Conformational mobility of thianthrene-5-oxide
[reaction: see text] Data on the apparent dipole moment of thianthrene-5-oxide (1) and (1)H NMR spectra in different solvents support the conformational mobility of 1, which flaps between two limit boat conformations with the sulfinyl group in pseudoequatorial and pseudoaxial positions, respectively. The conformational equilibrium of 1 occurs too fast for the (1)H NMR (500 MHz) time-scale even at -130 degrees C, and the equilibrium constant has not been determined. The apparent dipole moments of 1 in n-hexane and 1,4-dioxane and the (1)H NMR spectra of 1 and the model compounds cis- and trans-thianthrene-5,10-dioxides (2) and thianthrene (5) in different solvents and at various temperatures confirm that the relative position of the conformational equilibrium of 1 is solvent-dependent, and more polar solvents favor the conformation with the sulfoxide group in the pseudoaxial position (1(')(ax)). Variable-temperature (1)H NMR spectra have established the interconversion barrier of trans-2 and confirmed that the conformational equilibrium of cis-2 is strongly displaced toward the conformation with both sulfinyl groups in the pseudoequatorial position. The (1)H NMR data support the transannular interaction of the functional groups in 1 and trans-2.
| Medienart: |
Artikel |
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| Erscheinungsjahr: |
2005 |
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| Erschienen: |
2005 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:70 |
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| Enthalten in: |
The Journal of organic chemistry - 70(2005), 9 vom: 29. Apr., Seite 3450-7 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
González-Núñez, María Elena [VerfasserIn] |
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| Themen: |
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| Anmerkungen: |
Date Completed 24.05.2005 Date Revised 22.04.2005 published: Print Citation Status PubMed-not-MEDLINE |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM154938882 |
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| 100 | 1 | |a González-Núñez, María Elena |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Conformational mobility of thianthrene-5-oxide |
| 264 | 1 | |c 2005 | |
| 336 | |a Text |b txt |2 rdacontent | ||
| 337 | |a ohne Hilfsmittel zu benutzen |b n |2 rdamedia | ||
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| 500 | |a Date Completed 24.05.2005 | ||
| 500 | |a Date Revised 22.04.2005 | ||
| 500 | |a published: Print | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a [reaction: see text] Data on the apparent dipole moment of thianthrene-5-oxide (1) and (1)H NMR spectra in different solvents support the conformational mobility of 1, which flaps between two limit boat conformations with the sulfinyl group in pseudoequatorial and pseudoaxial positions, respectively. The conformational equilibrium of 1 occurs too fast for the (1)H NMR (500 MHz) time-scale even at -130 degrees C, and the equilibrium constant has not been determined. The apparent dipole moments of 1 in n-hexane and 1,4-dioxane and the (1)H NMR spectra of 1 and the model compounds cis- and trans-thianthrene-5,10-dioxides (2) and thianthrene (5) in different solvents and at various temperatures confirm that the relative position of the conformational equilibrium of 1 is solvent-dependent, and more polar solvents favor the conformation with the sulfoxide group in the pseudoaxial position (1(')(ax)). Variable-temperature (1)H NMR spectra have established the interconversion barrier of trans-2 and confirmed that the conformational equilibrium of cis-2 is strongly displaced toward the conformation with both sulfinyl groups in the pseudoequatorial position. The (1)H NMR data support the transannular interaction of the functional groups in 1 and trans-2 | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Mello, Rossella |e verfasserin |4 aut | |
| 700 | 1 | |a Royo, Jorge |e verfasserin |4 aut | |
| 700 | 1 | |a Asensio, Gregorio |e verfasserin |4 aut | |
| 700 | 1 | |a Monzó, Isidro |e verfasserin |4 aut | |
| 700 | 1 | |a Tomás, Francisco |e verfasserin |4 aut | |
| 700 | 1 | |a López, Jesús García |e verfasserin |4 aut | |
| 700 | 1 | |a Ortiz, Fernando López |e verfasserin |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t The Journal of organic chemistry |d 1945 |g 70(2005), 9 vom: 29. Apr., Seite 3450-7 |w (DE-627)NLM000006343 |x 1520-6904 |7 nnns |
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