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fluoroacetone imine was distilled off. The remaining color-
less liquid was distilled using a Vigreux column; bp 78 8C
(25 hPa), yield 1.63 g (68%). 1H NMR, d (ppm): 0.99 (CH3
were pumped off in vacuo and quantitatively 14 was
1
obtained as a white solid; mp 121 8C, 9.4 g (100%). H
NMR (CDCl3), d (ppm): 1.15 (i-Pr, 6H, d; 3JHH ¼ 6:2 Hz),
2
i-Pr JHH ¼ 6:2 Hz, d), 1.81 (CH3, s), 2.55 (CH2, s), 2.86
1.50–2.94 (CH2, 6H, m), 3.52 (CH, 2H, m), 3.78 (i-Pr, 1H,
sep, JHH ¼ 6:2 Hz). 19F NMR (CDCl3), d (ppm): À76.7
(NH2, sa), 3.52 (CH i-Pr 2JHH ¼ 6:2 Hz, sep); 19F, d (ppm):
À80.4 (CF3, s), À83.9 (CF3, s). MS (EI), m/e (%): 264 (Mþ,
30), 263 (Mþ À H, 45), 207 (Mþ À ðCH3Þ2C¼NH, 42), 195
(Mþ À CF3, 7), 165 ((CF3)2NHþ, 10), 42 (C3H6, 100).
Analysis: C9H14F6N2 (MG 264.21), Calcd.: C 40.9, H
5.3, F 43.2; Found: C 40.0, H 5.3, F 43.5.
3
(anti-CF3, 6F, m), À80.1 (syn-CF3, 6F, m). 13C NMR
(DMSO), d (ppm): 20.2 (CH3, s), 26.5 (C4, s), 29.4 (C3,5
s), 41.2 (C2,6, s), 47.8 (CH, s), 90.7 (C(CF3)2, sep,
,
1
2JCF ¼ 31:7 Hz), 121.5 (CF3, q, JCF ¼ 290:5 Hz), 176.5
(CN, s). MS, m/e (%): 471 (Mþ, 28), 402 (Mþ À CF3, 24),
360 (Mþ À CF3, –i-Pr, 36), 220 (Mþ À CF3, –CH3, –
(CF3)2CO, 39), 43 (i-Prþ, 100) and other fragments. Ana-
lysis: C15H17F12NO2 (MG 471.29), Calcd.: C 38.2, H 3.6, F
48.4; Found: C 38.6, H 3.9, F 47.7.
4.8. 2-Amino-1,1,1,7,7,7-hexafluoro-6-hydroxy-2,6-
bis(trifluoromethyl)-4-isopropylimino-heptane (10)
To 2.7 g (10 mmol) 9 2.0 g (12 mmol) HFA was added at
À196 8C. The mixture was allowed to warm up to ambient
temperature. The colorless liquid was dissolved in petrol
ether and kept for 12 h at À20 8C. White crystal were
4.11. 2,6-Diethoxy-2,6-bis(trifluoromethyl)-3,5-dimethyl-
1,1,1,7,7,7-hexafluoro-heptan-4,4-diol (15)
1
obtained; mp 34 8C, 3.70 g (85%). H NMR (CDCl3), d
To 4.3 g (9.4 mmol) 13 20 ml of ethanol/water (3:1)
were added and heated under reflux for 1 h, then three
times washed with 20 ml chloroform and the organic
phase dried over Na2SO4. The solvent was removed
and the remaining liquid distilled; bp 75 8C (25 hPa), yield
(ppm): 1.19 (d, 6H, CH3, 3JHH ¼ 6:2 Hz), 1.75 (NH2, 2H, s
(broad)), 2.74 (syn-CH2, 2H, s), 2.83 (anti-CH2, 2H), 3.79
(CH, 1H, sep, 3JHH ¼ 6:2 Hz). 19F NMR (CDCl3), d (ppm):
À80.9 (anti-CF3, 6F, s), À82.0 (syn-CF3, 6F, s). MS, m/e
(%): 430 (Mþ, 2), 429 (Mþ À H, 3), 415 (Mþ À CH3, 7), 361
(Mþ À CF3, 25), 319 (Mþ À CF3, –CH3, 6), 264
(Mþ À ðCF3Þ2CO, 100), 250 (Mþ À 2CF3, –i-Pr, 17), 208
(Mþ À 3CF3, –CH3, 42) and other fragments. HRMS: for
C11H14F9N2O (Mþ without one CF3 fragment): Calcd.:
361.09625; Found: 361.09729.
1
2.20 g (48%). H NMR (CDCl3), d (ppm): 1.0 (CH3CH2,
3
3
6H, t, JHH ¼ 7:3 Hz), 1.3 (CH3, 6H, d, JHH ¼ 7:0 Hz),
3
2.6 (CH3CH2, 4H, q, JHH ¼ 7:3 Hz), 3.1 (CH, 2H, q,
3JHH ¼ 7:0 Hz), 6.4 (OH, 2H, s). 19F NMR (CDCl3), d
4
(ppm): À77.7 (CF3, 6F, q, JFF ¼ 10:6 Hz), À79.9 (CF3,
6F, q, JFF ¼ 10:6 Hz). MS, m/e (%): 223 (MþÀ
4
CH3CHC(CF3)2OC2H5, 19), 175 (Mþ À CH3CHC-
(CF3)2OC2H5, –C2H5CO, 14), 57 (C2H5COþ, 100) and
other fragments. Analysis: C15H20F12O4 (MG 492.30),
Calcd.: C 36.6, H 4.1, F 46.3; Found: C 38.3, H 4.1, F 45.7.
4.9. 1,1,1,7,7,7-Hexafluoro-3,5-dimethyl-2,6-dihydroxy-
2,6-bis(trifluoromethyl)-4-isopropylimino-heptane (14)
To 2.50 g (20 mmol) 11 in 10 ml diethyl ether 6.70 g
(40 mmol) HFA were added at À196 8C. The reaction
mixture allowed to warm up to ambient temperature. After
pumping off all volatiles a pure white solid was obtained;
4.12. Ethylene-bis[1,1,1,7,7,7-hexafluoro-2,6-dihydroxy-
2,6-bis(trifluoromethyl)-4-imino-heptane] (17)
1
mp 101 8C, 6.60 g (75%). H NMR (CDCl3), d (ppm): 1.0
To 2.10 g (15 mmol) 16 in 10 ml diethyl ether 10.00 g
(60 mmol) HFA were added at À196 8C and allowed to
warm up to ambient temperature. After pumping off all
volatiles a white solid was obtained, which was re-crystal-
lized from petroleum ether/acetone 3:1; mp 149 8C, yield
11.0 g (91%). 1H NMR (CD3CN), d (ppm): 2.98 (CH2, 8H,
s), 3.69 (NCH2, 4H, s), 7.16 (OH, 4H, s). 19F NMR (DMSO),
d (ppm): À75.4 (anti-CF3, 12F, s), À76.6 (syn-CF3, 12F, s).
MS, m/e (%): 735 (Mþ À CF3, 10), 638 (Mþ À ðCF3Þ2CO,
11), 402 (Mþ/2, 100), 236 (Mþ/2 –(CF3)2CO, 55) and other
fragments. Analysis: C20H16F24N2O4 (MG 804.32), Calcd.:
C 29.9, H 2.0, F 56.7; Found: C 30.5, H 2.1, F 56.4.
3
(CH3, 6H, d, JHH ¼ 4:5 Hz), 1.1 (CH3 i-Pr, 6H, d,
3
3JHH ¼ 6:2 Hz), 1.8 (CH, 2H, q, JHH ¼ 4:5 Hz), 3.8 (CH
3
i-Pr, 1H, sep, JHH ¼ 6:2 Hz), 10.2 (OH, 2H, s); 19F NMR
4
(CD3CN), d (ppm): À70.1 (CF3, 3F, q, JFF ¼ 10:5 Hz),
4
À71.5 (CF3, 3F, q, JFF ¼ 10:5 Hz), À72.6 (CF3, 3F, q,
4
4JFF ¼ 10:5 Hz), À74.9 (CF3, 3F, q, JFF ¼ 10:5 Hz). MS,
m/e (%): 444 (Mþ À CH3, 7), 390 (Mþ À CF3, 8), 264
(Mþ À 2CH3, –CF3, –i-Pr, 30), 222 (Mþ À CF3H, –
CF3)2CO, 100) and other fragments. Analysis: C14H17F12-
NO2 (MG 459.28), Calcd.: C 36.6, H 3.7, F 49.6; Found: C
36.45, H 3.7, F 49.6.
4.10. 1-Isopropylimino-2,6-bis(perfluoroisopropanol)-
cyclohexane (14)
4.13. 2-Isopropylimino-1,1,1-trifluoropropane (19)
To a mixture of trifluoroacetone (5.6 g, 50 mmol) and
9.0 g (150 mmol) isopropylamine in 20 ml diethyl ether
4.8 g (25 mmol) titanium tetrachloride in 20 ml n-pentane
was added at 0 8C. The mixture was allowed to warm up to
To 2.8 g (20 mmol) 12 in 20 ml diethyl ether 6.70 g
(40 mmol) HFA was added at À196 8C and the mixture
allowed to warm up to ambient temperature. All volatiles