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H.G. Bonacorso et al. / Journal of Fluorine Chemistry 166 (2014) 44–51
4.2.2.1. 2-Phenyl-3-(trifluoromethyl)-2,4-dihydro-spiro(chro-
4.2.2.5. 1-Methyl-3-(trifluoromethyl)-1,4-dihydro-spiro(chro-
men[4,3-c]pyrazole-4,10-cyclopentane) (4a). Creamy thick liquid,
men[4,3-c]pyrazole-4,10-cyclohexane) (5b). White solid, yield 51%,
yield 41%. 1H NMR (CDCl3):
d
= 7.82 (d, J = 8 Hz, 2H, Ar); 7.49 (s, 5H,
mp 122–123 8C. 1H NMR (CDCl3):
d = 7.55 (d, J = 7 Hz, 1H, Ar); 7.27
Ph); 7.24 (t, J = 8 Hz, 1H, Ar); 7.03–6.92 (m, 2H, Ar); 2.32–1.81 (m,
(t, J = 7 Hz, 1H, Ar); 7.11–7.00 (m, 2H, Ar); 4.17 (s, 3H, Me); 2.10–
8H, CH2).
1.57 (m, 10H, CH2).
13C NMR: CDCl3,
d
(ppm): 152.65 (Ar); 144.60 (C-9b); 139.80
13C NMR: CDCl3,
d (ppm): 152.32 (Ar); 135.50 (C-9b); 134.55 (q,
(Ph, C-ipso); 130.05 (Ar); 129.26 (Ph, 1C-p); 129.08 (Ph, 2C-m);
126.50 (q, 2JCF = 39 Hz, C-3); 125.90 (q, J = 1 Hz, Ph, 2C-o); 122.41
(Ar); 122.03 (C-3a); 121.67 (Ar); 120.11 (q, JCF = 270 Hz, CF3);
2JCF = 37 Hz, C-3); 130.21 (Ar); 121.82 (Ar); 121.57 (q, 1JCF = 267 Hz,
CF3); 121.71 (Ar); 120.25 (C-3a); 118.67 (Ar); 78.44 (C-4); 39.85
(Me); 34.81 (2CH2); 24.95 (CH2); 21.55 (2CH2).
19F NMR (CDCl3):
MS [m/z (%)] para C17H17F3N2O (322.12): 322 (M+, 21), 279
(100), 77 (2).
1
117.83 (Ar); 116.76 (Ar); 87.57 (C-4); 40.02 (2CH2); 24.48
(2CH2).
d
= ꢀ58.56 ppm.
19F NMR (CDCl3):
d
= ꢀ52.98 ppm.
MS [m/z (%)] para C21H17F3N2O (370.129): 370 (M+, 95), 341
(100), 301 (24), 77 (10).
Anal. Calc. para C17H17F3N2O: C, 63.35; H, 5.32; N, 8.69. Found:
C, 63.52; H, 5.53; N, 8.49%.
Anal. Calc. for C21H17F3N2O: C, 68.10; H, 4.63; N, 7.56. Found: C,
68.26; H, 4.63; N, 7.18%.
4.2.2.6. 1-Methyl-3-(trifluoromethyl)-1,4-dihydro-spiro(chro-
men[4,3-c]pyrazole-4,10-cycloheptane) (5c). White solid, yield 39%,
4.2.2.2. 2-Phenyl-3-(trifluoromethyl)-2,4-dihydro-spiro(chro-
mp 133–134 8C. 1H NMR (CDCl3):
d = 7.54 (d, J = 7 Hz, 1H, Ar); 7.29
(t, J = 7 Hz, 1H, Ar); 7.10–6.99 (m, 2H, Ar); 4.16 (s, 3H, Me); 2.52–
men[4,3-c]pyrazole-4,10-cyclohexane) (4b). Creamy thick liquid,
yield 49%. 1H NMR (CDCl3):
d
= 7.80 (d, J = 7 Hz, 1H, Ar); 7.49 (s,
1.61 (m, 12H, CH2).
5H, Ph); 7.25–7.23 (m, 1H, Ar); 7.05–6.96 (m, 2H, Ar); 2.21–1.61
(m, 10H, CH2).
13C NMR: CDCl3,
d
(ppm): 152.392 (Ar); 134.88 (C-9b); 134.46
2
(q, JCF = 37 Hz, C-3); 130.22 (Ar); 121.69 (Ar); 121.69 (C-3a);
121.56 (q, 1JCF = 268 Hz, CF3); 121.38 (Ar); 118.76 (Ar); 81.92 (C-4);
39.89 (Me); 39.04 (2CH2); 27.60 (2CH2); 21.37 (2CH2).
13C NMR: CDCl3,
d (ppm): 152.37 (Ar); 144.24 (C-9b); 140.04
(Ph, C-ipso); 130.11 (Ar); 129.19 (Ph, 1C-p); 129.03 (Ph, 2C-m);
2
126.44 (q, JCF = 39 Hz, C-3); 125.94 (q, J = 1 Hz, Ph, 2C-o); 123.73
19F NMR (CDCl3):
d
= ꢀ58.55 ppm.
1
(C-3a); 122.44 (Ar); 121.63 (Ar); 120.12 (q, JCF = 270 Hz, CF3);
MS [m/z (%)] para C18H19F3N2O (336,14): 336 (M+, 42), 279
(100), 267 (17), 253 (16), 69 (1).
117.71 (Ar); 116.92 (Ar); 78.16 (C-4); 34.93 (2CH2); 24.90 (CH2);
21.23 (2CH2).
Anal. Calc. for C18H19F3N2O: C, 64.28; H, 5.69; N, 8.33. Found: C,
64.35; H, 5.81; N, 8.46%.
19F NMR (CDCl3):
d
= ꢀ52.15 ppm.
MS [m/z (%)] para C22H19F3N2O (384.145): 384 (M+, 71), 341
(100), 315 (20), 77 (9).
4.2.2.7. 1-Methyl-3-(trifluoromethyl)-1H,4H-20,30,50,60-tetrahydro-
Anal. Calc. for C22H19F3N2O: C, 68.74; H, 4.98; N, 7.29. Found: C,
68.76; H, 4.91; N, 7.24%.
spiro(chromen[4,3-c]pyrazole-4,40-pyran) (5d). Yellow solid, yield
48%, mp 178–174 8C. 1H NMR (CDCl3):
d = 7.57 (d, 1H, J = 7 Hz, Ar);
7.32 (t, 1H, J = 7 Hz, Ar); 7.15–7.04 (m, 2H, Ar); 4.18 (s, 3H, Me);
4.03–3.80 (m, 4H, CH2); 2.28–2.13 (m, 2H, CH2); 1.98–1.91 (m, 2H,
CH2).
4.2.2.3. 2-Phenyl-3-(trifluoromethyl)-2,4-dihydro-spiro(chro-
men[4,3-c]pyrazole-4,10-cycloheptane) (4c). Creamy thick liquid,
yield 49%. 1H NMR (CDCl3):
d
= 7.73 (d, J = 7 Hz, 1H, Ar); 7.41 (s, 5H,
13C NMR: CDCl3,
d (ppm): 151.73 (Ar); 135.51 (C-9b); 134.55 (q,
Ph); 7.18 (t, J = 8 Hz, 1H, Ar); 6.96–6.89 (m, 2H, Ar); 2.09–1.51(m,
2JCF = 37 Hz, C-3); 130.47 (Ar); 122.01 (Ar); 121.98(Ar); 121.36 (q,
1JCF = 268 Hz, CF3); 118.63 (Ar); 118.52 (C-3a); 115.23 (Ar); 75.80
(C-4); 63.09 (2CH2); 39.92 (Me); 34.84 (2CH2).
12H, CH2).
13C NMR: CDCl3,
d (ppm): 152.56 (Ar); 143.77 (C-9b); 140.15
(Ph, C-ipso); 130.17 (Ar); 129.21 (Ph, 1C-p); 129.04 (Ph, 2C-m);
19F NMR (CDCl3):
d
= ꢀ58.60 ppm.
2
126.57 (q, JCF = 39 Hz, C-3); 126.06 (q, J = 1 Hz, Ph, 2C-o); 125.39
MS [m/z (%)] para C16H15F3N2O2 (324.109): 324 (M+, 30), 295
(44), 280 (80), 266 (100), 77 (3).
1
(C-3a); 120.22 (q, JCF = 267 Hz, CF3); 122.43 (Ar); 121.60 (Ar);
117.85 (Ar); 116.91 (Ar); 81.57 (C-4); 39.52 (2CH2); 27.48 (2CH2);
21.72 (2CH2).
Anal. Calc. for C16H15F3N2O2: C, 59.26; H, 4.66; N, 8.64. Found: C,
59.81; H, 4.94; N, 8.37%.
19F NMR (CDCl3):
d
= ꢀ52.46 ppm.
HRMS Calc. for C16H15F3N2O2: 324.1086. Found: 324.1123.
MS [m/z (%)] para C23H21F3N2O (398.16): 398 (M+, 62), 369 (11),
341 (100), 315 (15) 77 (8).
Acknowledgements
Anal. Calc. for C23H21F3N2O: C, 69.34; H, 5.31; N, 7.03. Found: C,
68.76; H, 4.91; N, 7.24%.
The authors thank the Coordination for the Improvement of
Higher Education Personnel (CAPES) for fellowships, and the
National Council for Scientific and Technological Development
(CNPq) and the Rio Grande do Sul Foundation for Support of
Research (FAPERGS) for financial support (Process numbers
303.013/2011-7, 470.788/2010.0-CNPq/Universal, and 12/0982-
1/FAPERGS/PqG).
HRMS Calc. for C23H21F3N2O: 398.1606. Found: 398.1575.
4.2.2.4. 1-Methyl-3-(trifluoromethyl)-1,4-dihydro-spiro(chro-
men[4,3-c]pyrazole-4,10-cyclopentane) (5a). White solid, yield 47%,
mp 119–120 8C. 1H NMR (CDCl3):
d = 7.53 (dd, J = 1 Hz, J = 8 Hz, 1H,
Ar); 7.25 (td, J = 8 Hz, J = 1.5 Hz, 1H, Ar); 7.03–6.97 (m, 2H, Ar); 4.15
(s, 3H, Me); 2.28–1.79 (m, 8H, CH2).
13C NMR: CDCl3,
d (ppm): 152.52 (Ar); 135.92 (C-9b); 134.33 (q,
2JCF = 37 Hz, C-3); 130.11 (Ar); 122.87 (Ar); 121.75 (Ar); 121.53 (q,
1JCF = 267 Hz, CF3); 118.74 (Ar); 117.88 (C-3a); 115.37 (Ar); 88.00
(C-4); 39.90 (Me); 38.35 (2CH2); 23.65 (2CH2).
References
19F NMR (CDCl3):
d
= ꢀ59.00 ppm.
MS [m/z (%)] para C16H15F3N2O (308.11): 308 (M+, 21), 279
(100), 239 (9), 77 (3).
Anal. Calc. for C16H15F3N2O: C, 62.33; H, 4.90; N, 9.09. Found: C,
62.42; H, 5.09; N, 8.75%.