7
834 Inorganic Chemistry, Vol. 49, No. 17, 2010
used as an external reference (δ C
Durot et al.
3
(300 MHz, CDCl ,
Me Si) 8.55-8.53 (2H, m, CH-N), 7.76-7.60 (4H, m, -CH-CH-
C
CFCl ). A typical spectrum consisted of 32K data points, 1000
6
F
6
6
F
6
= -162.17 ppm vs
(30%) of pure F
2
-HLCH3 as a brown oil: δ
H
3
4
scans on a 28-kHz bandwidth, and a 100-ms relaxation delay.
An exponential weighting function (LB=20 Hz) was used
during the processing.
CF and -CH-CH-CH-N), 7.48-7.40 (4H, m, N-CH-CH- and -
FC-N-C-CH-), 7.17-7.12 (2H, m, CH-N-C-CH-), 6.97 (2H, s,
3
3
Me-C-CH-), 6.75 (2H, dd, JHH 3.6, JHF 7.9, -CH-CF-), 3.89
(4H, s, N-CH -Py-F), 3.80 (4H, s, N-CH -Py), 3.78 (4H, s, Ph-
CH -N), 2.23 (3H, s, Me); δ
Synthesis. 2-Fluoro-6-(dibromomethyl)pyridine (2). A 5-g
45 mmol) portion of commercially available 2-fluoro-6-methyl-
2
2
(
pyridine was dissolved in 400 mL of CCl . A 16-g (90 mmol)
2
F
(282.395 MHz, acetone-d
6
, C
6
F
6
)
þ
93.7 (s, py-F); m/z (DCI) 567 (M þ H (100%); C33
F
H
0.5CH
N
32
O
6
4
2
requires 566). Elemental analysis for C33
COOCH CH
8.38; H, 5.21; N, 13.43.
Complex 1: [Cu (F -LCH3)(OH)][ClO
mmol) of F -HLCH3 dissolved in CH
a solution of 76 mg of Cu(ClO
CH
H
32
F
2
ON
6
3
-
portion of N-bromosuccinimide (NBS) was added, and the
medium was refluxed for 24 h in the presence of 100 mg of
benzoyl peroxide. An additional amount (100 mg, 4 mmol) of
benzoyl peroxide was added, and the mixture was refluxed for
30 h. The solvent was then evaporated, and the crude compound
was purified by silica gel chromatography using hexane/ethyl
3
2
3
, calcd: C, 68.84; H, 5.94; N, 13.76. Found: C,
6
]
. To 60 mg (0.106
CN (1.5 mL) was added
6H O (0.206 mmol) in
2
2
4 2
2
3
4
)
2
3
2
acetate (9/1) as eluent. Evaporation of the solvent gave 2 (9.2 g,
7
3
CN (0.5 mL). The initial yellow solution turned brown
5%) as a pale yellow oil: δ (300 MHz, CDCl ) 7.92 (1H, q,
and was stirred for 10 min at room temperature. Next 44 μL
(0.31 mmol) of Et N was added, and the solution, which turned
H
3
3
3
4
3
J
HH 10.9, JHF 7.5, JHF 8.0, CH-CH-CH), 7.66 (1H, dd, JHH
3
3
3
4
7
.1, JHH 2.7, -CH-C-CHBr
CH-CF), 6.59 (1H, s, CHBr
5.97 (s, Py-F).
3
-Fluoro-2-pyridinecarboxaldehyde (3). AgNO (10 g, 59 mmol),
2
), 6.92 (1H, dd, JHH 10.9, JHF 2.7,
dark green, was stirred for 30 min at room temperature. The
solvent was partially removed under reduced pressure, and after
addition of some amount of THF, the resulting solution was
allowed to stand overnight at -20 ꢀC. Afterward, 22 mg of a
green powder was collected by filtration: EPR silent (frozen
-
2
); δ (282.395 MHz, CDCl , C F )
F
3
6 6
9
6
dissolved in 10 mL of distilled water, was added drop by drop to
a solution of dibrominated species 2 (4.0 g, 15 mmol) dissolved
in 3 mL of acetonitrile. After 3 h, brine solution was added to
precipitate excess silver ions. The suspension was then filtrated
over Celite deposited on a glass frit, and the aqueous layer of the
filtrate was extracted with dichloromethane (5ꢀ20 mL). The
combined organic layers were carefully concentrated under
reduced pressure to give a crude product (without heating, low
boiling point). Distillation (65 ꢀC) gave 3 as a clear oil (1,1 g,
solution of CH CN/DMSO 1:1 at 100 K, 3 mM).
3
1
meso 3 3C
4
H
8
O. Crystals of X-ray quality were obtained at
-
20 ꢀC in 2 days in a CH CN/THF solution of 1. The crystalline
material, when crushed and exposed to air, loses some non-
coordinated THF. Elemental analysis for C33 Cu
3
H
32
F
2
O
2
N
6
2
3
(
4
ClO ) 0.5C H O, calcd: C, 44.50; H, 3.84; N, 8.90. Found: C,
4 2 4 8
3
4.56; H, 4.01; N, 8.68.
CN. Crystals of X-ray quality were obtained after 6
weeks by slow evaporation of a CH CN/H O (1/1) solution of 1.
The crystalline material, when crushed and exposed to air, loses
non-coordinated CH CN. Elemental analysis for C33
Cu (ClO , calcd: C, 43.63; H, 3.55; N, 9.25. Found: C,
1rac CH
3
3
6
J
7
0%): δ
H
(300 MHz, CDCl
3
) 9.96 (1H, s, CHO), 8.01 (1H, q,
3
2
3
3
4
3
HH 7.9, JHH 7.5, JHF 8.0, CH-CH-CH), 7.87 (1H, dd, JHH
5
3
3
.5, JHF 1.7, -CH-C-CHO), 7.24 (1H, dd, JHH 7.9, JHF 2.4,
3
H F O -
32 2 2
-
CH-CF); δ
F
(282.395 MHz, CDCl
0
3
, C
6
F
6
) 95.8 (s, Py-F).
N-(2-Pyridylmethyl),N -(6-fluoro-2-pyridinemethyl)amine (4).
N
6
2
4 2
)
3
43.74; H, 3.87; N, 8.95.
Crystal Structure Determination and Refinement. Single crys-
To a solution of 3 (438 mg, 3.5 mmol) in dry methanol (4 mL)
was added 2-(aminomethyl)pyridine (367 mg, 3.4 mmol) in dry
methanol(5 mL) at room temperature under aninert atmosphere
tals of complexes 1meso 3 3C
4
H
8
O and 1rac 3 CH
3
CN were
mounted on a Nonius Kappa CCD diffractometer equipped
with graphite-monochromated Mo KR radiation (λ=0.71073
A) at 150 K. The reflections were corrected for Lorentz and
of nitrogen. After 2 h, NaBH (358 mg, 9.5 mmol) was slowly
4
˚
added as a solid, and the mixture was stirred for an additional
3
polarization effects but not for absorption. The structures were
solved by direct methods and refined using TEXSAN soft-
.5 h. After acidic treatment (4 N HCl) to pH 1, the solvent was
removed under reduced pressure. The resulting product was
dissolved in water (100 mL) and washed with dichloromethane.
The aqueous solution was then neutralized with saturated NaH-
3
7
ware. For both structures, all non-hydrogen atoms were refined
with anisotropic thermal parameters. Hydrogen atoms were
generated in idealized positions, riding on the carrier atoms,
with isotropic thermal parameters, except for the hydrogen
atom of the hydroxyl group, which was localized on a difference
Fourier map and was added. It was refined riding on the carrier
atoms with isotropic thermal parameters.
CO
3
until pH 8 and extracted with dichloromethane (2 ꢀ 100
mL). The combined organic layers were washed with saturated
NaCl, dried over Na SO , and concentrated under reduced
pressure to give a yellow oil (860 mg, 82%), which was used
2
4
without further purification: δH (300 MHz, CDCl , Me Si) 8.56
3
4
3
3
3
4
The CCDC reference numbers are 693925 and 724449 for
(
1H, d, JHH 4.7, CH-N), 7.73 (1H, q, JHH 8.2, JHH 7.3, JHF
1
4 8 3
meso 3C H O and 1rac CH CN, respectively. Pertinent crystallo-
8
.0, FC-CH-CH-), 7.6 (1H, m, C-CH-CH-CH), 7.34 (1H, m,
CH-CH-C-N), 7.26 (1H, dd, JHH 7.3, JHF 2.6, -CH-CH-CH-
3
3
3
5
graphic data and refinement details are summarized in Table 1.
Computational Methods. Spin-unrestricted DFT calculations
were performed with the Gaussian03 software package.
3
CF), 7.14 (1H, m, -CH-CH-N), 6.77 (1H, dd, JHH 8.2, JHF 2.6,
3
3
8
-
2 2
CH-CF-), 3.97 (2H, s, -CH -Py-F), 3.93 (2H, s, -CH -Py), 2.41
(
1H, s, NH); δ (282.395 MHz, CDCl , C F ) 94.1 (s, Py-F).
F
3
6 6
F2-HLCH3. Under a dinitrogen atmosphere, a mixtureofamine
(382 mg, 1.8 mmol) and triethylamine (494 μL, 3.5 mmol) in
mL of dry tetrahydrofuran (THF) was added dropwise to a
(
37) TEXSAN, Single Crystal Structure Analysis Software, Version 1.7;
Molecular Structure Corp.: The Woodlands, TX, 1995.
38) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
4
8
(
stirred solution of 2,6-bis(chloromethyl)-4-methylphenol (179 mg,
.9 mmol) in 9 mL of dry THF at 0 ꢀC. When the addition was
completed, the resulting mixture was allowed to warm to room
temperature. After 2.5 days, the resulting mixture was filtered,
and the filtrate was concentrated under reduced pressure. The
residue was dissolved in 100 mL of methylene chloride, washed
M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.; Stratmann,
J. R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin,
K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi,
R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.;
Petersson, G.; Ayala, A. P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.;
Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz,
J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.;
Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-
Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill,
P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.;
Head-Gordon, M.; Pople, J. A. Gaussian03, Revision A1.1; Gaussian Inc.:
Pittsburgh, PA, 2003.
0
2 4
with brine, and dried over anhydrous Na SO . The solution was
evaporated to dryness under reduced pressure, and a crude
product was obtained as a brown oil. Chromatography on silica
gel using ethyl acetate was performed, and the desired com-
pound was collected. Evaporation of the solvent yielded 179 mg