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Crystal structure of (1S,2R,6R,7R,8S,12S)-4,10,17-triphenyl-15-thia-4,10-diaza-penta-cyclo[5.5.5.0(1,16).0(2,6).0(8,12)]hepta-deca-13,16-diene-3,5,9,11-tetrone p-xylene hemisolvate.

Noland WE, Kroll NJ, Huisenga MP, Yue RA, Lang SB, Klein ND, Tritch KJ - Acta Crystallogr Sect E Struct Rep Online (2014)

Bottom Line: The title tetrone compound, C32H22N2O4S· 0.5C8H10, is the major product (50% yield) of an attempted Diels-Alder reaction of 2-(α-styr-yl)thio-phene with N-phenyl-male-imide (2 equivalents) in toluene.Recrystallization of the resulting powder from p-xylene gave the title hemisolvate; the p-xylene mol-ecule is located about an inversion center.In the crystal, the primary tetrone contacts are between a carbonyl O atom and the four flagpole H atoms of the bi-cyclo-[2.2.2]octene core, forming chains along [001].

View Article: PubMed Central - HTML - PubMed

Affiliation: Department of Chemistry, University of Minnesota, Minneapolis, MN 55455-0431, USA.

ABSTRACT
The title tetrone compound, C32H22N2O4S· 0.5C8H10, is the major product (50% yield) of an attempted Diels-Alder reaction of 2-(α-styr-yl)thio-phene with N-phenyl-male-imide (2 equivalents) in toluene. Recrystallization of the resulting powder from p-xylene gave the title hemisolvate; the p-xylene mol-ecule is located about an inversion center. In the crystal, the primary tetrone contacts are between a carbonyl O atom and the four flagpole H atoms of the bi-cyclo-[2.2.2]octene core, forming chains along [001].

No MeSH data available.


Related in: MedlinePlus

Contextual compounds. Double adducts (7) and (8) were previously reported. In acid, aromatized adduct (9) was favored over double addition. Double adduct (10) is the closest reported kin of (3). Recently reported (11) supports the proposed mechanism. Hydro­peroxide (12) is a likely inter­mediate to (3). Dianhydride (13) is commonly used for ligand synthesis.
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fig3: Contextual compounds. Double adducts (7) and (8) were previously reported. In acid, aromatized adduct (9) was favored over double addition. Double adduct (10) is the closest reported kin of (3). Recently reported (11) supports the proposed mechanism. Hydro­peroxide (12) is a likely inter­mediate to (3). Dianhydride (13) is commonly used for ligand synthesis.

Mentions: Mechanism: Mechanisms proposed for double adducts (7) (Lovely et al., 2007 ▶) and (8) (Noland et al., 1993 ▶) suggest a Diels–Alder reaction (Fig. 3 ▶), with loss of H2 by an unknown pathway, and then a second cyclo­addition. Noland et al. (1993 ▶) observed that formation of (8) was accelerated by exposure to oxygen, and aromatization to (9) was favored over (8) in acid. Brewer & Elix (1975a ▶) reported a double adduct (10) and a hydro­per­oxy inter­mediate thereof; they proposed loss of H2 in an autoxidation followed by elimination of H2O2, a pathway that fits both observations made by the Noland group. The crystal structures of (3) and the hydro­peroxide (11) (Noland et al., 2014 ▶), and preliminary HRMS and 1H NMR evidence that (12) is an inter­mediate to (3), all support the mechanism proposed by Brewer & Elix (1975a ▶).


Crystal structure of (1S,2R,6R,7R,8S,12S)-4,10,17-triphenyl-15-thia-4,10-diaza-penta-cyclo[5.5.5.0(1,16).0(2,6).0(8,12)]hepta-deca-13,16-diene-3,5,9,11-tetrone p-xylene hemisolvate.

Noland WE, Kroll NJ, Huisenga MP, Yue RA, Lang SB, Klein ND, Tritch KJ - Acta Crystallogr Sect E Struct Rep Online (2014)

Contextual compounds. Double adducts (7) and (8) were previously reported. In acid, aromatized adduct (9) was favored over double addition. Double adduct (10) is the closest reported kin of (3). Recently reported (11) supports the proposed mechanism. Hydro­peroxide (12) is a likely inter­mediate to (3). Dianhydride (13) is commonly used for ligand synthesis.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4257460&req=5

fig3: Contextual compounds. Double adducts (7) and (8) were previously reported. In acid, aromatized adduct (9) was favored over double addition. Double adduct (10) is the closest reported kin of (3). Recently reported (11) supports the proposed mechanism. Hydro­peroxide (12) is a likely inter­mediate to (3). Dianhydride (13) is commonly used for ligand synthesis.
Mentions: Mechanism: Mechanisms proposed for double adducts (7) (Lovely et al., 2007 ▶) and (8) (Noland et al., 1993 ▶) suggest a Diels–Alder reaction (Fig. 3 ▶), with loss of H2 by an unknown pathway, and then a second cyclo­addition. Noland et al. (1993 ▶) observed that formation of (8) was accelerated by exposure to oxygen, and aromatization to (9) was favored over (8) in acid. Brewer & Elix (1975a ▶) reported a double adduct (10) and a hydro­per­oxy inter­mediate thereof; they proposed loss of H2 in an autoxidation followed by elimination of H2O2, a pathway that fits both observations made by the Noland group. The crystal structures of (3) and the hydro­peroxide (11) (Noland et al., 2014 ▶), and preliminary HRMS and 1H NMR evidence that (12) is an inter­mediate to (3), all support the mechanism proposed by Brewer & Elix (1975a ▶).

Bottom Line: The title tetrone compound, C32H22N2O4S· 0.5C8H10, is the major product (50% yield) of an attempted Diels-Alder reaction of 2-(α-styr-yl)thio-phene with N-phenyl-male-imide (2 equivalents) in toluene.Recrystallization of the resulting powder from p-xylene gave the title hemisolvate; the p-xylene mol-ecule is located about an inversion center.In the crystal, the primary tetrone contacts are between a carbonyl O atom and the four flagpole H atoms of the bi-cyclo-[2.2.2]octene core, forming chains along [001].

View Article: PubMed Central - HTML - PubMed

Affiliation: Department of Chemistry, University of Minnesota, Minneapolis, MN 55455-0431, USA.

ABSTRACT
The title tetrone compound, C32H22N2O4S· 0.5C8H10, is the major product (50% yield) of an attempted Diels-Alder reaction of 2-(α-styr-yl)thio-phene with N-phenyl-male-imide (2 equivalents) in toluene. Recrystallization of the resulting powder from p-xylene gave the title hemisolvate; the p-xylene mol-ecule is located about an inversion center. In the crystal, the primary tetrone contacts are between a carbonyl O atom and the four flagpole H atoms of the bi-cyclo-[2.2.2]octene core, forming chains along [001].

No MeSH data available.


Related in: MedlinePlus