SAKAMOTO, Masami ; MINO, Takashi ; UBUKATA, Yoshihito ; ABE, Taichi</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c2657-dc48afa59916bb35ba5feaa608511cfe536f42baa97a20507c2da3a039d79b543</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng ; jpn</language><creationdate>1999</creationdate><topic>allylic ketone</topic><topic>ar-turmerone</topic><topic>symmetrical ketone</topic><topic>thermolysis</topic><topic>vinyl ketone</topic><toplevel>online_resources</toplevel><creatorcontrib>SUGAHARA, Kotoji</creatorcontrib><creatorcontrib>INABA, Teruhiko</creatorcontrib><creatorcontrib>FUJITA, Tsutomu</creatorcontrib><creatorcontrib>SAKAMOTO, Masami</creatorcontrib><creatorcontrib>MINO, Takashi</creatorcontrib><creatorcontrib>UBUKATA, Yoshihito</creatorcontrib><creatorcontrib>ABE, Taichi</creatorcontrib><creatorcontrib>Nippon Medical School</creatorcontrib><creatorcontrib>Faculty of Engineering</creatorcontrib><creatorcontrib>Department of Chemistry</creatorcontrib><creatorcontrib>Takasago International. CO</creatorcontrib><creatorcontrib>LTD</creatorcontrib><creatorcontrib>Chiba University</creatorcontrib><creatorcontrib>Department of Materials Technology</creatorcontrib><collection>CrossRef</collection><jtitle>Journal of Japan Oil Chemists' Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>SUGAHARA, Kotoji</au><au>INABA, Teruhiko</au><au>FUJITA, Tsutomu</au><au>SAKAMOTO, Masami</au><au>MINO, Takashi</au><au>UBUKATA, Yoshihito</au><au>ABE, Taichi</au><aucorp>Nippon Medical School</aucorp><aucorp>Faculty of Engineering</aucorp><aucorp>Department of Chemistry</aucorp><aucorp>Takasago International. CO</aucorp><aucorp>LTD</aucorp><aucorp>Chiba University</aucorp><aucorp>Department of Materials Technology</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Convenient Preparation of Allylic and Vinylic Ketones from Carboxylic Esters and Grignard Reagents. Synthesis of ar-Turmerone</atitle><jtitle>Journal of Japan Oil Chemists' Society</jtitle><addtitle>J. Jpn. Oil Chem. Soc.</addtitle><date>1999</date><risdate>1999</risdate><volume>48</volume><issue>11</issue><spage>1257</spage><epage>1262,1320</epage><pages>1257-1262,1320</pages><issn>1341-8327</issn><eissn>1884-1996</eissn><abstract>A method was established for the synthesis of long chain ketones by reactions of 3, 4-unsaturated carboxylic esters with alkyl and alkenyl Grignard reagents. Grignard reaction of ethyl (E) -3-hexenoate (1b) with n-pentylmagnesium bromide (2a) gave 3-dodecen-6-one (3b) and 6-n-pentyl-3-dodecen-6-ol (5b). Subsequent to reactions in the presence of Et3N at 253K, greater ketone selectivity was noted. Reactions of other 3, 4-unsaturated carboxylic esters (1b-d) and acids (1a'-c') with Grignard reagents (2a-c) gave ketones (3b, c, d, f) in good yields under the same conditions. Dialkylmonohomoallyl alcohols (5b, f-i), produced as by-products, readily underwent conversion to symmetrical ketones (6b, f-i) by thermolysis. With trihomoallyl alcohols (5q, r, t), diallylic ketones (3q, r, t) were obtained. The ketones quickly underwent isomerization to conjugated ketones (7q, t) by treatment with acid catalysts. By these reactions, various unsaturated ketones including ar-turmerone (8h) could be prepared selectively from 1, 4-addition reaction of conjugated ketones with Grignard reagents.</abstract><pub>Japan Oil Chemists' Society</pub><doi>10.5650/jos1996.48.1257</doi><tpages>64</tpages><oa>free_for_read</oa></addata></record> |
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| identifier | ISSN: 1341-8327 |
| ispartof | Journal of Japan Oil Chemists' Society, 1999/11/20, Vol.48(11), pp.1257-1262,1320 |
| issn | 1341-8327 1884-1996 |
| language | eng ; jpn |
| recordid | cdi_crossref_primary_10_5650_jos1996_48_1257 |
| source | J-STAGE Free; EZB Electronic Journals Library |
| subjects | allylic ketone ar-turmerone symmetrical ketone thermolysis vinyl ketone |
| title | Convenient Preparation of Allylic and Vinylic Ketones from Carboxylic Esters and Grignard Reagents. Synthesis of ar-Turmerone |
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