Ionic‐Liquid Controlled Nitration of Double Bond: Highly Selective Synthesis of Nitrostyrenes and Benzonitriles
Unprecedented in literature, the conversion of aryl alkenes into β‐nitrostyrenes (2) or benzonitriles (3) with sodium nitrite can be governed by an appropriate choice of ionic liquid (IL) medium. A general trend was found for the selectivity of these processes, which depends on the nature of IL, wit...
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| Veröffentlicht in: | European journal of organic chemistry 2020-10, Vol.2020 (37), p.6012-6018 |
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| container_title | European journal of organic chemistry |
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| creator | Casiello, Michele Caputo, Daniela Fusco, Caterina Cotugno, Pietro Rizzi, Vito Dell'Anna, Maria Michela D'Accolti, Lucia Nacci, Angelo |
| description | Unprecedented in literature, the conversion of aryl alkenes into β‐nitrostyrenes (2) or benzonitriles (3) with sodium nitrite can be governed by an appropriate choice of ionic liquid (IL) medium. A general trend was found for the selectivity of these processes, which depends on the nature of IL, with imidazolium‐based ILs, such as [Bmim]Cl, that favor the C–H nitration leading to β‐nitrostyrenes, while tetraalkylammonium‐based ILs, such as TBAA, privilege the C=C bond cleavage affording benzonitriles. Besides a substrate scope, mechanistic hypotheses were provided on the origin of the different selectivity in the two kinds of ILs, based on their own tunable properties such as polarity, viscosity, and solvent cage effects.
The conversion of aryl alkenes into β‐nitrostyrenes or benzonitriles with NaNO2 can be governed by an appropriate choice of ionic liquid medium. A general trend was found for the selectivity of these processes, which depends on the nature of IL, with imidazolium‐based ILs, such as [Bmim] Cl, that favor the formation of β‐nitrostyrenes, while tetraalkylammonium‐based ILs, such as TBAA, that favor the formation of benzonitriles. |
| doi_str_mv | 10.1002/ejoc.202001027 |
| format | Article |
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The conversion of aryl alkenes into β‐nitrostyrenes or benzonitriles with NaNO2 can be governed by an appropriate choice of ionic liquid medium. A general trend was found for the selectivity of these processes, which depends on the nature of IL, with imidazolium‐based ILs, such as [Bmim] Cl, that favor the formation of β‐nitrostyrenes, while tetraalkylammonium‐based ILs, such as TBAA, that favor the formation of benzonitriles.</description><identifier>ISSN: 1434-193X</identifier><identifier>EISSN: 1099-0690</identifier><identifier>DOI: 10.1002/ejoc.202001027</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Alkenes ; Aromatic compounds ; Ionic liquids ; Nitration ; Nitriles ; Nitro compounds ; Polarity ; Selectivity ; Sodium nitrite ; Substrates ; Synthetic methods</subject><ispartof>European journal of organic chemistry, 2020-10, Vol.2020 (37), p.6012-6018</ispartof><rights>2020 Wiley‐VCH GmbH</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3177-355fe10c4deee3817560337d0ad74057506c90f2482a6b0b439c35a95eed0dfa3</citedby><cites>FETCH-LOGICAL-c3177-355fe10c4deee3817560337d0ad74057506c90f2482a6b0b439c35a95eed0dfa3</cites><orcidid>0000-0002-7092-9689 ; 0000-0001-8860-9141 ; 0000-0002-6487-9152 ; 0000-0001-9862-0248 ; 0000-0002-4960-728X ; 0000-0002-8271-0692 ; 0000-0002-0836-9318 ; 0000-0002-6232-4452</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fejoc.202001027$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fejoc.202001027$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids></links><search><creatorcontrib>Casiello, Michele</creatorcontrib><creatorcontrib>Caputo, Daniela</creatorcontrib><creatorcontrib>Fusco, Caterina</creatorcontrib><creatorcontrib>Cotugno, Pietro</creatorcontrib><creatorcontrib>Rizzi, Vito</creatorcontrib><creatorcontrib>Dell'Anna, Maria Michela</creatorcontrib><creatorcontrib>D'Accolti, Lucia</creatorcontrib><creatorcontrib>Nacci, Angelo</creatorcontrib><title>Ionic‐Liquid Controlled Nitration of Double Bond: Highly Selective Synthesis of Nitrostyrenes and Benzonitriles</title><title>European journal of organic chemistry</title><description>Unprecedented in literature, the conversion of aryl alkenes into β‐nitrostyrenes (2) or benzonitriles (3) with sodium nitrite can be governed by an appropriate choice of ionic liquid (IL) medium. A general trend was found for the selectivity of these processes, which depends on the nature of IL, with imidazolium‐based ILs, such as [Bmim]Cl, that favor the C–H nitration leading to β‐nitrostyrenes, while tetraalkylammonium‐based ILs, such as TBAA, privilege the C=C bond cleavage affording benzonitriles. Besides a substrate scope, mechanistic hypotheses were provided on the origin of the different selectivity in the two kinds of ILs, based on their own tunable properties such as polarity, viscosity, and solvent cage effects.
The conversion of aryl alkenes into β‐nitrostyrenes or benzonitriles with NaNO2 can be governed by an appropriate choice of ionic liquid medium. A general trend was found for the selectivity of these processes, which depends on the nature of IL, with imidazolium‐based ILs, such as [Bmim] Cl, that favor the formation of β‐nitrostyrenes, while tetraalkylammonium‐based ILs, such as TBAA, that favor the formation of benzonitriles.</description><subject>Alkenes</subject><subject>Aromatic compounds</subject><subject>Ionic liquids</subject><subject>Nitration</subject><subject>Nitriles</subject><subject>Nitro compounds</subject><subject>Polarity</subject><subject>Selectivity</subject><subject>Sodium nitrite</subject><subject>Substrates</subject><subject>Synthetic methods</subject><issn>1434-193X</issn><issn>1099-0690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNqFkL9OwzAQhyMEEqWwMltiTjnHTlKz0VBoUUWHgsQWpfaFugo2tVNQmHgEnpEnIVERjEx3w_fdn18QnFIYUIDoHNdWDiKIAChE6V7QoyBECImA_bbnjIdUsMfD4Mj7NQCIJKG9YDO1Rsuvj8-Z3my1Ipk1tbNVhYrc6doVtbaG2JJc2e2yQjKyRl2QiX5aVQ1ZYIWy1q9IFo2pV-i179DOs75uHBr0pDCKjNC8t2tqpyv0x8FBWVQeT35qP3i4Ht9nk3A2v5lml7NQMpqmIYvjEilIrhCRDWkaJ8BYqqBQKYc4jSGRAsqID6MiWcKSMyFZXIgYUYEqC9YPznZzX5zdbNHX-dpunWlX5hHnggJLIW6pwY6S7c3eYZm_OP1cuCankHex5l2s-W-srSB2wlv7TPMPnY9v59mf-w0pUX4T</recordid><startdate>20201008</startdate><enddate>20201008</enddate><creator>Casiello, Michele</creator><creator>Caputo, Daniela</creator><creator>Fusco, Caterina</creator><creator>Cotugno, Pietro</creator><creator>Rizzi, Vito</creator><creator>Dell'Anna, Maria Michela</creator><creator>D'Accolti, Lucia</creator><creator>Nacci, Angelo</creator><general>Wiley Subscription Services, Inc</general><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0002-7092-9689</orcidid><orcidid>https://orcid.org/0000-0001-8860-9141</orcidid><orcidid>https://orcid.org/0000-0002-6487-9152</orcidid><orcidid>https://orcid.org/0000-0001-9862-0248</orcidid><orcidid>https://orcid.org/0000-0002-4960-728X</orcidid><orcidid>https://orcid.org/0000-0002-8271-0692</orcidid><orcidid>https://orcid.org/0000-0002-0836-9318</orcidid><orcidid>https://orcid.org/0000-0002-6232-4452</orcidid></search><sort><creationdate>20201008</creationdate><title>Ionic‐Liquid Controlled Nitration of Double Bond: Highly Selective Synthesis of Nitrostyrenes and Benzonitriles</title><author>Casiello, Michele ; Caputo, Daniela ; Fusco, Caterina ; Cotugno, Pietro ; Rizzi, Vito ; Dell'Anna, Maria Michela ; D'Accolti, Lucia ; Nacci, Angelo</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3177-355fe10c4deee3817560337d0ad74057506c90f2482a6b0b439c35a95eed0dfa3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Alkenes</topic><topic>Aromatic compounds</topic><topic>Ionic liquids</topic><topic>Nitration</topic><topic>Nitriles</topic><topic>Nitro compounds</topic><topic>Polarity</topic><topic>Selectivity</topic><topic>Sodium nitrite</topic><topic>Substrates</topic><topic>Synthetic methods</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Casiello, Michele</creatorcontrib><creatorcontrib>Caputo, Daniela</creatorcontrib><creatorcontrib>Fusco, Caterina</creatorcontrib><creatorcontrib>Cotugno, Pietro</creatorcontrib><creatorcontrib>Rizzi, Vito</creatorcontrib><creatorcontrib>Dell'Anna, Maria Michela</creatorcontrib><creatorcontrib>D'Accolti, Lucia</creatorcontrib><creatorcontrib>Nacci, Angelo</creatorcontrib><collection>CrossRef</collection><jtitle>European journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Casiello, Michele</au><au>Caputo, Daniela</au><au>Fusco, Caterina</au><au>Cotugno, Pietro</au><au>Rizzi, Vito</au><au>Dell'Anna, Maria Michela</au><au>D'Accolti, Lucia</au><au>Nacci, Angelo</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Ionic‐Liquid Controlled Nitration of Double Bond: Highly Selective Synthesis of Nitrostyrenes and Benzonitriles</atitle><jtitle>European journal of organic chemistry</jtitle><date>2020-10-08</date><risdate>2020</risdate><volume>2020</volume><issue>37</issue><spage>6012</spage><epage>6018</epage><pages>6012-6018</pages><issn>1434-193X</issn><eissn>1099-0690</eissn><abstract>Unprecedented in literature, the conversion of aryl alkenes into β‐nitrostyrenes (2) or benzonitriles (3) with sodium nitrite can be governed by an appropriate choice of ionic liquid (IL) medium. 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The conversion of aryl alkenes into β‐nitrostyrenes or benzonitriles with NaNO2 can be governed by an appropriate choice of ionic liquid medium. A general trend was found for the selectivity of these processes, which depends on the nature of IL, with imidazolium‐based ILs, such as [Bmim] Cl, that favor the formation of β‐nitrostyrenes, while tetraalkylammonium‐based ILs, such as TBAA, that favor the formation of benzonitriles.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/ejoc.202001027</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0002-7092-9689</orcidid><orcidid>https://orcid.org/0000-0001-8860-9141</orcidid><orcidid>https://orcid.org/0000-0002-6487-9152</orcidid><orcidid>https://orcid.org/0000-0001-9862-0248</orcidid><orcidid>https://orcid.org/0000-0002-4960-728X</orcidid><orcidid>https://orcid.org/0000-0002-8271-0692</orcidid><orcidid>https://orcid.org/0000-0002-0836-9318</orcidid><orcidid>https://orcid.org/0000-0002-6232-4452</orcidid></addata></record> |
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| subjects | Alkenes Aromatic compounds Ionic liquids Nitration Nitriles Nitro compounds Polarity Selectivity Sodium nitrite Substrates Synthetic methods |
| title | Ionic‐Liquid Controlled Nitration of Double Bond: Highly Selective Synthesis of Nitrostyrenes and Benzonitriles |
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