5-nitro-2-thienylvinylation. Nucleophilic substitution on 2-(2-bromovinyl)-5-nitrothiophene, new one-step method for preparation of new biologically active ethylenic derivatives of 5-nitro--2-thiophene

Végh, Dániel; Kováč, J.; Dandarova, M.

doi:10.1016/s0040-4039(00)77753-7

Cited by 12 publications

(5 citation statements)

References 4 publications

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“…The thiophene-based organic reagents 2-bromo-5-nitrothiophene, 2-iodothiophene, thiophene, and 2,2′-bithiophene were purchased from Aldrich, while 2-ethynyl-5-nitrothiophene was synthesized via established methods. 23,36,37 5,15-Bis[3,5-di-(3,3-dimethyl-1-butyloxy)phenyl]porphyrin, 3 [5-bromo-10,20-bis(3,5-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II) 3 (porphyrin 1), [5,15-dibromo-10,20-bis(3,5-bis(3,3dimethyl-1-butyloxy)phenyl)porphinato]zinc(II) 3,38 (porphyrin 2), [5-(4′dimethylaminophenylethynyl)-15-bromo-10,20-bis(3,5-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II) 11 (porphyrin 4), and [5-(4′,4′,5′,5′tetramethyl[1′,3′,2′]dioxaborolan-2′-yl)-10,20-bis(3,5-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II) 39 (porphyrin 5) were prepared using methods similar to that reported previously. 1 H NMR spectra were recorded on either a Bru ¨ker AC-250 or Bru ¨ker AM-360 spectrometer.…”

Section: Methodsmentioning

confidence: 99%

Design, Synthesis, Linear, and Nonlinear Optical Properties of Conjugated (Porphinato)zinc(II)-Based Donor−Acceptor Chromophores Featuring Nitrothiophenyl and Nitrooligothiophenyl Electron-Accepting Moieties

et al. 2005

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An extensive series of conjugated (porphinato)zinc(II)-based chromophores featuring nitrothiophenyl and nitrooligothiophenyl electron-accepting moieties has been synthesized using metal-catalyzed cross-coupling reactions involving [5-bromo-15-triisopropylsilylethynyl-10,20-diarylporphinato]zinc(II) and an unusual electron-rich Suzuki-porphyrin synthon, [5-(4-dimethylaminophenylethynyl)-15-(4',4',5',5'-tetramethyl[1',3',2']dioxaborolan-2'-yl)-10,20-diarylporphinato]zinc(II), with appropriately functionalized aryl and thienyl precursors. These donor-acceptor chromophores feature thiophenyl, [2,2']bithiophenyl, and [2,2';5',2' ']terthiophenyl units terminated with a 5-nitro group; one series of structures features these acceptor moieties appended directly to the porphyrin macrocycle meso-carbon position, while a second set utilizes an intervening meso-ethynyl moiety to modify porphyrin-to-thiophene conjugation. The dynamic hyperpolarizability of these compounds was determined from hyper-Rayleigh light scattering (HRS) measurements carried out at fundamental incident irradiation wavelengths (lambda(inc)) of 800 and 1300 nm; interestingly, measured beta(1300) values ranged from 650 --> 4350 x 10(-30) esu. The combined linear and nonlinear optical properties of these compounds challenge the classical concept of the nonlinearity/transparency tradeoff in charge-transfer chromophores: the magnitude of the molecular hyperpolarizability is observed to vary substantially despite approximately uniform ground-state absorptive signatures for a given porphyrin-to-thiophene linkage topology. These data show that these neutral dipolar molecules can express substantial beta(1300) values; such conjugated, electronically asymmetric porphyrin-thiophene chromophores may thus find utility for electrooptic applications at telecom-relevant wavelengths.

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Section: Methodsmentioning

confidence: 99%

Design, Synthesis, Linear, and Nonlinear Optical Properties of Conjugated (Porphinato)zinc(II)-Based Donor−Acceptor Chromophores Featuring Nitrothiophenyl and Nitrooligothiophenyl Electron-Accepting Moieties

et al. 2005

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“…2-Ethynyl-5-nitrothiophene was synthesized via established methods. [34][35][36] 5-(Trimethylsilylethynyl)-thiophene-2-carbaldehyde was synthesized following a literature method. 37 The syntheses of 5,15-bis(3,5-bis(3,3-dimethyl-1-butyloxy)phenyl)porphyrin, [5- phyrin 3), and [5-ethynyl-15-(4-nitrophenylethynyl)-10,20-diarylporphinato]zinc(II) (porphyrin 4) have been reported previously.…”

Section: Methodsmentioning

confidence: 99%

“…Diphenylamine, 9 H -carbazole, 2-iodothiophene, 2-bromothiazole, 2-amino-6-nitrobenzothiazole, isoamylnitrite, diiodomethane, 5-(trimethylsilylethynyl)-thiophene-2-carbaldehyde, and malononitrile were purchased from Aldrich. 2-Ethynyl-5-nitrothiophene was synthesized via established methods. − 5-(Trimethylsilylethynyl)-thiophene-2-carbaldehyde was synthesized following a literature method . The syntheses of 5,15-bis(3,5-bis(3,3-dimethyl-1-butyloxy)phenyl)porphyrin, [5-bromo-10,20-bis(3,5-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II), [5,15-dibromo-10,20-bis(3,5-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II), [5-bromo-15-triisopropylsilylethynyl-10,20-diarylporphinato]zinc(II) ( porphyrin 1 ), [5-(4-dimethylaminophenylethynyl)-15-bromo-10,20-bis(3,5-bis(3,3-dimethyl-1butyloxy)phenyl)porphinato]zinc(II) ( porphyrin 2 ), [5-(4-dimethylaminophenylethynyl)-15-ethynyl-10,20-diarylporphinato]zinc(II) ( porphyrin 3 ), and [5-ethynyl-15-(4-nitrophenylethynyl)-10,20-diarylporphinato]zinc(II) ( porphyrin 4 ) have been reported previously. ,,,, The synthesis and electrooptic properties of the nonlinear optical chromophore [5-(4-dimethylaminophenylethynyl)-15-(5-nitrothienyl-2-ethynyl)-10,20-bis(3,5-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II) ( compound 1 ) have been described recently …”

Section: Methodsmentioning

confidence: 99%

Electronic Modulation of Hyperpolarizable (Porphinato)zinc(II) Chromophores Featuring Ethynylphenyl-, Ethynylthiophenyl-, Ethynylthiazolyl-, and Ethynylbenzothiazolyl-Based Electron-Donating and -Accepting Moieties

et al. 2006

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A series of conjugated (porphinato)zinc(II)-based chromophores structurally related to [5-(4-dimethylaminophenylethynyl)-15-(5-nitrothienyl-2-ethynyl)-10,20-bis(3,5-bis(3,3-dimethyl-1-butyloxy)phenyl)]zinc(II) were synthesized using metal-catalyzed cross-coupling reactions involving [5-bromo-15-triisopropylsilylethynyl-10,20-diarylporphinato]zinc(II), [5-bromo-15-(4-dimethylaminophenylethynyl)-10,20-diarylporphinato]zinc(II), [5-(4-dimethylaminophenylethynyl)-15-ethynyl-10,20-diarylporphinato]zinc(II), and [5-(4-nitrophenylethynyl)-15-ethynyl-10,20-diarylporphinato]zinc(II), along with appropriately functionalized aryl, thienyl (or thiophenyl), thiazolyl, benzothiazolyl, and carbazolyl precursors. The linear and nonlinear optical properties of these asymmetrically 5,15-substitued-(10,20-diarylporphinato)zinc(II) chromophores that bear either 2-(9H-carbazol-9-yl)-thiophen-5-yl-ethynyl, 4-dimethylaminophenylethynyl, or 2-(N,N-diphenylamino)thiophen-5-yl-ethynyl electron-releasing groups and an electron-withdrawing group selected from 2-formyl-thiophen-5-yl-ethynyl, 2-(2,2-dicyanovinyl)-thiophen-5-yl-ethynyl, 4-nitrophenylethynyl, 6-nitrobenzothiazol-2-yl-ethynyl, or 5-nitrothiazol-2-yl-ethynyl are reported. The dynamic hyperpolarizabilities of these compounds were determined from hyper-Rayleigh light scattering measurements carried out at a fundamental incident irradiation wavelength (lambda(inc)) of 1300 nm; these measured beta1300 values ranged from 690 --> 1400 x 10(-30) esu. These data (i) show that these neutral dipolar molecules express substantial beta1300 values, (ii) highlight that reductions in the magnitude of the aromatic stabilization energy of (porphinato)metal-pendant arylethynyl groups have a significant impact upon the magnitude of the molecular hyperpolarizability, and (iii) provide insights into advantageous design modifications for closely related structures having potential utility in long-wavelength electrooptic applications.

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“…However, the major product was 5-vinyluracil (6). Since traces of 5-ethynyluraciI (7) were detected as an intermediate in the reaction, it appeared that hydrogenolysis of the C-Br bond preceded the hydrogenation of the triple bond. Attempts to alter this situation by changing the solvent and the catalyst were unsuccessful.…”

Section: "7mentioning

confidence: 99%

Synthesis and antiviral properties of (Z)-5-(2-bromovinyl)-2'-deoxyuridine

Jones¹,

Rahim²,

Walker³

et al. 1981

J. Med. Chem.

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(Z)-5-(2-Bromovinyl)uracil was obtained by photoisomerization of the E. isomer. Similarly, (E)-5-(2-bromovinyl)-2'-deoxyuridine gave the required Z isomer. (Z)-5-(2-Bromovinyl)-2'-deoxyuridine is much less active against herpes simplex virus type 1 (HSV-1) and somewhat less active against herpes simplex virus type 2 than is the E isomer. Both isomers show similar activity against vaccinia virus. Therefore, the highly potent and selective activity of (E)-5-(2-bromovinyl)-2'-deoxyuridine against HSV-1 is due to its E configuration.

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5-nitro-2-thienylvinylation. Nucleophilic substitution on 2-(2-bromovinyl)-5-nitrothiophene, new one-step method for preparation of new biologically active ethylenic derivatives of 5-nitro--2-thiophene

Cited by 12 publications

References 4 publications

Design, Synthesis, Linear, and Nonlinear Optical Properties of Conjugated (Porphinato)zinc(II)-Based Donor−Acceptor Chromophores Featuring Nitrothiophenyl and Nitrooligothiophenyl Electron-Accepting Moieties

Design, Synthesis, Linear, and Nonlinear Optical Properties of Conjugated (Porphinato)zinc(II)-Based Donor−Acceptor Chromophores Featuring Nitrothiophenyl and Nitrooligothiophenyl Electron-Accepting Moieties

Electronic Modulation of Hyperpolarizable (Porphinato)zinc(II) Chromophores Featuring Ethynylphenyl-, Ethynylthiophenyl-, Ethynylthiazolyl-, and Ethynylbenzothiazolyl-Based Electron-Donating and -Accepting Moieties

Synthesis and antiviral properties of (Z)-5-(2-bromovinyl)-2'-deoxyuridine

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