1452
C. Zarantonello et al. / Journal of Fluorine Chemistry 128 (2007) 1449–1453
3.3.5. Synthesis of 3–SF5–C6H4–COH (4a)
8.0, CH(5), 1H); 8.15 (ddd, 3JHH 8, 4JHH 2, 4JHF 1, CH(6)CSF5,
1H); 8.18 (d, 3JHH 8.0, CH(4), 1H); 8.35 (dd, 4JHH 2.1, CH(2),
1H), 11.40 (1H, COOH). 13C NMR (CD3COCD3; d, ppm; J,
Hz): 153.9 (qt, 2JCF 17.1, C(1)-SF5); 127.2 (qt, 3JCF 4.8, C(2));
132.2 (C(3)–COOH); 133.5 (C(4)); 130.2 (C(5)); 130.5 (qt d,
3JCF 4.7, C(6)); 165.54 (C O). 19F NMR (CD3COCD3; d, ppm;
J, Hz): 60.9 (dt, 2JFF 149, 4JHF 2.0, 4F), 84.3 (quintet, 1F). MS
(EI+, 70 eV, m/z, rel.ab.%): 248([M]+, 100%); 229 ([M–F]+,
5%); 231 ([M–OH]+, 60%); 203 ([M–CO2H]+, 10%); 121([M–
SF5]+, 20%).
An Et2O solution (15 ml) of 3a (7.0 g, 0.024 mol) was
cooled at ꢁ78 8C. Then LiBut pentane solution (25.2 ml,
1.6 M) was added dropwise. The solution turned from pale
brown to red. The solution was stirred at low temperature for
1 h. 1-Formyl-piperidine (4.20 ml, 0.035 mol) was then added
dropwise and the mixture was stirred for additional 30 min.
Then the solution was stirred at room temperature for 4 h.
Deionised water (70.0 ml) was added to the solution, which was
also treated three times with HCl (140 ml, 2,5% solution).
Organic phase was collected, treated with Na2SO4 and taken to
dryness obtaining a reddish oil which slowly crystallized. Yield
5.5 g, 96%.
3.3.8. Synthesis of 4-SF5-C6H4-COOH (5b)
The synthesis was performed starting from 4b (5.0 g;
0.02 mol) following the same procedure described for 3b. Yield
4.8 g, 98%. mp 192–193 8C.
Anal. Calc. for C7H5F5OS (PM = 232.17.): C, 36.21; H,
2.17; Found: C, 36.10; H, 2.08%.
IR (n¯, KBr film): 1606 (m, CCPh), 842 (vs, SF5); 1707 (vs,
CO). 1H NMR (CD3COCD3; d, ppm; J, Hz): 7.76 (t, 3JHH 8.0,
CH(5), 1H); 8.10 (ddd, 3JHH 8.0, 4JHF 2.0, 4JHH 1.0, CH(6), 1H);
Anal. Calc. for C7H5F5O2S (PM = 232.17.): C, 33.88; H,
2.03; Found: C, 33.75; H, 1.98%.
IR (n¯, KBr film): 1603 (m, CCPh), 843 (vs, SF5); 1706 (vs,
1
CO). H NMR (CD3COCD3; d, ppm; J, Hz): 8.26, 8.21 and
3
4
4
8.26 (d, JHH 8.0, CH(4), 1H); 8.40 (dd, JHH 2.0, JHH 2.1,
CH(2), 1H), 10.15 (1H, CHO). 13C NMR (CD3COCD3; d, ppm;
8.06, 7.99 (AA0BB0 pattern, 4H, Ph); 11.05 (1H, COOH). 13C
NMR (CD3COCD3; d, ppm; J, Hz): 156.9 (qt, 2JCF 18.1, C(1)-
SF5); 126.7 (qt, 3JCF 4.8, C(2) and C(6)); 130.9 (C(3) and C(5));
134.4 (C(4)), 165.6 (C O). 19F NMR (CD3COCD3; d, ppm; J,
2
3
J, Hz): 154.5 (qt, JCF 18.6, C(1)-SF5); 126.2 (qt, JCF 5.0,
C(2)); 137.8 (C(3)-CHO); 132.9 (C(4)); 130.7 (C(5)); 131.4 (qt
3
d, JCF 4.7, C(6)); 190.9 (CH O). 19F NMR (CD3COCD3; d,
ppm; J, Hz): 61.4 (d, 2JFF 147, 4F), 82.7 (quintet, 1F). MS (EI+,
70 eV, m/z, rel.ab.%): 232 ([M]+, 80%); 231 ([M–H]+, 100%);
213 ([M–F]+, 5%); 203 ([M–CHO]+, 10%); 105 ([M–SF5]+,
25%); 95 ([C6H4F]+, 60%).
Hz): 62.7 (dt, JFF 140, JFH 1, 4F), 83.58 (quintet, 1F). MS
(EI+, 70 eV, m/z, rel.ab.%): 248([M]+, 100%); 229 ([M–F]+,
10%); 231 ([M–OH]+, 50%); 203 ([M–CO2H]+, 8%); 121 ([M–
SF5]+, 30%).
2
4
3.3.6. Synthesis of 4–SF5–C6H4–COH (4b)
4. X-ray measurements and structure determination
4.1.1. Crystal data for compound 3–SF5–C6H4–COOH (5a)
Empirical formula C7H4F5O2S, Mr = 247.16, monoclinic,
The synthesis was performed starting from 3b (7.0 g;
0.024 mol) following the same procedure described for 4a.
Yield 5.6 g, 98%.
Anal. Calc. for C7H5F5OS (PM = 232.17.): C, 36.21; H,
2.17; Found: C, 36.10; H, 1.99%.
space group P21/n, with a = 8.723(2), b = 9.682(2),
3
˚
˚
IR (n¯, KBr film): 1601 (m, CCPh), 845 (vs, SF5); 1712 (vs,
CO). 1H NMR (CD3COCD3; d, ppm; J, Hz): 8.15-8.02 (m, 4H,
Ph); 10.16 (1H, CHO). 13C NMR (CD3COCD3; d, ppm; J, Hz):
c = 11.641(3) A, b = 111.44(2)8, V = 915.1(4) A , Z = 4,
r
3
calc = 1.794 Mg/m , F (0 0 0) = 492, l = 0.71073 A, T =
293(2) K, m (Mo Ka) = 0.410 mmꢁ1
˚
.
2
3
157.5 (qt, JCF 17.1, C(1)-SF5); 127.3 (qt, JCF 6.3, C(2) and
C(6)); 130.4(C(3) and C(5)); 139.2 (C(4)–CHO), 191.3
(CH O). 19F NMR (CD3COCD3; d, ppm; J, Hz): 61.1 ppm
A prismatic colorless crystal was centered on a four-circle
Philips PW1100 (Febo System) diffractometer operating in u/2u
scan mode with graphite-monochromated Mo Ka radiation
2
˚
(d, JFF 151, 4F), 81.9 (quintet, 1F). MS (EI+, 70 eV, m/z,
(l = 0.71073 A), following standard procedures at room
rel.ab.%): 232 ([M]+, 75%); 231 ([M–H]+, 100%); 213 ([M–
F]+, 8%); 203 ([M–CHO]+, 15%); 105 ([M–SF5]+, 20%); 95
([C6H4F]+, 65%).
temperature. There were no significant fluctuations of
intensities other than those expected from Poisson statistics.
The intensity data were corrected for Lorentz-Polarization
effects and for absorption, as described by North et al. [14].
The structure was solved by direct methods SIR-97 [15].
Refinement was carried out by full-matrix least-squares
procedures using anisotropic temperature factors for all non-
hydrogen atoms. The H-atoms were placed in calculated
positions with fixed, isotropic thermal parameters (1.2 Uequiv
3.3.7. Synthesis of 3–SF5–C6H4–COOH (5a)
An H2O solution (25 ml) of 4a (5.0 g, 0.02 mol) was reacted
with Ag2O (7.0 g, 0.030 mol) and NaOH (15.0 ml, 10%
solution). The reaction mixture was stirred at room temperature
in the dark for 20 h. The mixture was then treated with charcoal;
the solids filtered off and the solution was acidified with HCl
(37%, ca. 5 ml) until 5a precipitates. Yield 4.9 g, 98%. mp 153–
155 8C.
of the parent carbon atom). For a total of 157 parameters and for
P
1968 reflections having (I ꢃ 2s(I)), wR0ð½ wðFo2 ꢁ Fc2Þ2=
P
2
1=2
wðFo2Þ ꢄ Þ = 0.158, S = 1.140 and conventional R = 0.059.
Structure refinement and final geometrical calculations were
carried out with SHELXL-97 [16] and PARST [17] programs,
drawings were produced using ORTEP II [18]. Crystal-
lographic data for the structures here reported have been
Anal. Calc. for C7H5F5O2S (PM = 248.17.): C, 33.88; H,
2.03; Found: C, 33.50; H, 2.00%.
IR (n¯, KBr film): 1606 (m, CCPh), 836, 803 (vs, SF5); 1697
(vs, CO). 1H NMR (CD3COCD3; d, ppm; J, Hz): 7.84 (tm, 3JHH