Synlett 2010(3): 493-495  
DOI: 10.1055/s-0029-1219188
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Diamondoid Nitro Compounds from Amines with m-Chloroperbenzoic Acid [¹]

Hartmut Schwertfegera, Christian Würteleb, Peter R. Schreiner*a
a Institut für Organische Chemie, Justus-Liebig University, Heinrich-Buff-Ring 58, 35392 Gießen, Germany
Fax: +49(641)9934309; e-Mail: prs@org.chemie.uni-giessen.de;
b Institut für Anorganische und Analytische Chemie, Justus-Liebig University, Heinrich-Buff-Ring 58, 35392 Gießen, Germany
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Publikationsverlauf

Received 26 November 2009
Publikationsdatum:
11. Januar 2010 (online)

Abstract

We report the synthesis of diamondoid nitro derivatives via the selective oxidation of the corresponding amines using m-chloroperbenzoic acid in 1,2-dichloroethane as solvent.

1

Functionalized nanodiamonds, part 27. For part 26, see: Schwertfeger H., Machuy M. M., Würtele C., Dahl J. E. P., Carlson R. M. K., Schreiner P. R., submitted.

1

Functionalized nanodiamonds, part 27. For part 26, see: Schwertfeger H., Machuy M. M., Würtele C., Dahl J. E. P., Carlson R. M. K., Schreiner P. R., submitted.

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General Procedure for Amine Oxidation MCPBA was dissolved in DCE (30 mL) and heated to reflux. Then the respective amine was dissolved in DCE (10 mL) and added dropwise to the MCPBA solution. After 3 h (4 h in the case of 14) the mixture was cooled to r.t., washed with 10% NaOH solution (3 × 70 mL) and dried over anhyd Na2SO4. The obtained crude product was purified by column chromatography on silica gel to receive nitro derivatives as colorless solids.
4-Nitrodiamantane (9)
Pentane-Et2O (9:1); R f = 0.39; mp 118-122 ˚C. ¹H NMR (400 MHz, CDCl3): δ = 2.23-2.17 (m, 6 H, H-3,5,13), 2.05 (br s, 3 H, H-2,6,12), 1.87-1.82 (m, 1 H, H-9), 1.82-1.75 (m, 9 H, H-1,7,8,10,11,14). ¹³C NMR (100 MHz, CDCl3): δ = 84.0 (C-4), 41.4 (C-3,5,13), 38.6 (C-2,6,12), 36.8 (C-8,10,14), 35.9 (C-1,7,11), 25.2 (C-9). IR (KBr): ν = 2912, 2893, 2879, 2853, 1539, 1471, 1443, 1384, 1363, 1249, 1046, 887, 805 cm. Anal. Calcd for C14H19NO2 (233.31): C, 72.07; H, 8.21; N, 6.00. Found: C, 71.79; H, 8.33; N, 5.78.
1-Nitrodiamantane (11) Pentane-Et2O (9:1; and HPLC, see Supporting Information); R f = 0.46; mp 244-245 ˚C. ¹H NMR (400 MHz, CDCl3): δ = 2.59 (br s, 2 H, H-2,12), 2.14-2.07 (m, 3 H, H-7,9,11), 2.06-2.00 (m, 2 H, H-14), 1.81-1.65 (m, 10 H, H-3,4,5,6,8,10,13), 1.63-1.55 (m, 2 H, H-3,13). ¹³C NMR (100 MHz, CDCl3): δ = 90.6 (C-1), 44.6 (C-14), 39.2 (C-7,11), 38.8 (C-2,12), 37.4 (C-5), 36.6 (C-8,10), 35.9 (C-6), 33.5 (C-3,13), 28.6 (C-9), 24.3 (C-4). IR (KBr): ν = 2914, 2853, 1528, 1465, 1450, 1382, 1357, 1077, 1058, 987, 861, 797 cm. Anal. Calcd for C14H19NO2 (233.31): C, 72.07; H, 8.21; N, 6.00. Found: C, 71.86; H, 8.23; N, 6.30.
4,9-Dinitrodiamantane (13) Hexane-EtOAc (3:1); R f = 0.39; mp 235-239 ˚C. ¹H NMR (400 MHz, CDCl3): δ = 2.29 (s, 12 H, H-3,5,8,10,13,14), 2.14 (s, 6 H, H-1,2,6,7,11,12). ¹³C NMR (100 MHz, CDCl3): δ = 82.7 (C-4,9), 40.0 (C-3,5,8,10,13,14), 37.0 (C-1,2,6,7,11,12). IR (KBr): ν = 2967, 2945, 2918, 2899, 2870, 1540, 1470, 1442, 1367, 1249, 1083, 1052, 801 cm. Anal. Calcd for C14H18N2O4 (278.30): C, 60.42; H, 6.52; N, 10.07. Found: C, 60.20; H, 6.54; N, 9.99.
1,6-Dinitrodiamantane (15) CH2Cl2-hexane (1:1); R f = 0.25; mp >300 ˚C (dec.). ¹H NMR (400 MHz, CDCl3): δ = 2.79 (s, 4 H, H-2,7,11,12), 2.10-2.00 (m, 6 H, H-4,5,9,14), 1.80-1.60 (m, 8 H, H-3,8,10,13). ¹³C NMR (100 MHz, CDCl3): δ = 88.8 (C-1,6), 43.9 (C-5,14), 40.1 (C-2,7,11,12), 32.1 (C-3,8,10,13), 26.9 (C-4,9). IR (KBr): ν = 2937, 2868, 1538, 1468, 1455, 1445, 1377, 1356, 1326, 1112, 993, 797 cm. HRMS: m/z calcd for C14H18N2O4: 278.1267; found: 278.1299. Anal. Calcd for C14H18N2O4 (278.30): C, 60.42; H, 6.52; N, 10.07. Found: C, 60.33; H, 6.53; N, 9.73.
9,15-Dinitrotriamantane (17)
Pentane-Et2O (1:1); R f = 0.35; mp 223-226 ˚C. ¹H NMR (400 MHz, CDCl3): δ = 2.30-2.13 (m, 8 H, H-8,10,14,18), 2.11 (br s, 4 H, H-3,7,11,13), 1.94 (br s, 4 H, H-16,17), 1.82-1.74 (m, 4, H-4,5,6), 1.57 (br s, 2 H, H-2,12). ¹³C NMR (100 MHz, CDCl3): δ = 83.8 (C-9,15), 46.7 (C-16,17), 43.5 (C-2,12), 40.8 (C-8,10,14,18), 38.2 (C-3,7,11,13), 37.4 (C-1), 35.8 (C-5), 32.8 (C-4,6). IR (KBr): ν = 2921, 2894, 2867, 1533, 1474, 1446, 1363, 1352, 1149, 1029, 868, 811, 799 cm. Anal. Calcd for C18H22N2O4 (330.38): C, 65.44, H, 6.71; N, 8.48. Found: C, 65.17; H, 6.73; N, 8.31.

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The structures have been deposited in the Cambridge Crystallographic Data Centre and can be retrieved using the following numbers: CCDC 755751 for 13 and 755752 for 15.