108
J.A. Barten et al. / Journal of Fluorine Chemistry 113 62002) 105±109
4.7. 4-Isopropylimino-3-methyl-2-phenyl-1,1,1-
trifluoro-heptan-2-ol 616)
remaining white solid was recrystallized from n-hexane/
1
THF 2:1. Selected data for: H NMR 2CDCl3): d 1:08
2CH3 iPr, 6H, d, 3JHH 6.2 Hz), 1.54 2CH3, 6H, s), 3.23 2CH
iPr, 1H, sep, 3JHH 6.2 Hz), 4.77 2CH, 1H, s), 7.80 2=CH, 1H,
s). 19F NMR 2CDCl3): d À79:5, À86.3, À89.2, À89.7
The mp is 30 8C. 1HNMR 2CDCl3): d 0:71 2CH3, 3H, d,
3JHH 6.7 Hz), 1.10 2CH3 Et, 3H, t, 3JHH 7.2 Hz), 1.24 2CH3
iPr, 6H, d, 3JHH 6.2 Hz), 2.17 2CH2 Et, 2H, q, 3JHH 7.2 Hz),
3.09 2CH, 1H, q, 3JHH 6.7 Hz), 3.82 2CH iPr, 1H, sep, 3JHH
6.2 Hz), 7.33 2Ph, 5H, m), 8.88 2OH, 1H, s). 19F NMR
2CDCl3): d À78:9 2CF3, s). Analysis: C16H22F3NO 2MG
301.35), C 63.75, H 7.36, F 18.92, found: C 63.28, H 7.43, F
19.25.
2CF3, s). MS: m/e ꢀ% 309 2M , 11), 294 2M ÀCH3,
100), 240 2M ÀCF3, 37), 196 2M ÀHOC2CF3)2, 14), 44
2C3H7 , 85). Analysis: HRMS 2for C11H17F6NO): calcd.:
309.11636; found: 309.11710.
4.12. 2-Hydroxy-2-phenyl-1,1,1-trifluoro-pentan-2-on 621)
4.8. 1-Isopropylimino-2-610-hydroxy-10-phenyl-
To a solution of 5 mmol 11 in 10 ml ethanol 5 ml HCl
220%) was added and re¯uxed for1 h. Diethylether 23x 20 ml)
was added, the organic layer separated anddried over MgSO4,
®ltered and the solvent removed under reduced pressure. A
white solid remained. Yield 56%, mp 51 8C. Selected data for:
1H NMR 2CDCl3): d 2:08 2CH3, 3H, s), 3.24 2CH2, 2H, s),
7.32 2Ph, 5H, m). 19F NMR 2CDCl3): d À84:4 2CF3, s).
20,20,20-trifluoroethyl)-cyclohexane 617)
Thempis66 8C. 1H NMR2CDCl3):d 1:202CH3 iPr, 6H,
d; 3JHH 6.2 Hz), 1.54 2CH2, 8H, m), 2.26 2CH, 1H, m), 3.04
2CH iPr, 1H, sep, 3JHH 6.2 Hz), 7.25 2Ph, 5H, m). 19F NMR
2C6D6): d À77:9 2CF3, s). MS: m/e ꢀ% 313 2M , 35),
270 2M ÀiPr, 17), 244 2M ÀCF3, 28), 202 2M ÀCF3, ÀiPr,
MS: m/e ꢀ% 232 2M , 21), 175 2M ÀCH3COCH2, 11),
13), 139 2M ÀPhCOCF3, 100). Analysis: C17H22F3NO 2MG
163 2M ÀCF3, 46), 105 2C6H5CO , 100).
313.36); calcd.: C 65.15, H 7.08, F 18.19; found: C 64.95, H
7.13, F 17.91.
4.13. 4-Isopropylamino-4-phenyl-2-trifluoromethyl-
butan-2-ol 622A,B)
4.9. 2,6-Dimethyl-2-610-hydroxy-10-phenyl-20,20,20-
trifluoroethyl)-1-isopropylimino-cyclohexane 618)
Compound 11 28 mmol) in 20 ml diethylether was added
dropwise at 0 8C to a suspension of 18 mmol LiAlH4 in
30 ml diethylether. Afterwards, water is added to the mixture
and the residue is ®ltered and washed with diethylether. The
organic layer was separated, dried over MgSO4, and the
solvent was removed under reduced pressure to leave a white
solid recrystallized from n-hexane. The data for two dia-
stereomers A:B 5:1): 1H NMR 2CDCl3): d 0:952B),
1.122A) 2iPr, 6H, d,3JHH 6.2 Hz), 1.27 2B), 1.502A) 2CH3,
3H, s), 1.922B), 2.142A) 2CH2, 2H, ABX-system), 2.652B),
2.712A) 2iPr, 1H, sep,3JHH 6.2 Hz), 4.242B), 4.262A) 2PhCH,
1H, m), 7.202B), 7.252A) 2Ph, 5H, m). 19F NMR 2CDCl3):
d À83:12B), À88.82A) 2CF3, s), MS: m/e ꢀ% 276
1H NMR 2CDCl3): d 1:07 2CH3, 12H, m), 1.88 2CH2,
CH, 7H, m), 3.82 2CH iPr, 1H, sep, 3JHH 6.2 Hz), 7.70 2Ph,
5H, m). 19F NMR 2CDCl3): d À75:7 2CF3, s). MS: m/e
ꢀ% 341 2M , 22), 284 2M ÀCH3,ÀiPr, 52), 273
2M ÀCF3, 100). Analysis: C19H26F3NO 2MG 341.42);
calcd.: C 66.84, H 7.68, F 16.69; found: C 67.35, H 7.79,
F 16.30.
4.10. Ethylen-bis-[2-hydroxy-4-imino-2-phenyl-
1,1,1-trifluoro-pentane] 619)
In 10 ml diethylether 15 mmol 7 were dissolved and
30 mmol tri¯uoroacetophenone were added. All volatile sub-
stances were removed under reduced pressure to give a white
solid recrystallized from petroleum ether. Yield: 50%, mp
128 8C. The data for 1H NMR 2CDCl3): d 1:7 2CH3, 6H, s),
2.9 2CH2, 4H, s), 3.22NCH2, 4H, s), 7.3 2Ph, 5H, m). 19F NMR
2M H, 18), 260 2M ÀCH3, 22), 217 2M ÀCH3,ÀiPr,
12), 148 2M ÀHOCCH3CF3CH2, 100). Analysis: C14H20-
F3NO 2MG 2 75.31); calcd.: C 61.07, H 7.32, F 20.70; found:
C 61.01, H 7.13, F 20.60.
2CDCl3): d À84:0 2CF3, s). MS: m/e ꢀ% 488 2M , 7),
Acknowledgements
418 2M ÀCF3H, 8), 314 2M ÀPhCOCF3, 14), 244 2M /2,
100), 176 2M /2 ÀCF3, 32). Analysis: C24H26F6N2O2 2MG
Dr. K.-H. Hellberg, Solvay Fluor und Derivate GmbH,
Hannover 2Germany) is thanked for the generous gift of
tri¯uoroacetone. We thank GIF 2German Israel: Foundation)
for ®nancial support 2Grant 1-618-20.5/1999).
488.47); C 59.01, H 5.36, F 23.34; found: C 58.87, H 5.40, F
23.22.
4.11. 3-Isopropylmethyliden-2,4-bis6trifluoromethyl)-
pentan-2,4-diol 620)
References
To a solution of 50 mmol tri¯uoroacetone in 20 ml diethy-
lether were added 20 mmol aldimine 3 in 20 ml diethylether
at 0 8C and stirred for 1 h. After removal of the solvent the
[1] K. Funabiki, K. Matsanaga, M. Matsui, K. Shibata, Synlett 21999) 1477.
[2] K. Funabiki, M. Nojiri, M. Matsui, K. Shibata, J. Chem. Soc., Chem.
Commun. 1998, 2051.