6
64
G. Yang and R. G. Raptis
Vol. 40
mixture of 2'-acetonaphthone (8.5 g, 0.05 mol) and methyl trifluo-
roacetate (8.87 g, 0.05 mol). The mixture was stirred for 12 hours,
then it was neutralized by aqueous HCl. After toluene had been
removed by evaporation, the residue was recrystallized from
aqueous ethanol to yield 2-naphthoyltrifluoroacetone [14]. The b-
diketone was taken up in 50 mL of warm 95% ethanol. To the
solution, hydrazine monohydrate (2.5 g, 0.05 mmol) was added
dropwise. After cooling down, white powder was obtained, 7.0 g
corrected for Lorentz and polarization effects were employed
for crystal structure determination by direct method and struc-
ture refinement based on F2 using the SHELXTL crystallo-
graphic package programs [15]. All non-hydrogen atoms were
refined anisotropically, while H-atom positions were not
refined. All the H-atom positions on aromatic rings were calcu-
lated at ideal positions, while other H-atoms including N-H, O-
H and CH were located from the difference fourier maps. For
2
(
50%), ir (KBr pellet): 3312 (OH), 3158 (NH), 3050, 2916,
3, due to the disorder of CF3 groups, six F-atoms are used to
model this group with occupancy factors fixed at 0.75 (F1 –
F3) and 0.25 (F4 – F6). Other important crystallographic and
experimental data are listed in Table 1.
1
1
600,1449, 1351, 1334, 1255 (CF ), 1199, 1185, 1170, 1133,
065, 1032, 958, 904, 864, 856, 833, 753, 710, 509, 481 cm ; H
3
-
1 1
nmr (DMSO-d ): d 8.03 (d, 1H, J = 9.4 Hz, naphthyl), 7.93 (m,
6
3
3
H, naphthyl), 7.51 (m, 2H, naphthyl), 7.36 (s, 1H, naphthyl),
Supplementary Material.
.48 (d, 1H,J = 16.8 Hz, pyrazole 4-H), 3.35 ppm (d, 1H, J = 16.8
1
3
Hz, pyrazole 4-H); C nmr (DMSO-d ): d 147.5 (pyrazole 3-C),
X-ray crystallographic files (CIF) have been deposited with
the Cambridge Crystallographic Data Center, CCDC Nos.
205587 - 205589 for compound 1, 2 and 3, respectively. Copies
of this information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
www:http://www.ccdc.cam.ac.uk).
6
1
1
32.9, 132.8, 129.8, 128.1, 128.0, 127.6, 126.6, 126.5, 125.4,
1
2
24.2 (q, J = 282.6 Hz, CF ), 122.8, 91.1 (q, J = 30.4 Hz,
C - F
3
C - F
+
pyrazole 5-C), 41.3 ppm (pyrazole 4-C); EI ms: m/z 280.0802 M
(
+
+
11 .5), 263.0777 M -OH (14.3), 262.0631 M - HO (100).
2
Anal. Calcd. for C14H N OF : C, 59.95; H, 3.93; N, 9.99.
11
2
3
Found: C, 60.04; H, 3.93; N, 9.96. Single crystals of X-ray qual-
ity are grown by slow evaporation of a diethylether solution of 2.
3
-Trifluoromethyl-5-(2-naphthyl)-pyrazole (3).
REFERENCES AND NOTES
Method A.
[
*] Author to whom correspondence should be addressed
E-mail: Raphael@adam.uprr.pr).
1] C. Foces-Foces, I. Alkorta and J. Elguero, Acta Cryst., B56,
018 (2000).
2] R. M. Claramunt, C. López, M. A. García, M. Pierrot,
M. Giorgi and J. Elguero, J. Chem. Soc., Perkin Trans. 2, 2049 (2000).
3] S. Trofimenko, A. L. Rheingold, L. M. Liable-Sands, R. M.
3
-(2-Naphthyl)-5-hydroxy-5-trifluoromethyl-4,5-dihydropyra-
(
zole (2) (1.0 g, 3.5 mmol) and NaOH (0.28 g, 7 mmol) were
mixed in methanol with stirring. The two solids gradually dis-
solved and the solution became clear. After one day, the solvent
evaporated to dryness and the residue was extracted with hot
toluene. After cooling, large colorless crystals precipitated from
the toluene solution in 0.57 g (60%) yield.
[
1
[
[
Claramunt, C. López, M. D. S. María and J. Elguero, New J. Chem., 25,
Method B.
819 (2001).
[
4] G. La Monica and G. A. Ardizzoia, Prog. Inorg. Chem., 46,
51 (1997); H. H. Murray, R. G. Raptis and J. P. Fackler, Jr., Inorg.
Chem., 27, 26 (1988); G. Yang and R. G. Raptis, Inorg. Chem., 42, 261
2003); G. Yang and R. G. Raptis, Inorg. Chim. Acta (in press).
5] R. G. Raptis and J. P. Fackler, Jr., J. Chem. Soc., Chem.
Commun., 737 (1987).
In a test tube, neat 3-(2-naphthyl)-5-hydroxy-5-trifluo-
romethyl-4,5-dihydropyrazole (2) was heated to 160 °C in an oil
bath for 30 minutes. After the molten product had cooled down
and solidified, it was recrystallized from toluene giving colorless
prismatic crystals in 70% yield, mp 178 –179 °C; ir (KBr pellet):
1
(
[
3
235 (NH), 3060, 1606, 1581, 1567, 1501, 1418, 1297, 1258
[
6] C. Hansch, A. Leo and D. Hoekman, Exploring QSAR.
(
CF ), 1156, 1123, 1109, 1057, 994, 977, 890, 862, 826, 807,
3
Hydrophobic, Electronic, and Steric Constants, ACS Professional
Reference Book. American Chemical Society, Washington, DC (1995).
-
1 1
7
43, 716, 682, 477 cm ; H nmr (DMSO-d ): d 8.41 (s, 1H,
6
pyrazole 4-H), 8.04 – 7.93 (m, 4H, naphthyl), 7.56 (m, 2H, naph-
thyl), 7.33 (s, 1H, naphthyl); C nmr (DMSO-d ): d 144.0 (pyra-
zole 5-C), 142.1 (q, J = 36.9 Hz, pyrazole 3-C), 132.9, 132.8,
[
7] A. L. Rheingold, L. M. Liable-Sands and S. Trofimenko,
1
3
6
Inorg. Chem., 40, 6509 (2001).
2
C-F
[8] K. N. Zelenin, V. V. Alekseyev, A. R. Tygysheva and
S. I. Yakimovitch, Tetrahedron, 51, 11251 (1995).
[9] W. R. Thiel and J. Eppinger, Chem. Eur. J., 3, 696 (1997).
[10] S. P. Singh, D. Kumar, B. G. Jones and M. D. Threadgill,
J. Fluorine Chem., 94, 199 (1999).
1
1
28.8,128.1, 128.1, 127.7,126.9, 126.8, 125.4, 124.4, 123.4,
21.8 (q, J
1
= 268.2 Hz, CF ), 101.4 ppm (pyrazole 4-C); EI
C-F
3
+
+
ms: m/z 263.0742 M +1 (19.1), 262.0701 M (100), 165.0665
+
M -(H+N +CF ) (17.1).
2
3
Anal. Calcd. for C14H N F : C, 64.07; H, 3.43; N, 10.68.
Found: C, 64.08; H, 3.47; N, 10.70.
[11] C. A. Hunter, Chem. Soc. Rev., 101 (1994).
[12] C. Janiak, J. Chem. Soc., Dalton Trans., 3885 (2000).
9
2 3
[
13] H. Suezawa, T. Yoshida, Y. Umezawa, S. Tsuboyama and
X-ray Crystallography.
M. Nishio, Eur. J. Inorg. Chem., 3148 (2002) and references therein.
[14] J. C. Reid and M. Calvin, J. Am. Chem. Soc., 72, 2948 (1950).
[15a] SAINT-NT, version 4.0 (1996) Bruker AXS, Inc., Madison,
WI; [b] G. M. SHELXTL-NT, version 5.1 (1999) Bruker AXS, Inc.,
Madison, WI.
Single crystals were mounted atop glass fibers with epoxy
glue. Diffraction measurements were carried out with a
Siemens SMART 1K CCD diffractometer with graphite
monochromated Mo-Ka ( = 0.71073 Å) radiation. Data