Cocyclotrimerization of Aryl Acetylenes: Substituent Effects on Reaction Rate

Dawson, Daniel J.; Frazier, Janice D.; Brock, Phillip J.; Twieg, Robert J.

doi:10.1021/bk-1987-0346.ch038

Polymers for High Technology

1987

DOI: 10.1021/bk-1987-0346.ch038

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Cocyclotrimerization of Aryl Acetylenes: Substituent Effects on Reaction Rate

Daniel J. Dawson

Janice D. Frazier

Phillip J. Brock

et al.

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Cited by 11 publications

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“…Protodesilylation of 1 with K 2 CO 3 in wet MeOH/THF (5:1) effected removal of the trimethylsilyl (TMS) moiety, while leaving the more robust triisopropylsilyl (TIPS) protecting group intact. This monodesilylated derivative was then carried on directly, following workup, to a Pd-catalyzed cross-coupling with p -iodo- N,N -dimethylaniline to afford the donor-substituted monomer 2 in 63% yield. The analogous sequence of protodesilylation and cross-coupling of deprotected 1 with p -iodonitrobenzene gave acceptor-substituted monomer 3 .…”

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Cross-Conjugated Chromophores: Synthesis of iso-Polydiacetylenes with Donor/Acceptor Substitution

Ciulei

Tykwinski²

2000

Org. Lett.

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The iterative construction of cross-conjugated donor (D), acceptor (A), and donor-acceptor (D-A) substituted iso-polydiacetylene (iso-PDA) oligomers has been achieved utilizing palladium-catalyzed cross-coupling techniques. Structure-property relationships for these compounds have been analyzed for cross-conjugated pi-electronic communication as a result of contributions from donor, acceptor, or donor-acceptor functionalization.

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Cross-Conjugated Chromophores: Synthesis of iso-Polydiacetylenes with Donor/Acceptor Substitution

Ciulei

Tykwinski²

2000

Org. Lett.

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Donor–acceptor substituted tetraethynylethenes

et al. 1996

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Communications CED MATERIALScompositions were determined using ninhydrin detection (Dionex BIOLC) after hydrolysis in 6 N HCl.Precipitation of CaC03: In vitro CaC03 precipitation was performed by slow diffusion of ammonium carbonate vapor in a 25 mM calcium chloride solution doped with aliquots of the proteins extracted from the biogenic amorphous CaC03 phases and the calcitic cores of sponge spicules. Protein concentrations were determined from amino acid composition analyses.Atomic absorption measurements: After precipitation, the mother liquor (0.75 ml) was quantitatively separated and diluted to 25 ml. The precipitate was washed in the experimental dish, dried and dissolved in 1 N HN03. The solution obtained was then diluted to the same volume as the mother liquor. The amounts of calcium were measured in the initial solution, in the solution that underwent precipitation and in the dissolved precipitate, using atomic absorption (Perkin Elmer 5100 GFAAS).X-ray measurements: The powder diffraction data were collected at the National Synchrotron Light Source in Brookhaven National Laboratory, on beam line X7B (operated under contract DE-AC02-76CH00016 with the US Department of Energy). The samples were finely ground, and 0.3 mm glass capillaries were filled completely with the powder to ensure that the same amount of material was subjected to the X-ray beam in each experiment. Narrow slit measurements were performed with a step size of 0.01" and sampling time of 10 s/step using a Huber diffractometer. The data presented are after subtraction of the corresponding reference measurements of the empty capillaries.Infrared analyses: Ground samples were dispersed in 7 mm KBr pellets. The infrared spectra were collected using a computer-controlled spectrometer (MIDAC Corporation, Costa Mesa, CA, USA). The data presented are after subtraction of the corresponding reference KBr spectra.

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Donor/Acceptor‐Substituted Tetraethynylethenes: Systematic Assembly of Molecules for Use as Advanced Materials

Tykwinski¹,

Schreiber²,

Carlón³

et al. 1996

Helvetica Chimica Acta

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A comprehensive series of tetraethynylethenes ( = 3,4-diethynyIhex-3-ene-l,S-diynes, TEEs) bearing electrondonating (p-methoxyphenyl or p-aminophenyl) and/or electron-accepting (p-nitrophenyl) groups was prepared via [I'd]-catalyzed Sonogashira cross-coupling reactions. The electronic and photonic properties of these molecules were investigated with a special emphasis on the effects caused by degree and pattern of donor/acceptor substitution around the central TEE core. This analysis showed that intramolecular donor-acceptor interactions, as evidenced by a long-wavelength charge-transfer band, are considerably more effective in TEES 44 and 46, with trans and cis, linearly-conjugated electronic pathways between donor and acceptor, than in 11, with a geminal, cross-conjugated electronic pathway. UVjVIS Spectroscopy revealed a steady bathochromic shift of the longestwavelength absorption band (Amax) as the number of donor-acceptor conjugation paths increased upon changing from his-arylated (11, 44, and 46) to tetrakis-arylated (14, 31, and 35) TEEs. The position of the longest-wavelength absorption was also found to be strongly dependent on the nature of the N-substituents in the R,NC,H,-donor groups. Electronic emission spectroscopic investigations demonstrated a considerable solvent dependency of the fluorescence of donor-acceptor-substituted TEES such as 11 or 44, in agreement with the presence of highly polarized excited states in these molecules. Correspondingly, fluorescence spectra of TEES bearing only donor or acceptor substituents showed little solvent dependency. The large majority of the donor/acceptor-substituted TEEs are thermally and environmentally stable molecules. They can be stored for months as solids in the air at room temperature, and many decompose only upon heating to temperatures above 200°. X-Ray analysis showed the conjugated C-atom scaffolds of 44, 46, and 67 to be essentially planar, whereas the aryl substituents in 28 and 30 are rotated out of the plane of the TEE core by varying degrees. 1.Introduction. -Conjugated organic molecules and polymers show great promise as components for advanced electronic and photonic applications [ 1-31. For the rational design of tailor-made organic materials with specific function, it is necessary to develop a profound understanding of how and to what degree changes in molecular electronic structure affect physical properties [4].Tetraethynylethene ( = 3,4-diethynylhex-3-ene-l,5-diyne, TEE 1) provides a unique C-atom framework for the incorporation of functional groups into planar, fully conjugated, two-dimensional n -chromophores [5-81. Essentially every desired substitution pattern on the TEE core can be achieved through the proficient use of various (trialkylsily1)alkyne-protecting groups. Together, these molecules make up a 'molecular construction kit' which has been readily elaborated into acyclic [9] and cyclic [lo] acetylenic molecular scaffolding, formation of oligomers [9] and polymers [l 11 with the conjugated poly(triacety1ene) backbone, a...

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Cocyclotrimerization of Aryl Acetylenes: Substituent Effects on Reaction Rate

Cited by 11 publications

References 0 publications

Cross-Conjugated Chromophores: Synthesis of iso-Polydiacetylenes with Donor/Acceptor Substitution

Cross-Conjugated Chromophores: Synthesis of iso-Polydiacetylenes with Donor/Acceptor Substitution

Donor–acceptor substituted tetraethynylethenes

Donor/Acceptor‐Substituted Tetraethynylethenes: Systematic Assembly of Molecules for Use as Advanced Materials

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