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DOI: 10.1055/s-0029-1219803
An Efficient Synthesis of Carborane Amines via One-Step Reaction of Carborane Triflates with N-Nucleophiles
Publication History
Publication Date:
07 April 2010 (online)
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Abstract
1-Trifluoromethanesulfonylmethyl-o-carborane and cesium 1-trifluoromethanesulfonylmethyl-1-carba-closo-dodecaborate react with amines in refluxing acetonitrile in the presence of NaOAc without a catalyst to give the corresponding amino derivatives. This approach allows for simple synthesis of neutral and anionic carborane amines not readily available via other synthetic routes.
Key words
carboranes - triflates - N-nucleophiles - amino carboranes
- Supporting Information for this article is available online:
- Supporting Information
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References and Notes
General Procedure
for the Synthesis of Amines 3a-e and 4a-c
A
mixture of triflate 1 (1.0 g, 3.3 mmol),
corresponding amine (3.3 mmol), and NaOAc (0.74 g, 9 mmol) in MeCN (10
mL) was refluxed for 4-8 h until the complete disap-pearance
of 1 was proved by TLC (heptane-EtOAc,
7:3). Then the reaction mixture was poured into H2O (20
mL) and extracted with EtOAc (3 × 7 mL).
The organic layers were combined, washed with H2O, and
dried over MgSO4. Then the mixture was filtered, and
the solvent was removed under reduced air pressure. The residue
was chromatographed on SiO2 (eluent: heptane-EtOAc,
10:1) to afford the products as colorless solids.
Analytical Data for Compound 3a
Yield
76% (0.62 g); mp 92-93 ˚C. IR (KBr):
3392, 3069, 2595 cm-¹. ¹H
NMR (400.13 MHz, CDCl3): δ = 1.52-2.90 (m,
10 H), 3.77 (s, 1 H), 3.92 (d, J = 6.5
Hz, 2 H), 4.03 (s, 1 H), 7.24-6.60 (m, 5 H). ¹¹B
NMR (128.32 MHz, CDCl3): δ = -2.32
(d, J = 149
Hz, 1 B), -5.20 (d, J = 149
Hz, 1 B),
-9.11 (d, J = 150
Hz, 2 B), -11.47 (d, J = 169
Hz, 2 B),
-12.96 (d, J = 149
Hz, 4 B). Anal. Calcd (%) for C9H19B10N: C,
43.35; H, 7.63; N, 5.62. Found: C, 43.46; H, 7.81; N, 5.58.
Synthesis of Compound 5
To a stirred
mixture of sodium amide prepared from sodium (0.16 g, 7.0 mmol)
in liquid ammonia (50 mL), triflate 1 (2 g,
6.6 mmol) was added at -50 ˚C in anhyd
toluene (10 mL). The reaction mixture was stirred at -50 ˚C
for 1 h, then NH4Cl (0.37 g, 7 mmol) was slowly added.
The liquid ammonia was evaporated and H2O (20 mL) was
added. The product was extracted with EtOAc and dried over Na2SO4. The
solvents were evaporated, and the crude product was purified by
chromatography on SiO2 (eluent: heptane) to afford 0.95
g (84% yield) of 5. White solid;
mp 158 ˚C. ¹H NMR (400.13
MHz, CDCl3): δ = 1.20-3.10
(m, 10 H), 2.80 (s, 2 H), 3.89 (s, 1 H), 4.06 (s, 2 H). ¹¹B
NMR (128.32 MHz, CDCl3): δ = -2.66
(d, J = 148
Hz, 1 B), -4.94 (d, J = 149
Hz, 1 B), -9.04 (d, J = 150
Hz, 2 B), -11.79 (d, J = 164
Hz, 2 B), -13.10 (d, J = 165
Hz, 4 B). Anal. Calcd (%) for C3H15B10N: C,
20.81; H, 8.67; B, 62.43; N, 8.09. Found: C, 21.04; H, 8.57; B,
62.84; N, 8.15.
Synthesis of Compound 9 A mixture of triflate 2 (1.6 g, 3.6 mmol) and pyridine (0.28 g, 3.6 mmol) in CH2Cl2 (10 mL) was stirred at ambient temperature for 2 h. The solvent was removed to dryness in vacuo. The residue was washed with H2O (15 mL), filtered off, and dried in vacuo to afford 0.81 g (94%) of 9. ¹H NMR (400.13 MHz, CDCl3): d = 1.10-2.50 (m, 11 H), 3.60 (s, 2 H), 8.33 (dd, J = 5.6, 7.6 Hz, 2 H), 8.87 (t, J = 7.6 Hz, 1 H), 9.17 (d, J = 5.6 Hz, 1 H). Anal. Calcd (%) for C7H18B11N: C, 35.78; H, 7.67; B 50,60, N, 5.96. Found: C 35.22; H, 7.53; B, 51.02, N, 6.11.