Exploring the Limits of Reactivity of <i>N</i>-Methyl-1,2,4-triazoline-3,5-dione (MeTAD) with Disubstituted Bicycloalkadienes in the Homo-Diels–Alder Reaction
The [2+2+2] cycloaddition (homo-Diels–Alder reaction) of <i>N</i>-substituted 1,2,4-triazoline-3,5-diones (TADs) with bicycloalkadienes produces strained heterocyclic compounds. A reaction with the unsubstituted dienes occurs readily to produce only the expected homo-Diels–Alder adducts....
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-12-01
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| Series: | Organics |
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| Online Access: | https://www.mdpi.com/2673-401X/4/1/2 |
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| author | Gary W. Breton Kenneth L. Martin |
| author_facet | Gary W. Breton Kenneth L. Martin |
| author_sort | Gary W. Breton |
| collection | DOAJ |
| description | The [2+2+2] cycloaddition (homo-Diels–Alder reaction) of <i>N</i>-substituted 1,2,4-triazoline-3,5-diones (TADs) with bicycloalkadienes produces strained heterocyclic compounds. A reaction with the unsubstituted dienes occurs readily to produce only the expected homo-Diels–Alder adducts. However, previous work in the literature showed that the attachment of a single electron-withdrawing group to the diene system results in the formation of not only the expected homo-Diels–Alder adducts, but also interesting “insertion” products. To probe the limits of reactivity of these diene systems, we investigated the reaction of <i>N</i>-methyl-1,2,4-triazoline-3,5-dione (MeTAD) with bicycloalkadienes substituted with two electron-withdrawing groups, i.e., two carbomethoxy or two cyano groups. We hoped to learn whether the reaction still proceeded, and if so, whether the homo-Diels–Alder adducts and/or other types of products were formed. We found that a reaction between MeTAD and the dienes takes place upon substitution with two carbomethoxy groups, albeit at a considerably slower rate than other reactions. The only products observed were the homo-Diels–Alder adducts. However, attachment of two CN groups completely inhibited reactivity. |
| first_indexed | 2024-03-11T06:03:56Z |
| format | Article |
| id | doaj.art-27414aaf7a1843e39a1034b5c1c42174 |
| institution | Directory Open Access Journal |
| issn | 2673-401X |
| language | English |
| last_indexed | 2024-03-11T06:03:56Z |
| publishDate | 2022-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Organics |
| spelling | doaj.art-27414aaf7a1843e39a1034b5c1c421742023-11-17T13:07:59ZengMDPI AGOrganics2673-401X2022-12-0141414810.3390/org4010002Exploring the Limits of Reactivity of <i>N</i>-Methyl-1,2,4-triazoline-3,5-dione (MeTAD) with Disubstituted Bicycloalkadienes in the Homo-Diels–Alder ReactionGary W. Breton0Kenneth L. Martin1Department of Chemistry and Biochemistry, Berry College, Mount Berry, GA 30149, USADepartment of Chemistry and Biochemistry, Berry College, Mount Berry, GA 30149, USAThe [2+2+2] cycloaddition (homo-Diels–Alder reaction) of <i>N</i>-substituted 1,2,4-triazoline-3,5-diones (TADs) with bicycloalkadienes produces strained heterocyclic compounds. A reaction with the unsubstituted dienes occurs readily to produce only the expected homo-Diels–Alder adducts. However, previous work in the literature showed that the attachment of a single electron-withdrawing group to the diene system results in the formation of not only the expected homo-Diels–Alder adducts, but also interesting “insertion” products. To probe the limits of reactivity of these diene systems, we investigated the reaction of <i>N</i>-methyl-1,2,4-triazoline-3,5-dione (MeTAD) with bicycloalkadienes substituted with two electron-withdrawing groups, i.e., two carbomethoxy or two cyano groups. We hoped to learn whether the reaction still proceeded, and if so, whether the homo-Diels–Alder adducts and/or other types of products were formed. We found that a reaction between MeTAD and the dienes takes place upon substitution with two carbomethoxy groups, albeit at a considerably slower rate than other reactions. The only products observed were the homo-Diels–Alder adducts. However, attachment of two CN groups completely inhibited reactivity.https://www.mdpi.com/2673-401X/4/1/2triazolinedionesMeTADbicyclo[2.2.1]heptadienebicyclo[2.2.2]octadienenorbornadienehomo-Diels–Alder |
| spellingShingle | Gary W. Breton Kenneth L. Martin Exploring the Limits of Reactivity of <i>N</i>-Methyl-1,2,4-triazoline-3,5-dione (MeTAD) with Disubstituted Bicycloalkadienes in the Homo-Diels–Alder Reaction Organics triazolinediones MeTAD bicyclo[2.2.1]heptadiene bicyclo[2.2.2]octadiene norbornadiene homo-Diels–Alder |
| title | Exploring the Limits of Reactivity of <i>N</i>-Methyl-1,2,4-triazoline-3,5-dione (MeTAD) with Disubstituted Bicycloalkadienes in the Homo-Diels–Alder Reaction |
| title_full | Exploring the Limits of Reactivity of <i>N</i>-Methyl-1,2,4-triazoline-3,5-dione (MeTAD) with Disubstituted Bicycloalkadienes in the Homo-Diels–Alder Reaction |
| title_fullStr | Exploring the Limits of Reactivity of <i>N</i>-Methyl-1,2,4-triazoline-3,5-dione (MeTAD) with Disubstituted Bicycloalkadienes in the Homo-Diels–Alder Reaction |
| title_full_unstemmed | Exploring the Limits of Reactivity of <i>N</i>-Methyl-1,2,4-triazoline-3,5-dione (MeTAD) with Disubstituted Bicycloalkadienes in the Homo-Diels–Alder Reaction |
| title_short | Exploring the Limits of Reactivity of <i>N</i>-Methyl-1,2,4-triazoline-3,5-dione (MeTAD) with Disubstituted Bicycloalkadienes in the Homo-Diels–Alder Reaction |
| title_sort | exploring the limits of reactivity of i n i methyl 1 2 4 triazoline 3 5 dione metad with disubstituted bicycloalkadienes in the homo diels alder reaction |
| topic | triazolinediones MeTAD bicyclo[2.2.1]heptadiene bicyclo[2.2.2]octadiene norbornadiene homo-Diels–Alder |
| url | https://www.mdpi.com/2673-401X/4/1/2 |
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