618
J.A. Bennett et al. / Journal of Fluorine Chemistry 130 (2009) 615–620
3JHH = 7.0 Hz, CH3), 1.91 (2H, m, CH2), 2.31 (2H, m, CH2), 4.04 (2H,
dq, 2JHH = 10.2 Hz, 3JHH = 7.0 Hz, CHA), 4.10 (2H, dq, 2JHH = 10.2 Hz,
4.1.6. 4-Trifluoromethylphenyldiethylphosphonate (6)
4-Trifluoromethylphenyldiethylphosphonate (6) [19] was pre-
pared similarly. Yield 69%. Anal. Calcd. for C11H14F3O3P: C, 46.8; H,
3JHH = 7.0 Hz, CHB). 13C{1H} NMR (CDCl3):
d
16.26 (d, 3JPC = 6.0 Hz,
1
2
CH3), 17.05 (d, JPC = 147.2 Hz, CH2), 25.03 (t, JFC = 22.7 Hz, CH2),
62.11 (d, JPC = 6.0 Hz, CH2). 31P{1H} NMR (CDCl3):
5.0. Found: C, 46.7; H, 5.0. 1H NMR (CDCl3):
d
1.33 (6H, t,
2
2
3
d
28.36 (s).
3JHH = 7.3 Hz, CH3), 4.03 (2H, ddq, JHH = 10.2 Hz, JPH = 7.9 Hz,
19F{1H} NMR (CDCl3):
d
À81.04 (3F, t, JFF = 9.5 Hz, CF3), À115.53
3JHH = 7.0 Hz, CHA), 4.12 (2H, ddq, JHH = 10.2 Hz, JPH = 8.2 Hz,
4
2
3
(2F, m,
a
-CF2), À124.28 (2F, m, CF2), À126.04 (2F, m, CF2). m/z (ES+)
3JHH = 7.0 Hz, CHB), 7.65 (2H, dd, 3JHH = 8.2 Hz, 4JPH = 3.5 Hz, 3-CH),
385 (MH+, 100%).
7.88 (2H, dd, JPH = 12.9 Hz, JHH = 8.5 Hz, 2-CH).13C{1H} NMR
3
3
(CDCl3):
d
16.16 (d, 3JPC = 6.0 Hz, CH3), 62.44 (d, 2JCP = 6.0 Hz, CH2),
1
3
4.1.3. 1H,1H,2H,2H-tridecafluorooctyldiethylphosphonate (3)
1H,1H,2H,2H-tridecafluorooctyldiethylphosphonate (3) was pre-
pared similarly as a pale yellow oil. Yield 48%. Anal. Calcd. for
123.45 (q, JFC = 272.4 Hz, CF3), 125.22 (dq, JPC = 14.4 Hz,
3JFC = 3.6 Hz, 3-CH), 132.15 (d, JPC = 10.8 Hz, 2-CH), 132.76 (d,
2
1JPC = 187.9 Hz, 1-C), 133.95 (qd, JFC = 32.3 Hz, JPC = 3.6 Hz, 4-C).
2
4
C
12H14F13O3P: C, 29.8; H, 2.9. Found: C, 29.8; H, 2.7. 1H NMR
31P {1H} NMR (CDCl3):
d
16.34 (s). 19F {1H} NMR (CDCl3):
d
À63.31
3
(CDCl3):
d
1.29 (6H, t, JHH = 7.0 Hz, CH3), 1.92 (2H, m, CH2), 2.30
(s). m/z (ES+) 282 (M+, 30%).
2
3
(2H, m, CH2), 4.07 (2H, ddq, JHH = 10.2 Hz, JPH = 7.9 Hz,
3JHH = 7.0 Hz, CHA), 4.08 (2H, ddq, JHH = 10.2 Hz, JPH = 8.5 Hz,
4.1.7. 4-Tridecafluorohexylphenyldiethylphosphonate (7)
4-Tridecafluorohexylphenyldiethylphosphonate (7) was prepared
similarly. Yield 85%. Anal. Calcd. for C16H14F13O3P: C, 36.1; H, 2.6.
2
3
3JHH = 7.0 Hz, CHB). 13C{1H} (CDCl3):
d
16.26 (d, 3JPC = 6.0 Hz, CH3),
1
18.71 (d, JPC = 143.6 Hz, CH2), 25.14 (m, CH2), 62.19 (d,
2JPC = 6.0 Hz, CH2). 31P{1H} NMR (CDCl3):
NMR (CDCl3):
d
28.38 (s). 19F{1H}
Found: C, 35.9; H, 2.5. 1H NMR (CDCl3):
CH3), 4.04 (2H, ddq, JHH = 10.2 Hz, JPH = 7.9 Hz, JHH = 7.0 Hz,
d
1.27 (6H, t, 3JHH = 7.0 Hz,
2
3
3
d
À80.80 (3F, t, 4JFF = 9.5 Hz, CF3), À115.31 (2F, m,
a
-
2
3
3
CF2), À121.90 (2F, m, CF2), À122.86 (2F, m, CF2), À123.33 (2F, m,
CHA), 4.14 (2H, ddq, JHH = 10.2 Hz, JPH = 7.9 Hz, JHH = 7.0 Hz,
CF2), À126.12 (2F, m, CF2). m/z (ES+) 485 (MH+, 40%).
CHB), 7.62 (2H, dd, 3JHH = 8.2 Hz, 4JPH = 3.5 Hz, 3-CH), 7.89 (2H, dd,
3JHH = 8.2 Hz, JPH = 13.2 Hz, 2-CH). 1H{31P} NMR (CDCl3):
d 1.27
3
4.1.4. 1H,1H,2H,2H,3H,3H-
(6H, t, 3JHH = 7.0 Hz, CH3), 4.04 (2H, dq, 2JHH = 10.2 Hz,
2
3
heptadecafluoroundecyldiethylphosphonate (4)
1H,1H,2H,2H,3H,3H-heptadecafluoroundecyldiethylphosphonate
(4) was prepared similarly as a pale yellow oil. Yield 62%. Anal.
3JHH = 7.0 Hz, CHA), 4.14 (2H, dq, JHH = 10.2 Hz, JHH = 7.0 Hz,
CHB), 7.62 (2H, d, 3JHH = 8.2 Hz, 3-CH), 7.89 (2H, d, 3JHH = 8.2 Hz, 2-
CH). 13C{1H} NMR (CDCl3):
d
16.14 (d, 3JPC = 6.0 Hz, CH3), 62.47 (d,
Calcd. for C15H16F17O3P: C, 30.1; H, 2.7. Found: C, 30.0; H, 2.7. 1H
2JPC = 6.0 Hz, CH2) 126.86 (dt, JPC = 14.4 Hz, JFC = 6.0 Hz, 3-CH),
3
3
3
2
2
NMR (CDCl3):
d
1.26 (6H, t, JHH = 7.0 Hz, CH3), 1.75 (2H, m, CH2),
131.93 (d, JPC = 10.8 Hz, 2-CH), 132.60 (td, JFC = 23.9 Hz,
1
1.88 (2H, m, CH2), 2.15 (2H, m, CH2), 3.96–4.14 (4H, m, CH2).
4JPC = 3.6 Hz, 4-C), 133.23 (d, JPC = 167.6 Hz, 1-C). 31P{1H} NMR
13C{1H} NMR (CDCl3):
25.00 (d, JPC = 143.6 Hz, CH2), 31.04 (m, CH2), 62.00 (d,
2JPC = 7.2 Hz, CH2). 31P{1H} NMR (CDCl3):
d
14.04 (m, CH2), 16.26 (d, 3JCP = 6.0 Hz, CH3),
(CDCl3):
d
16.31 (s); 19F{1H} NMR (CDCl3):
d
a
À80.82 (3F, t,
-CF2), À121.42
1
4
4JFF = 9.5 Hz, CF3), À111.29 (2F, t, JFF = 14.2 Hz,
d
30.11 (s). 19F{1H}
(2F, m, CF2), À121.69 (2F, m, CF2), À122.79 (2F, m, CF2), À123.33
NMR (CDCl3):
d
À80.81 (3F, t, 4JFF = 10.0 Hz, CF3), À114.50 (2F, m,
(2F, m, CF2). m/z (ES+) 533 (MH+, 100%).
a
-CF2), À121.71 (2F, m, CF2), À121.92 (4F, m, CF2), À122.70 (2F, s,
CF2), À123.55 (2F, m, CF2), À126.11 (2F, m, CF2). m/z (ES+) 599
4.1.8. 1H,1H,2H,2H-nonafluorohexylphosphonic acid (8)
(MH+, 100%).
F9C4-C2H4-PO(OEt)2 (2) (3.17 g, 8.2 mmol) was refluxed
(110 8C) with vigorous stirring for 48 h in H2O (20 cm3) with
12 M HCl (20 cm3). The solvent was removed in vacuo, the white
solid was washed with chloroform and dried under vacuum to
yield the product as white powder (1.80 g, 67%). Anal. Calcd. for
C6H6F9O3P: C, 22.0; H, 1.8. Found: C, 22.1; H, 1.7. 1H NMR (C3D6O):
4.1.5. 4-Fluorophenyldiethylphosphonate (5)
A solution of Pd(PPh3)4 (2.65 g, 2.3 mmol) and F-C6H4-Br
(8.00 g, 0.046 mol) in toluene (20 cm3) was added under N2 to a
mixture of HPO(OEt)2 (6.4 cm3, 0.050 mol) and NEt3 (7.0 cm3,
0.050 mol), and the mixture was stirred at 90 8C for 3.5 h. After
cooling, Et2O (50 cm3) was added, the solution was filtered, the
solvent was removed in vacuo and the crude product was distilled
in a Kugelro¨hr to yield the product as a clear oil. Yield 69%. Anal.
d
2.05 (2H, m, CH2), 2.51 (2H, m, CH2), 10.45 (2H, s, OH). 31P{1H}
NMR (C6D6):
NMR (C3D6O):
d d
25.77 (s). 31P{1H} NMR (C3D6O): 27.56 (s). 19F{1H}
d
À81.01 (3F, t, 4JFF = 9.5 Hz, CF3), À115.90 (2F, m,
a-
CF2), À124.91 (2F, m, CF2), À126.84 (2F, m, CF2); 13C {1H} NMR
Calcd. for C10H14FO3P: C, 51.7; H, 6.0. Found: C, 51.7; H, 6.2. 1H
(C3D6O): d
18.85 (d, 1JPC = 146.0 Hz, CH2), 25.93 (m, CH2). m/z (ESÀ)
3
NMR (CDCl3):
d
1.25 (6H, t, JHH = 7.0 Hz, CH3), 4.00 (2H, ddq,
327 ([MÀH]À, 100%).
3
3
2JHH = 10.0 Hz, JPH = 7.6 Hz, JHH = 7.0 Hz, CHA), 4.06 (2H, ddq,
3
3
2JHH = 10.0 Hz, JPH = 7.9 Hz, JHH = 7.0 Hz, CHB), 7.07 (2H, ddd,
4.1.9. 1H,1H,2H,2H-tridecafluorooctylphosphonic acid (9)
1H,1H,2H,2H-tridecafluorooctylphosphonic acid (9) was prepared
similarly. Yield 91%. Anal. Calcd. for C8H6F13O3P: C, 22.4; H, 1.4.
3JPH = 12.8 Hz, JFH = 8.8 Hz, JHH = 8.8 Hz, 2-CH), 7.75 (2H, ddd,
4
3
3JHH = 8.8 Hz, JFH = 5.5 Hz, JPH = 3.2 Hz, 3-CH). 1H{31P} NMR
3
4
3
(CDCl3):
d
1.23 (6H, t, JHH = 7.0 Hz, CH3), 4.00 (2H, dq,
Found: C, 22.6; H, 1.4. 1H NMR (C3D6O):
d
1.92 (2H, m, CH2), 2.36
(2H, m, CH2), 8.59 (2H, s, OH). 31P{1H} NMR (C3D6O):
27.81 (s).
À81.82
-CF2), À122.52 (2F, m,
2JHH = 10.0 Hz, JHH = 7.0 Hz, CHA), 4.06 (2H, dq, JHH = 10.0 Hz,
d
3
2
3JHH = 7.0 Hz, CHB), 7.07 (2H, dd, 4JFH = 8.8 Hz, 3JHH = 8.8 Hz, 2-CH),
31P{1H} NMR (C6D6):
d d
32.93 (s). 19F{1H} NMR (C3D6O):
3
3
7.75 (2H, dd, JFH = 5.5 Hz, JHH = 8.8 Hz, 3-CH). 1H{19F} NMR
(3F, t, 4JFF = 10.4 Hz, CF3), À115.66 (2F, m,
a
3
(CDCl3):
d
1.25 (6H, t, JHH = 7.0 Hz, CH3), 4.00 (2H, ddq,
CF2), À123.53 (2F, m, CF2), À123.98 (2F, m, CF2), À126.80 (2F, m,
3
3
2JHH = 10.0 Hz, JPH = 7.6 Hz, JHH = 7.0 Hz, CHA), 4.06 (2H, ddq,
CF2). 13C{1H} NMR (C3D6O): 18.91 (d, 1JPC = 149.6 Hz, CH2), 25.95
d
3
3
2JHH = 10.0 Hz, JPH = 7.9 Hz, JHH = 7.0 Hz, CHB), 7.07 (2H, dd,
(m, CH2). m/z (ESÀ) 427 ([MÀH]À, 100%).
3JPH = 12.8 Hz, JHH = 8.8 Hz, 2-CH), 7.75 (2H, dd, JHH = 8.8 Hz,
3
3
4JPH = 3.5 Hz, 3-CH). 13C{1H} NMR (CDCl3):
d
16.23 (d, 3JPC = 6.0 Hz,
4.1.10. 4-Fluorophenylphosphonic acid (10)
2
3
CH3), 62.17 (d, JPC = 6.0 Hz, CH2), 115.79 (dd, JPC = 15.6 Hz,
4-Fluorophenylphosphonic acid (10) [19] was prepared similarly.
Yield 89%. Anal. Calcd. for C6H6FO3P: C, 40.9; H, 3.4. Found: C, 40.8;
2JFC = 21.5 Hz, 3-CH), 124.4 (d, JPC = 193.2 Hz, 1-C), 134.33 (dd,
1
2JPC = 10.8 Hz, JFC = 8.4 Hz, 2-CH), 165.53 (d, JFC = 252.8 Hz, 4-C).
H, 3.3. 1H NMR (C3D6O): 7.25 (2H, ddd, 3JFH = 8.5 Hz, 3JHH = 8.5 Hz,
d
3
1
31P{1H} NMR (CDCl3):
(s). m/z (ES+) 232 (M+, 80%).
d
18.36 (s). 19F{1H} NMR (CDCl3):
d
À106.04
4JPH = 2.9 Hz, 3-CH), 7.85 (2H, ddd, JPH = 13.1 Hz, JHH = 8.7 Hz,
3
3
4JFH = 5.8 Hz, 2-CH), 10.17 (2H, s, OH). 13C{1H} NMR (C3D6O):
d