1528
A.-M. B a´ lint et al. / Journal of Fluorine Chemistry 126 (2005) 1524–1530
4.16. Bis(4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-
nonyl)amine (4b)
2926s, 2855s. Anal. calcd. for C H N (213.41): C, 78.8; H,
14 31
14.6; N, 6.6. Found: C, 79.0; H, 14.8; N, 6.4.
Yield: 0.99 g (56%) colorless oil, GC purity: 99%; following
short-path distillation from Raschig rings (16mmHg,
4.20. Dinonyl amine (4f)
1
3
bath: 190 8C). H NMR: d 2.72 (2 ꢃ 2H, t, J = 6.5 Hz,
Yield: 498 mg (77%) white crystals, mp 35–36 8C, GC purity:
96%, after ether evaporated (Rotavap). Ref. [16] mp 32–33 8C
HH
3
3
H-1), 2.32 (2 ꢃ 2H, tt, J = 7.8 Hz, J = 20 Hz, H-3), 1.76
HH
HF
3
13
1
(2 ꢃ 2H, m, J = 6.9 Hz, H-2), no NH proton observed;
NMR (partial): d 48.2 (s, C-1), 28.6 (t, J = 23 Hz, C-3), 20.8
C
and Ref. [17] bp 188 8C/12 mmHg. H NMR: d 2.54 (2 ꢃ 2H, t,
HH
2
3
3
J
HH
= 7.5 Hz, H-1), 1.44 (2 ꢃ 2H, p, J = 6.5 Hz, H-2), 1.22
CF
HH
1
9
3
3
(
s, C-2); F NMR: d ꢂ82.5 (6F, t, J = 12 Hz, 2 ꢃ CF ),
(2 ꢃ 12H overlap), 0.83 (2 ꢃ 3H, t, J = 6.8 Hz, H-9), no NH
HH
FF
3
1
proton observed; C NMR: d 50.3 (s, C-1), 32.0, 30.3, 29.8, 29.7,
3
ꢂ115.4 (4F, 2 ꢃ CF ), ꢂ123.1 (4F, m, 2 ꢃ CF ), ꢂ124.1 (4F,
2
2
m, 2 ꢃ CF ), ꢂ124.8 (4F, m, 2 ꢃ CF ), ꢂ127.5 (4F, m,
29.5, 27.6, 22.8 (C-8), 14.2 (C-9); IR (KBr): 3277w, 2924s,
2853s. Anal. calcd. for C H N (269.52): C, 80.2; H, 14.6; N,
5.2. Found: C, 80.0; H, 14.4; N, 5.0.
2
2
2
ꢃ CF ); IR (neat): 2835w, 1365m, 1240s, 1206s, 708m;
2
18 39
+
HRMS (EI) calcd. for C H F N (M ꢂ H ): 736.0555.
1
8 12 26
Found: 736.0527.
4.21. Diundecyl amine (4g)
4.17. Bis(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-
heptadecafluoro-undecyl)amine (4c)
Yield: 688 mg (88%) white crystals, mp 43–44 8C, GC purity:
5%, after ether evaporated (Rotavap). Ref. [18] mp 51.5–
9
1
3
Yield: 2.07 g (92%) of white crystals, GC: 99% pure, mp
1
52.5 8C/C H -EtOH. H NMR: d 2.56 (2 ꢃ 2H, t, J = 6.8 Hz,
6
6
HH
13 19
4
2–43 8C/iso-octane, Ref. [2a] mp 43–44 8C. H, C, F NMR
and IR spectra are in agreement with the reported ones [2b]: H
H-1), 1.46 (2 ꢃ 2H, br p, H-2), 1.24 (2 ꢃ 16H overlap), 0.85
1
3
13
(2 ꢃ 3H, t, J = 6.8Hz, H-11), no NH proton observed;
C
HH
3
NMR: d 2.72 (2 ꢃ 2H, t, J = 6.5 Hz, H-1), 2.32 (2 ꢃ 2H, m,
NMR: d 50.3 (C-1), 32.1, 30.3, 29.8 (three peaks overlap), 29.78,
29.5, 27.6, 22.9 (C-10), 14.3 (C-11); IR (KBr): 3268w, 2916s,
2849s. Anal. calcd. for C H N (325.63): C, 81.2; H, 14.6; N,
HH
3
3
3
J
= 7.8 Hz,
J
JHH = 6.5 Hz, H-2), no NH proton observed; C NMR
= 20 Hz, H-3), 1.76 (2 ꢃ 2H, m,
HH
HF
13
22
47
2
partial): d 48.1 (s, C-1), 28.6 (t, J = 23 Hz, C-3), 20.8 (s, C-
(
4.3. Found: C, 81.3; H, 14.6; N, 4.1.
CF
1
9
3
2
); F NMR: d ꢂ82.4 (6F, t, J = 12Hz, 2 ꢃ CF ), ꢂ115.4
FF
3
(
4F, m, 2 ꢃ CF ), ꢂ123.0 (12F, m, three peaks overlap,
4.22. Ditridecyl amine (4h)
2
2
ꢃ 3CF ), ꢂ123.9 (4F, m, 2 ꢃ CF ), ꢂ124.8 (4F, m, 2 ꢃ CF ),
2
2
2
ꢂ127.4 (4F, m, 2 ꢃ CF ); IR (KBr): 2830w, 1355m, 1203s,
Yield: 834 mg (91%) white crystals, mp 47–48 8C, GC purity:
96%, after ether evaporated (Rotavap). Ref. [19] mp 56.5 8C/
2
+
1
9
149s, 656s; HRMS (EI) calcd. for C H F N (M ꢂ H ):
1
8 12 26
1
3
36.0427. Found: 936.0402.
C H -EtOH. H NMR: d 2.56 (2 ꢃ 2H, t, J = 7.1 Hz, H-1),
6
6
HH
1
.46 (2 ꢃ 2H, br m, H-2), 1.24 (2 ꢃ 20H overlap), 0.86 (2 ꢃ 3H,
3
t, J = 6.8 Hz, H-13), no NH proton observed; C NMR: d
13
4
1
.18. Bis(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,
3,13-heneicosafluoro-tridecyl)amine (4d)
HH
50.3 (C-1), 32.1, 30.4, 29.8 (six peaks overlap), 29.6, 27.6, 22.9
(C-12), 14.3 (C-13); IR (KBr):3266w, 2919s, 2850s. Anal. calcd.
forC H N (381.73):C, 81.8;H, 14.5;N, 3.7. Found:C, 81.6;H,
14.3; N, 3.6.
Yield: 2.29 g (84%) white crystals, mp 80–82 8C/iso-octane,
2
6 55
1
3
GC purity: 99%. H NMR: d 2.74 (2 ꢃ 2H, t, J = 6.5 Hz, H-
HH
3
3
1
), 2.31 (2 ꢃ 2H, m, J = 7.6 Hz, J = 20 Hz, H-3,), 1.78
HH
HF
3
13
(2 ꢃ 2H, m, J = 6.5 Hz, H-2), no NH proton observed;
NMR (partial): d 49.0 (s, C-1), 29.6 (t, J = 22.1 Hz, C-3),
C
4.23. General procedure for the synthesis of amine
hydrochlorides (5a–h)
HH
2
CF
1
9
3
2
1.6 (s, C-2); F NMR: d ꢂ82.5 (6F, t, J = 10 Hz, 2 ꢃ CF ),
FF
3
ꢂ115.5 (4F, m, 2 ꢃ CF ), ꢂ122.9 (20F, m, five peaks overlap,
The liquid or melted amines 4a–h (1.5 mmol) were
dissolved in methanol (5–10 ml), then mixed with trimethyl-
chlorosilane (1–2 ml, 8–16 mmol) and stirred at RT for 1 h.
Then, the crystalline precipitate formed was filtered, washed
with cold ether (3ꢃ 5 ml) and dried over KOH pellets in
vacuum to afford the appropriate hydrochlorides. GC assays:
5 mg of the hydrochloride was shaken with 5% NaOH (2 ml)
and ether (3 ml) for 2 min, then the ether phase was separated
and dried (Na SO ) and 0.1 ml injected to the column.
2
2
ꢃ 5CF ), ꢂ123.9 (4F, m, 2 ꢃ CF ), ꢂ124.8 (4F, m, 2 ꢃ CF ),
2
2
2
ꢂ127.4 (4F, m, 2 ꢃ CF ); IR (KBr): 2832w, 1355m, 1226s,
2
+
151s, 644s; HRMS (EI) calcd. for C H F N (M ):
137.0377. Found: 1137.0374.
1
1
2
6 13 42
4
.19. Diheptyl amine (4e)
Yield: 476 mg (93%) colorless oil, GC purity: 98%, after
ether evaporated (Rotavap). Ref. [15] mp 32–33 8C {with
2
4
1
3
H O} and bp 147–148 8C/15 mmHg. H NMR: d 3.32
4.24. Bis(4,4,5,5,6,6,7,7,7-nonafluoro-heptyl)amine
hydrochloride (5a)
2
3
3
(
2 ꢃ 2H, t, JHH = 7.5 Hz, H-1), 1.61 (2 ꢃ 2H, p, JHH
=
6
3
.8 Hz, H-2), 1.28–1.29 (2 ꢃ 8H, overlap), 0.87 (2 ꢃ 3H, t,
13
= 6.8 Hz, H-7), no NH proton observed; C NMR: d 48.6
J
C-1), 31.8, 29.0, 28.6, 26.6, 22.7 (C-6), 14.1 (C-7); IR (neat):
Yield: 0.68 g (79%) white crystals, mp 180 8C, GC purity:
HH
1
+
(
99.5%. H NMR: d 6.74 (2H, br, NH ), 2.62 (2 ꢃ 2H, br, H-1),
2