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Short Note

4,8-Bisallyl-2,6-dimethylnaphthalene-1,5-diyl Diacetate

Department of Chemistry, University of Copenhagen, Thorvaldsensvej 40, DK-1871 Frederiksberg C, Denmark
*
Author to whom correspondence should be addressed.
Molbank 2014, 2014(1), M812; https://doi.org/10.3390/M812
Submission received: 4 December 2013 / Accepted: 8 January 2014 / Published: 13 January 2014

Abstract

:
4,8-Diallyl-2,6-dimethylnaphthalene-1,5-diyl diacetate (1) which is a highly substituted naphthalene derivative has been synthesized in two steps starting from 2,6-dimethyl-1,5-naphthalenediol (3) using a modified Claisen-rearrangement.

Graphical Abstract

Peri-substituted aromatic compounds [1] such as 1,4,5,8-tetrasubstituted napthalenes are notoriously difficult to synthesize due to the short distance between the peri-positions and in compounds such as 1,4,5,8-tetramethyl naphthalene the methyl groups are interlocking giving rise to restricted rotation [2]. Peri-strain also affects the reactivity of the compounds as for example seen in 4,8-dibromo-1,5-dimethoxynaphthalene, which isomerizes to 2,7-dibromo-1,5-dimethoxy- and finally 2,6-dibromo-1,5-dimethoxynaphthalene upon even short heating in acetic acid [3].
1,4,5,8-tetrasubstituted naphthalenes can serve as staring materials for the synthesis of pyrenes and heterocyclic pyrenes such as dioxapyrenes, which are interesting compounds for conducting radical cation salts. We [4,5,6,7] and other groups [8,9,10,11] have previously reported different methodologies for the synthesis of 1,6-dioxa- and 1,6-dithiapyrenes from naphthalene derivatives and while the 1,6-dithiapyrenes can be synthesized from 1,5-disubstituted naphthalenes through an acid catalyzed ring closure, the synthesis of 1,6-dioxapyrenes requires either 1,2,5,6-tetrasubstituted naphthalenes or 1,4,5,8-tetrasubstituted napthalenes as intermediates.
The Claisen-rearrangement is an efficient method for introducing substitutents ortho to a phenol via the allyl aryl ether, however if the ortho-positions are blocked, the product is the corresponding 4-allyl substituted compound. [12] This led us to consider the double Claisen-rearrangement of 2,6-disubsubstituted bis allyl ethers of 1,5-naphthalenediols as a synthetic route to bisperisubstituted naphthols for subsequent uses for the synthesis of 1,6-dioxapyrenes.
2,6-Dimethyl-1,5-naphthalenediol (3) [4] was alkylated with allyl bromide in DMF with K2CO3 as the base to give the crude bisallyl ether (2), which was subjected to a modified Claisen-rearrangement [13] by reflux in a mixture of N,N-diethylaniline and acetic anhydride (Scheme 1). Under these conditions, the highly air sensitive tetrasubstituted naphthalenediol is immediately protected by acetylation to give a stable product, that can be purified without any special precautions.
4,8-Bisallyl-2,6-dimethylnaphthalene-1,5-diyl diacetate (1)
2,6-Dimethyl-1,5-dihydroxynaphthalene (3) [4] (10.2 g; 0.05 mol) and allyl bromide (10 mL; 14 g; 0.12 mol) was added to a degassed suspension of dry K2CO3 (0.15 mol) in DMF (50 mL). The mixture was stirred at 20 °C under N2 overnight. The reaction mixture was poured into water (500 mL) and extracted with diethyl ether (100 mL). The organic phase was dried over MgSO4, filtered and concentrated in vacuo. The crude bis(allyl ether) was dissolved in a mixture of N,N-diethyl aniline (50 mL) and acetic anhydride (20 mL) and refluxed under N2 for 3 days (200–210 °C). The product separated upon cooling to room temperature was isolated by filtration, washed with petroleums ether (Bp. 35 °C) until free of N,N-diethyl aniline and acetic acid and air dried to give (1) as an off-white powder.
Yield: 9.6 g (55%).
An analytical sample was crystallized from EtOH. Mp. 166–168 °C.
Calcd. for C22H24O4, C, 74.98; H, 6.86. Found: C, 74.56; H, 6.70.
1H-NMR (500 MHz; CDCl3): δ 7.08 (s, 2 H); 6.07 (m; 2H); 5.03 (m; 2H); 4.92 (m; 2H); 3.78 (m, 4H); 2.30 (s, 6H); 2.13 (s, 6H).
13C-NMR (125 MHz; CDCl3): δ 168.9; 143.9; 137.7; 132.5; 132.1; 127.4; 126.9; 116.2; 40.3; 21.5; 16.7.

Supplementary materials

Supplementary File 1Supplementary File 2Supplementary File 3

Acknowledgments

We would to thank University of Copenhagen for technical support.

Conflict of Interest

The authors declare no conflict of interest.

References

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Scheme 1. The synthesis of 4,8-Bisallyl-2,6-dimethylnaphthalene-1,5-diyl Diacetate.
Scheme 1. The synthesis of 4,8-Bisallyl-2,6-dimethylnaphthalene-1,5-diyl Diacetate.
Molbank 2014 m812 sch001

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MDPI and ACS Style

Christensen, J.B.; Sørensen, J.N.; Schaumburg, K.; Bechgaard, K. 4,8-Bisallyl-2,6-dimethylnaphthalene-1,5-diyl Diacetate. Molbank 2014, 2014, M812. https://doi.org/10.3390/M812

AMA Style

Christensen JB, Sørensen JN, Schaumburg K, Bechgaard K. 4,8-Bisallyl-2,6-dimethylnaphthalene-1,5-diyl Diacetate. Molbank. 2014; 2014(1):M812. https://doi.org/10.3390/M812

Chicago/Turabian Style

Christensen, Jørn B., Jeanett N. Sørensen, Kjeld Schaumburg, and Klaus Bechgaard. 2014. "4,8-Bisallyl-2,6-dimethylnaphthalene-1,5-diyl Diacetate" Molbank 2014, no. 1: M812. https://doi.org/10.3390/M812

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