C.-R Yu et al. / Journal of Fluorine Chemistry 127 (2006) 1540–1546
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1
125.6, 122.9 (q, JCF = 270 Hz, CF3), 122.3, 122.2 (q,
2JCF = 33 Hz), 119.17, 116.4, 76.8, 60.9, 29.0, 14.1, 9.8;
GC–MS, m/z (%): 429 ([M]+, 27%), 431 ([M + 2]+, 9%), 383,
340, 326, 199, 180 (100%), 115, 91; Anal. Calcd. (%) for
C20H19ClF3NO4: C, 55.89; H, 4.46; N, 3.26. Found: C, 55.79;
H, 4.63; N, 3.17.
4.4.5. Methyl 2-((4-(3-chloro-5-(trifluoromethyl)pyridin-2-
yloxy)phenoxy)(furan-2-yl)methyl)acrylate (2e)
Yield 61% of pale yellow solid: mp 107–109 8C; IR (KBr) n:
3070, 2960, 1710, 1460, 1320, 1070, 1020, 915, 820,
750 cmꢀ1 1H NMR (300 MHz, CDCl3) d: 8.26–8.27 (m,
;
1H, Ar–H), 7.96 (d, 1H, J = 2.1 Hz, Ar–H), 7.43–7.44 (m, 1H,
Ar–H), 6.99–7.09 (m, 4H, Ar–H), 6.17–6.51 (m, 5H, Ar–H,
C CH2, CH), 3.79 (s, 3H, OCH3); Anal. Calcd. (%) for
C21H15ClF3NO5: C, 55.58; H, 3.33; N, 3.09. Found: C, 55.63;
H, 3.28; N, 3.20.
4.4.2. Methyl 2-((4-(3-chloro-5-(trifluoromethyl)pyridin-2-
yloxy)phenoxy)(phenyl)methyl)acrylate (2b)
Yield 92% of colorless oil: IR (KBr) n: 3060, 2950, 1720,
1460, 1400 1320, 1070 cmꢀ1; 1H NMR (300 MHz, CDCl3) d:
8.25 (d, 1H, J = 1.8 Hz, Ar–H), 7.95 (d, 1H, J = 1.8 Hz,
Ar–H), 7.44–7.47 (m, 2H, Ar–H), 7.31–7.39 (m, 3H, Ar–H),
7.04 (d, 2H, J = 9.3 Hz, Ar–H), 6.97 (d, 2H, J = 9.3 Hz, Ar–
H), 6.42 (s, 1H, CH), 6.13 (s, 1H, C CH2), 5.99 (s, 1H,
C CH2), 3.76 (s, 3H, OCH3); 13C NMR (75 MHz, CDCl3,
4.4.6. Ethyl 2-((3-(3-chloro-5-(trifluoromethyl)pyridin-2-
yloxy)phenoxy)(ethyl)methyl)acrylate (2f)
Yield 52% of pale yellow oil: IR (film) n: 3070, 2980, 1715,
;
1590, 1460, 1400, 1325, 1130, 960, 760 cmꢀ1 1H NMR
(300 MHz, CDCl3) d: 8.29 (d, 1H, J = 2.1 Hz, Ar–H), 7.97 (d,
1H, J = 2.1 Hz, Ar–H), 7.29 (t, J = 8.1 Hz, 1H, Ar–H), 6.69–
6.80 (m, 3H, Ar–H), 6.30 (s, 1H, C CH2), 5.85 (s, 1H,
C CH2), 5.04–5.07 (m, 1H, CH), 4.25 (q, 2H, J = 7.2 Hz,
OCH2), 1.81–1.94 (m, 1H, CH2), 1.65–1.77 (m, 1H, CH2), 1.31
(t, 3H, J = 7.2 Hz, OCH2CH3), 1.01 (t, 3H, J = 7.2 Hz,
CH2CH3); Anal. Calcd. (%) for C20H19ClF3NO4: C, 55.89;
H, 4.46; N, 3.26. Found: C, 55.74; H, 4.42; N, 3.11.
3
TMS) d: 165.8, 161.3, 155.2, 146.4, 142.4 (q, JCF = 5 Hz),
3
140.0, 138.6, 136.1 (q, JCF = 3 Hz), 128.5, 128.2, 127.3,
1
126.3, 122.8 (q, JCF = 270 Hz, CF3), 122.3, 121.9 (q,
2JCF = 33 Hz), 119.0, 116.7, 77.8, 51.9; 19F NMR (282
MHz, CCl3F) d: ꢀ62.0 (s, CF3); Anal. Calcd. (%) for
C23H17ClF3NO4: C, 59.56; H, 3.69; N, 3.02. Found: C, 59.69;
H, 3.80; N, 2.86.
4.4.3. Ethyl 2-((4-(3-chloro-5-(trifluoromethyl)pyridin-2-
yloxy)phenoxy)(4-nitrophenyl)methyl)acrylate (2c)
Yield 86% of pale yellow oil: IR (KBr) n: 3080, 2990,
4.4.7. Methyl 2-((3-(3-chloro-5-(trifluoromethyl)pyridin-2-
yloxy)phenoxy)(phenyl)methyl)acrylate (2g)
Yield 66% of pale yellow oil: IR (KBr) n: 3070, 2960,
1715, 1610, 1460, 1325, 1190, 915 cmꢀ1
;
(300 MHz, CDCl3) d: 8.21–8.25 (m, 3H, Ar–H), 7.96 (qd,
1H NMR
1720, 1590, 1130, 1065, 970 cmꢀ1 1H NMR (300 MHz,
;
CDCl3) d: 8.25 (d, 1H, J = 2.4 Hz, Ar–H), 7.96 (d, 1H,
J = 2.4 Hz, Ar–H), 7.25–7.45 (m, 5H, Ar–H), 6.72–6.86 (m,
4H, Ar–H), 6.40 (s, 1H, CH), 6.15 (s, 1H, C CH2), 5.98 (s,
1H, C CH2), 3.73 (s, 3H, OCH3); 13C NMR (75 MHz,
4
4
1H, JHF = 0.6 Hz, JHH = 2.1 Hz, Ar–H), 7.67 (dd, 2H,
J = 6.9, 2.4 Hz, Ar–H), 7.06 (d, 2H, J = 9.3 Hz, Ar–H), 6.96
(d, 2H, J = 9.3 Hz, Ar–H), 6.48 (s, 1H, CH), 6.21 (s, 1H,
C CH2), 6.09 (s, 1H, C CH2), 4.20–4.24 (m, 2H, OCH2),
1.28 (t, 3H, J = 6.9 Hz, CH3); 13C NMR (75 MHz, CDCl3,
TMS) d: 165.1, 161.3, 154.7, 147.0, 146.2, 142.5 (q,
4
CDCl3, TMS) d: 165.9, 160.9 (q, JCF = 1 Hz), 158.6, 153.6,
3
142.6 (q, JCF = 4 Hz), 139.8, 138.4, 136.2 (q, JCF = 3 Hz),
3
1
129.9, 128.5, 128.2, 127.3, 122.8 (q, JCF = 270 Hz, CF3),
3
2
3JCF = 5 Hz), 139.4, 136.3 (q, JCF = 3 Hz), 128.2, 127.0,
122.4 (q, JCF = 34 Hz), 119.3, 114.2, 113.2, 109.7, 77.5,
1
123.8, 122.9 (q, JCF = 270 Hz, CF3), 122.7, 119.2, 116.9,
52.0; 19F NMR (282 MHz, CCl3F) d: ꢀ62.0 (s, CF3); GC–
MS, m/z (%): 463 ([M]+, 11%), 465 ([M + 2]+, 4%), 431, 404,
368, 288, 223, 180 (98%), 152, 91, 77, 59 (100%); Anal.
Calcd. (%) for C23H17ClF3NO4: C, 59.56; H, 3.69; N, 3.02.
Found: C, 59.75; H, 3.81; N, 3.17.
61.3, 14.1; 19F NMR (282 MHz, CCl3F) d: ꢀ62.1 (s, CF3);
Anal. Calcd. (%) for C24H18ClF3N2O6: C, 55.13; H, 3.47; N,
5.36. Found: C, 55.20; H, 3.29; N, 5.32.
4.4.4. Methyl 2-((4-(3-chloro-5-(trifluoromethyl)pyridin-2-
yloxy)phenoxy)(2-methoxyphenyl)methyl)acrylate (2d)
Yield 80% of white solid: mp 83–84 8C; IR (KBr) n: 3080,
4.4.8. Methyl 2-((4-(3-chloro-5-(trifluoromethyl)pyridin-2-
yloxy)phenyl)(phenoxy)methyl)acrylate (3e)
1
2960, 1730, 1320, 1190, 1070, 1030, 840 cmꢀ1; H NMR
Yield 97% of pale yellow oil: IR (KBr) n: 3070, 2920, 1720,
1460, 1325, 1135, 1070 cmꢀ1; 1H NMR (300 MHz, CDCl3) d:
8.27–8.28 (m, 1H, Ar–H), 7.98 (d, 1H, J = 2.4 Hz, Ar–H), 7.54
(d, 2H, J = 8.7 Hz, Ar–H), 7.23–7.28 (m, 2H, Ar–H), 7.16 (d,
2H, J = 8.7 Hz, Ar–H), 6.92–6.97 (m, 3H, Ar–H), 6.41 (s, 1H,
CH), 6.19 (s, 1H, C CH2), 6.04 (s, 1H, C CH2), 3.77 (s, 3H,
OCH3); 13C NMR (75 MHz, CDCl3, TMS) d: 166.4, 161.3 (q,
(300 MHz, CDCl3) d: 8.25 (d, 1H, J = 2.4 Hz, Ar–H), 7.95 (d,
1H, J = 2.4 Hz, Ar–H), 7.39–7.43 (m, 1H, Ar–H), 7.28–7.34
(m, 1H, Ar–H), 6.90–7.04 (m, 6H, Ar–H), 6.56 (s, 1H,
C CH2), 6.40 (s, 1H, C CH2), 5.73 (s, 1H, CH), 3.85 (s, 3H,
Ar–OCH3), 3.77 (s, 3H, OCH3); 13C NMR (75 MHz, CDCl3,
4
TMS) d: 166.3, 161.4 (q, JCF = 1 Hz), 156.7, 155.8, 146.3,
3
142.6 (q, JCF = 4 Hz), 139.8, 136.1, 129.4, 127.9, 127.1,
3
4JCF = 1 Hz), 157.8, 152.9, 143.0 (q, JCF = 4 Hz), 140.4,
1
126.5, 122.9 (q, JCF = 270 Hz, CF3), 122.2, 122.0 (q,
136.8, 136.7 (q, 3JCF = 3 Hz), 131.8, 129.9, 129.3, 126.8, 123.2
(q, 1JCF = 270 Hz, CF3), 123.0 (q, 2JCF = 34 Hz), 122.8, 121.9,
121.8, 119.9, 116.3, 77.0, 52.4; 19F NMR (282 MHz, CCl3F) d:
ꢀ62.1 (s, CF3); Anal. Calcd. (%) for C23H17ClF3NO4: C, 59.56;
H, 3.69; N, 3.02. Found: C, 59.52; H, 3.90; N, 3.19.
2JCF = 33 Hz), 120.7, 119.2, 116.8, 110.7, 72.1, 55.5, 52.0;
19F NMR (282 MHz, CCl3F) d: ꢀ62.1 (s, CF3); Anal. Calcd.
(%) for C24H19ClF3NO5: C, 58.37; H, 3.88; N, 2.84. Found: C,
58.19; H, 4.02; N, 2.74.