52
M. Paramanik et al. / Journal of Fluorine Chemistry 178 (2015) 47–55
2943, 2860, 2519, 2315, 1959, 1732, 1460, 1352, 1172, 1096, 952,
832, 741, 695, 612, 521 cmꢀ1 1H NMR (200 MHz, CDCl3):
1.50–
(2H, m, CH2), 1.93–1.99 (2H, m, CH2), 3.01 (3H, s, SO2CH3), 3.90 (2H,
t, 3JHH = 6.5 Hz, OCH2), 3.95 (2H, t, 3JHH = 6.0 Hz, OCH2), 4.31 (2H, t,
3JHH = 6.0 Hz, CH2OSO2Me), 6.81 (4H, s, Ar). 13C NMR (125 MHz,
CDCl3): d 14.0, 22.5, 25.4, 25.9, 26.1, 29.0, 29.3, 31.7, 37.3, 67.5,
68.6, 69.6, 115.3 (2C), 115.4 (2C), 152.7, 153.4. HRMS (ESI), m/z
calcd. for C18H30O5SNa+ 381.1712 (M+Na)+, found 381.1711.
.
d
1.85 (m, 6H, 3 ꢂ CH2), 2.99 (s, 3H, OSO2CH3), 3.48 (t, 2H,
3
3JHH = 6.0 Hz, CH2OCH2Ph), 4.22 (t, 2H, JHH = 6.4 Hz, SO2CH2),
4.50 (s, 2H, PhCH2), 7.27–7.35 (m, 5H, Ph). 13C NMR (50 MHz,
CDCl3):
d
22.0, 28.6, 28.8, 36.9, 69.6, 69.9, 72.6, 127.3, 127.4 (2C),
128.1 (2C), 138.3.
4.12. Dodecyl methanesulfonate (7g) [61]
4.7. 3-(Naphthalene-1-yloxy)propyl methanesulfonate (7b) [55]
This compound has been made following the procedure
This compound has been made following the procedure
described for the preparation of 7a. Yield: 99%. IR (film): y
¯
described for the preparation of 7a. Yield: 99%. 1H NMR
3041, 2908, 2849, 1467, 1360, 1178, 971, 946, 822, 747, 722 cmꢀ1
1H NMR (300 MHz, CDCl3): 0.85 (3H, t, 3JHH = 6.6 Hz, CH3), 1.15–
.
(500 MHz, CDCl3):
d
2.34–2.40 (2H, m, CH2), 2.95 (3H, s, SO2Me),
d
3
3
3
4.27 (2H, t, JHH = 5.5 Hz, CH2OSO2Me), 4.55 (2H, t, JHH = 6.0 Hz,
CH2OAr), 6.82 (1H, d, 3JHH = 7.5 Hz, Ar), 7.36–7.53 (4H, m, Ar), 7.82
1.49 (18H, m, 9 ꢂ CH2), 1.72 (2H, quint, JHH = 6.3 Hz, CH2), 2.98
3
(3H, s, CH2OSO2CH3), 4.19 (2H, t, JHH = 6.3 Hz, CH2OSO2Me). 13C
3
4
3
(1H, dd, JHH = 6.5 Hz, JHH = 2.5 Hz, Ar), 8.25 (1H, dd, JHH = 9.0,
4JHH = 2.0 Hz, Ar). 13C NMR (125 MHz, CDCl3):
29.3, 37.3, 63.6,
NMR (75 MHz, CDCl3): d 14.1, 22.7, 25.4, 29.0, 29.1, 29.3, 29.4, 29.5,
29.6 (2C), 31.9, 37.3, 70.3.
d
67.0, 104.9, 120.8, 121.8, 125.5, 125.6, 125.9, 126.6, 127.7, 134.6,
154.2.
4.13. [{(5-Fluoropentyl)oxy}methyl]benzene (8a)
4.8. 3-(Naphthalene-2-yloxy)propyl methanesulfonate (7c)
Cesium fluoride (456 mg, 3 mmol) was added to a stirred
solution of mesylate 7a (272 mg, 1 mmol) and ionic liquid 1
(232 mg, 0.5 mmol) in t-BuOH (0.25 mL) and the mixture was
heated at 100 8C for 45 min. The reaction mixture was diluted with
water and extracted with 15% ethyl acetate in hexanes. The organic
extract was concentrated under reduced pressure and the residue
was purified by silica gel column chromatography using 5% ethyl
acetate in hexanes to give compound 8a (190 mg, 97%) as a
colorless oil.
This compound has also been prepared from chloride 10a. The
procedure is same as from mesylate 7a except the mixture was
heated at 100 8C for 75 min which provided a mixture of fluoride
8a and alkene 11 in a ratio of 95:5. Yield of 8a: 94% as a colorless oil.
This compound has also been prepared from bromide 2. The
procedure is same as from mesylate 7a except the mixture was
heated at 100 8C for 60 min which provided a mixture of fluoride
8a and alkene 11 in a ratio of 90:10. Yield of 8a: 87% as a colorless
oil. This compound has also been prepared from iodide 10b. The
procedure is same as from mesylate 7a except the mixture was
heated at 100 8C for 30 min which provided a mixture of fluoride
8a and alkene 11 in a ratio of 70:30. Yield of 8a: 68% as a colorless
oil. Yield of 11: 23%.
This compound has been made following the procedure
described for the preparation of 7a. Yield: 99%. IR (film):
y
¯
3653, 3424, 3056, 3028, 2961, 2933, 1651, 1517, 1360, 1211, 1170,
963, 831, 747 cmꢀ1 1H NMR (500 MHz, CDCl3):
. d 2.31 (2H, quint,
3
3JHH = 6.0 Hz, CH2), 3.00 (3H, s, SO2Me), 4.22 (2H, t, JHH = 6.0 Hz,
3
CH2OSO2Me), 4.50 (2H, t, JHH = 6.0 Hz, CH2OAr), 7.14 (1H, d,
3
3JHH = 10.0 Hz, Ar), 7.16 (1H, s, Ar), 7.37 (1H, t, JHH = 7.0 Hz, Ar),
3
7.47 (1H, t, JHH = 7.0 Hz, Ar), 7.74–7.80 (3H, m, Ar). 13C NMR
(125 MHz, CDCl3):
d 29.3, 37.4, 63.4, 66.9, 107.0, 118.7, 124.0,
126.6, 126.9, 127.8, 129.3, 129.7, 134.6, 156.6. HRMS (ESI), m/z
calcd. for C14H16O4SNa+ 303.0667 (M+Na)+, found 303.0664.
4.9. Decane-1,10-diyl dimethanesulfonate (7d) [59]
This compound has been made following the procedure
described for the preparation of 7a. Yield: 99%. IR (film):
y
¯
3048, 2983, 2949, 2916, 2842, 1467, 1344, 1153, 996, 954, 847,
757, 722 cmꢀ1 1H NMR (300 MHz, CDCl3):
1.29–1.49 (12H, m,
.
d
6 ꢂ CH2), 1.70–1.78 (4H, m, 2 ꢂ CH2), 3.00 (6H, s,
3
2 ꢂ CH2OSO2CH3), 4.22 (4H, t, JHH = 6.3 Hz, 2 ꢂ CH2OSO2Me).
13C NMR (75 MHz, CDCl3):
(2C), 37.3 (2C), 70.2 (2C).
d
25.4 (2C), 28.9 (2C), 29.1 (2C), 29.2
Data for 8a: IR (film): y 3334, 2493, 2866, 2367, 1960, 1723,
¯
1600, 1454, 1362, 1277, 1208, 1101, 1024, 909, 749, 717, 649 cmꢀ1
.
1H NMR (200 MHz, CDCl3):
d
1.50–1.82 (m, 6H, 3 ꢂ CH2), 3.49 (t,
3
2 3
4.10. (ꢃ)-3,7-Dimethyloct-6-en-1-yl methanesulfonate (7e) [57]
2H, JHH = 6.2 Hz, OCH2), 4.45 (dt, 2H, JHF = 47.2 Hz, JHH = 6.2 Hz,
CH2F), 4.51 (s, 2H, PhCH2), 7.30–7.36 (m, 5H, Ph). 13C NMR
3
This compound has been made following the procedure
described for the preparation of 7a. Yield: 99%. IR (film):
(50 MHz, CDCl3):
d
21.9 (d, JCF = 5.5 Hz), 29.3, 30.1 (d,
1
y
¯
2JCF = 19.5 Hz), 70.0, 72.8, 83.8 (d, JCF = 163.5 Hz), 127.4, 127.5
(2C), 128.2 (2C), 138.5. HRMS (ESI), m/z calcd. for C12H17FONa+
219.1156 (M+Na)+, found 219.1157.
3561, 3031, 2966, 292, 2370, 1650, 1476, 136, 1170, 1053, 988,
946, 896, 739 cmꢀ1 1H NMR (500 MHz, CDCl3):
0.92 (3H, d,
.
d
3JHH = 6.5 Hz, CHCH3), 1.14–1.23 (1H, m, CHAHB), 1.29–1.38 (1H, m,
CHAHB), 1.50–1.63 (2H, m, CH2), 1.59 (3H, s, C55CCH3), 1.67 (3H, s,
C55CCH3), 1.74–1.82 (1H, m, CHMe), 1.90–2.04 (2H, m, CH2), 2.99
(3H, s, OSO2CH3), 4.20–4.30 (2H, m, CH2OSO2Me), 5.06 (1H, t,
Data for 11: 1H NMR (500 MHz, CDCl3):
d 1.73 (2H, quint,
3JHH = 6.5 Hz), 2.14–2.18 (2H, m, CH2), 3.50 (2H, t, JHH = 6.5 Hz,
3
3
CH2OAr), 4.51 (2H, s, CH2OAr), 4.97 (1H, d, JHH = 10.0 Hz,
CH55CHACHB), 5.03 (1H, dd, 3JHH = 17.0 Hz, 4JHH = 1.5 Hz,
CH55CHACHB), 5.79–5.87 (1H, m, CH55CH2), 7.28–7.37 (5H, m,
broad, 3JHH = 9 Hz, HC55C). 13C NMR (125 MHz, CDCl3):
d 17.5, 19.0,
25.2, 25.6, 28.9, 35.8, 36.7, 37.2, 68.5, 124.2, 131.4.
Ar). 13C NMR (125 MHz, CDCl3):
d 29.0, 30.3, 69.7, 72.9, 114.7,
127.5, 127.6 (2C), 128.3 (2C), 138.3, 138.6.
4.11. 4-(4-(Heptyloxy)phenoxy)butyl methanesulonate (7f)
4.14. 1-(3-Fluoropropoxy)naphthalene (8b) [56]
This compound has been made from 7b following the procedure
This compound has been made following the procedure
described for the preparation of 7a. Yield: 99%. IR (film):
y
¯
3031, 2924, 2842, 1526, 1459, 1344, 1228, 1153, 1054, 931, 839,
described for the preparation of 8a from 7a. Yield: 90%. 1H NMR
3
764, 664 cmꢀ1
.
1H NMR (500 MHz, CDCl3):
d
0.89 (3H, t,
(500 MHz, CDCl3):
d
2.33 (2H, dquint, JHF = 25.5 Hz, 3JHH = 6.0 Hz,
3
3JHH = 6.0 Hz, CH3), 1.26–1.37 (6H, m, 3 ꢂ CH2), 1.44 (2H, quint,
CH2CH2F), 4.30 (2H, t, JHH = 6.5 Hz, CH2OAr), 4.77 (2H, dt,
3
3
3
3JHH = 7.0 Hz, CH2), 1.75 (2H, quint, JHH = 6.5 Hz, CH2), 1.86–1.91
2JHF = 47.0 Hz, JHH = 6.0 Hz, CH2F), 6.84 (1H, d, JHH = 7.5 Hz, Ar),