580
A. Ohno et al. / Journal of Fluorine Chemistry 129 (2008) 577–582
(broad) Hz, b), 2.41–2.45 (dt, 4H, J = 5.5 (1.5) Hz, c), 9.758–9.766 (t,
2H, J = 1.7 Hz, d) for [CH2aCH2bCH2cCHdO]2; EI-MS: 142 [M]+ (0.5),
124 [MÀH2O]+ (14), 95 [MÀH2OÀCHO]+ (26), 81 [C6H9]+ (100), 67
[C5H8]+ (36), 57 [(CH2)2CHO]+ (100), 55 [C4H7]+ (69); IR: 2627–
(t, 3F, J = 10.9 Hz, f), À115.3 (m, 2F, a), À122.95 (m, 2F, b), À123.85
(m, 2F, c), À124.5 (m, 2F, d), À127.3 (m, 2F, e) for
f
[CF3 CF2eCF2dCF2cCF2bCF2a(CH2)2CH(OH)(CH2)2]2CH2; EI-MS: 788
[MÀ2OH]+ (13), 474 [MÀOHÀ(CH2)2(CF2)6F]+ (31), 441
3017 (
nC–H), 1656–1837 (nC O).
[C7H14(CH2)2(CF2)6F]+ (100), 377 [CH(OH) (CH2)2(CF2)6F]+ (38), 55
[C4H7]+ (15); IR: 3219–3523 (
nO–H), 2857–2939 (nC–H), 1256 (nC–F).
4.4.2. H7Ad
Colorless liquid, yield (%) 3.6 g (40%), bp 52 8C/16 Pa, 1H NMR:
d
4.6.2. F4(H6)F4A
1.27–1.37 (s, 6H, a, b), 1.61–1.64 (tb, 4H, J = 7.1 (broad) Hz, c), 2.40–
2.44 (dt, 4H, J = 5.6 (1.5) Hz, d), 9.756–9.765 (t, 2H, J = 1.7 Hz, e) for
White solid, yield (%) 5.21 g (58%), mp 84–96 8C, 1H NMR:
d
1.30–1.51 (m, 12H, a, b, c), 1.68 (m, 4H, e), 2.27 (m, 4H, f), 3.56 (m,
2H, d) for [CH2aCH2bCH2cCHd(OH)CH2eCH2 (CF2)4F]2; 19F NMR:
CH2a[CH2bCH2cCH2dCHeO]2; EI-MS: 156 [M]+ (0.6), 138 [MÀH2O]+
d
f
+
(6), 110 [MÀH2OÀCHO]+ (11), 95 [C7H11
]
(100), 67 [C5H8]+ (48),
À82.7 (t, 3F, J = 9.6 Hz, d), À115.5 (m, 2F, a), À125.45 (m, 2F, b),
À127.2 (m, 2F, c) for [CF3dCF2cCF2bCF2a(CH2)2CH(OH)(CH2)3]2; EI-
MS: 602 [MÀ2OH]+(3), 374 [MÀOH-(CH2)2(CF2)4F]+ (35), 355
[C8H16(CH2)2(CF2)4F]+ (100), 277 [CH(OH)(CH2)2(CF2)4F]+(56), 55
57 [(CH2)2CHO]+ (64), 55 [C4H7]+ (48); IR: 2649–2997 (
nC–H),
1675–1787 (nC O).
4.4.3. H8Ad
[C4H7]+ (16); IR: 3277–3458 (
nO–H), 2854–2937 (nC–H), 1239 (nC–F).
Colorless liquid, yield (%) 7.0 g (70%), bp 80 8C/10 Pa, 1H NMR:
d
1.28–1.37 (s, 8H, a, b), 1.61–1.64 (tb, 4H, J = 7.5 (broad) Hz, c), 2.40–
2.44 (dt, 4H, J = 5.5 (1.5) Hz, d), 9.756–9.765 (t, 2H, J = 1.7 Hz, e) for
[CH2aCH2bCH2cCH2dCHeO]2; EI-MS: 170 [M]+ (0.3), 152 [MÀH2O]+
(2), 123 [MÀH2OÀCHO]+ (6.4), 95 [C7H11]+ (27), 81 [C6H9]+ (48), 67
[C5H8]+ (100), 57 [(CH2)2CHO]+ (79), 55 [C4H7]+ (87); IR: 2658–
4.6.3. F6(H6)F6A
White solid, yield (%) 7.08 g (60%), mp 95–103 8C, 1H NMR:
d
1.29–1.50 (m, 12H, a, b, c), 1.67 (m, 4H, e), 2.28 (m, 4H, f), 3.55 (m,
2H, d) for [CH2aCH2bCH2cCHd(OH)CH2eCH2 (CF2)6F]2; 19F NMR:
f
d
À82.4 (t, 3F, J = 10.9 Hz, f), À115.3 (m, 2F, a), À112.9 (m, 2F, b),
3003 (
nC–H), 1669–1790 (nC O).
À123.8 (m, 2F, c), À124.5 (m, 2F, d), À127.3 (m, 2F, e) for
f
[CF3 CF2eCF2dCF2cCF2bCF2a(CH2)2CH(OH)(CH2)3]2;
EI-MS: 802
4.5. Synthesis of 1,11-bis(perfluorobutyl)-3,9-undecanediol
(F4(H5)F4A)
[MÀ2OH]+ (3), 474 [MÀOHÀ(CH2)2(CF2)6F]+ (39), 455
[C8H16(CH2)2(CF2)6F]+ (100), 377 [CH(OH)(CH2)2(CF2)6F]+ (47),
55 [C4H7]+ (10); IR: 3250–3489 (
nO–H), 2857–2933 (nC–H), 1253
All reactions were performed under nitrogen atmosphere.
Magnesium (0.84 g, 34.6 mmol) was taken into a two-neck round
bottom flask in an ice bath and a dilute 2-(perfluorobutyl)ethyl
iodide (16.4 g, 34.6 mmol) solution in diethyl ether was added
dropwise to the flask. After the iced solution was stirred for 2 h,
H5Ad (1.5 g, 34.6 mmol) (20 times diluted (in volume) diethyl
ether solution) was added dropwise to it. The Grignard reaction
was stopped by adding water and 1 M hydrochloric acid to the
reaction mixture after it was stirred for 24 h at room temperature.
The diethyl ether-soluble part was extracted and separated from
the reaction mixture and sodium borohydride (0.18 g, 4.89 mmol),
tetrahydrofuran (15 mL), and methanol (3.13 g, 97.8 mmol) were
added in this order to the ether solution and the resultant solution
was stirred for 6 h at room temperature. The reaction product was
then recrystallized from chloroform to give F4(H5)F4A [14,15].
(nC–F).
4.6.4. F4(H7)F4A
White solid, yield (%) 3.25 g (40%), mp 86–96 8C, 1H NMR:
1.50 (m, 14H, a, b, c, d), 1.66 (m, 4H, f), 2.25 (m, 4H, g), 3.55 (m, 2H, e)
forCH2a[CH2bCH2cCH2dCHe(OH)CH2 CH2g(CF2)4F]2;19FNMR:
d
1.32–
f
d
À82.7
(t, 3F, J = 9.6 Hz, d), À115.5 (m, 2F, a), À125.45 (m, 2F, b), À127.25 (m,
2F, c) for [CF3dCF2cCF2bCF2a(CH2)2CH(OH)(CH2)3]2CH2; EI-MS: 616
[MÀ2OH]+ (3), 387 [MÀOHÀ(CH2)2(CF2)4F]+ (41), 369
[C9H18(CH2)2(CF2)4F]+ (100), 277 [CH(OH)(CH2)2(CF2)4F]+ (86), 55
[C4H7]+ (19); IR: 3200–3497 (
nO–H), 2854–2930 (nC–H), 1250 (nC–F).
4.6.5. F6(H7)F6A
White solid, yield (%) 6.66 g (41%), mp 105–110 8C, 1H NMR:
d
1.30–1.51 (m, 14H, a, b, c, d), 1.67 (m, 4H, f), 2.28 (m, 4H, g), 3.56 (m,
2H,e)forCH2a[CH2bCH2cCH2dCHe(OH)CH2 CH2g(CF2)6F]2;19FNMR:
f
d
4.5.1. F4(H5)F4A
À82.4 (t, 3F, J = 10.9 Hz, f), À115.35 (m, 2F, a), À112.9 (m, 2F, b),
White solid, yield (%) 4.62 g (64%), mp 88–93 8C, 1H NMR:
d
À123.8 (m, 2F, c), À124.5 (m, 2F, d), À127.3 (m, 2F, e) for
f
1.30–1.52 (m, 10H, a, b, c), 1.68 (m, 4H, e), 2.28 (m, 4H, f), 3.56 (m,
2H, d) for CH2a[CH2bCH2cCHd(OH)CH2eCH2 (CF2)4F]2; 19F NMR:
[CF3 CF2eCF2dCF2cCF2bCF2a(CH2)2CH(OH)(CH2)3]2CH2; EI-MS: 816
f
d
[MÀ2OH]+ (3), 487 [MÀOHÀ(CH2)2(CF2)6F]+ (42), 469
À82.7 (t, 3F, J = 9.6 Hz, d), À115.65 (m, 2F, a), À125.5 (m, 2F, b),
À127.25 (m, 2F, c) for [CF3dCF2cCF2bCF2a(CH2)2CH(OH)(CH2)2]2-
CH2; EI-MS: 588 [MÀ2OH]+ (2), 360 [MÀOHÀ(CH2)2(CF2)4F]+ (27),
341 [C7H14(CH2)2(CF2)4F]+ (100), 277 [CH(OH)(CH2)2(CF2)4F]+ (39),
[C9H18(CH2)2(CF2)6F]+ (100), 377 [CH(OH) (CH2)2(CF2)6F]+ (66), 55
[C4H7]+ (21); IR: 3246–3636 (
nO–H), 2855–2930 (nC–H), 1249 (nC–F).
4.6.6. F4(H8)F4A
55 [C4H7]+ (19); IR: 3216–3517 (
C–F).
nO–H), 2857–2938 (
nC–H), 1253
White solid, yield (%) 2.71 g (69%), mp 88–99 8C, 1H NMR:
d
(
n
1.29–1.49 (m, 16H, a, b, c, d), 1.66 (m, 4H, f), 2.27 (m, 4H, g), 3.55 (m,
2H, e) for [CH2aCH2bCH2cCH2dCHe(OH)CH2 CH2g(CF2)4F]2; 19F NMR:
f
4.6. Syntheses of 1,11-bis(perfluorohexyl)undecane-3,9-diol
(F6(H5)F6A) and other diols
d
À82.7 (t, 3F, J = 9.6 Hz, d), À115.55 (m, 2F, a), À125.4 (m, 2F, b),
À127.25 (m, 2F, c) for [CF3dCF2cCF2bCF2a(CH2)2CH(OH)(CH2)4]2; EI-
MS: 630 [MÀ2OH]+ (7), 401 [MÀOHÀ(CH2)2(CF2)4F]+ (57), 383
[C10H20(CH2)2(CF2)4F]+ (97), 277 [CH(OH)(CH2)2(CF2)4F]+ (100), 55
These diols were obtained from heptanedial (H5Ad), octanedial
(H6Ad), nonanedial (H7Ad), and decanedial (H8Ad) according to
the method in Section 4.5.
[C4H7]+ (24); IR: 3247–3635 (
nO–H), 2854–2930 (nC–H), 1250 (nC–F).
4.6.7. F6(H8)F6A
4.6.1. F6(H5)F6A
Whitesolid,yield(%)5.08 g(50%),mp99–101 8C, 1HNMR:
d
1.29–
White solid, yield (%) 6.42 g (50%), mp 104–109 8C, 1H NMR:
d
1.50 (m, 16H, a, b, c, d), 1.67 (m, 4H, f), 2.26 (m, 4H, g), 3.56 (m, 2H, e)
f
1.31–1.52 (m, 10H, a, b, c), 1.69 (m, 4H, e), 2.28 (m, 4H, f), 3.56 (m, 2H,
d) for CH2a[CH2bCH2cCHd(OH)CH2eCH2 (CF2)6F]2; 19F NMR:
for[CH2aCH2bCH2cCH2dCHe(OH)CH2 CH2g(CF2)6F]2;19FNMR:
d
À82.4
f
d
À82.4
(t, 3F,J = 10.9 Hz,f),À115.35(m, 2F,a), À123.8(m, 2F,b),À123.85(m,