Symmetrical and unsymmetrical derivatives of distyrylbenzene

Arient, J.

doi:10.1135/cccc19810101

Cited by 6 publications

(4 citation statements)

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“…Synthesis. Two important building blocks for the synthesis of the target compounds are 4,7,12,15-tetra(diethylphosphonatemethyl)[2.2]paracyclophane ( 1 ) and 1,4-bis(diethylphosphonatemethyl)benzene ( 2 ). 33a, Reaction of 1 or 2 with the appropriately substituted benzaldehydes via the Horner−Emmons−Wittig reaction yields the DSB and pCp molecules in Scheme 1. The synthesis of 1 is available in the literature …”

Section: Resultsmentioning

confidence: 99%

Solvatochromism of Distyrylbenzene Pairs Bound Together by [2.2]Paracyclophane: Evidence for a Polarizable “Through-Space” Delocalized State

et al. 2005

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A series of compounds were designed and synthesized to examine how through-space and through-bond electron delocalization respond to solvent effects. The general strategy involves the study of "dimers" of the distyrylbenzene chromophore held in close proximity by the [2.2]paracyclophane core and a systematic dissection of the chromophore into components with through-space and through-bond electronic delocalization. Steady state and time-resolved fluorescence spectroscopy in a range of solvents reveals a red-shift in emission and an increase in the intrinsic fluorescence lifetime for the emitting state in polar solvents when donor substituents are absent. We propose that through-space delocalization across the [2.2]paracyclophane core is more polarizable in the excited state, relative to the through-bond (distyrylbenzene based) excited state. When strong donors are attached to the distyrylbenzene chromophore, the charge transfer character of the distyrylbenzene-based excited state dominates fluorescence properties.

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Section: Resultsmentioning

confidence: 99%

Solvatochromism of Distyrylbenzene Pairs Bound Together by [2.2]Paracyclophane: Evidence for a Polarizable “Through-Space” Delocalized State

et al. 2005

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“…1 , 5 , 6 , 8 , 10 , 11 , 12 , 13 , 15 , 18 , 20 , and 24 were synthesized according to the literature procedures.…”

Section: Methodsmentioning

confidence: 99%

“…1 [17] , 5 [18] , 6 [19] , 8 [20] , 10 [21] , 11 [22] , 12 [23] , 13 [24] , 15 [25] , 18 [26] , 20 [27] and 24 [28] were synthesized according to the literature procedures.…”

Section: Reagents and Instrumentationsmentioning

confidence: 99%

A Chiroptical Study of Chiral Λ- and X- Type Oligothiophenes Toward Modelling the Interchain Interactions of Chiral Conjugated Polymers

et al. 2008

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A variety of chiral -type and X-type oligothiophenes (MDC 1-10) was synthesized and studied by means of UV-vis and CD spectroscopy in order to model the chiral interchain interactions of conjugated polymers with optically active side chains in both neutral and oxidized state. It was found that, within the class of chiral -type oligothiophenes, the interchain chiral exciton coupling was only present when using an electronwithdrawing imine linkage between the oligothiophene and the chiral unit (MDC 7-9). Together with the observed decrease in g-value (dissymmetry factor for absorption) by extending the oligothiophene moiety, these linkage and elongation restrictions impose crucial drawbacks 2 on chiral -type oligothiophenes as study model in both neutral and oxidized state. Therefore, a new chiral X-type oligothiophene (MDC 10) was developed, which combines chiral exciton coupling in neutral state with the additional ability of oxidation.

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“…Dimethyl ( S )-hydroxy-( p -chlorophenyl)methylphosphonate (18c). 8a According to the procedure described for preparation of phosphonate 18a , phosphonate 17c (184 mg, 0.75 mmol) was treated with NaHMDS (1.15 mL, 1 M in hexanes, 1.15 mmol) and oxaziridine (+)- 16 (450 mg, 1.51 mmol). Standard workup and final purification by flash column chromatography (gradient of 20:80 acetone/chloroform to 30:70 acetone/chloroform) gave phosphonate 18c as a white solid (143 mg, 76%, 87% ee): mp 68−69 °C, lit 8a.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Nonracemic Dimethyl α-(Hydroxyfarnesyl)phosphonates via Oxidation of Dimethyl Farnesylphosphonate with (Camphorsulfonyl)oxaziridines

Cermak

Wiemer

1999

J. Org. Chem.

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Several strategies for synthesis of nonracemic dimethyl α-(hydroxyfarnesyl)phosphonate and the parent phosphonic acid have been explored. Separation of diastereomeric derivatives prepared by esterification of racemic α-hydroxy phosphonate with (S)-(+)-O-methylmandelic acid was possible, and these diastereomers could be assigned absolute stereochemistry on the basis of literature precedent. However, hydrolysis to the α-hydroxy phosphonic acid was accompanied by extensive isomerization. Addition of a nonracemic phosphonamidite to farnesal also gave nonracemic material, but again hydrolysis was problematic. Oxidation of dimethyl farnesylphosphonate anion with nonracemic (camphorsulfonyl)oxaziridines was shown to be regio- and stereoselective for formation of the α-hydroxy phosphonate. Enantiomeric excess of ∼70% ee was established by conversion of the oxidation products to their (S)-(+)-O-methylmandelate derivatives. Although hydrolysis of these methyl esters was accompanied by extensive racemization, both enantiomers of α-(hydroxyfarnesyl)phosphonic acid were obtained in low ee by this strategy.

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Symmetrical and unsymmetrical derivatives of distyrylbenzene

Abstract: The symmetrically substituted derivatives I-V of 1,4-distyrylbenzene have been prepared via the Horner reaction. A modification of the latter enabled preparation of unsymmetrical derivatives of 1,4-distyrylbenzene.

Cited by 6 publications

References 0 publications

Solvatochromism of Distyrylbenzene Pairs Bound Together by [2.2]Paracyclophane: Evidence for a Polarizable “Through-Space” Delocalized State

Solvatochromism of Distyrylbenzene Pairs Bound Together by [2.2]Paracyclophane: Evidence for a Polarizable “Through-Space” Delocalized State

A Chiroptical Study of Chiral Λ- and X- Type Oligothiophenes Toward Modelling the Interchain Interactions of Chiral Conjugated Polymers

Synthesis of Nonracemic Dimethyl α-(Hydroxyfarnesyl)phosphonates via Oxidation of Dimethyl Farnesylphosphonate with (Camphorsulfonyl)oxaziridines

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