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S. Malfait et al. / Journal of Fluorine Chemistry 132 (2011) 760–766
2.20–2.53 (4H, m, CH2Rf), 2.65 (2H, d, J = 1.9 Hz, CH), 3.11 (2H, t,
J = 1.9 Hz, CH), 4.32–4.40 (4H, m, CH2), 6.22 (2H, t, J = 1.9 Hz,
added acylchloride 25 [18] (1.93 g, 10.7 mmol) dropwise. The
mixture was stirred and heated 41 h and then poured into ice-cold
water and extracted with ethyl acetate. The pale yellow precipitate
was filtered and rinsed twice with acetone. After recrystallization
from acetone, compound 28 was isolated as a white solid (16.6 g,
CHCH); 19F NMR (235 MHz, CDCl3):
d
ꢁ81.4 (3F, CF3), ꢁ114.0 (2F,
CF2), ꢁ122.6 (6F, CF2), ꢁ123.5 (2F, CF2), ꢁ124.0 (2F, CF2), ꢁ126.0
(2F, CF2).
72%); mp 90–91 8C; IR (KBr)
1H NMR (250 MHz, CDCl3):
n
3123, 1755, 1666, 1404, 1203 cmꢁ1
d 2.40–2.75 (8H, m, CH2Rf), 2.85 (2H, t,
;
4.13.2. (ꢄ)-Di[(perfluorooctyl)ethyl] (exo,endo)-bicyclo[2.2.1]hept-5-
ene-2,3-dicarboxylate (rac-22)
J = 10.0 Hz, CH2CHCH2), 3.90 (1H, t, J = 10.0 Hz, CHCH2), 4.05–4.30
(8H, m, CH2), 4.41–4.50 (8H, m, NCH2COO), 5.05–5.23 (2H, m,
(13.0 g, 80% from 20); mp 82–83 8C; 1H NMR (250 MHz, CDCl3):
d
1.50 (1H, dd, J = 1.9 Hz, J = 8.8 Hz, CH2), 1.60 (1H, d, J = 8.8 Hz,
CH2all), 5.85 (1H, m, CHall); 19F NMR (235 MHz, CDCl3):
CF3), ꢁ114.1 (2F, CF2), ꢁ122.3 (6F, CF2), ꢁ123.2 (2F, CF2), ꢁ124.0
(2F, CF2), ꢁ126.6 (2F, CF2); Anal. calcd for C54H30F68N2O10: C,
30.02; H, 1.39; found: C, 29.93; H, 1.12.
d
ꢁ81.3 (3F,
CH2), 2.48–2.55 (4H, m, CH2Rf), 2.72 (1H, dd, J = 1.5 Hz, J = 4.6 Hz),
3.12 (1H, m, CH), 3.33 (1H, ma, CH), 3.35 (1H, t, J = 4.6 Hz), 4.35 (2H,
t, J = 6.1 Hz, CH2), 4.43 (2H, dt, J = 1.9 Hz, J = 5.5 Hz, CH2), 6.08 (1H,
dd, J = 2.7 Hz, J = 5.7 Hz, CHCH), 6.29 (1H, dd, J = 3.0 Hz, J = 5.7 Hz,
CHCH); 13C NMR (62.5 MHz, CDCl3):
48.5, 56.3, 57.5, 135.2, 138.3, 174.0; 19F NMR (235 MHz, CDCl3):
d 30.5 (CH2), 31.3, 45.0, 47.2,
Acknowledgments
d
ꢁ81.0 (3F, CF3), ꢁ114.2 (2F, CF2), ꢁ122.6 (6F, CF2), ꢁ123.8 (2F, CF2),
ꢁ124.4 (2F, CF2), ꢁ126.6 (2F, CF2); Anal. calcd for C29H16F34O4: C,
32.46; H, 1.49; found: C, 31.97; H, 1.38.
The authors acknowledge the contribution of Dr. Paul Branlard,
Dr. Caroll Vergelati, Dr. Alfred Greiner and Dr. Philippe Olier to
fruitful discussions during the development of this project. We are
grateful to Rhodia Silicones (now Bluestar Silicones) for financial
support of this work.
4.14. Di-[1,3-bis((perfluorooctyl)ethyloxy)propan-2-yl] 2-
allylmalonate (24)
A mixture of alcohol 3 (27 g, 28.3 mmol), allylmalonic acid
(1.63 g, 11.34 mmol) and a catalytic amount of concentrated
sulfuric acid was stirred for 18 h at 75 8C. The crude product, after
cooling, was directly purified by flash chromatography (petroleum
ether/EtOAc, 80/20) to afford 24 as a colorless oil (13.7 g, 58%); IR
References
[1] Recent reviews on various aspects of fluorous chemistry:
(a) K.L. O’Neal, H. Zhang, Y. Yang, L. Hong, D. Lu, S.G. Weber, J. Chromatogr. A 1217
(2010) 2287–2295;
(b) W. Zhang, Chem. Rev. 109 (2009) 749–795;
(c) W. Zhang, Green Chem. 11 (2009) 911–920;
See also:, J.A. Gladysz, D.P. Curran, I.T. Hiraki (Eds.), Handbook of Fluorous
Chemistry, Wiley-VCH, Weinheim, 2004.
(neat)
CDCl3):
n
2878, 1736, 1323, 1234, 1145 cmꢁ1
;
1H NMR (250 MHz,
3
d
2.20–2.51 (8H, tt, JH,F = 18.3 Hz, J = 6.3 Hz, CH2Rf), 2.65
(2H, t, J = 6.9 Hz, CH2CHCH2), 3.54 (1H, t, J = 7.3 Hz, CH(COO)2), 3.66
(8H, d, J = 7.3 Hz, CH2), 3.78–3.82 (8H, m, CH2), 5.03–5.21 (4H, t,
J = 21 Hz, CH2all), 5.65–5.85 (1H, m, CHall); 13C NMR (62.5 MHz,
[2] S. Breuning, J. Chardon, N. Ghennouni, G. Mignani, P. Olier, A. van der Spuy, C.
Vergelati, in: N. Auner, J. Weis (Eds.), Organosilicon Chemistry, from Molecules to
Materials, IV, Wiley-VCH, 2000, pp. 645–658.
[3] G. Guichard, G. Mignani, P. Olier, PCT Int. Appl. WO 2000005315 A1 20000203
CAN 132:124038 (2000).
CDCl3):
d 31.3, 32.6, 51.4, 63.2, 68.7, 68.8, 71.9, 117.5, 133.6, 168.1
(CO); 19F NMR (235 MHz, CDCl3):
d
ꢁ81.5 (3F, CF3), ꢁ114.1 (2F,
[4] C. Vergelati, C.G. Mignani, unpublished results
[5] (a) W. Huang, C. Jin, D.K. Derzon, T.A. Huber, J.A. Last, P.P. Provencio, A.S. Gopalan,
M. Dugger, D.Y. Sasaki, J. Colloid Interf. Sci. 272 (2004) 457–464;
(b) H. Tamiaki, T. Nishiyama, R. Shibata, Bioorg. Med. Chem. Lett. 17 (2007) 1920–
1923.
CF2), ꢁ122.6 (6F, CF2), ꢁ123.4 (2F, CF2), ꢁ124.3 (2F, CF2), ꢁ126.8
(2F, CF2); Anal. calcd for C52H34F68O4: C, 30.05; H, 1.64; found: C,
29.84; H, 1.37.
[6] The preparation of compounds similar to 3 was reported from epichlorhydrine via
a stepwise procedure and the intermediate glycidyl ether. See Ref. [5a].
[7] M. Tanabe, R.H. Peters, Org. Synth. Coll. 7 (1990) 386.
[8] E. Rogalska, R. Bilewicz, T. Brigaud, C. El Moujahid, G. Foulard, C. Portella, M.-J.
Ste´be´, Chem. Phys. Lipids 105 (2000) 71–91.
4.15. Di[2-(perfluorooctyl)ethyl] iminodiacetate (27)
2-(Perfluorooctyl)ethanol (65 g, 140 mmol) was melt with
iminodiacetic acid 26 (3.72 g, 28 mmol) in a round-bottomed
flask under argon. BF3ꢀEt2O (10.6 mL) was slowly added and the
mixture was stirred for 96 h. After addition of ethyl acetate, the
solution was washed with an aqueous solution of ammonium
chloride. Residual alcohol was eliminated by sublimation (110 8C,
0.5 mm Hg) and the crude mixture was purified by flash
chromatography over silica gel to furnish 27 as a white solid
[9] Z. Szla´vik, G. Ta´rka´nyi, G. Tarczay, A. Go¨mo¨ry, R.J. Ra´bai, J. Fluorine Chem. 98
(1999) 83–87.
[10] Y. Tsuzuki, M. Koyama, K. Tanabe, Bull. Chem. Soc. Jpn. 41 (1968) 1008–1013.
[11] Compound 12 is a white solid; mp 73–75 8C; 1H NMR (250 MHz, CDCl3): d 2.57–
2.86 (4H, m, CH2Rf), 4.52–4.63 (4H, m, CH2O), 4.85 (1H, d, J = 3.4 Hz), 4.97 (1H, d,
J = 3.4 Hz), 5.42 (1H, d, J = 10.3 Hz), 5.56 (1H, d, J = 17.2 Hz, CH2all), 5.59 (1H, d,
J = 6.5 Hz), 5.93 (1H, ddd, J = 6.5 Hz, J = 10.3 Hz, J = 17.2 Hz, CHall); 13C NMR
2
(62.5 MHz, CDCl3): d 30.9 (t, JC,F = 21.7 Hz, CH2Rf), 58.3, 77.5, 78.0, 107.0,
122.0, 135.0, 169.5, 169.7; 19F NMR (235 MHz, CDCl3): d ꢁ80.6 (3F, CF3),
ꢁ112.9 (2F, CF2), ꢁ121.2 (6F, CF2), ꢁ122.2 (2F, CF2), ꢁ123.1 (2F, CF2), ꢁ125.7
(2F, CF2).
(19.8 g, 69%); mp 68–69 8C; IR (KBr)
1H NMR (250 MHz, CD3COCD3):
2.51–2.85 (4H, m, CH2Rf), 3.58
(4H, s, NCH2), 4.13 (4H, t, J = 5.1 Hz, CH2); 19F NMR (235 MHz,
CDCl3):
ꢁ81.3 (3F, CF3), ꢁ114.2 (2F, CF2), ꢁ122.7 (6F, CF2), ꢁ123.1
(2F, CF2), ꢁ124.8 (2F, CF2), ꢁ126.3 (2F, CF2); Anal. calcd for
24H13F34NO4: C, 28.09; H, 1.26; found: C, 28.08; H, 1.24.
n ;
1743, 1203, 1140, 663 cmꢁ1
d
[12] N. Magashima, M. Ohno, Chem. Lett. (1987) 141–144.
[13] T. Nishimura, Y. Maeda, N. Kakiuchi, S. Uemura, J. Chem. Soc., Perkin Trans. 1
(2000) 4301–4305.
[14] K. Wewerka, A. Wewerka, F. Stelzer, B. Gallot, L. Andruzzi, G. Galli, Macromol.
Rapid Commun. 24 (2003) 906–910.
[15] Direct condensation of iminodiacetate 27 with commercially available dimethyl
allylmalonate using various Lewis acids or bases as catalyst failed.
[16] G.C.R. Ellis-Davies, J.H. Kaplan, J. Org. Chem. 53 (1988) 1966–1969.
[17] This paper being devoted to the synthesis of unsaturated fluorinated grafts,
hydrosilylation procedures and analytical methods are nor further detailed. These
procedures and methods are similar to the ones exemplified in the patent given in
Ref. [3].
d
C
4.16. 2-Allyl-N1,N1,N3,N3-tetra[2(-perfluorooctyl)ethyl]malonamide
(28)
To a cold mixture (0 8C) of ester 27 (22 g, 21.5 mmol) and
triethylamine (2.8 mL) in 1,1,2,2-tetrachloroethane (150 mL) was
[18] F. Sorm, J. Beranek, J. Smrt, J. Sicher, Coll. Czech. Chem. Commun. 20 (1955) 593–
596.