Rearrangement of the carbon skeleton in the intramolecular photoadduct of anthracene and benzene rings

Cao, Derong; Dobis, Silvia; Schollmeyer, Dieter; Meier, Herbert

doi:10.1016/s0040-4020(03)00787-7

Cited by 6 publications

(5 citation statements)

References 12 publications

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“…[31] 7-Methoxy-3-oxahexacyclo [ To the spectroscopic characterization of 4c see reference. [33] The quantitative process 3c Ǟ 4c can be quantitatively reversed (4c Ǟ 3c) by heating to 110°C or by irradiation with λ = 254 nm. Crystal Structure Analysis of 5a and 5b: The measurement was done on an Enraf-Nonius CAD-4-diffractometer with the software Collect V5 (Enraf-Nonius B. V., 1989, Delft, The Netherlands).…”

Section: Irradiation Of 3b 3cmentioning

confidence: 99%

Structure Determination of Photoproducts of Anthracenes with (Arylmethoxymethyl) Sidechains

et al. 2007

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Section: Irradiation Of 3b 3cmentioning

confidence: 99%

Structure Determination of Photoproducts of Anthracenes with (Arylmethoxymethyl) Sidechains

et al. 2007

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“…The shorter tether A-CH 2 -O-B does not permit the photocyclization. 41 Scheme 9 summarizes our experiments with compounds 26a-r. 2,8,14,38,39,42,43 The cycloisomerization 26 -27 requires electron rich benzene rings, in particular at the para-position C-4 which is connected to C-10 of the anthracene moiety for the formation of a new s bond in 27. Therefore 26a, 26b and 26f, 26h, 26i and 26j do not show photocyclization.…”

Section: Anthracene-benzene Biplanemersmentioning

confidence: 99%

Optical switches with biplanemers obtained by intramolecular photocycloaddition reactions of tethered arenes

Meier

Cao

2013

Chem. Soc. Rev.

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The dimerization of anthracene by a [4π + 4π] cycloaddition is one of the oldest and best known reactions in photochemistry. In the series of tethered bichromophoric arenes, this reaction type could be extended to anthracene-naphthalene, naphthalene-naphthalene and recently even to anthracene-benzene and naphthalene-benzene systems. Cyclophanes, which can be regarded as twofold or multiple tethered systems, are not discussed here. The cycloisomerizations are performed by irradiation at the long-wavelength absorption (λ > 270 nm), whereas shorter wavelengths (λ < 270 nm) lead to cycloreversions, which can be also achieved by a thermal route. The systems represent therefore a P- and T-type photochromism, which can be used for optical or chiroptical switches. An acceleration of the switch is possible by a singlet energy transfer (light harvesting antenna effect) in dendritic compounds. In the past 5 to 10 years many applications of these switches were studied in the context of photonic devices, sensor techniques, lithographic processes, imaging techniques, data processing and data storage.

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“…The other cyclomers 4d and 4g have comparable sensitivity toward acids, but additionally the enol ether cleavage can be accompanied by a scaffold rearrangement. 6 All resulting ketones are incapable of photochemical or thermal cleavage to 9-[(arylmethoxy)methyl]anthracenes in which the aryl group would be a phenol unit.…”

Section: Figurementioning

confidence: 99%

“…The photoproducts 4 can be subjected to an enol ether cleavage according to the literature. 6 However, the monoketones 5b and 6e could also be obtained in a one-pot reaction from 3b and 3e, respectively. After the irradiation as described above, the solvent was removed and the residue was treated with toluene (30 mL) and HCO 2 H (0.5 mL, 610 mg, 13.25 mmol) at 0°C for 1 h. Column chromatography (30 × 2 cm, silica gel, cyclohexane-EtOAc, 97:3 to 92:8) yielded the crude monoketones 6b,e, which could be recrystallized (CH 2 Cl 2 -cyclohexane, 1:9).…”

Section: Enol Ether Cleavagementioning

confidence: 99%

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Competition between Inter- and Intramolecular Photocycloaddition Reactions of 9-Substituted Anthracenes

Cao¹,

Gao²,

Dobis³

et al. 2007

Synthesis

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I n t r a -a n d I n t e r m o l e c u l a r P h o t o c y c l o a d d i t i o n o f 9 -S u b s t i t u t e d A n t h r a c e n e sAbstract: A number of 9-[(arylmethoxy)methyl]anthracenes were prepared and their photoreactivity was studied. The intramolecular [4p+4p]cycloaddition competes with the intermolecular head-totail [4p+4p] cyclodimerization. The aryl substituents control the selectivity; concentration only plays a role in selectivity in certain cases. The complete reversibility of the cycloaddition makes this process suitable as a molecular switch, provided that traces of acids are avoided; when acid is present the cyclomers pursue an irreversible enol ether cleavage route.Reversible photochemical reactions between compounds that have different absorption (and/or emission) are of great interest for optical switching and optical data storage processes. 1 Recently, we developed such a system, which is based on the intramolecular [4p+4p] cycloaddition of benzene and anthracene moieties. 2 A prerequisite condition for this reaction is that the two chromophores are linked by a three-atom chain, like CH 2 -O-CH 2 . Useful switching systems should have clean, uniform reactions in both directions. The [4p+4p] cyclodimerization is an alternative photoreaction of anthracenes and is an old and well-known process. 1e,3 Therefore, we have now studied the competition between the desired intramolecular [4p+4p] cycloaddition and possible intermolecular [4p+4p] cyclodimerizations. For this purpose, 9-[(arylmethoxy)methyl]anthracenes 3 were generated. Their preparation was based on the nucleophilic substitution of 1 and 2 (Williamson synthesis), whereby the role of nucleophile and electrophile can be exchanged (Table 1, Methods A and B). The best results were obtained by using phase-transfer conditions (KOH, TBAB).The possible photoproducts of 3a-n are shown in Scheme 1. 4-8 Apart from the cyclomers 4, head-to-tail dimers 5 and head-to-head dimers 5¢ can be expected. 9,10 Compared to 5, the dimers 5¢ are highly thermolabile. In the past such compounds were usually detected in solution by NMR measurements of the crude product mixture. Nevertheless, many head-to-head dimers 5¢ have been reported. 4,11,12 In the first approximation, the compounds 3a-n contain two separate chromophores. Therefore, selective irradiation (l ≥300 nm) into the anthracene chromophore is possible. This precondition is necessary in order to prevent the light-induced reverse reactions 4,5,5¢ → 3. Table 2 shows the product ratios 4/5 that were obtained in the irradiation experiments of 3a-h. The halogen-containing compounds 3i-k are highly light sensitive. However, their irradiation yields product mixtures in which dimers, but no cyclomers, can be detected by 1 H NMR and FD-MS measurements; 3k reacts even in daylight. Compound 3l was studied in another context. 7 For the compounds 3a and 3m, no cyclomers 4a and 4m were reported, but mixtures of dimers 5a/5¢a and 5m/5¢m, respectively, were found; 4 on irradiation compound 3n shows a quantitative intram...

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Rearrangement of the carbon skeleton in the intramolecular photoadduct of anthracene and benzene rings

Cited by 6 publications

References 12 publications

Structure Determination of Photoproducts of Anthracenes with (Arylmethoxymethyl) Sidechains

Structure Determination of Photoproducts of Anthracenes with (Arylmethoxymethyl) Sidechains

Optical switches with biplanemers obtained by intramolecular photocycloaddition reactions of tethered arenes

Competition between Inter- and Intramolecular Photocycloaddition Reactions of 9-Substituted Anthracenes

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