Facile One-pot Synthesis of A Novel Propargyl-Azulene Hybrid Derivative: Cycloaddition Reaction and Some Spectroscopic Properties

Öz

Guaiazulene, 1,4-dimethyl-7-isopropylazulene, is one of the non-benzenoid aromatic compounds consisting of fused of the seven- and the five-membered ring. Guaiazulene is an important natural product and having great potential due to its unique optical and electronic properties. In this study, a method for propargyl insertion into the C-4 methyl group of the guaiazulene is developed. A one-pot reaction of the guaiazulene, LDA, and propargyl bromide in THF affords the corresponding a new propargyl-azulene hybrid derivative. Additionally, Diels-Alder cycloaddition reaction between the propargyl-GA and tetraphenylcyclopentadienone was performed, and the cycloadduct was obtained with excellent yield. The structures of new compounds were elucidated on the basis of extensive spectroscopic (IR, NMR, and UV-vis) data analysis. This approach may be potentially useful for the development of the new azulene derivatives.

Anahtar Kelimeler

• Azulene
• guaiazulene
• propargylation
• alkynylation
• one-pot synthesis
• Diels-Alder
• cycloaddition

Kaynakça

1. Amir E, Amir RJ, Campos LM, Hawker CJ, 2011. Stimuli-responsive azulene-based conjugated oligomers with polyaniline-like properties. Journal of the American Chemical Society, 133(26): 10046-10049.
2. Asato AE, Peng A, Hossain MZ, Mirzadegan T, Bertram, JS, 1993. Azulenic retinoids: novel nonbenzenoid aromatic retinoids with anticancer activity. Journal of Medicinal Chemistry, 36(21): 3137-3147.
3. Aumüller IB, Yli-Kauhaluoma J, 2009. Benzo [cd] azulene skeleton: Azulene, heptafulvene, and tropone derivatives. Organic Letters, 11(23): 5363-5365.
4. Aumüller IB, Yli-Kauhaluoma J, 2011. Synthesis and Tautomerization of Benzo [cd] azulen-3-ones. Organic Letters, 13(7): 1670-1673.
5. Balduzzi S, Müller‐Bunz H, McGlinchey MJ, 2004. A Convenient Synthetic Route to Benz [cd] azulenes: Versatile Ligands with the Potential To Bind Metals in an η5, η6, or η7 Fashion. Chemistry-A European Journal, 10(21): 5398-5405.
6. Barman S, Furukawa H, Blacque O, Venkatesan K, Yaghi OM, Berke H, 2010. Azulene based metal-organic frameworks for strong adsorption of H2. Chemical Communications, 46(42): 7981-7983.
7. Cao T, Li Y, Yang Z, Yuan M, Li Y, Yang H, Yin S, 2016. Synthesis and Biological Evaluation of 3, 8‐dimethyl‐5‐isopropylazulene Derivatives as Anti‐gastric Ulcer Agent. Chemical Biology & Drug Design, 88(2): 264-271.
8. Carret S, Blanc A, Coquerel Y, Berthod M, Greene AE, Deprés JP, 2005. Approach to the blues: a highly flexible route to the azulenes. Angewandte Chemie International Edition, 44(32): 5130-5133.

9. Chen D, Yu S, van Ofwegen L, Proksch P, Lin W, 2012. Anthogorgienes A-O, new guaiazulene-derived terpenoids from a Chinese gorgonian Anthogorgia species, and their antifouling and antibiotic activities. Journal of Agricultural and Food Chemistry, 60(1): 112-123.
10. Cowper P, Jin Y, Turton MD, Kociok‐Köhn G, Lewis SE, 2016. Azulenesulfonium Salts: accessible, stable, and versatile reagents for cross‐coupling. Angewandte Chemie International Edition, 55(7): 2564-2568.
11. Crombie AL, Kane JL, Shea KM, Danheiser RL, 2004. Ring expansion-annulation strategy for the synthesis of substituted azulenes and oligoazulenes. 2. Synthesis of azulenyl halides, sulfonates, and azulenylmetal compounds and their application in transition-metal-mediated coupling reactions. The Journal of Organic Chemistry, 69(25): 8652-8667.
12. Ghasimi S, Landfester K, Zhang KA, 2016. Water Compatible Conjugated Microporous Polyazulene Networks as Visible‐Light Photocatalysts in Aqueous Medium. ChemCatChem, 8(4): 694-698.
13. Ghazvini Zadeh EH, Woodward AW, Richardson D, Bondar MV, Belfield KD, 2015. Stimuli‐Responsive Cyclopenta [ef] heptalenes: Synthesis and Optical Properties. European Journal of Organic Chemistry, 2015(10): 2271-2276.
14. Gordon M, 1952. The Azulenes. Chemical Reviews, 50(1): 127-200.
15. Imamura M, Nakanishi K, Suzuki T, Ikegai K, Shiraki R, Ogiyama T, Yokota M, 2012. Discovery of ipragliflozin (ASP1941): a novel C-glucoside with benzothiophene structure as a potent and selective sodium glucose co-transporter 2 (SGLT2) inhibitor for the treatment of type 2 diabetes mellitus. Bioorganic & Medicinal Chemistry, 20(10): 3263-3279.
16. Kiriazis A, Aumüller IB, Arnaudova R. Brito V, Rüffer T, Lang H, Yli-Kauhaluoma J, 2017. Nucleophilic Substitution of Hydrogen Facilitated by Quinone Methide Moieties in Benzo [cd] azulen-3-ones. Organic Letters, 19(8): 2030-2033.
17. Kurokawa S, 1983. Synthesis of 2-(4-azulenyl) ethanamine derivatives as a nonbenzenoid analog of biogenic amine. Bulletin of the Chemical Society of Japan, 56(8): 2311-2318.
18. Narita M, Murafuji T, Yamashita S, Fujinaga M, Hiyama K, Oka Y, Ishiguro K, 2018. Synthesis of 2-iodoazulenes by the iododeboronation of azulen-2-ylboronic acid pinacol esters with copper (I) iodide. The Journal of Organic Chemistry, 83(3): 1298-1303.
19. Park S, Yong WS, Kim S, Lee PH, 2014. Diastereoselective N-Sulfonylaminoalkenylation of Azulenes from Terminal Alkynes and Azides via N-Sulfonyl-1, 2, 3-triazoles. Organic Letters, 16(17): 4468-4471.
20. Razus AC, Birzan L, Tecuceanu V, Cristea M, Enache C, 2008. Condensation of alkylazulenes with thiophene-2-carboxaldehyde and the corresponding azomethines. Arkivoc, 11: 210-226.
21. Seo Y, Rho JR, Geum N, Yoon JB, Shin J, 1996. Isolation of guaianoid pigments from the gorgonian Calicogorgia granulosa. Journal of Natural Products, 59(10): 985-986.
22. Shoji T, Sugiyama S, Kobayashi Y, Yamazaki A, Ariga Y, Katoh R, Ito S, 2020. Direct synthesis of 2-arylazulenes by [8+ 2] cycloaddition of 2H-cyclohepta [b] furan-2-ones with silyl enol ethers. Chemical Communications.
23. Székely A, Péter A, Aradi K, Tolnai GL, Novák Z, 2017. Gold-Catalyzed Direct Alkynylation of Azulenes. Organic Letters, 19(4): 954-957.
24. Takekuma SI, Yamamoto M, Nakagawa A, Iwata T, Minematsu T, Takekuma H, 2012. Preparation, crystal structure, and spectroscopic, chemical, and electrochemical properties of (2E, 4E)-1, 4-di (3-guaiazulenyl)-1, 3-butadiene compared with those of (E)-1, 2-di (3-guaiazulenyl) ethylene. Tetrahedron, 68(39): 8318-8329.
25. Tanaka Y, Shigenobu K, 2001. A Review of HNS‐32: A Novel Azulene‐l‐Carboxamidine Derivative with Multiple Cardiovascular Protective Actions. Cardiovascular Drug Reviews, 19(4): 297-312.
26. Tomiyama T, Yokota M, Wakabayashi S, Kosakai K, Yanagisawa T, 1993. Design, synthesis, and pharmacology of 3-substituted sodium azulene-1-sulfontes and related compounds: non-prostanoid thromboxane A2 receptor antagonists. Journal of Medicinal Chemistry, 36(7): 791-800.
27. Vlasceanu A, Andersen CL, Parker CR, Hammerich O, Morsing TJ, Jevric M, Nielsen MB, 2016. Multistate Switches: Ruthenium Alkynyl–Dihydroazulene/Vinylheptafulvene Conjugates. Chemistry-A European Journal, 22(22): 7514-7523.
28. Wang P, Zhu P, Ye C, Asato AE, Liu RS, 1999. Theoretical investigation and molecular design of some azulene derivatives with large hyperpolarizabilities. The Journal of Physical Chemistry A, 103(35): 7076-7082.
29. Woodward AW, Ghazvini Zadeh EH, Bondar MV, Belfield KD, 2016. Computer aided chemical design: using quantum chemical calculations to predict properties of a series of halochromic guaiazulene derivatives. Royal Society Open Science, 3(11): 160373.
30. Yanagisawa T, Wakabayashi S, Tomiyama T, Yasunami M, Takase K, 1988. Synthesis and anti-ulcer activities of sodium alkylazulene sulfonates. Chemical and Pharmaceutical Bulletin, 36(2): 641-647.
31. Zadeh EG, Tang S, Woodward AW, Liu T, Bondar MV, Belfield KD, 2015. Chromophoric materials derived from a natural azulene: syntheses, halochromism and one-photon and two-photon microlithography. Journal of Materials Chemistry C, 3(33): 8495-8503.
32. Zadeh EG, Tang S, Woodward AW, Liu T, Bondar MV, Belfield KD, 2015. Chromophoric materials derived from a natural azulene: syntheses, halochromism and one-photon and two-photon microlithography. Journal of Materials Chemistry C, 3(33): 8495-8503.
33. Zhang LY, Yang F, Shi WQ, Zhang P, Li Y, Yin SF, 2011. Synthesis and antigastric ulcer activity of novel 5-isoproyl-3, 8-dimethylazulene derivatives. Bioorganic & Medicinal Chemistry Letters, 21(19): 5722-5725.
34. Zhao L, Bruneau C, Doucet H, 2013. A straightforward access to guaiazulene derivatives using palladium-catalysed sp 2 or sp 3 C–H bond functionalisation. Chemical Communications, 49(49): 5598-5600.