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4-Methyl-N-(2,2,4,4-tetrachloro-5-methyl-3-oxo-8-oxabicyclo[3.2.1.]oct-6-en-1-ylmethyl)-benzenesulfonamide
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4-Methyl-N-(5-methyl-furan-2-ylmethyl)-benzenesulfonamide (N-(5-Methyl-furfuryl)-p-toluenesulfonamide)
 
 
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4-Methyl-N-(2,2,4,4-tetrachloro-3-oxo-8-oxabicyclo[3.2.1.]oct-6-en-1-ylmethyl)-benzenesulfonamide

Institut für Organische Chemie der Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
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Author to whom correspondence should be addressed.
Molbank 2005, 2005(2), M408; https://doi.org/10.3390/M408
Submission received: 8 March 2004 / Accepted: 24 June 2004 / Published: 1 August 2005
Molbank 2005 m408 i001
A mixture of N-furfuryl-p-toluenesulfonamide (1) (2.51 g, 10 mmol) [1] and pentachloroacetone [2] (3.23 g, 14 mmol) was cooled in an ice bath. With magnetic stirring, a 2-molar solution of sodium 2,2,2-trifluoroethoxide in 2,2,2-trifluoroethanol[3] (7 mL, 14 mmol) was added dropwise, over 15 min. Stirring was continued for 15 min at 0 °C and then at room temperature for 2–3 hours[4]. The mixture was allowed to stir for a further 2 hours. Then, the heterogeneous mixture was poured on saturated brine (20 mL). The precipitate was dissolved by adding a little of dichloromethane and water, and the organic layer was separated. The aqueous layer was acidified with hydrochlorid acid to pH 4–5 and then extracted with dichloromethane (4 ‘ 20 mL). The combined dichloromethane solutions were washed with saturated brine (20 mL) and dried overnight with magnesium sulfate. After filtration, the solution was concentrated in a rotary evaporator. The remaining yellow mass was recrystallized from dry ethanol (10 mL) to yield 3.60 g (81%) of 2 as a colourless crystalline solid.
Melting Point: 162–163 °C.
TLC (silica, hexane/tert-butylmethyl ether (1:1 v/v): A pale yellow spot emerged after spraying the sheet with vanillin/sulfuric acid reagent followed by heating with a hot-air gun; Rf = 0.27. The starting material (1) showed a brownish violet spot at Rf = 0.37.
1H-NMR (250 MHz, CDCl3): δ= 2.45 (s, 3 H, CH3C6H4SO2); ABX sub-spectrum (14 lines) with δ A = 3.89, δ B = 3.65, δ X = 5.10, JAB = (-)14 Hz, JAX = 9.6 Hz, JBX = 3.6 Hz, 3 H, diastereotopic CH2-NH); 5.16 (d, J = 1.7 Hz, 1 H, H-5), AB sub-spectrum with δ A = 6.48 (H-6), δ B = 6.46 (H-7), JAB = 5.5 Hz, the lines of the A part are split into doublets with J = 1.7 Hz; AA’BB’ sub-spectrum with δ A = 7.76, δ B = 7.35, JAB = 8.2 Hz (H-2/6 and H-3/5 from CH3C6H4SO2).
13C-NMR/DEPT (62.9 MHz, CDCl3): δ= 21.6 (+, CH3C6H4SO2); 42.2 (-, CH2-N); 81.9 (Cq, C-4); 85.05 (Cq, C-2); 87.9 (+, C-5); 93.3 (Cq, C-1); 127.0 (+, C-2/6 of the tosyl group); 130.0 (+, C-3/5 of the tosyl group); 134.4 (+, C-6); 135.7 (+, C-7); 136.7 (Cq, C-4 of the tosyl group); 144.1 (Cq, C-1 of the tosyl group); 183.9 (Cq, C-3).
IR (CHCl3 film, cm-1): 3395, 3280 (N-H); 3110 (=C-H); 1768 with shoulder at 1750 (C=O); 1600 (C=C); 1495 (NH); 1430, 1340 (SO2); 1163 cm-1 (SO2).
Elemental Analysis: Calculated for C15H13Cl4NO4S (445.15): C, 40.47%; H, 2.94%; Cl, 31.86%; N: 3.15%; S, 7.20%. Found: C, 40.24%; H, 3.02%; Cl, 31.63%; N, 3.15%; S, 7.15%.

Supplementary materials

Supplementary File 1Supplementary File 2Supplementary File 3

References and Notes

  1. a) Chooney, N.; Kuhnert, N.; Sammes, P. G.; Smith, G.; Ward, R. W. J. Chem. Soc., Perkin Trans 1 2002, 1999–2005. b) Meining, H.; Föhlisch, B. Molbank 2005, M407.
  2. Bugrova, L. V.; Rudnev, G. K.; Kristich, A. I.; Radchenko, V. I.; Mishchenko, L. F. Zh. Prikl. Khim. (Leningrad) 1973, 46, 1529–1533, J. Appl. Chem. USSR 1973, 2, 1627–1631.
  3. a) Föhlisch, B.; Gehrlach, E.; Herter, R. Angew. Chem. 1982, 94, 144, Angew. Chem. Suppl. 1982, 94, 241; Angew. Chem., Int. Ed. Engl. 1982, 21, 137. b) Sendelbach, S.; Schwetzler-Raschke, R.; Radl, A.; Kaiser, R.; Henle, G. H.; Korfant, H.; Reiner, S.; Föhlisch, B. J. Org. Chem. 1999, 64, 3398–3408. [CrossRef]
  4. If 1 has not disappeared after that time (check by TLC), more pentachloroacetone (0.7–1.2 g, 3–5 mmol) was added, and the base solution in such amount that a test with wet pH indicator paper showed an alkaline reaction.
  • Sample Availability: Available from MDPI.

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MDPI and ACS Style

Meining, H.; Föhlisch, B. 4-Methyl-N-(2,2,4,4-tetrachloro-3-oxo-8-oxabicyclo[3.2.1.]oct-6-en-1-ylmethyl)-benzenesulfonamide. Molbank 2005, 2005, M408. https://doi.org/10.3390/M408

AMA Style

Meining H, Föhlisch B. 4-Methyl-N-(2,2,4,4-tetrachloro-3-oxo-8-oxabicyclo[3.2.1.]oct-6-en-1-ylmethyl)-benzenesulfonamide. Molbank. 2005; 2005(2):M408. https://doi.org/10.3390/M408

Chicago/Turabian Style

Meining, Holger, and Baldur Föhlisch. 2005. "4-Methyl-N-(2,2,4,4-tetrachloro-3-oxo-8-oxabicyclo[3.2.1.]oct-6-en-1-ylmethyl)-benzenesulfonamide" Molbank 2005, no. 2: M408. https://doi.org/10.3390/M408

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