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

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.

Key words

amines - diamondoids - nanodiamonds - nitro compounds - oxidation

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.

References and Notes

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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^-¹. 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^-¹. 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^-¹. 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^-¹. 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^-¹. 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.