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DOI: 10.1055/s-0030-1261176
N,N-Dihydrotetraazaheptacene: A Synthetic Strategy towards Larger Acenes with Ambient Stability
Publikationsverlauf
Publikationsdatum:
10. August 2011 (online)
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Abstract
We report the synthesis of the first N,N-dihydrotetraazaheptacene, which is solution-processible and stable as a solid under ambient conditions for over three years.
Key words
alkynes - heteroacene - condensation
- Supporting Information for this article is available online:
- Supporting Information
- Primary data for this article are available online and can be cited using the following DOI: 10.4125/pd0018th:
- Primary Data
-
1a
Mondal R.Shah BK.Neckers DC. J. Am. Chem. Soc. 2006, 128: 9612 -
1b
Mondal R.Tonshoff C.Kohn D.Neckers DC.Bettinger HF. J. Am. Chem. Soc. 2009, 131: 14281 -
2a
Clar E. Ber. Dtsch. Chem. Ges. 1942, 75B: 1330 -
2b
Boggiano E.Clar E. J. Chem. Soc. 1957, 2681 -
2c
Marschalk C. Bull. Soc. Chim. 1943, 10: 511 -
2d
Bailey WJ.Liao C. J. Am. Chem. Soc. 1955, 77: 992 - 3
Schleyer PvR.Manoharan M.Jiao H.Stahl F. Org. Lett. 2001, 3: 3643 - 4
Payne MM.Parkin SR.Anthony JE. J. Am. Chem. Soc. 2005, 127: 8028 -
5a
Anthony JE.Eaton DL.Parkin SR. Org. Lett. 2002, 4: 15 -
5b
Maliakal A.Raghavachari K.Katz H.Chandross E.Siegrist T. Chem. Mater. 2004, 16: 4980 - 6
Chun D.Cheng Y.Wudl F. Angew. Chem. Int. Ed. 2008, 130: 8380 -
7a
Kaur I.Jia W.Kopreski RP.Selvarasah S.Dokmeci MR.Pramanik C.McGruer NE.Miller GP. J. Am. Chem. Soc. 2008, 130: 16271 -
7b
Kaur I.Stein NN.Kopreski RP.Miller GP. J. Am. Chem. Soc. 2009, 131: 3424 -
7c
Kaur I.Jazdzyk M.Stein NN.Prusevich P.Miller GP. J. Am. Chem. Soc. 2010, 132: 1261 - 8 There is only one example known of
a dibenzo-stabilized N,N-didodecyl(octaazaheptacene):
Richards GJ.Hill JP.Okamoto K.Shundo A.Akada M.Elsegood MRJ.Mori T.Ariga K. Langmuir 2009, 25: 8408 - For long heteroacenes that are interspersed with pyrene or other units, see:
-
9a
Fogel Y.Kastler M.Wang ZH.Andrienko D.Bodwell GJ.Müllen K. J. Am. Chem. Soc. 2007, 129: 11743 -
9b
Gao BX.Wang M.Cheng YX.Wang LX.Jing XB.Wang FS. J. Am. Chem. Soc. 2008, 130: 8297 - 10
Mateo-Alonso A.Kulisic N.Valenti G.Marcaccio M.Paolucci F.Prato M. Chem. Asian J. 2010, 5: 482 - 11
Appleton AL.Miao S.Brombosz SM.Berger NJ.Barlow S.Marder SR.Hardcastle KI.Bunz UHF. Org. Lett. 2009, 11: 5222 -
12a
Miao S.Brombosz SM.Schleyer PvR.Wu JI.Barlow S.Marder SR.Hardcastle KI.Bunz UHF. J. Am. Chem. Soc. 2008, 130: 7339 -
12b
Miao S.Appleton AL.Berger N.Barlow S.Marder SR.Hardcastle KI.Bunz UHF. Chem. Eur. J. 2009, 15: 4990 -
12c
Wu JI.Wannere CS.Mo YR.Schleyer PvR.Bunz UHF. J. Org. Chem. 2009, 74: 4343 -
12d
Appleton AL.Brombosz SM.Barlow S.Sears JS.Bredas J.-L.Marder SR.Bunz UHF. Nature Commun. 2010, 1: 91 -
12e
Bunz UHF. Pure Appl. Chem. 2010, 82: 953 -
12f
Tverskoy O.Rominger F.Peters A.Himmel HJ.Bunz UHF. Angew. Chem. Int. Ed. 2011, 50: 3557 - 13
Miao S.Appleton AL.Berger NJ.Barlow S.Marder SR.Hardcastle KI.Bunz UHF. Chem. Eur. J. 2009, 15: 4990
References and Notes
The original sample was prepared in October 2007 for single-crystal X-ray diffraction. The same sample has been continuously exposed to atmospheric conditions; exposure to light has not been continuous, but the sample has been in contact with light for weeks at a time. The original ¹H NMR is shown in the Supporting Information, as well as the ¹H NMR taken from the same sample in October 2010 without performing any purification. The October 2010 sample was simply dissolved in CDCl3 and the spectrum was taken.
15Into a thick-walled glass bomb (100 mL volume) were added 1,4-bis[(triisopropylsilyl)ethynyl]naphthalene-2,3-diamine (1; 0.400 g, 7.71 × 10-4 mol, 2 equiv) and 2,5-dihydroxy-benzoquinone (2; 0.054 g, 3.85 × 10-4 mol, 1 equiv), which were dissolved in AcOH (30 mL). The reaction vessel was sealed and heated to 120 ˚C for 6 d while stirring. The reaction was cooled to r.t. and extracted with CH2Cl2 (50 mL). The organic layer was washed with H2O (2 × 100 mL), dried with Na2SO4, and the solvent was removed in vacuo. The crude mixture was purified by column chromatography on silica gel using hexane-CH2Cl2 (3:1). Compound 3 was isolated as a dark purple solid (0.080 g, 18.7% yield); mp stable up to 400 ˚C. IR (KBr): 3375, 3055, 2958, 2931, 2719, 2434, 2360, 2133, 1739, 1720, 1596, 1569, 1488, 1461, 1377, 1261, 1226, 1153, 1107 cm-¹. ¹H NMR (CDCl3): δ = 8.60 (dd, J 1 = 3.3 Hz, J 2 = 6.7 Hz, 2 H), 7.94 (dd, J 1 = 3.2 Hz, J 2 = 6.2 Hz, 2 H), 7.62 (s, 2 H), 7.54 (dd, J 1 = 3.2 Hz, J 2 = 6.7 Hz, 2 H), 7.35 (dd, J 1 = 3.3 Hz, J 2 = 6.2 Hz, 2 H), 6.82 (s, 2 H), 1.29-1.30 (br m, 42 H), 1.25-1.26 (br m, 42 H). ¹³C NMR (CDCl3): δ = 145.7, 141.3, 135.8, 134.1, 130.9, 129.3, 127.3, 127.0, 126.0, 125.1, 119.1, 105.9, 105.7, 105.1, 103.4, 101.7, 99.5, 19.0, 18.9, 11.7, 11.4. HRMS: m/z [M+] calcd for C70H96N4Si4: 1104.6712; found: 1104.6485.