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Synlett 2012; 23(18): 2623-2626
DOI: 10.1055/s-0032-1317446
DOI: 10.1055/s-0032-1317446
letter
Solvent-Free Pivalic Acid/Copper Chloride Jointly Promoted Chlorination of 1,2,3-Triazoles
Weitere Informationen
Publikationsverlauf
Received: 26. Juni 2012
Accepted after revision: 20. September 2012
Publikationsdatum:
18. Oktober 2012 (online)
![](https://www.thieme-connect.de/media/synlett/201218/lookinside/thumbnails/10.1055-s-0032-1317446-1.jpg)
Abstract
A novel chlorination reaction on the 5-position of 1,2,3-triazoles, directly from 5H-substituted 1,2,3-triazoles was developed by using copper(II) chloride in pivalic acid. A series of triazoles were thus chlorinated in low to good yields.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
References and Notes
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- 12 General procedure: To a solution of triazole (0.3 mmol, 1 equiv) in pivalic acid (500 mg), was added CuCl2 (1 equiv) at room temperature. The reaction mixture was warmed to 140 °C and stirred under air for 46 h. Pivalic acid was evaporated under reduced pressure and the residue was dissolved in EtOAc. The organic layer was washed with water (3 × 20 mL), dried over MgSO4, and concentrated under reduced pressure. The residue was purified by flash chromatography. 5-Chloro-4-hexyl-1-phenethyl-1H-1,2,3-triazole (1): Yield: 62%; light-yellow oil; 1H NMR (CDCl3): δ = 7.26 (m, 3 H), 7.12 (dd, J = 7.6, 1.8 Hz, 2 H), 4.50 (t, J = 7.5 Hz, 2 H), 319 (t, J = 7.2 Hz, 2 H), 2.62 (t, J = 6.9 Hz, 2 H), 1.67 (m, 2 H), 1.30 (m, 6 H), 0.89 (t, J = 6.7 Hz, 3 H); 13C NMR (CDCl3): δ = 136.7, 128.72, 128.71, 127.0, 49.5, 36.0, 31.5, 28.7, 28.4, 24.5, 22.5, 14.0; HRMS: (DCI/CH4): m/z calcd for C16H23N3Cl: 292.1581; found: 292.1605. 1-Benzyl-5-chloro-4-hexyl-1H-1,2,3-triazole (3): Yield: 47%; yellow oil; 1H NMR (CDCl3): δ = 7.28 (m, 5 H), 5.48 (s, 2 H), 2.63 (t, J = 7.6 Hz, 2 H), 1.68 (m, 2 H), 1.30 (m, 6 H), 0.86 (t, J = 6.7 Hz, 3 H); 13C NMR (CDCl3): δ = 144.1, 134.1, 128.9, 128.4, 127.7, 122.3, 51.9, 31.4, 28.8, 28.4, 24.6, 22.5, 14.0, HRMS: (DCI/CH4): m/z calcd for C15H21N3Cl: 278.1424; found: 278.1415.
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- 15 Crystal data for compound 13: C18H18ClN3; M = 311.80; monoclinic; space group P 21/c; a = 8.7163(11) Å, b = 10.9837(13) Å, c = 17.052(2) Å, β = 98.365(6)°; V = 1615.2(3) Å3; Z = 4; crystal size 0.30 × 0.20 × 0.12 mm3; 24818 reflections collected (3975 independent, R int = 0.0344), 254 parameters, 225 restraints, R1 [I>2σ(I)]= 0.0515, wR2 [all data] = 0.1599, largest diff. peak and hole: 0.428 and –0.240 e·Å–3. CCDC 876302 (13) contains the supplementary crystallographic data for this Letter. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif
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