M. Sanchez-Dominguez et al. / Tetrahedron 64 (2008) 522e528
527
using silica gel and eluted, first with CHCl and then with ethyl
3
0.43; F5H10EO6 0.25 g, R 0.31; and F5H10EO7 0.21 g,
f
acetate to yield 0.204 g of the Z isomer of 20 as a colorless trans-
parent oil and 0.127 g of unseparated Z and E isomers (total yield
R 0.19. It was not possible to separate the isomers, but the
f
1
Z/E ratio was determined. H NMR (CDCl ) d /ppm:
3
H
1
0
.331 g, 27%). The Z/E molar ratiowas 87/13. H NMR (CDCl ):
F5H10EO3, d values were identical for Z and E isomers to
those of compound 6 obtained by using triethylene glycol
monomethyl ether. Z/E molar ratio¼85/15. F5H10EO4: Z
3
3
d /ppm, Z isomer: 0.89 (3H, t, CH CH , J
¼6.8 Hz), 1.29
2
H
2
3
HeH
5
(
10H, br, CH (CH ) CH ), 1.71 (2H, q, CH CH CH O, J
.9 Hz), 3.40(3H, s, CH CH OCH ), 3.57(2H, t, CH CH OCH ,
¼
3
2 5
2
2
2
HeH
3
6
isomer: 0.88 (3H, t, CH CH , J
¼6.8 Hz), 1.26 (14H, br,
2 2 2
2
2
3
2
2
3
2
3
HeH
3
3
5
JHeH¼4.7 Hz), 3.67 (2H, t, CH CH OCH , J
¼4.5 Hz),
CH (CH ) CH ), 1.70 (2H, q, CH CH CH O,
J
¼
2
2
3
HeH
3
2 7
2
HeH
3
3
.75 (2H, t, COOCH CH O,
J
¼4.8 Hz), 4.27 (2H, t,
6.9 Hz), 3.38 (3H, s, CH CH OCH ), 3.55 (2H, t,
2
2
HeH
2
2
3
3
3
COOCH CH O, J
¼6.5 Hz), 4.33 (2H, t, CH CH CH O,
CH CH OCH ,
JHeH¼4.6 Hz),
3.64
(10H,
m,
2
2
HeH
2
2
2
2
2
3
3
JHeH¼4.8 Hz), 5.80 (1H, s, C]CH ); E isomer: 3.81 (2H, t,
(CH CH O) CH CH OCH ), 3.73 (2H, t, COOCH CH O,
2 2 2 2 2 3 2 2
3
3
3
COOCH CH O, J
¼6.3 Hz), 5.51(1H, s, C]CH ). Element.
JHeH¼4.8 Hz), 4.25 (2H, t, COOCH CH O, JHeH¼
2 2 2
2
2
HeH
2
2
3
Anal. Calcd: Z isomer: C 41.20%, H 4.36%, F 42.50%; found: C
6.6 Hz), 4.30 (2H, t, CH CH CH O, JHeH¼4.8 Hz), 5.78
2 2
4
1.33%, H 4.33%, F 42.03%.
(1H, s, C]CH ); E isomer: 3.80 (2H, t, COOCH CH O,
3
JHeH¼6.4 Hz), 5.50 (1H, s, C]CH ); Z/E molar ratio¼86/
3
3
.16. Monomethyl ether diethylene glycol 3-F-octyl-3-
14. F5H10EO5: Z isomer: 0.88 (3H, t, CH CH , J
HeH
¼
2
3
decyloxypropenoate F7H10EO2 21
6.8 Hz), 1.26 (14H, br, CH (CH ) CH ), 1.70 (2H, q,
3 2 7 2
5
CH CH CH O, J
¼6.9 Hz), 3.38 (3H, s, CH CH OCH ),
2
2
2
HeH
2
2
3
3
3
-F-Heptyl-3-decyloxypropenoyl chloride 19 (1.16 g,
.9 mmol), anhydrous CH Cl (20 mL), and diethylene glycol
3.54 (2H, t, CH CH OCH , J
HeH
¼4.7 Hz), 3.65 (14H, m,
2 2
2
2
3
1
(CH CH O) CH CH OCH ), 3.73 (2H, t, COOCH CH O,
2 2 3 2 2 3
2
2
3
3
monomethyl ether (98%) (0.250 g, 0.2 mmol) were stirred un-
der N at room temperature for 48 h. CH Cl was removed
JHeH¼4.8 Hz), 4.25 (2H, t, COOCH CH O, JHeH¼
2
2
3
6.5 Hz), 4.30 (2H, t, CH CH CH O, JHeH¼4.7 Hz), 5.78
2
2
2
2 2 2
on a rotary evaporator. The crude viscous pale brown oil was
purified by flash column chromatography using silica gel and
elution first with chloroform and then with ethyl acetate to yield
the Z isomer of 21 as a pale yellow oil (0.38 g, 29%) and 0.04 g
(1H, s, C]CH ); E isomer: 3.80 (2H, t, COOCH CH O,
2 2
3
JHeH¼6.4 Hz), 5.50 (1H, s, C]CH ); Z/E molar ratio¼89/
3
11. F5H10EO6: Z isomer: 0.88 (3H, t, CH CH , J
HeH
¼
2
3
6.8 Hz), 1.26 (14H, br, CH (CH ) CH ), 1.70 (2H, q,
3
2 7
2
1
5
of unseparated Z and E isomers (total yield 0.42 g, 32%). H
NMR (CDCl ): d /ppm, Z isomer: 0.88 (3H, t, CH CH ,
CH CH CH O, J
¼6.9 Hz), 3.38 (3H, s, CH CH OCH ),
2 3
2
2
2
HeH
2
2
3
3
3.54 (2H, t, CH CH OCH , J
HeH
¼4.6 Hz), 3.65 (18H, m,
2 2
3
H
2
3
2
3
JHeH¼6.8 Hz), 1.27 (14H, br, CH (CH ) CH ), 1.71 (2H, q,
(CH CH O) CH CH OCH ), 3.73 (2H, t, COOCH CH O,
2 2 4 2 2 3
3
2 7
2
5
3
3
CH CH CH O, J
¼6.9 Hz), 3.39 (3H, s, CH CH OCH ),
JHeH¼4.8 Hz), 4.25 (2H, t, COOCH CH O, JHeH¼
2 2 2
2
2
2
HeH
2
2
3
2
2
3
3
3
.56 (2H, t, CH CH OCH ,
J
¼4.7 Hz), 3.65 (2H, t,
6.5 Hz), 4.30 (2H, t, CH CH CH O, JHeH¼4.7 Hz), 5.78
2 2
2
2
3
HeH
CH CH OCH , J
¼4.6 Hz), 3.75 (2H, t, COOCH CH O,
(1H, s, C]CH ); E isomer: 3.80 (2H, t, COOCH CH O,
2
2
3
HeH
2
2
3
3
3
JHeH¼4.8 Hz), 4.27 (2H, t, COOCH CH O, J
¼6.5 Hz),
JHeH¼6.3 Hz), 5.50 (1H, s, C]CH ); Z/E molar ratio¼92/
2
2
HeH
3
3
4
.32 (2H, t, CH CH CH O, J
¼4.8 Hz), 5.79 (1H, s, C]
8. F5H10EO7: Z isomer: 0.87 (3H, t, CH CH ,
J
HeH
¼
2
2
2
HeH
2
3
3
CH ); E isomer: 3.80 (2H, t, COOCH CH O, J
¼6.5 Hz),
6.8 Hz), 1.26 (14H, br, CH (CH ) CH ), 1.69 (2H, q,
3 2 7 2
2
2
HeH
5
5
4
4
.51 (1H, s, C]CH ). Element. Anal. Calcd: Z isomer: C
2.98%, H 4.76%, F 40.80%; found: C 43.37%, H 4.90%, F
0.41%.
CH CH CH O, J
¼6.9 Hz), 3.37 (3H, s, CH CH OCH ),
2 3
2
2
2
HeH
2
2
3
3
3.54 (2H, t, CH CH OCH , J
HeH
¼4.6 Hz), 3.65 (22H, m,
2 2
2
(CH CH O) CH CH OCH ), 3.73 (2H, t, COOCH CH O,
2
2
5
2
2
3
3
3
JHeH¼4.8 Hz), 4.25 (2H, t, COOCH CH O, JHeH
¼
2
2
3
3
.17. Library of five triaffine surfactants
6.5 Hz), 4.29 (2H, t, CH CH CH O, JHeH¼4.7 Hz), 5.78
2 2
2
2
2
(
F5H10EOy, y¼3e7) 6e10
(1H, s, C]CH ); E isomer: 3.80 (2H, t, COOCH CH O,
3
JHeH¼6.4 Hz), 5.50 (1H, s, C]CH ); Z/E molar ratio¼94/
3
.7 mmol), anhydrous CH Cl (20 mL), and MPEG 350
-F-Pentyl-3-decyloxypropenoyl chloride
4
(1.4 g,
6. Element. Anal. F5H10EO4 Calcd: C 47.23%, H 6.02%;
found: C 47.42%, H 6.04%; F5H10EO5 Calcd: C 47.67%,
H 6.21%; found: C 48.11%, H 6.42%; F5H10EO6 Calcd: C
48.06%, H 6.38%, F 26.97%; found: C 48.78%, H 6.47%, F
26.68%; F5H10EO7 Calcd: C 48.41%, H 6.52%; found: C
49.10%, H 6.83%.
2
2
2
(
under N for 30 h. CH Cl was removed on a rotary evapora-
0.95 g, 2.7 mmol) were stirred together at room temperature
2
2
2
tor. The crude brown oil was purified first by flash column
chromatography using silica gel and elution with acetone to
eliminate the remaining MPEG 350. Fractions with R <0.40
f
were discarded. Fractions with R ꢃ0.40 were purified by flash
f
column chromatography using silica gel and elution with ethyl
acetate/CHCl /EtOH (20/1/1), which allowed separation of
References and notes
3
1
2
. Riess, J. G. Tetrahedron 2002, 58, 4113e4131.
five compounds with EO units varying from 3 to 7. The total
yield was 36%. All products were obtained as colorless trans-
parent oils. The amount of each one and their R values in ethyl
. Riess, J. G. Handbook of Fluorous Chemistry; Gladysz, J. A., Horv a´ th, I.,
Curran, D. P., Eds.; Wiley-VCH: Weinheim, 2004; pp 521e573.
. Krafft, M. P. J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 4251e4258.
f
3
acetate/CHCl /EtOH (20/1/1) were: F5H10EO3 0.06 g, R
3
f
4. Kissa, E. Fluorinated Surfactants and Repellents, 2nd ed.; Marcel Dekker:
New York, NY, 2001; Vol. 97.
0
.62; F5H10EO4 0.11 g, R 0.55; F5H10EO5 0.18 g, R
f
f