V. G. Nenajdenko et al.
CH2), 1.52 (quin, J=7.3 Hz, 2H; CH2), 1.62 (quin, J=7.3 Hz, 2H; CH2),
1.84 (quin, J=7.1 Hz, 2H; CH2), 2.64 (sex, J=7.0 Hz, 1H; CHCH3), 4.04
(t, J=6.6 Hz, 2H; CH2O), 6.47 (d, JHF =36.4 Hz, 1H; CH=CF), 7.01 (d,
J=8.6 Hz, 2H; Ar), 7.20–7.23 (m, 4H; Ar), 7.54–7.68 ppm (m, 6H; Ar);
19F NMR (188 MHz, CDCl3): d=À74.2 (d, J=13.0 Hz; CF2-O),
6H; Ar); 19F NMR (188 MHz, CDCl3): d=À74.6 (d, J=13.8 Hz; CF2-O),
À129.4 ppm (dt,
J
H-F =36.4 Hz, J=12.1 Hz; CF=CH); 13C NMR
(100 MHz, CDCl3): d=14.0, 22.6, 25.7, 29.2, 31.6, 55.9 (s; CH3-O), 56.0
(s; CH3-O), 68.0 (CH2O), 106.5, 110.1 (d, JCF =2.9 Hz), 111.0, 114.8, 117.5
(td, 1JCF =265.2 Hz, 2JCF =36.6 Hz; CF2-CF), 126.7, 127.9, 128.7 (d, JCF
=
À129.5 ppm (dt,
J
HF =36.4 Hz, J=13.0 Hz; CF=CH); 13C NMR
2.9 Hz), 129.9 (d, JCF =7.3 Hz), 132.3, 139.1, 143.1, 141.3, 147.3, 147.6 (dt,
1JCF =267.9 Hz, 2JCF =35.1 Hz; CF-CF2,), 149.3, 159.1 ppm; IR (neat): n˜ =
1500, 1600 (Ar), 1700 cmÀ1 (C=C); HRMS (ESI): m/z calcd for
(100 MHz, CDCl3): d=12.1, 14.0, 21.7, 22.6, 25.7, 29.3, 31.2, 31.6, 41.1,
68.0 (CH2O), 110.1, 114.8, 117.5 (td, 1JCF =259.8 Hz, 2JCF =37.3 Hz; CF2-
4
+
CF,), 121.7, 126.7, 127.9, 128.7, 128.8 (d, 4JCF =3.7 Hz), 130.0 (d, JCF
=
C29H31F3NaO4 [M+Na+]: 523.2067; found: 523.2071.
2
7.3 Hz), 132.3, 141.3, 145.6, 147.6, 147.8 (dt, 1JCF =267.9 Hz, JCF
=
(Z)-4-(3-(4-Chlorophenoxy)-2,3,3-trifluoroprop-1-enyl)-4’-(hexyloxy)bi-
phenyl (9i): White solid, yield 81%; Rf =0.4 (hexane/CH2Cl2 =4:1);
1H NMR (400 MHz, CDCl3): d=0.97 (t, J=6.7 Hz, 3H; CH3), 1.37–1.45
(m, 4H; CH2), 1.53 (quin, J=7.2 Hz, 2H; CH2), 1.85 (quin, J=7.0 Hz,
2H; CH2), 4.04 (t, J=6.6 Hz, 2H; CH2O), 6.47 (d, JHF =36.2 Hz, 1H;
CH=CF), 7.02 (d, J=8.8 Hz, 2H; Ar), 7.25 (d, J=8.6 Hz, 2H; Ar), 7.39
(d, J=8.8 Hz, 2H; Ar), 7.54–7.67 ppm (m, 6H; Ar); 19F NMR (188 MHz,
CDCl3): d=À74.6 (d, J=13.8 Hz; CF2-O), À129.9 ppm (dt, JHF =36.2 Hz,
38.1 Hz; CF-CF2), 159.1 ppm; IR (neat): n˜ =1480, 1610 (Ar), 1700 cmÀ1
(C=C); HRMS (ESI): m/z calcd for C31H35F3NaO2+: 519.2481 [M+Na+];
found: 519.2467;
(Z)-4-(Hexyloxy)-4’-(2,3,3-trifluoro-3-(4-octylphenoxy)prop-1-enyl)bi-
phenyl (9e): White solid, yield 74%; Rf =0.4 (hexane/CH2Cl2 =4:1);
1H NMR (400 MHz, CDCl3): d=0.78 (t, J=6.1 Hz, 3H; CH3), 0.98 (t, J=
7.1 Hz, 3H; CH3), 1.37–1.45 (m, 18H; CH2), 1.53 (quin, J=7.3 Hz, 2H;
CH2), 1.86 (quin, J=7.0 Hz, 2H; CH2), 4.05 (t, J=6.6 Hz, 2H; CH2O),
6.47 (d, JHF =36.4 Hz, 1H; CH=CF), 7.03 (d, J=8.6 Hz, 2H; Ar), 7.22 (d,
J=8.6 Hz, 2H; Ar), 7.42 (d, J=8.6 Hz, 2H; Ar), 7.56–7.68 ppm (m, 6H;
Ar); 19F NMR (188 MHz, CDCl3): d=À74.3 (d, J=13.0 Hz; CF2-O),
J=12.1 Hz; CF=CH); 13C NMR (100 MHz, CDCl3): d=14.0, 22.6, 25.7,
1
29.2, 31.6, 68.1 (CH2O), 110.4 (d, JCF =2.9 Hz), 114.9, 117.4 (td, JCF
=
=
=
261.3 Hz, 2JCF =38.1 Hz; CF2-CF,), 123.3, 126.8, 128.0, 128.6 (d, JCF
1
3.6 Hz), 129.6, 130.0 (d, JCF =7.3 Hz), 131.7, 132.3, 141.5, 147.2 (dt, JCF
À129.4 ppm (dt,
J
HF =36.4 Hz, J=13.0 Hz; CF=CH); 13C NMR
267.9 Hz, 2JCF =38.1 Hz; CF-CF2,), 148.2, 159.1 ppm; IR (neat): n˜ =1500,
+
(100 MHz, CDCl3): d=14.0, 22.6, 25.7, 29.3, 31.5, 31.6–31.7 (m, 5CH2),
32.3, 38.3, 57.0, 68.0 (CH2O), 110.1 (d, JCF =2.2 Hz), 114.9, 117.5 (td,
1JCF =259.8 Hz, 2JCF =37.3 Hz; CF2-CF,), 121.1, 126.7, 127.2, 128.0, 128.7,
128.8 (d, JCF =3.7 Hz), 130.0 (d, JCF =7.3 Hz), 132.4, 141.3, 147.7 (dt,
1JCF =267.9 Hz, 2JCF =37.3 Hz; CF-CF2), 148.0, 159.1 ppm; IR (neat): n˜ =
1480, 1600 (Ar), 1680 cmÀ1 (C=C); HRMS (ESI): m/z calcd for
C35H43F3NaO2+:575.3107 [M+Na+]; found: 575.3111.
1600 (Ar), 1700 cmÀ1 (C=C); HRMS (ESI): m/z calcd for C27H26ClF3O2
497.1466 [M+Na+]; found: 497.1464.
:
(Z)-4-Butoxy-4’-(3-(4-sec-butylphenoxy)-2,3,3-trifluoroprop-1-enyl)bi-
phenyl (9j): White solid, yield 90%; Rf =0.4 (hexane/CH2Cl2 =4:1);
1H NMR (400 MHz, CDCl3): d=0.85 (t, J=7.5 Hz, 3H; CH3), 1.02 (t, J=
7.3 Hz, 3H; CH3), 1.26 (d, J=6.8 Hz, 3H; CH3), 1.54 (quin, J=7.3 Hz,
2H; CH2), 1.61 (quin, J=7.3 Hz, 2H; CH2), 1.83 (quin, J=7.0 Hz, 2H;
CH2), 2.64 (sex, J=7.0 Hz, 1H; CHCH3),4.04 (t, J=6.6 Hz, 2H; CH2O),
6.46 (d, JHF =36.4 Hz, 1H; CH=CF), 7.01 (d, J=8.8 Hz, 2H; Ar), 7.18–
7.23 (m, 4H; Ar), 7.54–7.67 ppm (m, 6H; Ar); 19F NMR (188 MHz,
(Z)-4-(Hexyloxy)-4’-(2,3,3-trifluoro-3-(2-fluorophenoxy)prop-1-enyl)bi-
phenyl (9 f): White solid, yield 92%; Rf =0.4 (hexane/CH2Cl2 =4:1);
1H NMR (400 MHz, CDCl3): d=0.95 (t, J=6.8 Hz, 3H; CH3), 1.36–1.43
(m, 4H; CH2), 1.51 (quin, J=7.1 Hz, 2H; CH2), 1.84 (quin, J=7.0 Hz,
2H; CH2), 4.03 (t, J=6.4 Hz, 2H; CH2O), 6.52 (d, JHF =36.4 Hz, 1H;
CH=CF), 7.00 (d, J=8.6 Hz, 2H; Ar), 7.15–7.27 (m, 3H; Ar), 7.41 (t,
1H; Ar), 7.56–7.69 ppm (m, 6H; Ar); 19F NMR (188 MHz, CDCl3): d=
CDCl3): d=À74.3 (d, J=13.8 Hz; CF2-O), À129.5 ppm (dt, JH-F
=
36.4 Hz, J=13.8 Hz; CF=CH); 13C NMR (100 MHz, CDCl3): d=12.1,
13.8, 19.2, 21.7, 29.7, 31.3, 41.1, 67.7 (CH2O), 110.1 (d, JCF =2.9 Hz),
114.8, 117.5 (td, 1JCF =259.8 Hz, 2JCF =38.1 Hz; CF2-CF,), 121.7, 126.7,
128.0, 128.7, 128.9 (d, 4JCF =2.9 Hz), 130.0 (d, 4JCF =6.6 Hz), 132.4, 141.3,
145.6, 147.6, 147.8 (dt, 1JCF =268.6 Hz, 2JCF =37.3 Hz; CF-CF2,),
À74.8 (d, J=13.0 Hz; CF2-O), À129.4 (m; Ar-F), À130.0 ppm (dt, JHF
=
36.4 Hz, J=13.0 Hz; CF=CH); 13C NMR (100 MHz, CDCl3): d=14.0,
22.6, 25.7, 29.2, 31.6, 68.1 (CH2O), 110.5 (d, JCF =2.9 Hz), 114.9, 117.0 (d,
159.1 ppm; IR (neat): n˜ =1500, 1610 (Ar), 1700 cmÀ1 (C=C); HRMS
+
J
CF =19.0 Hz), 117.5 (td, 1JCF =262.3 Hz, 2JCF =38.8 Hzl; CF2-CF,), 124.3
(ESI): m/z calcd for C29H31F3NaO2
:
491.2168 [M+Na+]; found:
(d, JCF =4.4 Hz), 124.8, 126.8, 127.5 (d, JCF =6.7 Hz), 128.0, 128.7 (d, JCF
=
491.2170.
1
2.9 Hz), 130.1 (d, JCF =7.3 Hz), 132.4, 136.9, 139.2, 141.5, 147.1 (dt, JCF
=
(Z)-4-(3-(4-sec-Butylphenoxy)-2,3,3-trifluoroprop-1-enyl)-4’-(decyloxy)bi-
phenyl (9k): White solid, yield 97%; Rf =0.4 (hexane/CH2Cl2 =4:1);
1H NMR (400 MHz, CDCl3): d=0.95 (t, J=7.3 Hz, 3H; CH3), 1.04 (t, J=
7.1 Hz, 3H; CH3), 1.35 (d, J=7.1 Hz, 3H; CH3), 1.37–1.45 (m, 12H;
CH2), 1.51 (quin, J=7.1 Hz, 2H; CH2), 1.61 (quin, J=7.3 Hz, 2H; CH2),
1.85 (quin, J=6.9 Hz, 2H; CH2), 2.65 (sex, J=6.9 Hz, 1H; CHCH3), 4.08
(t, J=6.4 Hz, 2H; CH2O), 6.56 (d, JHF =36.4 Hz, 1H; CH=CF), 7.08 (d,
J=8.8 Hz, 2H; Ar), 7.26–7.34 (m, 4H; Ar), 7.62–7.75 ppm (m, 6H; Ar);
19F NMR (188 MHz, CDCl3): d=À74.2 (d, J=13.8 Hz; CF2-O),
267.9 Hz, 2JCF =37.3 Hz; CF-CF2), 159.1 ppm; IR (neat): n˜ =1500, 1610
(Ar), 1700 cmÀ1 (C=C); HRMS (ESI): m/z calcd for C27H26F4NaO2
481.1761 [M+Na+]; found: 481.1745.
:
+
(Z)-4-(3-(2-tert-Butylphenoxy)-2,3,3-trifluoroprop-1-enyl)-4’-(hexyloxy)-
biphenyl (9g): White solid, yield 76%; Rf =0.4 (hexane/CH2Cl2 =4:1);
m.p. 63.4–64.38C; 1H NMR (400 MHz, CDCl3): d=0.99 (t, J=7.0 Hz,
3H; CH3), 1.39–1.45 (m, 4H; CH2), 1.50 (s, 9H; tBu), 1.55 (quin, J=
7.0 Hz, 2H; CH2), 1.87 (quin, J=7.0 Hz, 2H; CH2), 4.06 (t, J=6.6 Hz,
2H; CH2O), 6.56 (d, JHF =36.4 Hz, 1H; CH=CF), 7.04 (d, J=8.2 Hz, 2H;
Ar,), 7.22 (t, 1H; Ar), 7.27 (t, 1H; Ar), 7.45–7.53 (m, 2H; Ar), 7.56–
7.72 ppm (m, 6H; Ar); 19F NMR (188 MHz, CDCl3): d=À71.8 (d, J=
13.0 Hz; CF2-O), À128.9 ppm (dt, JH-F =36.4 Hz, J=13.0 Hz; CF=CH);
13C NMR (100 MHz, CDCl3): d=14.0, 22.6, 25.7, 29.3, 29.7, 30.2, 31.6,
68.1 (CH2O), 110.3 (d, JCF =2.9 Hz), 114.9, 117.8 (td, 1JCF =262.0 Hz,
2JCF =38.1 Hz; CF2-CF,), 119.9, 125.0, 126.8, 127.1, 127.6, 128.0, 128.8 (d,
À129.5 ppm (dt,
J
HF =36.4 Hz, J=13.8 Hz; CF=CH); 13C NMR
(100 MHz, CDCl3): d=12.1, 14.1, 21.7, 22.7, 26.1, 29.3, 29.4, 29.5, 29.6,
29.8, 31.2, 31.9, 41.1, 68.0 (CH2O), 110.0 (d, JCF =2.2 Hz), 114.8, 117.5 (td,
1JCF =259.8 Hz, 2JCF =38.1 Hz; CF2-CF,), 121.7, 126.7, 127.9, 128.7, 128.9
(d, 4JCF =2.9 Hz), 130.0 (d, 4JCF =7.3 Hz), 132.4, 141.3, 145.5, 147.7, 147.8
(dt, 1JCF =267.9 Hz, 2JCF =37.3 Hz; CF-CF2,), 159.1 ppm; IR (neat): n˜ =
1500, 1600 (Ar), 1700 cmÀ1 (C=C); HRMS (ESI): m/z calcd for
C35H43F3NaO2+: 575.3107 [M+Na+]; found: 575.3097.
J
CF =3.7 Hz), 130.0 (d, 4JCF =7.3 Hz), 132.38, 140.53, 141.46, 147.98 (dt,
1JCF =268.6 Hz, 2JCF =38.8 Hz; CF-CF2), 149.4, 159.1 ppm; IR (neat): n˜ =
1480, 1600 (Ar), 1700 cmÀ1 (C=C); HRMS (ESI): m/z calcd for
C31H35F3NaO2+: 519.2481 [M+Na+]; found: 519.2487.
(Z)-4-(3-(4-sec-Butylphenoxy)-2,3,3-trifluoroprop-1-enyl)-4’-(pentadecy-
loxy)biphenyl (9l): White solid, yield 87%; Rf =0.4 (hexane/CH2Cl2 =
4:1); 1H NMR (400 MHz, CDCl3): d=0.90 (t, J=7.3 Hz, 3H; CH3), 0.97
(t, J=6.6 Hz, 3H; CH3), 1.31 (d, J=6.8 Hz, 3H; CH3), 1.33–1.48 (m,
22H, CH2), 1.55 (quin, J=7.1 Hz, 2H; CH2), 1.66 (quin, J=7.3 Hz, 2H;
CH2), 1.88 (quin, J=6.9 Hz, 2H; CH2), 2.68 (sex, J=6.9 Hz, 1H;
CHCH3), 4.06 (t, J=6.4 Hz, 2H; CH2O), 6.51 (d, JHF =36.4 Hz, 1H; CH=
CF), 7.04 (d, J=8.6 Hz, 2H; Ar), 7.22–7.27 (m, 4H; Ar), 7.58–7.72 ppm
(m, 6H; Ar); 19F NMR (188 MHz, CDCl3): d=À74.2 (d, J=13.8 Hz;
CF2-O), À129.5 ppm (dt, JHF =36.4 Hz, J=13.8 Hz; CF=CH); 13C NMR
(Z)-4-(3-(3,4-Dimethoxyphenoxy)-2,3,3-trifluoroprop-1-enyl)-4’-(hexylox-
y)biphenyl (9h): White solid, yield 76%; Rf =0.4 (hexane/CH2Cl2 =2:1);
m.p. 116.4–118.58C; 1H NMR (400 MHz, CDCl3): d=0.94 (t, J=7.1 Hz,
3H; CH3), 1.35–1.42 (m, 4H; CH2), 1.51 (quin, J=7.3 Hz, 2H; CH2), 1.84
(quin, J=6.9 Hz, 2H; CH2), 3.91 (s, 3H; CH3-O), 3.92 (s, 3H; CH3-O),
4.03 (t, J=6.6 Hz, 2H; CH2O), 6.44 (d, JHF =36.4 Hz, 1H; CH=CF),
6.82–6.87 (m, 3H; Ar), 7.00 (d, J=8.6 Hz, 2H; Ar), 7.55–7.67 ppm (m,
&
8
&
ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
ÝÝ
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