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235
The flow rate was changed to 50, and 0 cm3/min N2/F2,
respectively, and the reactor was allowed to purge for 4 h.
The solution was then filtered to remove any NaF or NaHF2
and the solvent was distilled off.
Distillation of the product (72 8C/760 mmHg) gave a
clear, colorless liquid that was analyzed as N(CF2CF3)3.
CIMS (positive mode) m/z (rel. int.) 352 [M À F]þ (36.42).
19F NMR (282 MHz, CFCl3): d À91.262 (q, 6F, J ¼
2:5 Hz, NCF2CF3), À83.754 (t, 9F, J ¼ 2:5 Hz, NCF2CF3).
13C{19F} NMR (75 MHz, C6D6): d 111.991 (s, C-1),
117.549 (s, C-2).
(2.21 g, 0.0119 mol) was dissolved in 150 ml of Freon1
113 inside a round bottom flask, and then pumped into the
purged reactor at a rate of 25 ml/h. During the addition of tri-
n-butylamine to the reactor, a N2/F2 mixture was bubbled
through the reactor at a rate of 200, and 50 cm3/min,
respectively. After the solution containing tri-n-butylamine
was completely pumped into the reactor, the N2/F2 flow rate
and the temperature were kept constant for an additional
60 min. The flow rate was changed to 50, and 0 cm3/min N2/
F2, respectively, and the reactor was allowed to purge for 4 h.
The solution was then filtered to remove any NaF or NaHF2
and the solvent was distilled off.
3.3. ‘‘Direct fluorination of tri-n-propylamine’’
‘‘perfluorotri-n-propylamine (2)’’
Vacuum distillation of the product (75 8C/40 mmHg)
gave a clear, colorless liquid that was analyzed as
N(CF2CF2CF2CF3)3. CIMS (negative mode) m/z (rel. int.)
452 [M À perfluoroalkyl]À (100.00); 633 [M À 2F]2À
(14.30). Elemental compositions were studied by high reso-
lution mass spectroscopy in chemical ionization mode.
Results were consistent with NC8F18 (calculated:
451.974333; found: 451.974508), NC12F25 (calculated:
632.963155; found: 632.964237). 19F NMR (282 MHz,
CFCl3): d À128.231 (s, 6F, NCF2CF2CF2CF3), À119.674
(s, 6F, NCF2CF2CF2CF3), À85.204 (s, 6F, NCF2CF2-
CF2CF3), À82.880 (s, 9F, NCF2CF2CF2CF3). 13C{19F}
NMR (75 MHz, C6D6): d 108.628 (s, C-1), 109.780 (s, C-2),
114.520 (s, C-3), 117.346 (s, C-4).
The fluorination of tri-n-propylamine was carried out in a
solution-phase fluorination reactor that has been described
previously in the literature [14]. The reactor was filled with
350 ml of 1,1,2-trichlorotrifluoroethane (Freon1 113) and
30 g of NaF (0.714 mol), then cooled to 10 8C. The reactor
was then purged with N2 (200 cm3/min) for 1 h. Tri-n-
propylamine (2.33 g, 0.0162 mol) was dissolved in
150 ml of Freon1 113 inside a round bottom flask, and
then pumped into the purged reactor at a rate of 25 ml/h.
During the addition of tri-n-propylamine to the reactor, a
N2/F2 mixture was bubbled through the reactor at a rate of
200, and 50 cm3/min, respectively. After the solution con-
taining tri-n-propylamine was completely pumped into
the reactor, the N2/F2 flow rate and the temperature were
kept constant for an additional 60 min. The flow rate was
changed to 50, and 0 cm3/min N2/F2, respectively, and the
reactor was allowed to purge for 4 h. The solution was then
filtered to remove any NaF or NaHF2 and the solvent was
distilled off.
Vacuum distillation of the product (60 8C/100 mmHg)
gave a clear, colorless liquid that was analyzed as
N(CF2CF2CF3)3. CIMS (negative mode) m/z (rel. int.) 352
[M À perfluoroalkyl]À (100.00); 483 [M À 2F]2À (33.62).
Elemental compositions were studied by high resolution
mass spectroscopy in chemical ionization mode. Results
were consistent with NC6F14 (calculated: 351.980720; found:
351.981318), NC9F19 (calculated: 482.972736; found:
482.971305). 19F NMR (282 MHz, CFCl3): d À123.520
(s, 6F, NCF2CF2CF3), À86.244 (s, 6F, NCF2CF2CF3),
À83.731 (s, 9F, NCF2CF2CF3). 13C{19F} NMR (75 MHz,
C6D6): d 108.215 (s, C-1), 113.926 (s, C-2), 117.441 (s, C-3).
3.5. ‘‘Direct fluorination of tri-n-pentylamine’’
‘‘perfluorotri-n-pentylamine (4)’’
The fluorination of tri-n-pentylamine was carried out in a
solution-phase fluorination reactor that has been described
previously in the literature [14]. The reactor was filled with
350 ml of 1,1,2-trichlorotrifluoroethane (Freon1 113) and
30 g of NaF (0.714 mol), then cooled to 20 8C. The reactor
was then purged with N2 (200 cm3/min) for 1 h. Tri-n-
pentylamine (1.95 g, 8.59 mmol) was dissolved in 150 ml
of Freon1 113 inside a round bottom flask, and then pumped
into the purged reactor at a rate of 25 ml/h. During the
addition of tri-n-pentylamine to the reactor, a N2/F2 mixture
was bubbled through the reactor at a rate of 200, and 50 cm3/
min, respectively. After the solution containing tri-n-penty-
lamine was completely pumped into the reactor, the N2/F2
flow rate and the temperature were kept constant for an
additional 60 min. The flow rate was changed to 50, and
0 cm3/min N2/F2, respectively, and the reactor was allowed
to purge for 4 h. The solution was then filtered to remove any
NaF or NaHF2 and the solvent was distilled off.
Vacuum distillation of the product (80 8C/15 mmHg)
gave a clear, colorless liquid that was analyzed as
N(CF2CF2CF2CF2CF3)3. CIMS (negative mode) m/z (rel. int.)
552 [M À perfluoroalkyl]À (100.00); 783 [M À 2F]2À (7.69).
Elemental compositions were studied by high resolution
mass spectroscopy in chemical ionization mode. Results
were consistent with NC10F22 (calculated: 551.967946;
found: 551.966807), NC15F31 (calculated: 982.953575;
3.4. ‘‘Direct fluorination of tri-n-butylamine’’
‘‘perfluorotri-n-butylamine (3)’’
The fluorination of tri-n-butylamine was carried out in a
solution-phase fluorination reactor that has been described
in the literature [14]. The reactor was filled with 350 ml of
1,1,2-trichlorotrifluoroethane (Freon1 113) and 30 g of NaF
(0.714 mol), then cooled to 15 8C. The reactor was then
purged with N2 (200 cm3/min) for 1 h. Tri-n-butylamine