Synthesis of the isomeric mono- and bisoxiranylpyrenes

Harvey, Ronald G.; Konieczny, M.; Pataki, J.

doi:10.1021/jo00165a031

Cited by 19 publications

(31 citation statements)

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“…Synthesis of 2‐ and 4‐ethynylpyrenes and their incorporation into ONs : 2‐ and 4‐Substituted pyrenes are not readily available owing to the fact that electrophilic substitution on pyrene ( 8 , Scheme ) is directed to the electron‐rich position 1 39. Pyrene derivatives substituted in positions 240–43 and 444, 45 can be prepared from 4,5,9,10‐tetrahydropyrene ( 9 ) and 1,2,3,6,7,8‐hexahydropyrene ( 10 ), respectively, by electrophilic substitution followed by aromatization. Although 10 is commercially available, it is rather expensive.…”

Section: Resultsmentioning

confidence: 99%

“…m.p. 126–127 °C,40 137–138 °C,43 119–120 °C41); 1 H NMR (CDCl 3 ): δ =7.12 (m, 2 H, J 1,2 =7.1 Hz, 2‐H, 7‐H), 7.08 (m, 4 H, J 1,2 =7.1 Hz, 1‐H, 3‐H, 6‐H, 8‐H), 2.89 ppm (s, 8 H, CH 2 ). 1,2,3,6,7,8‐Hexahydropyrene ( 10 , 4.3 g, 20 %), colorless crystals, m.p.…”

Section: Methodsmentioning

confidence: 99%

“…m.p. 113–114 °C,40 110.5–112 °C66), R f =0.42 (5 % EtOAc/toluene, v/v). 1 H NMR (CDCl 3 ): δ =7.67 (s, 2 H, 1‐H, 3‐H), 7.18 (m, 1 H, J 6,7 =7.4 Hz, 7‐H), 7.10 (m, 2 H, J 6,7 =7.4 Hz, 6‐H, 8‐H), 2.92 (m, 8 H, CH 2 ), 2.60 ppm (s, 3 H, CH 3 ); 13 C NMR (CDCl 3 ): δ =198.00 (CO), 136.19 (2 C), 135.59, 135.48 (2 C), 135.30, 129.79, 128.36, 126.15 (2 C), 126.13 (2 C), 126.11, 28.23 (2 C), 28.13 (2 C), 26.60 ppm (CH 3 ).…”

Section: Methodsmentioning

confidence: 99%

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1‐, 2‐, and 4‐Ethynylpyrenes in the Structure of Twisted Intercalating Nucleic Acids: Structure, Thermal Stability, and Fluorescence Relationship

Filichev

Astakhova

Malakhov

et al. 2008

Chemistry A European J

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A postsynthetic, on-column Sonogashira reaction was applied on DNA molecules modified by 2- or 4-iodophenylmethylglycerol in the middle of the sequence, to give the corresponding ortho- and para-twisted intercalating nucleic acids (TINA) with 1-, 2-, and 4-ethynylpyrene residues. The convenient synthesis of 2- and 4-ethynylpyrenes started from the hydrogenolysis of pyrene that has had the sulfur removed and separation of 4,5,9,10-tetrahydropyrene and 1,2,3,6,7,8-hexahydropyrene, which were later converted to the final compounds by successive Friedel-Crafts acetylation, aromatization by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, and a Vilsmeier-Haack-Arnold transformation followed by a Bodendorf fragmentation. Significant alterations in thermal stability of parallel triplexes and antiparallel duplexes were observed upon changing the attachment of ethynylpyrenes from para to ortho in homopyrimidine TINAs. Thus, for para-TINAs the bulge insertion of an intercalator led to high thermal stability of Hoogsteen-type parallel triplexes and duplexes, whereas Watson-Crick-type duplexes were destabilized. In the case of ortho-TINA, both Hoogsteen and Watson-Crick-type complexes were stabilized. Alterations in the thermal stability were highly influenced by the ethynylpyrene isomers used. This also led to TINAs with different changes in fluorescence spectra depending on the secondary structures formed. Stokes shift of approximately 100 nm was detected for pyren-2-ylethynylphenyl derivatives, whereas values for 1- and 4-ethynylpyrenylphenyl conjugates were 10 and 40 nm, respectively. In contrast with para-TINAs, insertion of two ortho-TINAs opposite each other in the duplex as a pseudo-pair resulted in formation of an excimer band at 505 nm for both 1- and 4-ethynylpyrene analogues, which was also accompanied with higher thermal stability.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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1‐, 2‐, and 4‐Ethynylpyrenes in the Structure of Twisted Intercalating Nucleic Acids: Structure, Thermal Stability, and Fluorescence Relationship

Filichev

Astakhova

Malakhov

et al. 2008

Chemistry A European J

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“…Pyrene was subjected to hydrogenation (40 psi, wet EtOAc, 10% Pd/C, 3 d) to afford a mixture of 4,5,9,10 tetrahydropyrene and 1,2,3,6,7,8-hexahydropyrene (85:15 by 1 H NMR). 21 Acylation (AcCl, CH 2 Cl 2 , AlCl 3 ) 22 gave the corresponding diacetyl compounds 2,7-diacetyl-4,5,9,10-tetrahydropyene and 4,10-diacetyl-1,2,3,6,7,8-hexahydropyrene. The more soluble hexahydro compound was easily removed by trituration (ether/ benzene 1:10).…”

Section: Results and Discusion Synthesismentioning

confidence: 99%

Pyrene and anthracene dicarboxylic acids as fluorescent brightening comonomers for polyester

Connor

Kriegel

Collard

et al. 2000

J. Polym. Sci. A Polym. Chem.

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“…[24] Those at m/z 230 have been ascribed to pyrenecarboxaldehydes (Scheme 2). The NMR spectrum of the photolysate mainly showed the presence of pyrene, 1-pyrenecarboxaldehyde (IV), and 4-pyrenecarboxaldehyde (III) [25] (pyrene/aldehyde molar ratio of 2.5/ 1.0, IV/III molar ratio of 1.5/1.0, see 1 H NMR in Figure S12 in the Supporting Information). [26] Column chromatography of the Py photolysate (hexane: ethyl acetate 9:1) made it possible to gain more information on the structure of the photoproducts responsible for the emission bands.…”

Section: Photostability Studies Of the Pyrene Systems Under Uv-a-lampmentioning

confidence: 99%

Further Insight into the Photostability of the Pyrene Fluorophore in Halogenated Solvents

et al. 2012

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Pyrene fluorophores of pyrene-functionalized CdSe quantum dots (QD@Py), as well as alkylpyrene and pyrene itself (Py), undergo fast degradation in aerated chloroform under ultraviolet-A (UV-A, 316<λ<400 nm) illumination. Steady-state fluorescence studies of irradiated chloroform solutions of QD@Py show formation of new bands, red-shifted compared to that of the pyrene moiety. Similar behaviour is observed for pyrene and the alkylpyrene system. Column chromatography of the pyrene photolysate in chloroform allowed us to isolate photoproducts arising from pyrene degradation, and to obtain information on the structure of the photoproducts responsible for the emission bands. The most predominant photoproducts were those originating from the reaction of pyrene with dichloromethyl radicals. The phototransformation of QD@Py and the alkylpyrene involves mainly detachment of the alkyl chain from the aromatic ring, induced also by dichloromethyl radicals, and oxidation of the alkyl chain at the benzylic position was detected as well. By contrast, these pyrene systems show a high photostability in aerated dichloromethane. Transient absorption measurements showed formation of both pyrene triplet and pyrene radical cation for all pyrene systems in these halogenated solvents. The yield of pyrene radical cations for Py is higher than for QD@Py and the alkylpyrene. In addition, pyrene radical cations were longer-lived in dichloromethane than in chloroform. The reason for the pyrene photostability in dichloromethane is the different reactivity of chloromethyl and dichloromethyl radicals towards pyrene and oxygen. These studies show that the use of dichloromethane can be a suitable alternative to chloroform when the good solubility properties of these halogenated solvents are needed to dissolve pyrene when this chromophore is used as a fluorescent probe.

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Synthesis of the isomeric mono- and bisoxiranylpyrenes

Cited by 19 publications

References 1 publication

1‐, 2‐, and 4‐Ethynylpyrenes in the Structure of Twisted Intercalating Nucleic Acids: Structure, Thermal Stability, and Fluorescence Relationship

1‐, 2‐, and 4‐Ethynylpyrenes in the Structure of Twisted Intercalating Nucleic Acids: Structure, Thermal Stability, and Fluorescence Relationship

Pyrene and anthracene dicarboxylic acids as fluorescent brightening comonomers for polyester

Further Insight into the Photostability of the Pyrene Fluorophore in Halogenated Solvents

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