in 100 ml of toluene. Formic acid (10 ml, 98%) was added and
the resulting solution was refluxed for 1 h and then cooled to
room temperature. The solvent was removed on a rotary
evaporator and the residue recrystallized in pentane to give
white crystals of a mixture of Z and E isomers of the product
H, alkyl chain); 19F NMR (CDCl ) d −129.2 (m, 4J 8.3);
3
cF
n
/cm−1 (CH Cl ) 2217; (Nujol) 2233, 2218 (Calc. for
O
(C N)
2 2
C H NAuClFO: C, 37.40; H, 4.18; N, 2.91. Found: C, 37.65;
15 20
H, 3.97; N, 3.08%); DSC/°C K–K∞ 146.9 (2.1), K∞–S 174.7
A
(17.3), S –I 201.5 (8.9).
A
(0.614 g, 93%); Z-isomer: 1H NMR (CDCl ) d 7.43, 7.14 and
3
6.8–7.0 (overlapped with Ha and Hc of the E-isomer) (Ha, Hb
Chloro(3-fluoro-4-hexyloxyphenyl isocyanide)gold(i)
and Hc, AMNX spin system, 4J 2.5, 3J 8.8, Ar-H), 8.32 (CH,
ab
bc
Yield 66%; n
/cm−1 (CH Cl ) 2218; (Nujol) 2238, 2220
J 1.6), 7.20 (NH, br), 4.03–3.99 (CH O, overlapped with the
O
13 16
(C N)
2 2
2
CH O of the E-isomer), 1.86–0.88 (m, alkyl chains of the two
2
(Calc. for C H NAuClFO: C, 34.42; H, 3.55; N, 3.09. Found:
C, 34.54; H, 3.38; N, 3.57%). DSC: K–K∞ 156.0 (2.6), K∞–S
isomers); 19F NMR (CDCl ) d −132.4 (m, 3J 12.5, 5J 1.3,
A
3
aF
bF
177.7 (16.1), S –I, 205.5 (8.9).
4J 9.1).
A
cF
E-isomer: 1H NMR (CDCl ) d 6.8–7.0 (Ha and Hc) (over-
3
lapped with Hc of the Z-isomer) and 6.79 (Hb) (AMNX spin
Chloro(3-fluoro-4-decyloxyphenyl isocyanide)gold(i)
system, 4J 2.6, 3J 8.8, Ar-H), 8.51 (CH, J 11.4), 7.70 (NH, br),
ab
bc
Yield 69%; n
/cm−1 (CH Cl ) 2217; (Nujol) 2235, 2218
O
17 24
4.03–3.99 (CH O, overlapped with the CH O of the Z-isomer),
(C N)
2 2
2
2
(Calc. for C H NAuClFO: C, 40.05; H, 4.75; N, 2.75. Found:
1.86–0.88 (m, alkyl chains of the two isomers); 19F NMR
C, 40.27; H, 4.54; N, 2.65%); DSC/°C K–K∞ 152.5 (2.2), K∞–S
(CDCl ) d −131.5 (m, 3J 11.5, 5J 1.4, 4J 8.8, J
1.4).
A
3
aF
bF
cF
CH–F
169.9 (17.5), S –I 196.5 (9.0).
A
N-(2-fluoro-4-octyloxyphenyl )formamide
Chloro(3-fluoro-4-dodecyloxyphenyl isocyanide)gold(i)
Z-isomer: 1H NMR (CDCl ) d 8.10 (Hb) and 6.73–6.64 (Ha
3
Yield 58%; n
)/cm−1 (CH Cl ) 2218; (Nujol) 2240, 2221
and Hc) (overlapped with Ha and Hc of the E-isomer) (AMNX
O
19 28
(C
N
2 2
(Calc. for C H NAuClFO: C, 42.43; H, 5.25; N, 2.60. Found:
spin system, 3J 8.9, Ar-H), 8.40 (CH, J 1.6), 7.30 (NH, br),
bc
C, 42.70; H, 5.07; N, 2.72%); DSC/°C K–K∞ 148.0 (2.2), K∞–S
3.94–3.89 (CH O, overlapped with the CH O of the E-isomer),
A
2
2
167.7 (18.3), S –I 190.6 (8.7).
1.86–0.88 (m, alkyl chains of the two isomers); 19F NMR
A
(CDCl ) d −128.4 (m, 4J 8.9).
3
bF
E-isomer: 1H NMR (CDCl ) d 6.73–6.64 (Ha and Hc)
Chloro(2-fluoro-4-octyloxyphenyl isocyanide)gold(i)
3
(overlapped with Ha and Hc of the Z-isomer) and 7.11 (Hb)
Yield 64%; 1H NMR (CDCl ) d 6.76, 7.46 and 6.75 (Ha, Hb
(AMNX spin system, 3J 8.8, Ar-H), 8.46 (CH, J 11.5), 7.35
3
bc
and Hc, AMNX spin system, 4J 2.6, 3J 8.5, Ar-H), 3.99 (t,
(NH, br), 3.94–3.89 (CH O, overlapped with the CH O of
ac
bc
2
2
J 6.5, CH O), 1.86–0.88 (m, 15 H, alkyl chain); 19F NMR
the Z-isomer), 1.86–0.88 (m, alkyl chains of the two isomers);
2
(CDCl ) d −113.9 (m, 3J 8.0, 4J 8.5, 5J 1.7); n
/cm−1
O
(C N)
19F NMR (CDCl ) d −125.1 (m, 4J 8.8, J
1.4).
3
aF
bF
cF
15 20
3
bF
CH–F
(CH Cl ) 2223; (Nujol) 2237 (Calc. for C H NAuClFO: C,
2
2
37.40; H, 4.18; N, 2.91. Found: C, 37.58; H, 4.04; N, 2.91%);
3-Fluoro-4-octyloxyphenyl isocyanide
DSC/°C K–S 114.7 (32.4), S –I 117.8 (4.8).
A
A
The procedure described by Ugi15 was followed, using triphos-
gene as dehydrating agent. To a solution of 3-fluoro-4-octyloxy-
formanilide (0.156 g, 0.58 mmol) and triethylamine (0.2 ml,
1.17 mmol) in 50 ml of CH Cl was added dropwise a solution
Chloro(2-fluoro-4-hexyloxyphenyl isocyanide)gold(i)
Yield 58%; n
/cm−1 (CH Cl ) 2222; (Nujol) 2232 (Calc.
O
(C N)
2 2
2
2
for C H NAuClFO: C, 34.42; H, 3.55; N, 3.09. Found: C,
of triphosgene (0.053 g, 0.19 mmol) in 25 ml of CH Cl . The
13 16
2
2
34.53; H, 3.38; N, 2.99%); DSC/°C K–K∞ 62.4 (4.6), K∞–N, N–I
mixture was stirred for 1 h and then the solvent was removed
on a rotary evaporator. The resulting residue was chromato-
graphed (silica gel, CH Cl –hexane, 351 as eluent) and the
114.1 (24.0).
2
2
Chloro(2-fluoro-4-decyloxyphenyl isocyanide)gold(i)
solvent was evaporated to obtain the product as a colourless
oil (0.112 g, 77%); 1H NMR (CDCl ) d 7.14–7.10 (Ha and Hb)
Yield 52%; n
/cm−1 (CH Cl ) 2223; (Nujol) 2238 (Calc.
3
O
and 6.91 (Hc) (AMNX spin system, 3J 8.5, Ar-H), 4.03 (t, J
(C N)
2 2
for C H NAuClFO: C, 40.05; H, 4.75; N, 2.75. Found: C,
bc
6.5, CH O), 1.86–0.88 (m, 15 H, alkyl chain); 19F NMR
2
17 24
40.18; H, 4.47; N, 2.99%); DSC/°C K–K∞, K∞–S 115.7 (32.9),
A
(CDCl ) d −131.4 (m, 3J 11.2, 5J 2.4, 4J 8.5).
S –I 124.2 (6.0).
3
aF
bF
cF
A
2-Fluoro-4-octyloxyphenyl isocyanide
Chloro(2-fluoro-4-dodecyloxyphenyl isocyanide)gold(i)
1H NMR (CDCl ) d 6.69, 7.30 and 6.66 (Ha, Hb and Hc,
3
Yield 68%; n
/cm−1 (CH Cl ) 2223; (Nujol) 2237 (Calc.
O
AMNX spin system, 4J 2.6, 3J 8.8), 3.95 (t, J 6.5, CH O),
(C N)
2 2
ac
bc
2
for C H NAuClFO: C, 42.43; H, 5.25; N, 2.60. Found: C,
1.86–0.88 (m, 15 H, alkyl chain); 19F NMR (CDCl ) d −116.2
19 28
3
42.52; H, 5.00; N, 2.65%); DSC/°C K–K∞ 95.6 (0.9), K∞–S
(m, 3J 11.4, 4J 8.1, 5J 1.2).
A
aF
bF
cF
119.3 (38.9), S –I 126.7 (6.6).
A
3,4,5-Trioctyloxyphenyl isocyanide
Chloro(3,4,5-trioctyloxyphenyl isocyanide)gold(i)
1H NMR (CDCl ) d 6.5 (s, 2 H, C H ), 3.9 (m, 6 H, CH O),
3
6
2
2
Yield 83%; 1H NMR (CDCl ) d 6.7 (s, 2 H, C H ), 3.9 (m, 6
1.9–0.8 (m, 45 H, alkyl chains).
3
6 2
H, CH O), 1.9–0.8 (m, 45 H, alkyl chains); n
/cm−1
(C N)
O
2
2
(CH Cl ) 2223; (Nujol) 2225 (Calc. for C H NAuClO : C,
Chloro(3-fluoro-4-octyloxyphenyl isocyanide)gold(i)
2
31 53
3
51.70; H, 7.42; N, 1.95. Found: C, 51.01; H, 7.05; N, 1.96%);
To a solution of [AuCl(tht)] (0.131 g, 0.41 mmol) in 30 ml of
DSC/°C Col –I 71.1 (3.2).
h
CH Cl was added 3-fluoro-4-octyloxyphenyl isocyanide
2
2
(0.112 g, 0.45 mmol). After stirring for 10 min the solvent was
removed on a rotary evaporator and the residue was washed
with diethyl ether. Recrystallization from CH Cl –EtOH
Chloro(3,4,5-tributoxyphenyl isocyanide)gold(i)
Yield 83%; n
/cm−1 (CH Cl ) 2223; (Nujol) 2228 (Calc.
O
(C N)
2
2
2 2
afforded the product as white crystals (0.145 g, 74%); 1H NMR
for C H NAuClO : C, 41.35; H, 5.30; N, 2.54. Found: C,
19 29
3
(CDCl ) d 7.34–7.26 (Ha and Hb) and 7.00 (Hc) (AMNX spin
41.42; H, 5.10; N, 2.57%); DSC/°C K–I 38.0 (8.8), I–Col
13.3 (−0.6).
3
h
system, 3J 8.3, Ar-H), 4.07 (t, J 6.5, CH O), 1.86–0.88 (m, 15
bc
2
22
J. Mater. Chem., 1997, 7(1), 19–23