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ꢀ74.13 (c, CF3). GC–MS (EI 70 eV), m/z (rel. int.): 236 [M]+
(20), 180 [M ꢀ CH2CH2CO]+ (49), 167 [M ꢀ CF3]+ (80), 152
[M ꢀ CH2COCH2CO]+ (35), 139 [M ꢀ CF3CO]+ (7), 124
[M ꢀ CF3CO–CH3]+ (100), 111 [M ꢀ CF3CO–CO]+ (29), 97
[CF3CO]+ (11), 83 [CHCOCH2CO]+ (93), 69 [CF3]+ (73), 55
[CHCH2CO]+ (34), 42 [CH2CO]+ (20). Anal. Calcd for
C10H11O3F3: C, 50.85; H, 4.69. Found: C, 50.69; H, 4.61.
2-Trifluoroacetylcyclohexane-1,3-dione (2b). This com-
pound was obtained as colorless crystals, mp 31–32 8C. IR
CF3), 126.46 (Car), 127.72 (Car), 129.36 (Car), 140.92 (Car-10),
184.24 (q, 2JC–F = 39 Hz, COCF3), 191.00 (C-3), 196.35 (C-1).
19F: d ꢀ74.18 (c, CF3). GC–MS (EI 70 eV), m/z (rel. int.): 284
[M]+ (17), 215 [M ꢀ CF3]+ (10), 131 [M ꢀ CH2COCH2CO]+
(9), 104 [M ꢀ 180]+ (100), 69 [CF3]+ (21). Anal. Calcd for
C14H11O3F3: C, 59.16; H, 3.90. Found: C, 59.25; H, 3.95.
2-Trifluoroacetyl-5-(4-methoxyphenyl)cyclohexane-1,3-
dione (2f). This compound was obtained as colorless crystals,
mp 104–107 8C. IR (KBr): n 1695, 1635, 1565 cmꢀ1. NMR: 1H
d 2.86 (4H, m, C-4, C-6), 3.39 (1H, m, C-5), 3.81 (3H, s, CH3O),
6.91 (2H, d, J = 8.7 Hz, Har at C-30, C-50), 7.15 (2H, d,
J = 8.7 Hz, Har at C-20, C-60), 15.27 (1H, bs, OH). 13C: d 36.07
(C-5), 39.47 (C-6), 45.34 (C-4), 55.35 (CH3O), 110.98 (C-2),
1
(KBr): n 1700, 1650, 1565 cmꢀ1. NMR: H d 2.10 (2H, qui,
J = 6.5 Hz, C-5), 2.57 (2H, t, J = 6.5 Hz, C-4), 2.82 (2H, t,
J = 6.5 Hz, C-6), 15.29 (1H, s, OH). 13C: d 18.91 (C-5), 31.95
1
(C-6), 37.86 (C-4), 111.35 (C-2), 116.32 (q, JC–F = 286 Hz,
CF3), 184.34 (q, 2JC–F = 39 Hz, COCF3), 191.75 (C-3), 197.45
(C-1). 19F: ꢀ74.17 (c, CF3). GC–MS (EI 70 eV), m/z (rel. int.):
208 [M]+ (17), 152 [M ꢀ CH2CH2CO]+ (20), 139 [M ꢀ CF3]+
(73), 124 [M ꢀ CH2COCH2CO]+ (100), 111 [M ꢀ CF3CO]+
(29), 97 [CF3CO]+ (8), 69 [CF3]+ (86), 55 [CHCH2CO]+ (27),
42 [CH2CO]+ (22). Anal. Calcd for C8H7O3F3: C, 46.17; H,
3.39. Found: C, 46.25; H, 3.42.
114.48 (C-30, C-50), 116.32 (q, JC–F = 286 Hz, CF3), 127.47
1
(C-20, C-60), 159.01 (C-40), 184.22 (q, 2JC–F = 39 Hz, COCF3),
191.17 (C-3), 196.45 (C-1). 19F: d ꢀ74.17 (c, CF3). GC–MS (EI
70 eV), m/z (rel. int.): 314 [M]+ (17), 134 [M ꢀ 180]+ (100),
121 [M ꢀ 193]+ (40), 69 [CF3]+ (13). Anal. Calcd for
C15H13O4F3: C, 57.33; H, 4.17. Found: C, 57.45; H, 4.21.
2-Pentafluoropropionyl-5,5-dimethylcyclohexane-1,3-dione
(2g). This compound was obtained as colorless crystals, mp 87–
2-Trifluoroacetyl-5-methylcyclohexane-1,3-dione (2c). This
compound was obtained as colorless crystals, mp 63–65 8C. IR
1
89 8C. IR (KBr): n 1700, 1625, 1575 cmꢀ1. NMR: H d 1.13
1
(KBr): n 1685, 1640, 1555 cmꢀ1. NMR: H d 1.14 (3H, d,
(6H, s, 2CH3), 2.43 (2H, s, CH2-4), 2.76 (2H, s, CH2-6), 15.08
(1H, bs, OH). 13C: d 28.12 (2CH3 at C-5), 31.13 (C-5), 45.53
J = 6.4 Hz, CH3 at C-5), 2.23 (1H, dd, 1J = 12.3 Hz,
2J = 15.8 Hz, Ha, C-4), 2.31 (1H, m, C-5), 2.51 (1H, dd,
1J = 10.3 Hz, 2J = 18.3 Hz, Ha, C-6), 2.64 (1H, bd, J = 15.8 Hz,
He, C-4), 2.83 (1H, bd, J = 18.3 Hz, He, C-6), 15.2 (1H, bs,
OH). 13C: d 20.65 (CH3 at C-5), 26.52 (C-5), 39.70 (C-6), 46.04
1
2
(C-6), 51.86 (C-4), 108.21 (tq, JC–F = 270 Hz, JC–F = 36 Hz,
CF2), 111.64 (C-2), 118.45 (qt, 1JC–F = 288 Hz, 2JC–F = 34 Hz,
CF3), 187.11 (t, 2JC–F = 30 Hz, COC2F5), 191.57 (C-3), 196.17
(C-1). 19F: d ꢀ80.29 (CF3), ꢀ118.31 (CF2). GC–MS (EI
70 eV), m/z (rel. int.): 286 [M]+ (5), 230 [M ꢀ CH2CH2CO]+
(14), 202 [M ꢀ CH2COCH2CO]+ (14), 174 [M ꢀ CF3–CH3–
CO]+ (50), 167 [M ꢀ C2F5]+ (100), 111 [M ꢀ C2F5CO–
2CH3 + 2H]+ (21), 83 [CHCOCH2CO]+ (54), 69 [CF3]+ (47),
55 [CHCH2CO]+ (25), 41 [CHCO]+ (22). Anal. Calcd for
C11H11O3F5: C, 46.16; H, 3.87. Found: C, 46.07; H, 3.81.
2-Pentafluoropropionylcyclohexane-1,3-dione (2h). This
compound was obtained as colorless crystals, mp 37–38 8C.
1
(C-4), 110.85 (C-2), 116.27 (q, JC–F = 286 Hz, CF3), 184.10
2
(q, JC–F = 39 Hz), 191.67 (C-3), 196.86 (C-1). 19F: d ꢀ74.17
(c, CF3). GC–MS (EI 70 eV), m/z (rel. int.): 222 [M]+ (14), 180
[M ꢀ CH2CO]+ (29), 153 [M ꢀ CF3]+ (66), 124 [M ꢀ H–
+
CF3CO]+ (73), 69 [CF3] (100), 55 [CHCH2CO]+ (18), 42
[M ꢀ 180]+ (22), 41 [CH2CO]+ (29). Anal. Calcd for
C9H9O3F3: C, 48.66; H, 4.08. Found: C 48.58; H, 3.99.
2-Trifluoroacetyl-4-carbomethoxy-5,5-dimethylcyclohex-
ane-1,3-dione (2d). This compound was obtained as colorless
crystals, mp 75–78 8C. IR (KBr): n 1740, 1700, 1650,
1
IR (KBr): n 1700, 1620, 1560 cmꢀ1. NMR: H d (2H, qui,
J = 6.5 Hz, C-5), 2.56 (2H, bt, C-4), 2.79 (2H, bt, C-6), 15.02
(1H, s, OH). 13C: d 18.92 (C-5), 31.99 (C-6), 37.84 (C-4),
108.17 (tq, 1JC–F = 270 Hz, 2JC–F = 36 Hz, CF2), 112.61 (C-2),
118.44 (qt, 1JC–F = 288 Hz, 2JC–F = 35 Hz, CF3), 187.61 (t, 2JC–
F = 30 Hz, COC2F5), 191.70 (C-3), 197.12 (C-1). 19F: d ꢀ80.21
(CF3), ꢀ118.29 (CF2). GC–MS (EI 70 eV), m/z (rel. int.): 258
[M]+ (8), 230 [M ꢀ CO]+ (10), 202 [M ꢀ CH2CH2CO]+ (16),
174 [M ꢀ CH2COCH2CO]+ (53), 139 [M ꢀ C2F5]+ (100), 119
[C2F5]+ (10), 111 [M ꢀ C2F5CO]+ (18), 69 [CF3]+ (81), 55
[CHCH2CO]+ (32), 42 [CH2CO]+ (31). Anal. Calcd for
C9H7O3F5: C, 41.88; H, 2.73. Found: C, 41.78; H, 2.67.
2-Heptafluorobutyryl-5,5-dimethylcyclohexane-1,3-dione
(2i). This compound was obtained as colorless crystals, mp 69–
72 8C. IR (KBr): n 1695, 1635, 1575 cmꢀ1. NMR: 1H d 1.13 (6H,
s, 2CH3), 2.43 (2H, s, CH2-4), 2.67 (2H, s, CH2-6), 14.98 (1H, bs,
OH). 13C: d 28.12 (2CH3 at C-5), 31.15 (C-5), 45.45 (C-6), 51.79
1
1560 cmꢀ1. NMR: H d 1.16 (3H, s, 5bCH3), 1.18 (3H, s,
5aCH3), 2.54 (1H, d, J = 18.9 Hz, Hb, C-6), 3.13 (1H, d,
J = 18.9 Hz, Ha, C-6), 3.34 (1H, s, H, C-4), 3.74 (3H, s,
CH3COO), 15.30 (1H, s, OH). 13C: d 25.85 (5aCH3), 28.16
(5bCH3), 33.33 (C-5), 43.15 (C-6), 52.4 (COOCH3), 64.37 (C-
1
4), 109.54 (C-2), 116.19 (q, JC–F = 286 Hz, CF3), 168.66
2
(COOCH3), 183.96 (q, JC–F = 39 Hz, COCF3), 187.36 (C-3),
196.46 (C-1). 19F: d ꢀ74.26 (c, CF3). GC–MS (EI 70 eV), m/z
(rel. int.): 294 [M]+ (5), 152 [M ꢀ 142]+ (10), 124 [M ꢀ 170]+
(20), 97 [CF3CO]+ (14), 83 [CHCOCH2CO]+ (100), 69 [CF3]+,
59 [CO2Me]+ (13), 55 [CHCH2CO]+ (22), 42 [CH2CO]+ (10),
41 [CHCO]+ (22). Anal. Calcd for C12H13O5F3: C, 48.99; H,
4.45. Found: C, 48.87; H, 4.37.
2-Trifluoroacetyl-5-phenylcyclohexane-1,3-dione (2e). This
compound was obtained as colorless crystals, mp 85–87 8C. IR
(KBr): n 1695, 1635, 1560 cmꢀ1. NMR: 1H d 2.86 (4H, m, C-4,
C-6), 3.44 (1H, m, C-5), 7.24 (2H, m, Har), 7.31 (1H, m, Har),
7.38 (2H, m, Har), 15.27 (1H, bs, OH). 13C: d 36.82 (C-5), 39.21
1
2
(C-4), 109.65 (m, CF2), 110.06 (tt, JC–F = 269 Hz, JC–
1
F = 31 Hz, CF2), 111.93 (C-2), 117.76 (qt, JC–F = 288 Hz,
2JC–F = 34 Hz, CF3), 187.34 (t, 2JC–F = 29 Hz, COC3F7), 191.65
(C-3), 195.59 (C-1). 19F: d ꢀ80.73 (3F, CF3), ꢀ113.73 (2F, CF2),
1
(C-6), 45.04 (C-4), 110.98 (C-2), 116.30 (q, JC–F = 286 Hz,