Fluorinated glycidyl ethers
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 11, November, 2008 2327
Table 3. 19F NMR data for the reaction products*
Compounds
RF
Isomers
δ (J/Hz)
36.40—36.45 (m, 2 Fc); 37.92—37.97 (m, 2 Fb);
a
3a—d
CF3dCF2cCF2bCF2
E
50.22—50.26 (m, 2 Fa); 81.01—81.06 (tt, 3 Fd, J = 9.7, J = 3.3)
36.13—36.18 (m, 2 Fc); 37.52—37.58 (m, 2 Fb); 54.08—54.12 (m, 2 Fa);
81.01—81.06 (tt, 3 Fd, J = 9.7, J = 3.3)
35.85—35.89 (m, 2 Fe); 38.71—38.75 (m, 2 Fd); 39.20—39.24
(m, 2 Fb); 40.43—40.46 (m, 2 Fc); 50.30—50.35 (m, 2 Fa);
81.13—81.17 (tt, 3 Ff, J = 10.7, J = 2.4)
Z
E
f
a
4a—d
CF3 CF2eCF2dCF2cCF2bCF2
Z
35.85—35.89 (m, 2 Fe); 38.71—38.75 (m, 2 Fd); 39.20—39.24
(m, 2 Fb); 40.43—40.46 (m, 2 Fc); 54.12—54.17 (m, 2 Fa);
81.13—81.17 (tt, 3 Ff, J = 10.7, J = 2.4)
CF3 CF2dCF2cCFbFa
37.95—37.99 (m, 2 Fd); 39.31—39.36 (m, 2 Fc); 49.62—49.65 (m, 1 Fa);
50.85—50.89 (m, 1 Fb); 82.60—82.65 (tt, 3 F, J = 9.7, J = 3.3)
37.70—37.73 (m, 2 Fg); 40.21—40.26 (m, 2 Ff); 41.02—41.07 (m, 2 Fc);
42.12—42.16 (m, 2 Fd); 49.85—49.89 (m, 1 Fa); 50.90—50.94 (m, 1 Fb);
82.73—82.76 (tt, 3 F, J = 10.2, J = 2.5)
f
5a,b
6a,b
f
CF3hCF2gCF2 CF2dCF2cCFbFa
* In the 19F NMR spectrum of compounds 3a, 4a, 5a, and 6a, the CF3 group resonates at 87.45—87.57 ppm (t, JF,H = 8.7 Hz).
(4,4,5,5,6,6,7,7,7ꢀNonafluoroꢀ2ꢀiodoheptyl)oxymethylꢀ
oxirane (1) and (4,4,5,5,6,6,7,7,8,8,9,9,9ꢀtridecafluoroꢀ
2ꢀiodononyl)oxymethyloxirane (2) were prepared by a known
procedure.8
analysis data for compounds 3c,d, 4c,d, 5a,b, and 6a,b
are summarized in Table 1 and 1H and 19F NMR data are in
Tables 2 and 3.
The IR spectra of compounds 3a—d and 4a—d exhibit
common characteristic absorption bands in the ranges, ν/cm–1
:
3ꢀAlkoxyꢀ1ꢀ[3ꢀ(perfluorobutyl)propꢀ2ꢀenyloxy]propanꢀ2ꢀols
(3a,c,d) and 3ꢀalkoxyꢀ1ꢀ[3ꢀ(perfluorohexyl)propꢀ2ꢀenyloxy]ꢀ
propanꢀ2ꢀols (4a,c,d) (general procedure). Sodium metal (0.81 g,
35 mmol) was added to the corresponding absolute alcohol
(0.35 mol), then epoxide 1 (or 2) (10 mmol) was added with
stirring at reflux over a period of 30 min, and the reaction mixture
was refluxed and stirred for additional 2 h. The mixture was
cooled, water (100 mL) was added, the mixture was acidified
with HCl and extracted with Et2O (2×50 mL), and the organic
layer was washed with an aqueous solution of sodium carbonate,
dried with MgSO4, and concentrated. The reaction products
were isolated by vacuum distillation (Table 1).
3ꢀPhenoxyꢀ1ꢀ[3ꢀ(perfluorobutyl)propꢀ2ꢀenyloxy]propanꢀ2ꢀol
(3b) and 3ꢀphenoxyꢀ1ꢀ[3ꢀ(perfluorohexyl)propꢀ2ꢀenyloxy]propanꢀ
2ꢀol (4b) (general procedure). Sodium metal (0.81 g, 35 mmol)
was added to phenol (400 mmol) in anhydrous diethylene glycol
dimethyl ether (80 ml), the mixture was heated to 100 °C, then
epoxide 1 (or 2, 10 mmol) was added over a period of 30 min,
and stirring was continued for 3 h at the same temperature. Pure
3d and 4d were isolated as described in the above procedure
(see Table 1).
3399—3431 (O—H), 2963—2859 (C—H), 1680—1682 (C=C),
1120—1122 (C—O—C, C—F); for compounds 5a,b and
6a,b: 3396—3432 (O—H), 2965—2859 (C—H), 1120—1122
(C—O—C, C—F).
References
1. D. N. Bazhin, T. I. Gorbunova, A. Ya. Zapevalov, V. E.
Kirichenko, V. I. Saloutin, Zh. Org. Khim., 2007, 43, 661
[Russ. J. Org. Chem., 2007, 43, 656 (Engl. Transl.)].
2. D. V. Solov´ev, L. V. Kolomenskaya, A. A. Rodin, I. G.
Zenkevich, A. N. Lavrent´ev, Zh. Org. Khim, 1991, 61, 673
[J. Gen. Chem. USSR, 1991, 61 (Eng. Transl.)].
3. V. A. Petrov, J. Fluorine Chem., 2004, 125, 531.
4. D. N. Bazhin, T. I. Gorbunova, A. Ya. Zapevalov, V. I.
Saloutin, Izv. Akad. Nauk. Ser. Khim., 2007, 2160 [Russ. Chem.
Bull., Int. Ed., 2007, 56, 2236 (Engl. Transl.)].
5. C. M. Timperley, W. E. White, J. Fluorine Chem., 2003,
123, 65.
Synthesis of 3ꢀalkoxyꢀ1ꢀ[3ꢀ(perfluoroalkyl)propꢀ2ꢀenyloxy]ꢀ
propanꢀ2ꢀols (3c,d and 4c,d) and 3ꢀalkoxyꢀ1ꢀ[2ꢀiodoꢀ3ꢀ(perꢀ
fluoroalkyl)propoxy]propanꢀ2ꢀols (5a,b and 6a,b) by phase
transfer catalysis (general procedure). Epoxide 1 or 2 (10 mmol)
was added at 35—40 °C to a stirred twoꢀphase system consisting
of CH2Cl2 (50 mL), 50% aqueous KOH (50 mL) containing
alcohol (0.35 mol), and Bu4N+I– (0.1 g, 2 mol.%). After 4 h, the
mixture was cooled, the organic layer was separated, and
the aqueous layer was extracted with CH2Cl2 (2×30 mL). The
combined organic layers were washed with aq. HCl and dried
with MgSO4. Pure 3c,d, 4c,d, 5a,b, and 6a,b were isolated by
vacuum distillation. The yields, boiling points, and elemental
6. A. Albert, E. Serjeant, Ionisation Constants of Acids and Bases,
Methuen, London , 1962.
7. X. Yang, Z. Wang, Y. Zhu, X. Fang, X. Yang, F. Wu, Y. Shen,
J. Fluorine Chem., 2007, 128, 1046.
8. D. N. Bazhin, T. I. Gorbunova, A. Ya. Zapevalov, V. I.
Saloutin, Izv. Akad. Nauk. Ser. Khim., 2007, 1476 [Russ. Chem.
Bull., Int. Ed., 2007, 56, No. 8].
Received April 4, 2008;
in revised form May 27, 2008
Bazhin
