REACTIONS OF PERFLUORO(2-METHYLPENT-2-ENE)
1433
(78.81) [CH3CCH3]+. Found: [M]+ 543.1975.
C23H28F11NO. Calculated: M 543.1995.
(1H, 11-H), 2.56 (1H, 12-H), 1.39 (3H, 19-H, CH3).
19F NMR spectrum (CDCl3), δF, ppm: 82.6 (6F, 7-F,
10-F), 47.5 (2F, 5-F), 48.3 and 46.5 (2F, 8-F, AB
system, JFF = 278 Hz), 37.4 (2F, 6-F), 36.7 (2F, 9-F).
13C NMR spectrum (CDCl3), δC, ppm: 151.2 (C16),
147.7 (C4, 2JCF = 23.4 Hz), 142.5 (C2, 2JC–F = 23.4 Hz),
135.9 (C15), 131.0 (C14), 123.1 (C13), 117.5 (C7, C 10,
2,6-Di-tert-butyl-4-{3-[2,4-difluoro-2-penta-
fluoroethyl-3-trifluoromethylazet-1(2H)-yl]propyl}-
phenol (VIIb). mp 118–119°C. IR spectrum, ν, cm–1:
3646 (OH); 2959, 2930, 2874 (C–H); 1669, 1645
(C=N); 1552 (C=Carom); 1466, 1436 (C–N); 1362, 1337
(C–O); 1228–1160 (C–F). 1H NMR spectrum (CDCl3),
δ, ppm: 7.58 (1H, OH), 6.87 (1H, 12-H), 4.12 (1H,
3-H), 3.21 (1H, 8-H), 2.63 (1H, 9-H), 2.54 (1H, 10-H),
1.39 (3H, 16-H). 19F NMR spectrum (CDCl3), δF, ppm:
111.0 (1F, 4-F), 107.0 (3F, 5-F), 82.8 (3F, 7-F),
49.9 and 49.4 (2F, 6-F, AB system, JFF = 240 Hz), 49.0
(1F, 2-F).
2
1
1JCF = 290.7, JCF = 28.5 Hz), 109.1 (C5, C8, JCF
=
2
1
259.9, JCF = 31.3 Hz), 107.7 (C6, C9, JCF = 267.9,
2JCF = 32.8 Hz), 48.2 (C11), 41.1 (C12), 32.4 (C13), 33.4
(C17), 29.9 (C18). Found, %: C 45.65; F 40.34; N 4.66.
[M]+ 654. C25H28F14N2O2. Calculated, %: C 45.87;
F 40.67; N 4.28. M 654.
1-[3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propyl]-
2,4-bis(heptafluoropropyl)-1,2-dihydro-1,3-diazet-
2-ol (XIIb). mp 123–124°C (from heptane). IR spec-
trum, ν, cm–1: 3646 (OH); 2958, 2921, 2874 (C–H);
1732, 1686 (C=N); 1551 (C=Carom); 1471, 1435 (C–N);
1390, 1359 (C–O); 1232–1157 (C–F). UV spectrum
2,6-Di-tert-butyl-4-(3-{2-[3-(3,5-di-tert-butyl-4-
hydroxyphenyl)propylimino]-4-pentafluoroethyl-3-
trifluoromethylazet-1(2H)-yl}propyl)phenol (VIII).
mp 110–112°C. IR spectrum, ν, cm–1: 3646 (OH);
2959, 2930, 2874 (C–H); 1665, 1645 (C=N); 1552
(C=Carom); 1466 (C=C); 1436 (C–N); 1362, 1337
(C–O); 1228–1160 (C–F). 1H NMR spectrum (CDCl3),
δ, ppm: 7.11 (OH), 6.95 (4H, 12-H, 21-H), 3.15 (4H,
8-H, 17-H), 2.63 (4H, 9-H, 12-H), 2.46 (4H, 10-H,
19-H), 1.86 (4H, 15-H, 24-H), 1.38 (36H, 16-H, 25-H).
19F NMR spectrum (CDCl3), δF, ppm: 106.4 s (3F,
5-F), 82.0 s (3F, 7-F), 48.8 d (2F, 6-F, J = 19 Hz).
13C NMR spectrum (CDCl3), δC, ppm: 157.6 (C4),
1
(EtOH): λmax 275 nm (ε 2000). H NMR spectrum
(CDCl3), δ, ppm: 7.70 (1H, OH), 6.99 (1H, 15-H), 3.17
(1H, 11-H), 2.56 (1H, 12-H), 2.22 (1H, 13-H), 1.39
(3H, 19-H, CH3). 19F NMR spectrum (CDCl3), δF,
ppm: 82.6 (6F, 7-F, 10-F), 47.5 (2F, 5-F), 48.3 and 46.5
(2F, 8-F, AB system, JFF = 278 Hz), 37.4 (2F, 6-F), 36.7
(2F, 9-F). 13C NMR spectrum (CDCl3), δC, ppm: 151.2
2
2
(C17), 147.7 (C4, JCF = 23.4 Hz), 142.5 (C2, JCF
=
23.4 Hz), 135.9 (C16), 131.0 (C14), 123.1 (C15), 117.5
2
152.5 (C14), 152.3 (C23), 142.1 (C2, JCF = 21.4 Hz),
(C7, C10, JCF = 290.7, JCF = 28.5 Hz), 109.1 (C5, C8,
1
2
136.1 (C13), 136 (C13, C22), 131.7 (C20), 131.6 (C11),
1JCF = 259.9, JCF = 31.3 Hz), 107.7 (C6, C9, JCF
=
2
1
1
123.8 (C12, C21), 121.6 (C5, JCF = 282 Hz), 119.6 (C7,
267.9, JCF = 32.8 Hz), 48.2 (C11), 41.1 (C12), 32.4
(C13), 33.4 (C18), 29.9 (C19). Found, %: C 44.87;
F 41.34; N 4.26. [M]+ 640. C24H26F14N2O2. Calculated,
%: C 45.00; F 41.56; N 4.38. M 640.
2
2
2
1JCF = 271.2, JCF = 30 Hz), 114.0 (C3, JCF = 38 Hz),
108.6 (C6, JCF = 266.9, JCF = 41.3 Hz), 53.2 (C8),
52.9 (C17), 50.6 (C9, C18), 34.2 (C10), 34.5 (C19), 32.3
(C16, C25), 30.1 (C15, C24). Mass spectrum, m/z (Irel, %):
746 (45.28) [M]+, 727 (3.56) [M – F]+, 527 (8.77) [M –
CH2C14H20OH]+, 514 (92.82) [M – CH2CH2C14H20O]+,
513 (24.11) [M – CH2CH2C14H20OH]+, 233 (7.09)
[CH2CH2C14H20OH]+, 219 (49.96) [CH2C14H20OH]+,
205 (1.64) [C14H20OH]+, 119 (4.00) [C2F5]+, 69 (3.15)
[CF3]+, 57 (100) [C(CH3)3]+.
1
2
N-[2-(3,5-Di-tert-butyl-4-hydroxyphenyl)ethyl]-
heptafluorobutanamide (XIIIa). bp 162–163°C
(0.2 mm). IR spectrum, ν, cm–1: 3645 (OH); 3448
(NH); 2960, 2921, 2874 (C–H); 1732 (C=O); 1528
1
(C=Carom); 1234–1187 (C–F). H NMR spectrum
(CDCl3), δ, ppm: 8.44 (1H, OH), 6.97 (1H, 8-H), 5.31
(1H, NH), 3.53 (1H, 5-H), 2.78 (1H, 6-H), 1.38 (3H,
12-H). 19F NMR spectrum (CDCl3), δF, ppm: 82.4 (3F,
1-F), 43.0 (2F, 3-F), 36.2 (2F, 2-F). Mass spectrum,
m/z (Irel, %): 445 (35.52) [M]+, 388 (1.03) [M –
C(CH3)3]+, 374 (24.63) [M – (CH3)3CCH2]+, 232
(99.02) [CH2=CHC14H20OH]+, 226 (1.46) [C3F7C(O)-
NHCH2]+, 219 (100) [CH2C14H20OH]+, 205 (1.26)
[C14H20OH]+, 169 (3.18) [C3F7]+, 119 (4.16) [C2F5]+,
100 (0.39) [CF2=CF2]+, 69 (5.29) [CF3]+, 57 (62.89)
[C(CH3)3]+. Found: [M]+ 445.1855. C20H26F7NO2. Cal-
culated: M 445.1852.
The reactions of compound II with aminophenols
III and IV were carried out as described above for
compound I.
1-[2-(3,5-Di-tert-butyl-4-hydroxyphenyl)ethyl]-
2,4-bis(heptafluoropropyl)-1,2-dihydro-1,3-diazet-
2-ol (XIIa). mp 119–120°C (from heptane). IR spec-
trum, ν, cm–1: 3646 (OH); 2958, 2921, 2874 (C–H);
1732, 1686 (C=N); 1551 (C=Carom); 1471, 1435 (C–N);
1390, 1359 (C–O); 1232–1157 (C–F). UV spectrum
1
(EtOH): λmax 275 nm (ε 2000). H NMR spectrum
(CDCl3), δ, ppm: 7.70 (1H, OH), 6.89 (1H, 14-H), 3.17
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 10 2006