1
6H), 2.91 (d, J=21.6 Hz, 2H), 1.62-1.53 (m, 2H), 1.31-1.19 (m,
24H), 0.82 (t, J=6.6 Hz, 3H); 13C NMR (100 MHz, CDCl3):
δ(ppm) 13.93, 16.16, 22.51, 25.63, 28.37, 29.07, 29.19, 29.35,
29.41, 29.47, 31.75, 33.51, 34.84, 62.43, 65.51, 165.68; IR (cm-
1): 2925.5, 2854.6, 1739.1, 1467.1; HRMS (EI) m/z (%): calcd
for C16H32O5P 335.1987, found 335.1985.
4.5.4. Product 1e: pale yellow oil; yield: 45%; E/Z = 79:21; H
ACCEPTED MANUSCRIPT
NMR( 300 MHz, CDCl3): δ (ppm) 6.97 (s, CH, 0.21H), 6.88 (s,
CH, 0.79H), 4.22 (t, J=6.9 Hz, OCH2C11H23, 2H), 1.71-1.62 (m,
CH2CH2C10H21, 2H), 1.30-1.25 (m, CH2CH2(CH2)9CH3, 18H),
0.86 (t, J=6.8 Hz, O(CH2)11CH3, 3H); 19F NMR (282
MHz,CDCl3): δ (ppm) -76.38 ~ -76.40 (m, 6F), -82.89 (d, J =
23.7 Hz, 3F), -108.07 (d, J = 32.2 Hz, 2F), -185.70 ~ -186.30 (m,
1F); 13C NMR (100 MHz, CDCl3): δ(ppm) 162.06, 136.43, 66.89,
31.86, 29.6-29.5 (2C), 29.47, 29.38, 29.28, 29.05, 28.12, 25.56,
22.60, 13.93; IR (cm-1): 2927.9, 2857.3, 1750.1, 1653.7; HRMS
(EI) m/z (%): calcd for C12H9O2F12 413.0411, found 413.0415.
4.4.5. Hexadecyl α-(diethoxyphosphinyl)acetate 3f: pale yellow
1
oil; yield: 92%; H NMR (300 MHz, CDCl3): δ (ppm) 4.18-4.06
(m, 6H), 2.92 (d, J=21.3 Hz, 2H), 1.65-1.54 (m, 2H), 1.32-1.21
(m, 32H), 0.83 (t, J=6.6 Hz, 3H); 13C NMR (100 MHz, CDCl3):
δ(ppm) 13.96, 16.19, 22.56, 25.66, 28.40, 29.10, 29.24, 29.39,
29.45, 29.5-29.6 (5C), 31.81, 33.54, 34.87, 62.46, 65.55, 165.74;
IR (cm-1): 2924.5, 2853.8, 1739.3, 1467.0; HRMS (EI) m/z (%):
calcd for C20H40O5P 391.2613, found 391.2617.
1
4.5.5. Product 1f: pale yellow oil; yield: 52%; E/Z = 79:21; H
NMR (300 MHz, CDCl3): δ (ppm) 6.98 (s, CH, 0.21H), 6.88 (s,
CH, 0.79H), 4.23 (t, J=6.8 Hz, OCH2C15H31, 2H), 1.72-1.62 (m,
CH2CH2C14H29, 2H), 1.29-1.25 (m, CH2CH2(CH2)13CH3, 26H),
0.87 (t, J=6.6Hz, O(CH2)11CH3, 3H); 19F NMR (282 MHz,
CDCl3): δ (ppm) -76.34~76.36 (m, 6F), -82.85 (d, J = 23.8 Hz,
4.5. Synthesis of product 1.
Compounds 1b, 1c, 1d,1e and 1f were synthesized as follows:
Compound 3 (10 mmol) was added dropwise to a slurry of
sodium hydride (0.26 g, 11 mmol) in 20 mL of dry THF at 0 °C
under argon atmosphere. The solution was stirred for 1 h at room
temperature until hydrogen gas evolution ceased. C6-
fluoroketone (3.48 g, 11 mmol) was added dropwise using a dry
ice-acetone bath to keep the reaction temperature at about -5 °C.
Then the mixture was stirred for 4 h at room temperature (20 °C),
30 mL of water was added to the mixture. The aqueous layer was
extracted with diethyl ether (3 × 30 mL). The combined organic
layers were washed by saturated sodium bisulfite solution and
dried with anhydrous Na2SO4, filtered and concentrated in vacuo,
the residue was purified upon column chromatography (EtOAc/
petroleum ether = 1/30) to give the desired product.
3F), -108.04 (d, J = 32.2 Hz, 2F), -185.80 ~ -186.40 (m, 1F); 13
C
NMR (100 MHz, CDCl3): δ(ppm) 162.07, 136.60, 66.90, 31.89,
29.7-29.5 (6C), 29.49, 29.40, 29.33, 29.07, 28.14, 25.57, 22.63,
13.97; IR (cm-1): 2926.0, 2855.4, 1750.3, 1653.9; HRMS (EI)
m/z (%): calcd for C12H9O2F12 413.0411, found 413.0408.
Acknowledgments
This research was financially supported by the National
Natural Science Foundation of China (NSFC2167020782).
Supplementary Material
Supplementary data related to this article can be found at
1
4.5.1. Product 1b: colorless oil; Yield: 40%; E/Z = 65:35; H
NMR(300 MHz, CDCl3): δ (ppm) 6.98 (s, CH, 0.35H), 6.88 (s,
CH, 0.65H), 4.24 (t, J=6.8 Hz, OCH2C3H7, 2H), 1.71-1.61 (m,
CH2CH2C2H5, 2H), 1.44-1.32 (m, CH2CH2CH2CH3, 2H), 0.93 (t,
J=7.4 Hz, O(CH2)3CH3, 3H); 19F NMR (282 MHz, CDCl3): δ
(ppm) -76.46~-76.48 (m, 6F), -82.99 (d, J = 23.7 Hz,3F), -108.16
(d, J = 32.1Hz, 2F), -185.90 ~ -186.40 (m, 1F); 13C NMR (100
MHz, CDCl3): δ(ppm) 161.96, 136.51, 66.47, 30.09, 18.75,
13.29; IR (cm-1): 2968.8, 2881.7, 1749.5, 1652.7; HRMS (EI)
m/z (%): calcd for C10H5O2F12 385.0098, found 385.0094.
References and notes
[1] A. X. Song, S. L. Dong, J. C. Hao, J. Fluorine Chem. 126 (2005) 1266.
[2] J. G. Riess, Colloid and Surface, A. 84 (1999) 33.
[3] T. Gramstad, R. N. Haszeldine, J. Chem. Soc. (1957) 4069.
[4] A. Zaggia, B. Ameduri, Curr. Opin. Colloid Interface Sci. 17(2012) 188.
[5] M. P. Krafft, J. G. Riess, J. Polym. Sci., Part A: Polym. Chem. 45(2007)
1185.
[6] R. Kaplánek, O. Paleta, I. Ferjentsiková, M. Kodícek, J. Fluorine Chem.
130 (2009) 308.
1
4.5.2. Product 1c: colorless oil; yield: 41%; E/Z = 64:36; H
[7] L. Caillier, E. Taffin de Givenchy, R. Levy, Y. Vandenberghe, S.
Geribaldi, F. Guittard, J. Colloid Interface Sci. 332 (2009) 201.
[8] J. Kovarova, Z. Svobodova, Neuroendocrinol. Lett. 29 (2008) 599.
[9] L. Javisn, W A. Zisman, J. Phys. Chem. 63 (1959) 727.
[10] N. Ishikawa, M .Sasabe, J. Fluorine Chem. 25 (1984) 241.
[11] E. Kissa, Fluorinated surfactants: synthesis, properties, applications.New
York, USA, Marcel Dekker Inc., 1994.
[12] H. Horiuchi, T. Kawase, et al. J. Appl. Polym. Sci., 96 (2005) 1467.
[13] H. Sawada, M. P. Turberg, J. E. Brady, J. Am. Chem. Soc. 110 (1988)
7797.
[14] B. P. Binks, P. D. I. Fletcher, W. F. C. Sager, et al. J. Mol. Liq, 72 (1997)
177.
[15] W. Huang, C. Jin, D. K. Derzon, et al. J. Colloid Interface Sci. 272 (2004)
457.
[16] Y. Ma, D. B. Collum, J. Am. Chem. Soc. 129 (2007) 14818.
[17] G. Kostov, B. Frédéric, A. Bruno, J. Fluorine Chem. 130 (2009) 1192.
[18] Ya. M. Vilenchik, G. I. Lekontseva, L. S. Semerikova, Zhurnal
Vsesoyuznogo Khimicheskogo Obshchestva im. D. I. Mendeleeva. 26
(1981) 210.
[19] F. Boschet, G. Kostov, B. Ameduri, A. Jackson, B. Boutevin, Polym.
Chem. 3 (2012) 217.
[20] J. Lapčík, O. Gimello, V. Ladmiral, C.M Friesen, B. Ameduri, Polym.
Chem. 6 (2015) 79.
[21] S. Banerjee, J. Schmidt, Y. Talmon, H. Horid, T. Asai, B. Ameduri,
Chem. Commun. 54 (2018) 11399.
[22] N. Gathergood, M. Teresa Garcia, P. J. Scammells, Green. Chem. 6
(2004) 166.
NMR(300 MHz, CDCl3 ): δ (ppm) 7.00 (s, CH, 0.36H), 6.91 (s,
CH, 0.64H ), 4.25 (t, J=6.8 Hz, OCH2C5H11, 2H), 1.74-1.65 (m,
CH2CH2C4H9, 2H), 1.42-1.27 (m, CH2CH2(CH2)3CH3, 6H), 0.90
(t, J=6.6 Hz, O(CH2)5CH3, 3H); 19F NMR (282 MHz, CDCl3): δ
(ppm) -76.39~76.41 (m, 6F), -82.91 (d, J = 23.7 Hz, 3F), -108.10
(d, J = 32.2Hz, 2F), -185.80 ~ -186.40 (m, 1F); 13C NMR (100
MHz, CDCl3): δ(ppm) 161.97, 136.43, 66.78, 31.39, 28.59,
25.20, 22.35, 13.68; IR (cm-1): 2963.4, 2937.3, 2864.7, 1749.7,
1654.1; HRMS (EI) m/z (%): calcd for C11H7O2F12 399.0254,
found 399.0252.
4.5.3. Product 1d: pale yellow oil; yield: 37%; E/Z = 78.5:21.5;
1H NMR( 300 MHz, CDCl3): δ (ppm) 6.97 (s, CH, 0.215H), 6.88
(s, CH, 0.785H), 4.22 (t, J=6.9 Hz, OCH2C7H15, 2H), 1.71-1.62
(m, CH2CH2C6H13, 2H), 1.30-1.26 (m, CH2CH2(CH2)5CH3, 10H),
0.86 (t, J=6.6Hz, O(CH2)7CH3, 3H); 19F NMR (282 MHz,
CDCl3): δ (ppm) -76.41 ~ -76.43 (m, 6F), -82.92 (d, J = 23.7 Hz,
3F), -108.08 (d, J = 32.2 Hz, 2F), -185.70 ~ -186.30 (m, 1F); 13
C
NMR (100 MHz, CDCl3): δ(ppm) 162.01, 136.43, 66.79, 31.65,
29.1-29.9 (2C), 28.10, 25.53, 22.51, 13.83; IR (cm-1): 2960.9,
2931.9, 2860.6, 1749.9, 1653.5; HRMS (EI) m/z (%): calcd for
C12H9O2F12 413.0411, found 413.0410.