Synthesis of 2,3,6,7-tetrabromoanthracene

Schäfer, Christian; Herrmann, Friederike; Mattay, Jochen

doi:10.3762/bjoc.4.41

Cited by 11 publications

(11 citation statements)

References 16 publications

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“…168 Similar conditions were applied to the synthesis of 2,3,6,7tetrabromoanthracene from the corresponding 1,2,4,5-tetrakis-(bromoethynyl)benzene. 169 Apart from acenes, polyenes have been likewise used for the synthesis of angularly fused derivatives. Phenanthrenes have been prepared adopting a photochemical approach starting from the so-called Y-enynes, viz.…”

Section: Scheme 37mentioning

confidence: 99%

(Hetero)aromatics from dienynes, enediynes and enyne–allenes

et al. 2016

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The construction of aromatic rings has become a key objective for organic chemists. While several strategies have been developed for the functionalization of pre-formed aromatic rings, the direct construction of an aromatic core starting from polyunsaturated systems is yet a less explored field. The potential of such reactions in the formation of aromatics increased at a regular pace in the last few years. Nowadays, there are reliable and well-established procedures to prepare polyenic derivatives, such as dienynes, enediynes, enyne-allenes and hetero-analogues. This has stimulated their use in the development of innovative cycloaromatizations. Different examples have recently emerged, suggesting large potential of this strategy in the preparation of (hetero)aromatics. Accordingly, this review highlights the recent advancements in this field and describes the different conditions exploited to trigger the process, including thermal and photochemical activation, as well as the use of transition metal catalysis and the addition of electrophiles/nucleophiles or radical species.

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Section: Scheme 37mentioning

confidence: 99%

(Hetero)aromatics from dienynes, enediynes and enyne–allenes

et al. 2016

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“…In 2008, the synthesis of 2,3,6,7-tetrabromoanthracene, which can serve as a precursor for the introduction of substituents in the terminal positions, was achieved for the first time by a double Bergman cyclization reaction. 15 However, the cyclization precursor was reported to be explosive in the dry state and the cyclization itself had to be carried out in an autoclave, which may explain why the number of reported 2,3,6,7-substituted anthracene derivatives has remained low. In 2019, Bunz et al published an alternative method for the synthesis of 2,3,6,7halogenated anthracene derivatives via Vollhardt cyclization.…”

Section: Introductionmentioning

confidence: 99%

Double Ring-Closing Approach for the Synthesis of 2,3,6,7-Substituted Anthracene Derivatives

et al. 2020

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Anthracene derivatives have been used for a wide range of applications and many different synthetic methods for their preparation have been developed. However, despite continued synthetic efforts, introducing substituents in some positions has remained difficult. Here we present a method for the synthesis of 2,3,6,7-substituted anthracene derivatives, one of the most challenging anthracene substitution patterns to obtain. The method is exemplified by the preparation of 2,3,6,7-anthracenetetracarbonitrile and employs a newly developed, stable protected 1,2,4,5-benzenetetracarbaldehyde as the precursor. The precursor can be obtained in two scalable synthetic steps from 2,5-dibromoterephthalaldehyde and is converted into the anthracene derivative by a double intermolecular Wittig reaction under very mild conditions followed by a deprotection and intramolecular double ring-closing condensation reaction. Further modification of the precursor is expected to enable the introduction of additional substituents in other positions and may even enable the synthesis of fully substituted anthracene derivatives by the presented approach. File list (3) download file view on ChemRxiv Draft_final.pdf (351.19 KiB) download file view on ChemRxiv SI_final.pdf (550.08 KiB) download file view on ChemRxiv all.cif (559.68 KiB)

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“…9,10‐Dimethyl‐2,3,6,7‐anthracenetetra(thioacetate) . Anthracene with four halogen atoms at the “end” positions is not easily accessible—only 2,3,6,7‐tetrabromoanthracene has been synthesized, and that required a four step procedure that involves an explosive intermediate and a two‐fold Bergman cyclization . We therefore chose to build the anthracene core through the known condensation reaction of 1,2‐dimethoxybenzene and acetaldehyde in 70 % H 2 SO 4 to form 9,10‐dimethyl‐2,3,6,7‐tetramethoxyanthracene, which can be conducted inexpensively on a large scale (see Scheme ) .…”

Section: Resultsmentioning

confidence: 99%

Synthesis of 9,10‐Dimethyl‐2,3,6,7‐Anthracenetetra(thioacetate) and Benzenepentathiol; Improved Syntheses of 1,2,4,5‐Benzenetetra(thioacetate) and Benzenehexathiol

Singh

Baghel

et al. 2016

ChemistrySelect

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A synthesis is reported for 9,10‐dimethyl‐2,3,6,7‐anthracenetetra(thioacetate), an anthracenetetrathiol derivative that may find use in molecular electronics and conducting metal‐organic frameworks (MOFs). The easily accessible 2,3,6,7‐tetrahydroxy‐9,10‐dimethylanthracene was treated with 2‐(4‐pyridyl)ethanethiol in molten p‐toluenesulfonic acid to yield the tetra(thioether), which was methylated and then deprotected with triethylamine in the presence of acetic anhydride to yield 9,10‐dimethyl‐2,3,6,7‐anthracenetetra(thioacetate), a protected form of the tetrathiol. Separately, the first synthesis of benzenepentathiol and streamlined syntheses of 1,2,4,5‐benzenetetra(thioacetate) and benzenehexathiol are reported.

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Synthesis of 2,3,6,7-tetrabromoanthracene

Abstract: The first synthesis of 2,3,6,7-tetrabromoanthracene is presented, starting from benzene in a straightforward four step synthesis.

Cited by 11 publications

References 16 publications

(Hetero)aromatics from dienynes, enediynes and enyne–allenes

(Hetero)aromatics from dienynes, enediynes and enyne–allenes

Double Ring-Closing Approach for the Synthesis of 2,3,6,7-Substituted Anthracene Derivatives

Synthesis of 9,10‐Dimethyl‐2,3,6,7‐Anthracenetetra(thioacetate) and Benzenepentathiol; Improved Syntheses of 1,2,4,5‐Benzenetetra(thioacetate) and Benzenehexathiol

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