144
W. Dmowski, A. Wolniewicz / Journal of Fluorine Chemistry 102 (2000) 141±146
[6, (M 2HF) ]; 151 [13, (M CF3) ]; 149 [23, (M
3.3.3. Preparation of 1-(trifluoromethyl)-1-cyclohexanoyl
fluoride (4a)
CF3±2H) ]; 145 [16, (M CH3±2HF) ]; 136 [56,
(M CF3±CH3) ]; 135 (10); 132 [5, (M F±CF3) ];
1,1-Cyclohexanedicarboxylic acid (2a) (8.3 g, 48 mmol)
and SF4 (32 g, 0.3 mol) were reacted at 308C for 3 h. The
reaction mixture was poured into saturated aqueous
NaHCO3 solution and an organic product was steam dis-
tilled The organic layer in the distillate was separated, dried
over MgSO4 and redistilled to give acid ¯uoride 3a as a
colorless liquid. Yield: 5.4 g (56%). b.p. 140±1428C. GLC
purity >99%. Analysis: Found: C, 48.2%; H, 5.0%; F,
38.3%. Calculated for C8H10F4O (198.16): C 48.5%; H,
131 [64, (M HF±CF3) ]; 111 (31); 90 (22); 77 (14 );
69 (9, CF3 ); 67 (18, C5H7 ); 56 (100, C4H8 ); 41 (68,
C3H5 ). HRMS: M 220.06862. Calculated for C8H10F6:
220.06866.
3.3.2. Preparation of 1,1-bis(trifluoromethyl)cycloalkanes
(3b±d)
Acids 2b±d (30 mmol) and SF4 (20 g, 180 mmol) were
reacted at 1208C for 24 h (6 h in the case of 2c). Compound
3b was isolated by steam distillation as described above.
Compounds 3c and 3d were distilled directly from the crude
reaction mixture to which NaF (0.5 g) was added as a HF
scavenger.
1
1
5.1%; F, 38.4%. IR (®lm) n: 1841.6 cm (vs, COF). H
NMR (in CDCl3): d: 1.5±1.1 ppm (m, 2H); 1.50±1.90 ppm
(m, 6H); 2.25±2.31 ppm (m, 1H); 2.32±2.38 ppm (m, 1H).
13C NMR (in CDCl3): d: 159.4 (d, 1JCF 375.4 Hz, COF);
1
3
124.9 (qd, JCF 283.8 Hz, JCF 2.7 Hz, CF3);54.3 (dq,
1,1-Bis(tri¯uoromethyl)cyclopentane (3b): Yield: 56%.
b.p. 90±928C. GLC purity: >99%. Analysis: Found: F,
55.6%. Calculated for C7H8F6 (206.13): F, 55.3%. 1H
NMR (in CDCl3): d: 1.70±1.81 ppm (m, 4H); 1.98±
2.10 ppm (m, 4H). 13C NMR (in CDCl3): d: 126.8 (qq,
1JCF 282.5 Hz, 3JCF 2.7 Hz, CF3); 54.3 (sept,
2JCF 43.0 Hz,
2JCF 25.5 Hz,
C-1);
27.4
(d,
3JCF 2.7 Hz, C-2); 24.5 (s, C-3); 21.9 ppm (s, C-4). 19F
NMR (in CDCl3): d: 38.95 (m, COF); 74.76 ppm (d,
4JFF 8.5 Hz, CF3). MS (EI, 70 eV) m/z (rel. int., ion):
198 (6, M ); 178 [8, (M HF) ]; 158 [8, (M 2HF) ];
156 (10); 151 [8, (M COF) ]; 150 [80, (M CO±HF) ];
2JCF 26.0 Hz, C-1); 29.9 (q, JCF 2.7 Hz, C-2);
136 (45); 131 [32, (M COF±HF) ]; 130 [50, (M CO±
3
26.7 ppm (s, C-3). 19F NMR (in CDCl3): d: 72.05 ppm
(s, CF3). MS (EI, 70 eV) m/z (rel. int., ion): 186 [6,
2HF) or (M 2HF±C2H4) ]; 123 [43, (M COF±
C2H4) ]; 117 (62); 111 [25, (M COF±2HF) ]; 107
(M HF) ]; 167 [35, (M HF2) ]; 166 [35,
(24); 101 [50, (M CF3±C2H4) ]; 81 (36, C6H9 ); 69
(7, CF3 ); 68 (44, C5H8 ); 59 (10); 56 (100, C4H8 ); 55
(M 2HF) ]; 145 (24) 117 [28, (M C2H4±HF2) or
(M CF3±HF) ]; 97 [20, (M CF3±2HF) ]; 69 (5,
(49, C4H7 ); 43 (22, C3H7 ); 42 (14, C3H6 ); 41 (58,
CF3 ); 42 (100, C3H6 ); 41 (16, C3H5 ).
C3H5 ).
1,1-Bis(tri¯uoromethyl)cyclobutane (3c): Yield: 51%.
b.p. 66±688C (Lit. b.p. 688C [19]). GLC purity: >99%.
Analysis: Found: F, 59.1%. Calculated for C6H6F6
(192.10): F, 59.3%. 1H NMR (in CDCl3): d: 2.00±
2.19 ppm (m, 2H); 2.40±2.57 ppm (m, 4H). 13C NMR (in
3.3.4. Preparation of 1-(trifluoromethyl)-1-cyclopentanoyl
fluoride (4b)
1,1-Cyclopentanedicarboxylic acid (2b) (6.0 g, 38 mmol)
and SF4 (32 g, 0.3 mol) were reacted at 308C for 3 h.
The reaction mixture was dissolved in CH2Cl2 (20 ml),
stirred overnight with solid NaF (5 g) (removal of HF),
®ltered and distilled under atmospheric pressure to give 4b
as a colorless liquid: Yield: 3.1 g (44%). b.p. 108±1108C.
GLC purity: >96%. Analysis: Found: F, 41.5%. Calculated
for C7H8F4O (184.13): F, 41.3% (C and H were not deter-
1
3
CDCl3): d: 125.0 (qq, JCF 279.3 Hz, JCF 2.4 Hz,
2
CF3); 48.7 (sept, JCF 29.0 Hz, C-1); 22.1 (sept,
3JCF 2.5 Hz, C-2); 14.8 ppm (s, C-3). 19F NMR (in
CDCl3): d: 72.3 ppm (s, CF3). MS (EI, 70 eV) m/z (rel.
int., ion): 192 (11, M ); 172 [8, (M HF) ]; 153 (27,
(M HF2) ]; 145 [100, (M C2H4±F) ]; 133 [12,
(M 2HF±F) ]; 123 [28, (M CF3) ]; 103 [18,
(M CF3±HF) ]; 95 [33, (M C2H4±CF3) ]; 69 (29,
mined due to a high volatility of 4b). IR (®lm) n:
1844.1 cm
CF3 ); 47 (36); 41 (20, C3H5 ).
(vs, COF). 1H NMR (in CDCl3): d:
1
1,1-Bis(tri¯uoromethyl)cyclopropane (3d): Yield: 59%.
b.p. 44±468C (Lit. b.p. 458C [20]). GLC purity: >99%.
Analysis: Found: F, 63.3% (an error occurred due to high
volatility of 3d). Calculated for C5H4F6 (178.08): F, 64.0%.
1H NMR (in CDCl3): d: 1.25 ppm (m, 4H). 13C NMR (in
1.75 1.90 ppm (m, 2H); 2.00±2.35 ppm (m, 2H). 13C
1
NMR (in CDCl3): d: 160.7 (d, JCF 364.3 Hz, COF);
125.7 (q, 1JCF 280.5 Hz, CF3); 58.2 (dq, 2JCF 47.2 Hz,
2JCF 27.0 Hz, C-1); 32.3 (s, C-2); 26.3 ppm (s, C-3). 19
F
NMR (in CDCl3): d: 38.95 (m, COF); 74.76 ppm (d,
4JFF 8.5 Hz, CF3). MS (EI, 70 eV) m/z (rel. int., ion):
1
3
CDCl3): d: 124.3 (qm, JCF 273.9 Hz, JCF 1.8 Hz,
2
165 [3, (M F) ]; 164 [2, (M HF) ]; 144 [6, (M
CF3); 26.2 (sept, JCF 34.9 Hz, C-1); 7.25 ppm (sept,
3JCF 1.9 Hz, C-2). 19F NMR (in CDCl3): d: 68.2 ppm
2HF) ]; 143 [17, (M H3F2) ]; 141(5); 136 [7,
(M HF±CO) ]; 123 [35, (M H2F3) ]; 117 [40,
(s, CF3). MS (EI, 70 eV) m/z (rel. int., ion): 178 (9, M ); 163
[21, (M CH3) ]; 159 [31, (M F) ]; 158 [20,
(M CO±HF2) ]; 116 [14, (M CO±2HF) ]; 115 [10,
(M CF3) ]; 97 (26); 95 [11, (M CF3±HF) ]; 89 [6,
(M HF) ]; 145 (100); 139 (53, (M HF2) ]; 109 [41,
(M CF3) ]; 95 [19, (M CF3 CH2) ]; 89 [29,
(M C2H4±CO±HF2) ]; 69(12, C5H9 ); 67 (35, C5H7 );
42 (100, C3H6 ); 41 (23, C3H5 ).
(M CF3±HF) ]; 75 (4, C3HF2 ); 69 (21, CF3); 46 (25).