B. Gourdet et al. / Journal of Fluorine Chemistry 131 (2010) 1133–1143
1141
4
.1.3.1. Di(1H,2H-perfluoro-1-octenyl)-dibenzo-18-crown-6 (12).
(CDCl
3
) 148.9 (C), 147.5 (C), 132.2 (C), 120.8 (CH), 114.0 (CH), 113.6
2
The resulting pale yellow solid was recrystallised from ethanol
to give the desired product as a white solid (0.9 g, 84%). mp 100–
(CH), 70.0 (CH ), 69.1 (CH ), 33.6 (t, JCF 22.4, CH ), 26.0 (CH ); m/z
(FAB) 1291 (MK , 90%), 1275 (MNa , 100), 1252 (M , 12).
2 2 2 2
+
+
+
1
2
6
02 8C; (Found: C, 41.16; H, 2.42. Calc. for C36
H
26
F
26
O
6
: C, 41.24; H,
) 7.02 (2H, dt, JHH 16.0, JHF 2.0, ArCH 55 CHCF ),
.95 (2H, dd, JHH 8.1, JHH 2.0, ArH), 6.89 (2H, d, JHH 1.8, ArH), 6.78
3
4
0
.50%);
d
H
(CDCl
3
2
4.1.5. Cis-4,4 -diheptylamido-dibenzo-18-crown-6 (16)
3
4
4
A solution of heptanoyl chloride (0.5 g, 3.1 mmol) in acetone
(10 mL) was added to a solution of cis-4,4 -diamino-dibenzo-18-
3
3
3
0
(
4
2H, d, JHH 8.1, ArH), 5.95 (2H, dt, JHH 16.0, JHF 12.3, ArH 55 CHCF
.12 (8H, m, ArOCH ), 3.96 (8H, m, ArOCH CH ); (CDCl
) ꢂ80.77
), ꢂ110.48 (2F, t, JFF 12.2, ArCH 55 CHCF ), ꢂ121.57
), ꢂ122.84 (2F, m, CF ), ꢂ123.07 (2F, m, CF ), ꢂ126.12
); (CDCl ) 150.7 (C), 148.9 (C), 139.4 (t, JCF 9.8, CH),
26.7 (C), 122.1 (CH), 112.8 (CH), 112.0 (CH), 111.8 (CH), 69.8
2
),
2
2
2
d
F
3
crown-6 (0.5 g, 1.3 mmol) in acetone (40 mL). The mixture was
stirred for 2 h at room temperature and for a further 12 h at 60 8C.
After cooling to room temperature, the solvent was removed under
reduced pressure. The resulting solid was dissolved in trifluor-
oethanol (40 mL), and water (40 mL) was added to the solution.
The mixture was stirred for 1 h at ꢂ5 8C. The resulting precipitate
was filtered and the solid was recrystallised from ethanol to afford
a pale red solid (0.4 g, 47%). mp 192–194 8C; (Found: C, 66.36; H,
4
4
(3F, t, JFF 9.9, CF
(2F, m, CF
(2F, m, CF
3
2
2
2
2
2
2
d
C
3
1
+
2 2 2 2
(CH ), 69.7 (CH ), 68.9 (CH ), 68.6 (CH ); m/z (FAB) 1087 (MK ,
+
+
3
0%), 1071 (MNa , 22), 1048 (M , 45).
4
.1.3.2. Di(1H,2H-perfluoro-1-decenyl)-dibenzo-18-crown-6 (13).
8.16; N, 4.42. Calc. for C34
50 2 8 H
H N O : C, 66.43; H, 8.20; N, 4.56%); d
4
After removing the DMF, the resulting solid was partitioned
between dichloromethane-ethyl acetate (20–20 mL) and water
(DMSO-d ) 9.70 (2H, br s, NHCO), 7.36 (2H, d, JHH 2.4, ArH), 7.09
6
3
4
3
(2H, dd, JHH 9.0, JHH 2.4, ArH), 6.88 (2H, d, JHH 9.0, ArH), 4.06 (8H,
3
(40 mL) and the normal work up procedure was followed. The
m, ArOCH
NHCOCH ), 1.56 (4H, quintet,
3 ꢁ CH ), 0.86 (6H, t, JHH 6.7, CH
(C), 143.7 (C), 133.0 (C), 112.6 (CH), 110.9 (CH), 104.8 (CH), 68.9
(CH ), 68.8 (CH ), 67.9 (CH ), 67.6 (CH ), 36.3 (CH ), 31.0 (CH ),
28.3 (CH ), 25.1 (CH ), 22.0 (CH ), 13.9 (CH ); m/z (FAB) 653 (MK ,
requires 614.35672, 100), 503 (12).
2
), 3.87 (8H, m, ArOCH
2
CH
HH 6.4, COCH
); (DMSO-d
2
), 2.26 (4H, t,
CH ), 1.27 (12H, s,
) 170.7 (CO), 147.6
JHH 7.3,
3
resulting yellow solid was recrystallised from ethanol to give the
desired product as a white solid (0.5 g, 40%). mp 130–132 8C;
2
J
2
2
3
2
3
d
C
6
(Found: C, 38.61; H, 2.01. Calc. for C40
H
26
F
34
O
6
: C, 38.48; H, 2.10%);
3
4
d
H
(CDCl
3
) 7.02 (2H, dt, JHH 16.2, JHF 2.1, ArCH 55 CHCF ), 6.97 (2H,
2
2
2
2
2
2
2
+
3
4
4
dd, JHH 8.2, JHH 2.0, ArH), 6.89 (2H, d, JHH 2.0, ArH), 6.74 (2H, d,
2
2
2
3
3
3
3
J
HH 8.2, ArH), 5.95 (2H, dt, JHH 16.2, JHF 12.0, ArCH 55 CHCF
8H, m, ArOCH ), 3.97 (8H, m, ArOCH CH ); (CDCl
) ꢂ80.71 (3F, t,
), ꢂ110.43 (2F, t, JFF 12.6, ArCH 55 CHCF ), ꢂ121.33 (2F,
), ꢂ121.84 (4F, m, 2 ꢁ CF ), ꢂ122.65 (2F, m, CF ), ꢂ123.01
2F, m, CF ); (CDCl ) 150.7 (C), 148.9 (C),
), ꢂ126.04 (2F, m, CF
39.4 (t, JCF 9.5, CH), 126.8 (C), 122.1 (CH), 112.9 (CH), 111.9 (CH),
11.8 (CH), 69.9 (CH ), 69.8 (CH ), 68.9 (CH ), 68.6 (CH ); m/z (FAB)
2
), 4.12
50 2 8
8%), 614.35679 (C34H N O
(
2
2
2
d
F
3
4
4
0
J
FF 10.0, CF
3
2
4.1.6. Cis-4,4 -di(perfluoroheptylamido)-dibenzo-18-crown-6 (17)
m, CF
2
2
2
A mixture of perfluoroheptanoyl chloride (4.8 g, 12.6 mmol),
0
(
2
2
d
C
3
cis-4,4 -diamino-dibenzo-18-crown-6 (2.1 g, 5.3 mmol) and po-
2
1
1
1
tassium carbonate (2.0 g, 14.5 mmol) in acetone (40 mL) was
stirred at room temperature for 2 h. The reaction mixture was then
heated at 60 8C for 12 h. After cooling to room temperature, the
solvent was eliminated under reduced pressure. The resulting solid
was stirred in trifluoroethanol–water (75:75 mL) at room temper-
ature for 1 h. The precipitate was filtered and recrystallised from
trifluoroethanol to afford a pale brown solid (0.5 g, 23%). mp 220–
2
2
2
2
+
+
287 (MK , 70%), 1271 (MNa , 100).
4.1.4. General procedure for synthesis of di(1H,1H,2H,2H-
perfluoroalkyl)-dibenzo-18-crown-6-ethers
The appropriate di(1H,2H-perfluoro-1-alkenyl)-dibenzo-18-
crown-6 (0.48 mmol), 5% rhodium on charcoal (20 mg) and
dichloromethane (25 mL) were stirred in a hydrogenation appara-
tus at 50 bar hydrogen pressure at room temperature for 48 h. The
organic phase was filtered through celite and the solvent was
removed under reduced pressure.
222 8C; (Found: C, 37.74; H, 2.18; N, 2.69. Calc. for C34
24 26 2 8
H F N O :
C, 37.72; H, 2.23; N, 2.59%); (DMSO-d ) 11.02 (2H, br s, NHCO),
d
H
6
4
3
4
7.33 (2H, d, JHH 2.3, ArH), 7.30 (2H, dd, JHH 8.8, JHH 2.3, ArH), 7.01
3
(2H, d,
ArOCH
J
HH 8.8, ArH), 4.12 (8H, m, ArOCH
2
), 3.90 (8H, m,
FF 9.7, CF
), ꢂ117.87
), ꢂ121.50 (2F, m, CF ), ꢂ121.98 (2F, m,
), ꢂ125.67 (2F, m, CF ); (DMSO-d
4
2
4
CH
2
);
d
F
(DMSO-d
6
) ꢂ80.17 (3F, t,
J
3
(
2F, t,
J
FF 14.2, NHCOCF
2
2
4
.1.4.1. Di(1H,1H,2H,2H-perfluorooctyl)-dibenzo-18-crown-6 (14).
CF
2
), ꢂ122.49 (2F, m, CF
2
2
d
C
6
)
2
Recrystallisation from ethanol gave the desired product as a white
solid (0.4 g, 79%). mp 118–120 8C; (Found: C, 41.13; H, 2.78. Calc.
155.2 (t, JCF 22.7, CO), 148.5 (C), 146.7 (C), 130.1 (C), 114.4 (CH),
113.7 (CH), 108.0 (CH), 69.5 (CH ), 69.4 (CH ), 68.8 (CH ), 68.7
2
2
2
3
+
+
+
for C36
ArH), 6.67 (4H, m, ArH), 4.09 (8H, m, ArOCH
ArOCH CH ), 2.76 (4H, m, ArCH ), 2.26 (4H, m, CH
ꢂ80.74 (3F, t,
ꢂ121.85 (2F, m, CF
ꢂ126.08 (2F, m, CF
H
30
F
26
O
6
: C, 41.08; H, 2.87%);
d
H
(CDCl
3
) 6.74 (2H, d, JHH 8.2,
2
(CH ); m/z (FAB) 1121 (MK , 88%), 1105 (MNa , 90), 1083 (MH ,
2
), 3.95 (8H, m,
CF ); (CDCl
FF 14.6, CH
), ꢂ123.47 (2F, m, CF
8%).
2
2
2
2
2
d
F
3
)
4
4
0
J
FF 9.5, CF
3
), ꢂ114.60 (2F, t,
J
2
CF
2
2
),
),
4.1.7. Cis-4,4 -di(heptylamino)-dibenzo-18-crown-6 (18)
0
2
), ꢂ122.80 (2F, m, CF
2
Cis-4,4 -Di(heptylamido)-dibenzo-18-crown-6 (0.5 g, 0.8 mmol)
2
);
d
C
(CDCl
3
) 148.9 (C), 147.5 (C), 132.1 (C),
and lithium aluminiumhydride(0.4 g, 10.4 mmol) were dissolved in
dry tetrahydrofuran (20 mL). The suspension was heated for 4 h at
70 8C underan inert atmosphere. Aftercooling toroom temperature,
water was added carefully until no reaction occurred. The mixture
was filtered and the filtrate was washed with hot diethyl ether. The
aqueous phase was extracted with diethyl ether (2 ꢁ 20 mL). The
combined organic phases were washed with water (2 ꢁ 20 mL), and
dried over magnesium sulfate. The solid was recrystallised from
diethyl ether to afford a pale brown solid (0.25 g, 50%). mp 122–
2
1
20.7 (CH), 113.7 (2 ꢁ CH), 69.9 (CH
CH ), 26.0 (CH ); m/z (FAB) 1091 (MK , 35%), 1075 (MNa , 30),
052 (M , 22).
2 2
), 68.9 (CH ), 33.2 (t, JCF 22.6,
+
+
2
2
+
1
4
.1.4.2. Di(1H,1H,2H,2H-perfluorodecyl)-dibenzo-18-crown-6 (15).
The same protocol was followed using di(1H,2H-perfluoro-1-
decenyl)-dibenzo-18-crown-6 (1.0 g, 0.8 mmol), 5% rhodium on
charcoal (20 mg) and dichloromethane (25 mL). Recrystallisation
from ethanol gave the desired product as a white solid (0.8 g, 80%).
124 8C; (Found: C, 69.51; H, 9.19; N, 4.68. Calc. for C34
54 2 6
H N O : C,
3
mp 136–138 8C; (Found: C, 38.51; H, 2.36. Calc. for C40
H
30
F
34
O
6
: C,
) 6.75 (2H, d, JHH 7.9, ArH), 6.67 (4H, m,
), 3.96 (8H, m, ArOCH CH ), 2.76 (4H, m,
CF ); (CDCl
) ꢂ80.71 (3F, t, JFF 9.5, CF
FF 15.2, CH CF
), ꢂ121.77 (6F, m, 3 ꢁ CF
), ꢂ123.42 (2F, m, CF ), ꢂ126.04 (2F, m, CF );
69.59; H, 9.28; N, 4.77%); d (CDCl ) 6.69 (2H, d, JHH 8.6, ArH), 6.53
H 3
3
4
3
4
3
8.36; H, 2.41%);
ArH), 4.09 (8H, m, ArOCH
ArCH ), 2.25 (4H, m, CH
d
H
(CDCl
3
(2H,d, JHH 2.6, ArH),6.07(2H,dd, JHH 8.6, JHH 2.6,ArH),4.04(8H,m,
ArOCH ), 3.91 (8H, m, ArOCH CH ), 3.28 (2H, br s, NH), 2.96 (4H, t,
HH 7.1, NHCH ), 1.52 (4H, quintet, JHH 7.2, NHCH
m, 4 ꢁ CH ), 0.81 (6H, t, JHH 6.7, CH
140.9 (C), 117.2 (CH), 104.7 (CH), 100.6 (CH), 70.6 (CH
2
2
2
2
2
2
4
3
3
2
2
2
d
F
3
3
2
),
),
d
J
2
2
CH
) 150.4 (C), 144.1 (C),
), 70.3 (CH ),
2
), 1.23 (16H,
4
3
ꢂ114.55 (2F, t,
J
2
2
2
3 C 3
); d (CDCl
ꢂ122.65 (2F, m, CF
2
2
2
C
2
2