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DOI: 10.1055/s-0029-1219188
Synthesis of Diamondoid Nitro Compounds from Amines with m-Chloroperbenzoic Acid [¹]
Publication History
Publication Date:
11 January 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.
Key words
amines - diamondoids - nanodiamonds - nitro compounds - oxidation
- Supporting Information for this article is available online:
- Supporting Information
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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References and Notes
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.
29
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.
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.