Tetraethynylbenzo[2,1,3]thiadiazole

Abstract

The synthesis and structural characterization of peralkynylated benzothiadiazole 2 is reported. The synthesis utilizes ­Vollhardt’s access to hexaethynylbenzene by coupling different alkynes to tetrabromobenzo[2,1,3]thiodiazole via the Heck-­Cassar-Sonogashira-Hagihara reaction.

Key words

Pd-catalysis - alkynes - heterocycles - peralkynylated π-systems - carbon rich materials

References

• 1a Diercks R. Armstrong JC. Boese R. Vollhardt KPC. Angew. Chem., Int. Ed. Engl.  1986,  25:  268 
• 1b Boese R. Green JR. Mittendorf J. Mohler DL. Vollhardt KPC. Angew. Chem., Int. Ed. Engl.  1992,  31:  1643 
• 1c Tovar JD. Jux N. Jarrosson T. Khan SI. Rubin Y. J. Org. Chem.  1997,  62:  3432 
• 2 Neenan TX. Whitesidedes GM. J. Org. Chem.  1988,  53:  2489 
• 3 Zhang DM. Tessier CA. Youngs WJ. Chem. Mater.  1999,  11:  3050 
• 4a Diederich F. Nature (London)  1994,  369:  199 
• 4b Anthony J. Knobler CB. Diederich F. Angew. Chem. Int. Ed. Engl.  1993,  32:  406 
• 4c Diederich F. Chem. Commun.  2001,  219 
• 4d Diederich F. Rubin Y. Angew. Chem., Int. Ed. Engl.  1992,  31:  1101 
• 5 Jux N. Holczer K. Rubin Y. Angew. Chem., Int. Ed. Engl.  1996,  35:  1986 
• 6a Bunz UHF. Rubin Y. Tobe Y. Chem. Soc. Rev.  1999,  28:  107 
• 6b Bunz UHF. Top. Curr. Chem.  1999,  201:  131 
• 7a Laskoski M. Steffen W. Morton JGM. Smith MD. Bunz UHF. Angew. Chem. Int. Ed.  2002,  41:  2378 
• 7b Laskoski M. Roidl G. Smith MD. Bunz UHF. Angew. Chem. Int. Ed.  2001,  40:  1460 
• 7c Bunz UHF. Roidl G. Altmann M. Enkelmann V. Shimizu KD. J. Am. Chem. Soc.  1999,  121:  10719 
• 8a Bunz UHF. Enkelmann V. Organometallics  1994,  13:  3823 
• 8b Bunz UHF. Enkelmann V. Räder J. Organometallics  1993,  12:  4756 
• 9 Bublitz DE. J. Heterocycl. Chem.  1972,  9:  539 
• 10 Bunz UHF. Chem. Rev.  2000,  100:  1605 
• 11a Koren AB. Curtis MD. Francis AH. Kampf JW. J. Am. Chem. Soc.  2003,  125:  5040 
• 11b Koren AB. Curtis MD. Kampf JW. Chem. Mater.  2000,  12:  1519 

12

Crystal Structure Determination: Empirical formula: C₃₀H₃₆N₂S. Formula weight: 456.67. T = 150 (1) K. Wavelength: 0.71073 Å. Crystal system: Monoclinic, P2₁/n. Unit cell dimensions: a = 9.0675 (5) Å, b = 12.4366 (6) Å, c = 24.629 (1) Å, α = 90°; β = 91.740 (1)°; γ = 90°. V = 2776.1 (3) ų. Z = 4. ρ_calcd = 1.093 g/cm³. Absorption coefficient:
0. 135 mm^-1, F(000): 984. Crystal size: 0.38 × 0.30 × 0.18 mm³. Theta range for data collection: 1.65° to 24.12°. Index ranges: -9 ≤ h ≤ 10, -11 ≤ k≤ 14, -27 ≤ l≤ 28. Reflections collected: 14498. Independent reflections: 4428 [R(int) = 0.0410]. Completeness to Θ = 24.12°, 99.9%. Absorption correction: None. Refinement method: Full-matrix least-squares on F². Data /restraints/parameters: 4428/0/346. Goodness-of-fit on F²: 1.046. Final R indices [I > 2σ(I)]: R1 = 0.0437, wR2 = 0.1177. R indices (all data): R1 = 0.0564, wR2 = 0.1226. Largest diff. peak and hole: 0.319 and -0.202 e Å^-3. Tables and details of the crystal structure determination can be obtained from Cambridge Crystallographic Data Centre (CCDC) utilizing the email [e-mail] and the reference number CCDC 222103.

13

Molecular geometries were determined by AM1 and B3LYP utilizing the 6-31G** basis set. The calculations were carried out with Spartan’04 on a Windows XP platform.