KOtBu as a Single Electron Donor? Revisiting the Halogenation of Alkanes with CBr4 and CCl4
The search for reactions where KOtBu and other tert-alkoxides might behave as single electron donors led us to explore their reactions with tetrahalomethanes, CX4, in the presence of adamantane. We recently reported the halogenation of adamantane under these conditions. These reactions appeared to m...
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| Format: | Article |
| Language: | English |
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MDPI AG
2018-05-01
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| Series: | Molecules |
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| Online Access: | http://www.mdpi.com/1420-3049/23/5/1055 |
| _version_ | 1818019943644397568 |
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| author | Katie J. Emery Allan Young J. Norman Arokianathar Tell Tuttle John A. Murphy |
| author_facet | Katie J. Emery Allan Young J. Norman Arokianathar Tell Tuttle John A. Murphy |
| author_sort | Katie J. Emery |
| collection | DOAJ |
| description | The search for reactions where KOtBu and other tert-alkoxides might behave as single electron donors led us to explore their reactions with tetrahalomethanes, CX4, in the presence of adamantane. We recently reported the halogenation of adamantane under these conditions. These reactions appeared to mirror the analogous known reaction of NaOH with CBr4 under phase-transfer conditions, where initiation features single electron transfer from a hydroxide ion to CBr4. We now report evidence from experimental and computational studies that KOtBu and other alkoxide reagents do not go through an analogous electron transfer. Rather, the alkoxides form hypohalites upon reacting with CBr4 or CCl4, and homolytic decomposition of appropriate hypohalites initiates the halogenation of adamantane. |
| first_indexed | 2024-04-14T07:58:28Z |
| format | Article |
| id | doaj.art-81773bdaabd4471f86c2b4f77bef61c8 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-04-14T07:58:28Z |
| publishDate | 2018-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-81773bdaabd4471f86c2b4f77bef61c82022-12-22T02:04:58ZengMDPI AGMolecules1420-30492018-05-01235105510.3390/molecules23051055molecules23051055KOtBu as a Single Electron Donor? Revisiting the Halogenation of Alkanes with CBr4 and CCl4Katie J. Emery0Allan Young1J. Norman Arokianathar2Tell Tuttle3John A. Murphy4Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, UKDepartment of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, UKDepartment of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, UKDepartment of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, UKDepartment of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, UKThe search for reactions where KOtBu and other tert-alkoxides might behave as single electron donors led us to explore their reactions with tetrahalomethanes, CX4, in the presence of adamantane. We recently reported the halogenation of adamantane under these conditions. These reactions appeared to mirror the analogous known reaction of NaOH with CBr4 under phase-transfer conditions, where initiation features single electron transfer from a hydroxide ion to CBr4. We now report evidence from experimental and computational studies that KOtBu and other alkoxide reagents do not go through an analogous electron transfer. Rather, the alkoxides form hypohalites upon reacting with CBr4 or CCl4, and homolytic decomposition of appropriate hypohalites initiates the halogenation of adamantane.http://www.mdpi.com/1420-3049/23/5/1055halogenationpotassium tert-butoxidealkanesdihalocarbeneshypohalite |
| spellingShingle | Katie J. Emery Allan Young J. Norman Arokianathar Tell Tuttle John A. Murphy KOtBu as a Single Electron Donor? Revisiting the Halogenation of Alkanes with CBr4 and CCl4 Molecules halogenation potassium tert-butoxide alkanes dihalocarbenes hypohalite |
| title | KOtBu as a Single Electron Donor? Revisiting the Halogenation of Alkanes with CBr4 and CCl4 |
| title_full | KOtBu as a Single Electron Donor? Revisiting the Halogenation of Alkanes with CBr4 and CCl4 |
| title_fullStr | KOtBu as a Single Electron Donor? Revisiting the Halogenation of Alkanes with CBr4 and CCl4 |
| title_full_unstemmed | KOtBu as a Single Electron Donor? Revisiting the Halogenation of Alkanes with CBr4 and CCl4 |
| title_short | KOtBu as a Single Electron Donor? Revisiting the Halogenation of Alkanes with CBr4 and CCl4 |
| title_sort | kotbu as a single electron donor revisiting the halogenation of alkanes with cbr4 and ccl4 |
| topic | halogenation potassium tert-butoxide alkanes dihalocarbenes hypohalite |
| url | http://www.mdpi.com/1420-3049/23/5/1055 |
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