Bicyclic Structures Prohibiting the Walden Inversion. The Synthesis of 1-Bromotriptycene

Bartlett, Paul D.; Cohen, Saul G.; Cotman, John D.; Kornblum, Nathan; Landry, Josephine Ryan; Lewis, Edward S.

doi:10.1021/ja01158a093

Cited by 22 publications

(3 citation statements)

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“…Under a nitrogen atmosphere, to a solution of 9-bromotriptycene (750 mg, 2.25 mmol) in 45 mL of benzene and 90 mL of diethyl ether at 0 °C was added 1.5 mL of n -BuLi (2.45 mmol, 1.63 N). After being stirred for 2 h, the supernatant liquid was removed from the fine suspension of 9-triptycyllithium by using the cannula, and 135 mL of benzene was added to the flask.…”

Section: Methodsmentioning

confidence: 99%

Evidence for Effective p(Z)−π(Ar) Conjugations (Z = S, Se, and Te, as Well as Z = O) in 9-(Arylchalcogenyl)triptycenes: Experimental and Theoretical Investigations

et al. 2009

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The p(Z)-pi(Ar) conjugations must operate fully in the ground states of 9-(arylchalcogenyl)triptycenes (p-YC(6)H(4)ZTpc:1 (Z = O), 2 (Z = S), 3 (Z = Se), and 4 (Z = Te)), where the p-YC(6)H(4) group is placed in the bisected area between two phenyl planes of the triptycyl group with the parallel orientation. The ground-state geometries, which we call (A: pl), are confirmed by X-ray analysis. However, the conjugations never operate in the transition states between (A: pl) and/or the topomeric structures (A': pl'), where the Z-C(Tpc) bond is perpendicular to the plane. The site-exchange processes correlate to the conjugations. Temperature-dependent (1)H NMR spectra are analyzed for 2 and 3 to demonstrate the effective p(Z)-pi(Ar) conjugations. The activation energies for the interconversion between (A: pl) and (A': pl') (GR: gear process) were obtained for 2 (DeltaG(GR)(2)) and 3 (DeltaG(GR)(3)). DeltaG(GR)(3) correlate well with DeltaG(GR)(2), and DeltaG(GR)(2) are well analyzed by the Hammett-type dual parameters. DeltaG(GR)(2) and DeltaG(GR)(3) are demonstrated to be controlled by the resonance interaction of the p(Z)-pi(C(6)H(4))-p(Y) conjugations. QC calculations are performed on the ground and exited states of 1-4, which clarify the effective p(Z)-pi(C(6)H(4))-p(Y) conjugations for Z of heavier atoms.

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Section: Methodsmentioning

confidence: 99%

Evidence for Effective p(Z)−π(Ar) Conjugations (Z = S, Se, and Te, as Well as Z = O) in 9-(Arylchalcogenyl)triptycenes: Experimental and Theoretical Investigations

et al. 2009

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“…Under an argon atmosphere, to a solution of 9-bromotriptycene (510 mg, 1.50 mmol) in 12 mL of benzene and 40 mL of diethyl ether at 0 °C was added 1.0 mL of n -BuLi (1.62 mmol, 1.62 M). After 1 h of stirring, the fine suspension of 9-triptycyllithum was added to an ethereal solution of 1.0 equiv of benzeneselenobromide.…”

Section: Methodsmentioning

confidence: 99%

⁷⁷Se NMR Chemical Shifts of 9-(Arylselanyl)triptycenes: New Standard for Planar Structures of ArSeR and Applications to Determine the Structures in Solutions

2008

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A set of new delta(Se) parameters is proposed as a standard for the planar (pl) orientational effect of p-YC(6)H(4) (Ar) in ArSeR, employing 9-(arylselanyl)triptycenes (1: p-YC(6)H(4)SeTpc). The Se-C(R) bond in ArSeR is placed on the Ar plane in pl and it is perpendicular to the plane in pd. Large upfield shifts are observed for Y = NMe(2), OMe, and Me (-22 to -6 ppm) and large downfield shifts for Y = COOEt, CN, and NO(2) (19-37 ppm), relative to Y = H, with small upfield and moderate downfield shifts by Y of halogens (-1 ppm for Y = F and 4 ppm for Y = Cl and Br). This must be the result of the p(Se)-pi(C(6)H(4))-p(Y) conjugation in 1 (pl). While the character of delta(Se) in 1 (pl) is very similar to that in 9-(arylselanyl)anthracenes (2 (pl)), it is very different from that of 1-(arylselanyl)anthraquinones (3 (pd)). Sets of delta(Se) of 1 and 2 must serve as the standard for pl and that of 3 does for pd in solutions. Structures of various ArSeR in solutions are determined from the viewpoint of the orientational effect based on the standard delta(Se) of 1-3. While the structure of 2-methyl-1-(arylselanyl)naphthalenes is concluded to be all pl in solutions, those of 8-chloro- and 8-bromo-1-(arylselanyl)naphthalenes are all pd, except for Y = COOEt, CN, and NO(2): The equilibrium between pd and pl contributes to those with Y = COOEt, CN, and NO(2). The structure of 1-(arylselanyl)naphthalenes changes depending on Y. The structures of ArSeMe and ArSeCOPh are shown to be pl and pd, respectively, in solutions. Those of ArSePh and ArSeAr seem to change depending on Y. delta(Se) of 1-3 are demonstrated to serve as the standard to determine the structures in solutions. The rules of thumb derived from the characters in delta(Se) for 1-3 are very useful to determine the structures of ArSeR in solutions, in addition to the analysis based on the plots.

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“…Allgemein bekannt ist die praparative Nutzung del' Uberfuhrung von Nitrogruppen in Aminogruppen [z.E. [191][192][193][194][195][196][197], wobei durch Folgereaktionen, wie in [158], [159] angegeben, die verschiedensten Cyclisierungen eintreten konnen, Als Clmge weitere Reaktionamoglichkeiten soli en genannt werden die Umsetzung von Dioximen zu Diaminen [200], die Reduktion von Sulfonen zu Sulfiden [201], die Ringoffnung von Episulfiden zu 1,2-Hydroxythiolen [202] die Bildung cy-c1ischer Thiaverbindungen aus Alkyl-Ld-disulfonaaureestem [203],…”

Section: Anhangunclassified

Zur Reaktion der Alkalimetallsulfide mit Organohalogenverbindungen unter besonderer Berücksichtigung entgiftender Vorgänge

Martinetz¹

1976

Zeitschrift fuer Chemie

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Bicyclic Structures Prohibiting the Walden Inversion. The Synthesis of 1-Bromotriptycene

Cited by 22 publications

References 0 publications

Evidence for Effective p(Z)−π(Ar) Conjugations (Z = S, Se, and Te, as Well as Z = O) in 9-(Arylchalcogenyl)triptycenes: Experimental and Theoretical Investigations

Evidence for Effective p(Z)−π(Ar) Conjugations (Z = S, Se, and Te, as Well as Z = O) in 9-(Arylchalcogenyl)triptycenes: Experimental and Theoretical Investigations

⁷⁷Se NMR Chemical Shifts of 9-(Arylselanyl)triptycenes: New Standard for Planar Structures of ArSeR and Applications to Determine the Structures in Solutions

Zur Reaktion der Alkalimetallsulfide mit Organohalogenverbindungen unter besonderer Berücksichtigung entgiftender Vorgänge

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Bicyclic Structures Prohibiting the Walden Inversion. The Synthesis of 1-Bromotriptycene

Cited by 22 publications

References 0 publications

Evidence for Effective p(Z)−π(Ar) Conjugations (Z = S, Se, and Te, as Well as Z = O) in 9-(Arylchalcogenyl)triptycenes: Experimental and Theoretical Investigations

Evidence for Effective p(Z)−π(Ar) Conjugations (Z = S, Se, and Te, as Well as Z = O) in 9-(Arylchalcogenyl)triptycenes: Experimental and Theoretical Investigations

77Se NMR Chemical Shifts of 9-(Arylselanyl)triptycenes: New Standard for Planar Structures of ArSeR and Applications to Determine the Structures in Solutions

Zur Reaktion der Alkalimetallsulfide mit Organohalogenverbindungen unter besonderer Berücksichtigung entgiftender Vorgänge

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⁷⁷Se NMR Chemical Shifts of 9-(Arylselanyl)triptycenes: New Standard for Planar Structures of ArSeR and Applications to Determine the Structures in Solutions