3982
G.-J. ten Brink et al. / Tetrahedron 58 +2002) 3977±3983
contaminated with a trace of 3-chloro-5-iodonitrobenzene).
Mp 1038C ꢀlit.: 103.58C); H NMR ꢀ300 MHz; CDCl ) d
was ®ltered off, washed with water ꢀ10 ml), 10% NaHCO3
ꢀ10 ml), 10% NaHSO ꢀ10 ml) and water ꢀ10 ml). The
3
7
1
3
3
8
H4); C NMR ꢀ75 MHz; CDCl ) d 151.0 ꢀC4), 148.5
.51 ꢀ2H, d, J1.5 Hz, H21H6), 8.37 ꢀ1H, d, J1.5 Hz,
product was crystallised from acetone and washed with
n-pentane to give light yellow ®ne needles. Yield2.09 g
1
3
3
1
ꢀC1), 131.8 ꢀC21C6), 94.1 ꢀC31C5); MS ꢀEI) m/z 375
100), 329 ꢀ44, M2NO ), 202 ꢀ31, M2NO ±I), 127 ꢀ11),
ꢀ2.1 mmol, 42%). Mp82.5±83.58C; H NMR ꢀ400 MHz;
1
3
ꢀ
CDCl /C F ) d 8.01 ꢀ2H, s, H21H6), 7.82 ꢀ1H, s, H4);
3
C
2
2
6 6
7
5 ꢀ81), 74 ꢀ50).
NMR ꢀ100 MHz; CDCl /C F ) d 140.4±140 ꢀm, C21C6),
3 6 6
19
1
37.9±137.4 ꢀm, C4), 134.4 ꢀt, C1), 132.7 ꢀt, C31C5);
F
4
ꢀ
.4.3. 3-Chloro-5-iodonitrobenzene. MS ꢀEI) m/z 283
100), 237 ꢀ58, M2NO ), 225 ꢀ12), 127 ꢀ8), 126 ꢀ11), 110
NMR ꢀ376.3 MHz; CDCl /C F ) d 281.3 ꢀ6F, t, J9.2 Hz,
3
6 6
2CF ), 2111.5 ꢀ4F, t, J15.3 Hz, 2CF ), 2121.3 ꢀ2CF ),
2122.0 ꢀ6CF ), 2122.9 ꢀ2CF ), 2126.4 ꢀ2CF ); MS ꢀEI)
2 2 2
2
3
2
2
ꢀ
50, C H Cl), 75 ꢀ48).
6
3
m/z 994 ꢀ20), 975 ꢀ16, M2F), 675 ꢀ6), 625 ꢀ100), 546 ꢀ11),
284 ꢀ6), 131 ꢀ13), 69 ꢀ32).
3
.4.4. 3,5-Diiodoaniline. A solution of 3,5-diiodonitro-
2
4
benzene ꢀ80 mmol, 30 g) in EtOH ꢀ100%, 150 ml) was
reduced with Raney Ni ꢀ0.5 g)/H ꢀ1 bar) at 158C. After
2
4.4.8. 3,5-Bis)per¯uorooctylꢀphenyl butylselenide. A
suspension of Se ꢀ40 mmol, 3.2 g) in THF was cooled to
2208C and 1.6 M BuLi in hexane ꢀ40 mmol, 25 ml) was
added. The solution turned from black to light red within
minutes. This cold solution of BuSeLi was added to a solu-
tion of 3,5-bisꢀper¯uorooctyl)-1-bromobenzene ꢀ5 mmol,
5.0 g) in anhydrous THF ꢀ75 ml) at 2758C and allowed to
warm-up to room temperature overnight. The reaction
mixture was poured in water ꢀ100 ml) and acidi®ed with
1 M HCl. The solution was extracted with ether
ꢀ4£50 ml). The organic phase was washed with 10%
4
h the stirring was stopped and the supernatant was poured
over a ®lter. Enough water ꢀca. 200 ml) was added to the
ltrate to precipitate an off-white ¯occulent solid. The solid
®
was ®ltered off, dissolved in ether, water was separated and
the organic phase was dried over MgSO . The salt was
4
®ltered of and the ®ltrate evaporated to dryness. The aniline
was crystallised from n-pentane/EtOH ꢀ9:1) to give white
needles of 3,5-diiodoaniline contaminated with a trace of
3
-chloro-5-iodoaniline. Yield18.8 g ꢀ54.5 mmol, 68%).
3
8
1
Mp1028C ꢀlit.: 1058C); H NMR ꢀ400 MHz; CDCl ) d
3
7.39 ꢀ1H, t, J1.4 Hz, H4), 6.98 ꢀ2H, d, J1.4 Hz,
H21H6), 3.6 ꢀ2H, s broad, NH ); C NMR ꢀ100 MHz;
NaHCO
MgSO
in vacuo and the brown residue was dissolved in per¯uoro-
hexanes ꢀ5 ml). This solution was extracted with CH Cl
ꢀ5 ml) to remove Bu Se . After evaporation of the per¯uoro-
3
ꢀ50 ml) and water ꢀ50 ml) and dried over
. The solid was ®ltered off, the ®ltrate evaporated
4
1
3
2
CDCl ) d 148.6 ꢀC1), 134.9 ꢀC4), 123.0 ꢀC21C6), 95.1
3
ꢀ
ꢀ
C31C5); MS ꢀEI) m/z 345 ꢀ100), 218 ꢀ41, M2I), 191
6), 172 ꢀ7), 127 ꢀ14), 91 ꢀ41, C H NH ), 63 ꢀ27).
2
2
6
3
2
2
2
hexanes the product was crystallised from acetone.
Yield2.6 g ꢀ2.5 mmol, 50%) of an off-white solid.
4
ꢀ
.4.5. 3-Chloro-5-iodoaniline. MS ꢀEI) m/z 253 ꢀ100), 126
57, M2I), 99 ꢀ24), 90 ꢀ27), 63 ꢀ30).
1
Mp56±578C; H NMR ꢀ300 MHz; CDCl
) d 7.84 ꢀ2H,
3
s, H21H6), 7.61 ꢀ1H, s, H4), 3.01 ꢀ2H, t, J7.3 Hz,
SeCH ), 1.71 ꢀ2H, m, SeCH CH ), 1.45 ꢀ2H, m, CH CH ),
0.92 ꢀ3H, t, J7.3 Hz, CH ); C NMR ꢀ75 MHz; CDCl ) d
134.0 ꢀC1), 133.1 ꢀC21C6), 130.4 ꢀ2C, t, J24.8 Hz,
C31C5), 123.3 ꢀC4), 31.8 ꢀSeCH ), 28.0 ꢀSeCH CH ),
); F NMR ꢀ282 MHz; CDCl
d 281.3 ꢀ6F, t, J9.8 Hz, 2CF ), 2111.7 ꢀ4F, t, J14.0 Hz,
2CF ), 2121.4 ꢀ2CF ), 2122.4 ꢀ6CF ), 2123.2 ꢀ2CF ),
2126.7 ꢀ2CF ); MS ꢀEI) m/z 1050 ꢀ63), 994 ꢀ30), 625 ꢀ17,
M2C 2C 15), 545 ꢀ12, C ꢀCF )C 15), 131 ꢀ12), 57
ꢀC , 100).
4
.4.6. 3,5-Bis)per¯uorooctylꢀaniline. A mixture of 3,5-
diiodoaniline ꢀ20 mmol, 6.9 g), copper bronze ꢀ100 mmol,
.4 g) and per¯uorooctyliodide ꢀ44 mmol, 24 g, 12.0 ml) in
2
2
1
2
2
3
3
3
3
6
anhydrous DMSO ꢀ60 ml) was stirred for 16 h at 1258C
under N . After cooling copper was ®ltered off and washed
with ether ꢀ200 ml). The ®ltrate was extracted with water to
remove DMSO and the organic phase was dried over
MgSO . The salt was ®ltered off, and the ®ltrate was evapo-
2
2
2
1
9
22.8 ꢀCH
CH
), 13.4 ꢀCH
3
)
3
2
2
3
3
2
2
2
2
4
2
rated in vacuo to leave a red syrup. The residue was crystal-
lised from CH Cl ꢀ100 ml) to give 10.9 g ꢀ11 mmol, 59%)
H
4
9
7
F
6
H
3
2
F
8
H
4 9
2
2
1
of a white wax-like solid. Mp60±618C; H NMR
ꢀ400 MHz; C F ) d 7.30 ꢀ1H, s, H4), 7.20 ꢀ2H, s,
H21H6), 4.39 ꢀ2H, s, NH2); C NMR ꢀ100 MHz; C F )
4.5. Materials
6
6
1
3
6
6
d 150.6 ꢀC1), 134.1 ꢀt, C31C5), 117.9 ꢀ2C, s, C21C6),
1
Bis[3,5-bisꢀtri¯uoromethyl)phenyl] diselenide was prepared
via reaction of 3,5-bisꢀtri¯uoromethyl)phenylmagnesium
bromide with elemental selenium and subsequent aerobic
oxidation of the corresponding benzeneselenol. Glacial
acetic acid, n-BuLi ꢀ1.6 M in hexane), per¯uorohexanes
ꢀFC 72), per¯uorodecalin ꢀ95%), cyclobutanone ꢀ981%),
cyclopentanone ꢀ991%) 3-phenylpropanal ꢀ97%), octanal
1
9
17.2 ꢀC4), 122±110 ꢀCF2); F NMR ꢀ376.3 MHz; C F )
6 6
d 281.0 ꢀ6F, t, J9.9 Hz, 2CF ), 2110.9 ꢀ4F, t, J15.3 Hz,
3
1
1
2
CF ), 2120.5 ꢀ2CF ), 2121.4 ꢀ4CF ), 2121.7 ꢀ2CF ),
2
2
2
2
2
122.2 ꢀ2CF ), 2125.7 ꢀ2CF ); MS ꢀEI) m/z 929 ꢀ100),
2 2
9
10 ꢀ53, M2F), 560 ꢀ72, M2C F ), 222 ꢀ10), 191 ꢀ12),
7 15
6
9 ꢀ15).
ꢀ99%), 3,4,5-trimethoxybenzaldehyde ꢀ99%), 4-nitro-
4.4.7. 3,5-Bis)per¯uorooctylꢀ-1-bromobenzene. A sus-
pension of 3,5-bisꢀper¯uorooctyl)aniline ꢀ5 mmol, 4.65 g)
benzaldehyde ꢀ99%) and 4-ꢀtri¯uoromethyl)benzaldehyde
ꢀ95%) were purchased from Acros. Anhydrous THF
ꢀ99.51%), ICl ꢀ97%), per¯uorooctyl iodide ꢀ981%),
2,2,2-tri¯uoroethanol ꢀ991%) and 1,1,1,3,3,3-hexa¯uoro-
2-propanol ꢀ991%) were purchased from Fluka; 1,2-
dichloroethane ꢀ991%), 48% HBr and 96% H SO from
in concentrated HBr ꢀ48%, 30 ml) was cooled to 58C and
a solution of NaNO ꢀ5.5 mmol, 0.38 g) in water ꢀ1 ml) was
2
added drop wise. The mixture was stirred for 1 h at 58C and
then poured in boiling concentrated HBr ꢀ48%, 20 ml)
containing CuBr ꢀ6 mmol, 0.86 g). The mixture was stirred
for 2 h at 1258C, cooled and diluted with water. The solid
2
4
Baker; copper powder ꢀ99%) and p-anisaldehyde ꢀ981%)
from Aldrich; elemental Se ꢀ991%) from Merck; CuBr