180
H. Trabelsi et al. / Journal of Fluorine Chemistry 107 (2001) 177±181
C13H11F13O4 (478.2): calcd. C, 32.65; H, 2.31; F, 51.64;
found C, 32.82; H, 2.35; F, 51.78%.
concentrated under reduced pressure and the resulting oil
was puri®ed by distillation to yield products 4a±f according
to Table 1.
4e (90%), Colorless oil, bp 908C/0.1 Torr Ð IR (n cm 1):
1753 (C=O), 1740 (C=O), 1300±1100 (CF) Ð H NMR
1
(d ppm; J Hz): 1.3 (t, 6H, 2 Â OCH2CH3; J 7), 2.21 (m,
4H, CH2CH2C8F17), 3.45 (t, 1H, CH; J 7), 4.3 (q, 4H,
2 Â OCH2CH3; J 7) Ð 19F NMR (d ppm): 81.2 (3F,
CF3), 115.3 (2F, CF2), 122.4 (4F, 2 Â CF2), 123.2 (2F,
CF2) 123.9 (2F, CF2), 126.5 (2F, CF2) Ð MS (70 eV); m/
4.5. Dimethyl(2-
perfluorobutylethoxycarbonyl)methylmalonate (7)
To a suspension of 1.5 g (50 Â 10 3 mol) of NaH (80% in
oil) in dry 100 ml of THF, 13.2 g (0.1 mol) of dimethyl
malonate was added dropwise over 30 min, and after cessa-
tion of H2 evolution the mixture was further stirred at room
temperature for 20 min. To this solution were added drop-
wise 19.2 g (50 Â 10 3 mol) of 2-per¯uorobutylethyl-a-
bromoacetate, and the mixture was stirred at room tempera-
ture for 24 h. The solvent was evaporated; then the residue
was dissolved in 100 ml of Et2O. The solution was washed
with 40 ml of H2O, and dried (Na2SO4). Removal of solvent
gives the crude product which is puri®ed by distillation
under vacuum; yield 18.5 g of 7 (85%), colorless oil, bp
858C/0.01 Torr Ð IR (n cm 1): 1743 (C=O), 1300±1100
(CF) Ð 1H NMR (d ppm; J Hz): 2.5 (m, 2H, CH2C4F9), 2.9
(d, 2H, CH2; J 7), 3.77 (s, 6H, 2 Â OCH3), 3.9 (t, 1H, CH;
J 7), 4.4 (t, 2H, OCH2; J 6:5) Ð 19F NMR (d ppm):
81.5 (3F, CF3), 114.4 (2F, CF2), 121.5 (2F, CF2), 126.5 (2F,
z (%): 606 (2) [M ], 55 (100) peak of base Ð Anal.
C17H15F17O4 (606.3): calcd. C, 33.67; H, 2.49; F, 53.26;
found C, 33.84; H, 2.45; F, 53.38%.
4f (85%), Colorless oil, bp 728C/0.1 Torr Ð IR (n cm 1):
1753 (C=O), 1740 (C=O), 1300±1100 (CF) Ð H NMR
1
(d ppm; J Hz): 2.19 (m, 4H, CH2CH2C8F17), 3.45 (t, 1H,
CH; J 7), 3.77 (s, 6H, 2 Â OCH3) Ð 19F NMR (d ppm):
81.2 (3F, CF3), 115.3 (2F, CF2), 122.4 (4F, 2 Â CF2), 122.7
(2F, CF2) 123.8 (2F, CF2), 126.6 (2F, CF2) Ð MS (70 eV);
m/z (%): 578 (2) [M ], 55 (100) peak of base Ð Anal.
C15H11F17O4 (578.2): calcd. C, 31.15; H, 1.91; F, 55.85;
found C, 31.31; H, 1.98; F, 55.78%.
4.3. Alkylation of diethyl malonate with 2-perfluorohexyl-
1-iodo ethane in presence of EtONa
CF2) Ð MS (70 eV); m/z (%): 436 (2) [M ], 55 (100) peak
of base Ð Anal. C13H13F9O6 (436.2): calcd. C, 35.79; H,
3.00; F, 39.20; found C, 35.65; H, 2.94; F, 39.45%.
To 1.15 g (50 Â 10 3 mol) of clean sodium cut into small
pieces, 10 ml of dry ethanol was added slowly. When all the
sodium was dissolved, 8 g (50 Â 10 3 mol) of diethyl mal-
onate was added dropwise over 10 min, and the mixture was
stirred at 408C for 15 min. Then, a solution of 23.7 g
(50 Â 10 3 mol) of 2-per¯uorohexyl-1-iodo ethane in
20 ml of dry ethanol was added slowly and heated for
another 28 h at 758C. After cooling, the mixture was
extracted with Et2O and concentrated. The residue was
analyzed by GC to show 3b (53%), 4c (39%) and 5c
(8%), and distilled to give pure 3b identi®ed by comparison
(GC) with an authentic sample, yield 7.9 g (46%) and 8.8 g
of pure 4c (35%) and 2.1 g of pure 5c (5%), colorless oil, bp
1268C/0.2 Torr Ð IR (n cm 1): 1753 (C=O), 1738 (C=O),
4.6. Bis(2-perfluorohexylethyl)disulfide (9)
Preparation of 9 was carried out as for 7 using (2-per-
¯uorohexylethylthio)methylbromide instead of (2-per¯uor-
obutylethyl) a-bromoacetate and 9 is obtained as an oil
crystallized at room temperature; mp 35±368C, litt [28] 36±
378C.
References
1
1300±1100 (CF) Ð H NMR (d ppm; J Hz): 1.3 (t, 6H,
[1] E.P. Mochalina, B.L. Dyatkin, I.V. Galakghov, I.L. Knunyants, Dokl.
Akad. Nauk SSSR 169 (1966) 1346 [66:45901].
[2] R.N. Fasick, US Patent 3 239 557 (1966), EI du Pont de Nemours &
Co.
2 Â OCH2CH3; J 7), 2.20 (m, 8H, CH2CH2C6F13), 4.3 (q,
4H, 2 Â OCH2CH3; J 7) Ð 19F NMR (d ppm): 81.1 (6F,
CF3), 115.1 (4F, CF2), 122.4 (4F, CF2), 123.3 (4F, CF2),
123.9 (4F, CF2), 126.5 (4F, CF2) Ð MS (70 eV); m/z (%):
[3] S. Rebsdat, E. Schuierer, K. Ulm, I. Wimmer, German Patent 2 028
459 (1970), Hoechst, AG.
852 (2) [M ], 55 (100) peak of base.
[4] M. Knell, P. Klemchuck, German Patent 2 062 622 (1972), Ciba-
Geigy Corp.
[5] T. Hayashi, M. Matsuo, French Patent 2 180 113 (1973), Asahi Glass
Co. Ltd.
4.4. Alkylation of dialkyl malonate with 2-perfluoroalkyl-
1-iodo ethane in presence of K2CO3
[6] L. Foulletier, A. Lantz, European Patent 24 224 (1981), PCUK.
[7] A. Lantz, P. Michaud, European Patent 275 771 (1988), Atochem.
[8] C.S. Rondestvedt Jr., G.L. Thayer Jr., J. Org. Chem. 42 (1977) 2680.
[9] F. SzoÈnyi, A. Cambon, J. Fluorine Chem. 42 (1989) 59.
To a mixture of 50 Â 10 3 mol of 2-per¯uoroalkyl-1-iodo
ethane and of 0.1 mol of dry potassium carbonate, a solution
of 0.1 mol of dialkyl malonate in dry 30 ml of THF
was added, and the mixture was stirred at 758C for 27 h.
The solvent was evaporated; then the residue was dissolved
in 100 ml of Et2O. The solution was washed with 2 Â 30 ml
of H2O, and dried (Na2SO4). The Et2O layer was then
È
[10] F. Szonyi, F. Guennouni, A. Cambon, J. Fluorine Chem. 55 (1991)
85.
È
[11] H. Trabelsi, F. Szonyi, N. Michelangeli, A. Cambon, J. Fluorine
Chem. 69 (1994) 115.
È
[12] A.M. Jouani, F. Szonyi, A. Cambon, J. Fluorine Chem. 56 (1992) 85.
[13] E. Bollens, F. SzoÈnyi, A. Cambon, J. Fluorine Chem. 53 (1991) 1.