Mendeleev Commun., 2010, 20, 220–222
2008, 73, 5643; (b) A. D. Dilman, V. V. Levin, P. A. Belyakov, A. A.
4
(a) V. V. Levin, M. A. Kozlov, Y.-H. Song, A. D. Dilman, P. A. Belyakov,
Korlyukov, M. I. Struchkova and V. A. Tartakovsky, Mendeleev Commun.,
2009, 19, 141.
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3108; (b) A. D. Dilman, V. V. Levin, M. Karni and Y. Apeloig, J. Org.
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‡‡ Synthesis of 3c–e. BF3·Et2O (190 μl, 1.5 mmol) was added dropwise to
a solution of oxime (1.0 mmol) and allyltrimethylsilane (238 μl, 1.5 μmol)
in 1,2-dichloroethane (2 ml), and the mixture was stirred for 1 h at room
temperature. The solvent was evaporated in a vacuum, the residue was
dissolved in MeCN (2 ml) followed by addition of (C6F5)3SiF (548 mg,
1.0 mmol) and NaOAc (98 mg, 1.2 mmol). The mixture was refluxed for
3 h, cooled to room temperature, and quenched by addition of saturated
aqueous Na2CO3 (0.25 ml) and water (0.25 ml). After stirring for addi-
tional 2 min, the mixture was diluted with Et2O–hexane (1:1, 10 ml), and
the resulting suspension was filtered through anhydrous Na2SO4. The
filtrate was concentrated and the residue was subjected to flash chromato-
graphy on silica gel.
2-Methoxy-6-[(methoxyamino)(pentafluorophenyl)methyl]phenol 3c.
Rf 0.23 (hexanes–EtOAc, 4:1), mp 89–90 °C. 1H NMR (300 MHz, CDCl3)
d: 3.62 (s, 3H, OMe), 3.88 (s, 3H, OMe), 5.99 (s, 1H, NCH), 6.36 (br. s,
1H, NH, Δn1/2 12.8 Hz), 6.73–6.89 (m, 4H, 3CHAr + OH). 13C NMR
(75 MHz, CDCl3) d: 55.1 (m), 56.1, 62.0, 111.0, 114.2 (tm, J 16.5 Hz),
119.5 (t, J 2.0 Hz), 119.8, 122.0, 137.6 (dm, J 252.1 Hz), 140.6 (dm,
J 258.6 Hz), 145.6 (dm, J 245.5 Hz). 19F NMR (282 MHz, CDCl3) d:
–163.2 (m, 2F, meta), –156.4 (t, 1F, para, J 21.2 Hz), –143.0 (dd, 1F,
ortho, J 21.5 and 7.0 Hz). Found (%): C, 51.69; H, 3.55; N, 4.07. Calc.
for C12H16N2O3 (%): C, 51.58; H, 3.46; N, 4.01.
5
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3189.
2-Allyl-6-[(methoxyamino)(pentafluorophenyl)methyl]phenol 3d. Rf 0.10
1
(hexanes–EtOAc, 40:1), mp 65–66 °C. H NMR (300 MHz, CDCl3) d:
3.47 (d, 2H, =CH–CH2, J 6.2 Hz), 3.74 (s, 3H, OMe), 5.02–5.23 (m,
2H, =CH2), 5.97–6.15 (m, 2H, =CH–CH2 + NCH), 6.18–6.30 (m, 1H,
NH), 6.53 (d, 1H, CHAr, J 7.7 Hz), 6.77 (t, 1H, CHAr, J 7.5 Hz), 7.17 (d,
1H, CHAr, J 7.7 Hz), 9.18 (s, 1H, OH). 13C NMR (75 MHz, CDCl3) d:
34.2, 57.6, 62.3, 112.2 (tm, J 15.5 Hz), 115.7, 119.0, 119.9, 125.3, 128.4,
130.9, 136.6, 137.7 (dm, J 254.5 Hz), 141.1 (dm, J 248.7 Hz), 145.5
(dm, J 249.7 Hz), 154.2. 19F NMR (282 MHz, CDCl3) d: –162.0 (m, 2F,
meta), –154.3 (t, 1F, para, J 21.2 Hz), –143.4 (dm, 1F, ortho, J 21.7 Hz).
Found (%): C, 56.77; H, 3.85; N, 3.91. Calc. for C12H16N2O3 (%): C, 56.83;
H, 3.93; N, 3.90.
7
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8
9
2-[(Methoxyamino)(pentafluorophenyl)methyl]-1-naphthol 3e. Glassy
oil, Rf 0.15 (hexanes–EtOAc, 8:1). 1H NMR (300 MHz, CDCl3) d: 3.67
10 (a) W. Kliegel, S. J. Rettig and J. Trotter, Can. J. Chem., 1984, 62,
1363; (b) W. Kliegel, G. Lubkowitz, J. O. Pokriefke, S. J. Rettig and
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(s, 3H, OMe), 6.05 (br. s, 1H, NH, Δn1/2 28.3 Hz), 7.16 (d, 1H, CHAr
,
J 8.6 Hz), 7.32 (d, 1H, CHAr, J 7.3 Hz), 7.47 (td, 1H, CHAr, J 7.6 and
1.1 Hz), 7.66 (d, 1H, CHAr, J 8.6 Hz), 7.72–7.82 (m, 2H, 2CHAr), 10.4
(br. s, 1H, OH, Δn1/2 43.2 Hz). 13C NMR (75 MHz, CDCl3) d: 56.3, 62.4,
108.9, 112.3 (tm, J 16.1 Hz), 120.0, 120.2 (t, J 2.0 Hz), 123.0, 127.3, 128.8,
129.1, 130.9, 132.1, 137.6 (dm, J 252.8 Hz), 141.2 (dm, J 255.6 Hz), 145.7
(dm, J 250.5 Hz), 156.2 (t, J 1.4 Hz). 19F NMR (282 MHz, CDCl3) d:
–161.6 (br. s, 2F, meta, Δn1/2 55.9 Hz), –153.7 (br. s, 1F, para, Δn1/2 57.5 Hz),
–140.8 (dm, 1F, ortho, J 22.7 and 7.0 Hz). Found (%): C, 60.87; H, 6.77;
N, 11.74. Calc. for C12H16N2O3 (%): C, 61.00; H, 6.83; N, 11.86.
§§ Crystallographic data for 2a: crystals of C8H8BF2NO2 are monoclinic,
space group P21/n, a = 7.3072(8), b = 11.8254(13) and c = 9.7344(11) Å,
b = 97.608(2)°, V = 833.75(16) Å3, Z = 4, M = 198.96, dcalc = 1.585 g cm–3,
m(MoKα) = 0.14 mm–1, F(000) = 408. Intensities of 9342 reflections
were measured with a Bruker Smart 1000 diffractometer at 120 K
[l(MoKα) = 0.71073 Å] and 2406 independent reflections (Rint = 0.0210)
were used in further refinement. The structure was solved by direct
method and refined by the full-matrix least-squares technique against F2
in the anisotropic-isotropic approximation. All hydrogen atoms were
calculated from geometrical point of view. Hydrogen atoms were refined
in the rigid body approximation with the Uiso(H) parameters equal to
1.2Ueq(C) and 1.5Ueq(CMe), where Ueq(C) are the equivalent thermal
parameters of the carbon atoms to which corresponding H atoms are
bonded. The refinement converged to wR2 = 0.0895 and GOF = 1.000
for all independent reflections [R1 = 0.0417 was calculated against F for
1352 observed reflections with I > 2s(I)].
12 H. Miyabe, R. Shibata, M. Sangawa, C. Ushiro and T. Naito, Tetrahedron,
1998, 54, 11431.
CCDC 766904 contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cambridge
For details, see ‘Notice to Authors’, Mendeleev Commun., Issue 1, 2010.
Received: 3rd March 2010; Com. 10/3481
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