FLUOROALKYL-CONTAINING LITHIUM 1,3-DIKETONATES
1455
2
CF2), 41.81–42.14 m (2F, CF2), 81.07 t (3F, CF3,
JFF = 9.8 Hz). Found, %: C 38.48; H 1.93; F 52.68;
N 2.94. C15H8F13NO. Calculated, %: C 38.73; H 1.73;
F 53.09; N 3.01.
įF 36.84 ppm, d (HCF2, JHF = 55.6 Hz). Found, %:
C 69.16; H 5.02; F 14.30; N 5.49. C15H13F2NO. Cal-
culated, %: C 68.96; H 5.02; F 14.54; N 5.36.
2-Difluoroacetyl-1-(1-naphthylamino)cyclopen-
tene (IIi). Yield 70%, colorless crystals, mp 67–68 °C.
IR spectrum, Ȟ, cm–1: 1600 (C=O), 3270 (NH). 1H NMR
spectrum, į, ppm: 1.88–1.96 m, 2.67–2.70 m, and 2.82–
2-Amino-1,1-difluoro-5,5-dimethyl-2-hexen-4-
one (IIIa). Yield 91%, colorless crystals, mp 58–59°C.
IR spectrum, Ȟ, cm–1: 1640 (C=O); 3185–3370 (NH).
1H NMR spectrum, į, ppm: 1.15 s (9H, t-Bu), 5.47 s
(1H, =CH), 6.00 t (1H, HCF2, 2JHF = 55.1 Hz), 7.26 br.s
(2H, NH). 19F NMR spectrum: įF 39.66 ppm, d (HCF2,
2JHF = 55.1 Hz). Found, %: C 54.12; H 7.39; F 21.52;
N 7.84. C8H13F2NO. Calculated, %: C 54.23; H 7.39;
F 21.44; N 7.90.
2
2.86 m (6H, CH2); 6.00 t (1H, HCF2, JHF = 54.6 Hz);
7.30–8.09 m (7H, Harom); 12.15 br.s (1H, NH). 13C NMR
spectrum, įC, ppm: 22.85 s (C4); 27.39 t (C3, JCF
=
4
2.8 Hz); 32.89 s (C5); 104.79 s (C2); 111.51 t (HCF2,
1JCF = 250.1 Hz); 171.81 s (C1); 181.81 t (C=O, 2JCF
=
23.9 Hz); 120.80, 121.99, 125.20, 126.74, 126.88,
127.15, 128.21, 128.38, 134.19, 134.76 (naphthyl).
3-Amino-4,4-difluoro-1-phenyl-2-buten-1-one
(IIIb). Yield 83%, colorless crystals, mp 60 °C [1].
2
19F NMR spectrum: įF 36.09 ppm, d (HCF2, JHF
=
54.6 Hz). Found, %: C 71.22; H 5.33; F 13.20; N 4.83.
C17H15F2NO. Calculated, %: C 71.07; H 5.26; F 13.22;
N 4.87.
3-Amino-4,4,4-trifluoro-1-phenyl-2-buten-1-one
(IIIc). Yield 50%, colorless crystals, mp 80–81°C [1].
General procedure for the synthesis of N-phenyl-
substituted aminovinyl ketones IIk and IIId. A so-
lution of 0.01 mol of lithium diketonate I and 0.01 mol
of aniline hydrochloride in 10 ml of methanol was kept
at 20°C until the initial compounds disappeared (TLC).
The mixture was poured into water, and the precipitate
was filtered off and recrystallized from hexane.
1,1,2,2-Tetrafluoro-5-(1-naphthylamino)-4-
hexen-3-one (IIj). Yield 78%, colorless crystals,
mp 80°C [11].
1,1,1-Trifluoro-4-(1-naphthylamino)-3-penten-2-
one (IIl). Yield 86%, colorless crystals, mp 39°C [11].
1-(1-Naphthylamino)-2-trifluoroacetylcyclopen-
1,1,1-Trifluoro-4-phenylamino-3-penten-2-one
(IIk). Yield 91%, colorless crystals, mp 60–61°C [1].
tene (IIm). Yield 75%, colorless crystals, mp 65°C. IR
1
spectrum, Ȟ, cm–1: 1610 (C=O), 3440 (NH). H NMR
spectrum, į, ppm: 1.88–1.95 m, 2.67–2.70 m, and
2.83–2.87 m (6H, CH2); 7.30–8.05 m (7H, Harom);
12.16 br.s (1H, NH). 19F NMR spectrum: įF 86.53 ppm,
s (CF3). Found, %: C 66.83; H 4.52; F 18.50; N 4.46.
C17H14F3NO. Calculated, %: C 66.88; H 4.62; F 18.67;
N 4.59.
4,4-Difluoro-1-phenyl-3-phenylamino-2-buten-1-
one (IIId). Yield 81%, colorless crystals, mp 54–55°C.
IR spectrum, Ȟ, cm–1: 1610 (C=O), 3350 (NH). 1H NMR
2
spectrum, į, ppm: 6.32 t (1H, HCF2, JHF = 53.1 Hz),
6.40 s (1H, =CH), 12.46 br.s (1H, NH), 7.25–7.99 m
(10H, Harom). 19F NMR spectrum: įF 44.62 ppm, d
2
(HCF2, JHF = 53.1 Hz). Found, %: C 70.35; H 4.68;
1-(1-Naphthylamino)-2-trifluoroacetylcyclo-
hexene (IIn). Yield 75%, colorless crystals, mp 92–
93°C. IR spectrum, Ȟ, cm–1: 1610 (C=O), 3070 (NH).
1H NMR spectrum, į, ppm: 1.53–1.69 m, 2.28–2.31 m,
and 2.61–2.64 m (8H, CH2); 7.29–7.92 m (7H, Harom);
13.43 br.s (1H, NH). 19F NMR spectrum: įF 89.91 ppm,
s (CF3). Found, %: C 67.73; N 4.90; F 17.94; N 4.33.
C18N16F3NO. Calculated, %: C 67.70; N 5.05; F 17.85;
N 4.39.
F 13.80; N 5.06. C16H13F2NO. Calculated, %: C 70.32;
H 4.80; F 13.90; N 5.13.
General procedure for the synthesis of N-aryl-
and N-hetaryl-substituted aminovinyl ketones IIh–
IIp and IIId–IIIn. A solution of 0.01 mol of lithium
diketonate I and 0.01 mol of the corresponding amine
in 10 ml of glacial acetic acid was kept at 20°C until
the initial compounds disappeared (TLC). The mixture
was poured into water, and the precipitate was filtered
off and recrystallized from hexane.
5,5,6,6,7,7,8,8,8-Nonafluoro-2-(1-naphthylamino)-
2-octen-4-one (IIo). Yield 82%, brown oily substance.
IR spectrum, Ȟ, cm–1: 1600 (C=O), 3060 (NH). 1H NMR
spectrum, į, ppm: 2.01 s (3H, Me), 5.79 s (1H, =CH),
7.39–7.97 m (7H, Harom), 12.87 br.s (1H, NH). 19F NMR
spectrum, įF, ppm: 35.89–36.25 m (2F, CF2), 38.47–
38.89 m (2F, CF2), 41.65–41.98 m (2F, CF2), 80.94 t
(3F, CF3, JFF = 9.8 Hz). Found, %: C 50.43; H 2.85;
1,1-Difluoro-4-(1-naphthylamino)-3-penten-2-one
(IIh). Yield 89%, colorless crystals, mp 102–103°C.
IR spectrum, Ȟ, cm–1: 1610 (C=O), 3350 (NH). 1H NMR
spectrum, į, ppm: 2.00 s (3H, Me), 5.65 s (1H, =CH),
2
5.88 t (1H, HCF2, JHF = 55.6 Hz), 7.32–7.96 m (7H,
Harom), 12.87 br.s (1H, NH). 19F NMR spectrum:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005