1272 J . Org. Chem., Vol. 62, No. 5, 1997
Louie et al.
and the product was collected by sublimation (110 °C, 0.05
Torr) as a white solid (41.3 mg, 94%). 1H NMR (CDCl3) δ 3.82
(s, 3H), 5.51 (s, 1H), 6.86 (tt, 7.3, 1.0 Hz, 1H), 6.89 (dt, 8.9, 2.2
Hz, 2H), 6.93 (dd, 8.5, 1.0 Hz, 2H), 7.09 (dt, 8.9, 2.2 Hz, 2H),
7.24 (td, 7.4, 2.0 Hz, 2H); 13C{1H} NMR: (CDCl3) δ 155.48,
145.38, 135.93, 129.50, 122.41, 119.77, 115.77, 114.87, 55.77.
Rea ction of 4-Meth oxyp h en yl tr ifla te w ith An ilin e
Usin g P d (d ba )2 a n d P (o-tolyl)3 (Ta ble 1, en tr y 2). 4-Meth-
oxyphenyl triflate (15.0 mg, 0.0586 mmol), Pd(dba)2 (1.5 mg,
0.0030 mmol), P(o-tolyl)3 (2.0 mg, 0.0066 mmol), and NaO-t-
Bu (8.0 mg, 0.083 mmol) were suspended in 2 mL of toluene
in a small screw-capped vial. The vial was sealed with a cap
containing a Teflon-lined septum and removed from the dry
box. Aniline (8.0 L, 0.083 mmol) was added to the reaction
mixture by syringe. The vial was heated at 105 °C for 6 h. A
GC/MS of the reaction mixture showed less than 5% conversion
to product, 4-methoxydiphenylamine.
The vial was heated at 105 °C for 6 h. A GC/MS of the reaction
mixture showed less than 5% conversion to product.
N-Isobu tyl-4-m eth ylan ilin e30 Usin g P d(dba)2 an d DP P F
(Ta ble 2, en tr y 3). General procedure B with 120 mg (0.50
mmol) of 4-methylphenyl triflate and 75 µL (0.75 mmol) of
isobutylamine gave the product as a pale yellow oil (37 mg,
45%). 1H NMR (CDCl3): δ 1.04 (d, 6.7 Hz, 6H), 1.97 (m, 1H),
2.03 (s, 3H), 2.97 (m, 2H), 3.63 (broad s, 1H), 6.66 (d, 8.0 Hz,
2H), 7.05 (d, 8.0 Hz, 2H); 13C{1H} NMR (CDCl3): 20.45, 20.31,
27.95, 52.15, 112.78, 126.06, 129.64, 146.28.
N-Isobu tyl-4-m eth yla n ilin e30 by Slow Tr ifla te Ad d i-
tion (Ta ble 2, en tr y 4). General procedure C with 107.0 mg
(0.469 mmol) of 4-methylphenyl triflate and 75 µL (0.76 mmol)
isobutylamine gave N-isobutyl-4-methylaniline (34.8 mg, 42%).
N-Isobu tyl-4-m eth yla n ilin e Usin g P d (d ba )2 a n d BI-
NAP (Ta ble 2, en tr y 5). Into a screw-capped test tube were
weighed 23 mg (0.042 mmol) of Pd(dba)2, 51.7 mg (0.083 mmol)
of BINAP, and 120 mg (1.25 mmol) of NaO-t-Bu. The solid
materials were suspended in 7 mL of toluene. 4-Methylphenyl
triflate (200 mg, 0.833 mmol) was dissolved in 1 mL of toluene
and added to the test tube. The test tube was sealed with a
cap containing a Teflon-lined septum and removed from the
dry box. Isobutylamine (126 µL, 1.25 mmol) was added to the
test tube by syringe. The reaction mixture was heated at 100
°C for 3 h. A TLC of the reaction mixture indicated complete
consumption of the starting triflate. The reaction mixture was
cooled to room temperature, and the mixture was absorbed
onto silica gel. Chromatography on a silica gel column using
30:1 hexanes:Et2O afforded the product as a pale yellow oil
(112 mg, 82%).
N-Bu tyl-2-m eth yla n ilin e31 (Ta ble 2, en tr y 6). General
procedure B using 55.1 mg (0.229 mmol) of o-tolyl triflate and
34.0 µL (0.344 mmol) of n-butylamine gave 68% yield after
silica gel chromatography using 5% EtOAc in hexanes. 1H
NMR: (CDCl3) δ 1.00 (t, 7.4 Hz, 3H), 1.48 (m, 2H), 1.68 (m,
2H), 2.15 (s, 3H), 3.18 (t, 7.1 Hz, 2H), 3.44 (bs, 1H), 6.60-6.70
(m, 2H) , 7.02 (d, 7.6 Hz, 1H), 7.14 (dd, 8.0, 7.5 Hz, 1H); 13C-
{1H} NMR: (CDCl3) δ 13.90, 17.40, 20.34, 31.69, 43.59, 109.54,
116.55, 121.60, 127.08, 129.94, 146.36.
4-(2-Na p h th yl)m or p h olin e27 (Ta ble 2, en tr y 8). General
procedure A with 150.0 mg (0.545 mmol) of 2-naphthyl triflate
and 70.9 µL (0.815 mmol) of morpholine gave the product as
a white solid (103.5 mg, 90% yield). 1H NMR: (CDCl3) δ 3.28
(m, 4H), 3.94 (m, 4H), 7.14 (d, 2.4 Hz, 1H), 7.30-7.42 (m, 2H),
7.45 (dt, 7.7, 1.1 Hz, 1H), 7.70-7.77 (m, 3H); 13C{1H} NMR:
(CDCl3) δ 49.89, 67.03, 110.17, 118.99, 123.63, 126.43, 126.85,
127.53, 128.74, 128.90, 134.58, 149.16.
N-Isobu tyl-2-n a p h th yla m in e (Ta ble 2, en tr y 9). Gen-
eral procedure B with 23.0 mg (0.083 mmol) of 2-naphthyl
triflate and 9.9 µL (0.10 mmol) of isobutylamine gave 72% yield
after silica gel chromatograph using 5% EtOAc in hexanes.
1H NMR: (CDCl3) δ 1.04 (d, 6.6 Hz, 6H), 2.00 (m, 1H), 3.06
(d, 7.0 Hz, 2H), 6.90 (s, 1H), 6.94 (dd, 8.9, 2.2 Hz, 1H), 7.20
(dd, 7.7, 6.9 Hz, 1H), 7.62 (d, 9.0 Hz, 2H), 7.66 (d, 8.1 Hz, 1H);
13C{1H} NMR: (CDCl3) δ 20.54, 27.91, 51.92, 104.33, 117.94,
121.76, 125.81, 126.24, 127.37, 127.57, 128.82, 135.23, 145.99.
HRMS calcd for C14H17N (M+) 199.1361. Found: 199.1361
Anal. Calcd for C14H17N: C, 84.37; H, 8.60; N, 7.03. Found:
C, 84.13; H, 8.40; N, 6.85.
4-P h en yld ip h en yla m in e2 (Ta ble 1, en tr y 3). Using the
general procedure for anilines with 68.4 mg (0.226 mmol) of
4-biphenylyl triflate and 30.0 L (0.329 mmol) of aniline yielded
the product as a white solid (55.4 mg, 99%). 1H NMR: (CDCl3)
δ 5.80 (s, 1H), 7.00 (t, 7.3 Hz, 1H), 7.16 (d, 7.3 Hz, 2H), 7.18
(d, 8.5 Hz, 2H), 7.32-7.38 (m, 3H), 7.46 (dd, 7.8, 7.3 Hz, 2H),
7.56 (d, 8.5 Hz, 2H), 7.62 (d, 7.3 Hz, 2H); 13C{1H} NMR:
(CDCl3) δ 117.91, 118.28, 121.33, 126.61, 126.65, 128.04,
128.80, 129.46, 133.86, 140.94, 142.69, 142.99.
N-Meth yl-N-p h en yl-4-a m in oben zop h en on e2 (Ta ble 1,
en tr y 4). The general procedure B using 200 mg (0.606 mmol)
of 4-benzophenone triflate and 98.0 µL (0.989 mmol) of
N-methylaniline gave 62% yield after silica gel chromatogra-
phy using 5% EtOAc in hexanes. 1H NMR: (CDCl3) δ 3.41 (s,
3H), 6.80 (d, 8.9 Hz, 2H), 7.25-7.28 (m, 3H), 7.38-7.54 (m,
5H), 7.73-7.78 (m, 4H); 13C{1H} NMR: (CDCl3) δ 40.43,
113.68, 125.84, 126.29, 127.06, 128.24, 129.71, 130.07, 131.50,
132.53, 139.24, 147.53, 152.78, 196.80.
N-(2-Meth ylp h en yl)a n ilin e29 (Ta ble 1, en tr y 5). The
general procedure B using 51.7 mg (0.215 mmol) of o-tolyl
triflate and 29.4 µL (0.323 mmol) of aniline gave 96% yield of
N-(2-methylphenyl)aniline after sublimation (130 °C, 0.1 Torr).
1H NMR: (CDCl3) δ 2.29 (s, 3H), 5.40 (br s, 1H), 7.00-6.90
(m, 4H), 7.17 (dd, 8.0, 7.0 Hz, 1H), 7.30-7.20 (m, 4H); 13C-
{1H} NMR: (CDCl3) δ 17.86, 117.39, 118.73, 120.41, 121.93,
126.71, 128.25, 129.25, 130.89, 141.16, 143.93.
N-P h en yl-2-n a p h th yla m in e (Ta ble 1, en tr y 6). Using
the general procedure for anilines with 66.8 mg (0.242 mmol)
of 2-naphthyl triflate and 30.0 µL (0.329 mmol) of aniline
yielded the product as a white solid (52.3 mg, 99%), whose
NMR spectra were identical to commercial material available
from Aldrich.
N-P h en yl-2-n a p h th yla m in e Usin g P d (d ba )2 a n d BI-
NAP (Ta ble 1, en tr y 7). Into a screw-capped test tube were
weighed 2.2 mg (0.0038 mmol) of Pd(dba)2, 4.0 mg (0.0064
mmol) of BINAP, 34.7 mg (0.361 mmol) of NaO-t-Bu, and 70.0
mg (0.253 mmol) of 2-naphthyl triflate. The solid materials
were suspended in 8 mL of toluene. Aniline (33.0 µL, 0.362
mmol) was added to the mixture, and the test tube was sealed
with a cap containing a Teflon-lined septum. The reaction was
stirred at 85 °C for 6 h. The volatile materials were removed
under vacuum, and the product was collected by sublimation
(110 °C, 0.05 Torr) as a white solid (53.4 mg, 96%).
N-(4-Bip h en ylyl)bu tyla m in e (Ta ble 2, en tr y 11). Gen-
eral procedure B with 50.0 mg (0.166 mmol) of 4-biphenylyl
triflate and 24.5 µL (0.249 mmol) of butylamine gave the
product as a pale yellow oil (19.2 mg, 50% yield). 1H NMR:
(CDCl3) δ 1.00 (t, 7.3 Hz, 3H), 1.47 (hex, 7.3 Hz, 2H), 1.66
(quin, 7.3 Hz, 2H), 3.21 (t, 7.0 Hz, 2H), 3.72 (s, 1H), 6.70 (d,
8.4 Hz, 2H), 7.28 (t, 7.3 Hz, 1H), 7.40-7.48 (m, 4H), 7.57 (d,
7.8 Hz, 2H); 13C{1H} NMR: (CDCl3) δ 14.02, 20.40, 31.75,
43.76, 112.96, 126.04, 126.33, 127.99, 128.70, 130.00, 141.44,
148.04. HRMS calcd for C16H19N (M+) 225.1518. Found:
225.1516 Anal. Calcd for C16H19N: C, 85.29; H, 8.5; N, 6.22.
Found: C, 85.14, H, 8.66, N, 5.99.
N-P h en yl-2-n a p h th yla m in e Usin g P d (d ba )2 a n d DP P F
in THF Solven t (Ta ble 1, en tr y 8). The general procedure
for anilines with 113.4 mg (0.411 mmol) of 2-naphthyl triflate
and 62 µL (0.680 mmol) of aniline, but in 8 mL of THF solvent,
gave 45.8 mg (51%) of N-phenyl-2-naphthylamine.
1-(4-Meth ylp h en yl)p ip er id in e Usin g P d (d ba )2 a n d P (o-
tolyl)3 (Ta ble 2, en tr y 2). 4-Methylphenyl triflate (15.0 mg,
0.0625 mmol), Pd(dba)2 (1.5 mg, 0.003 mmol), P(o-tolyl)3 (2.0
mg, 0.0066 mmol), and NaO-t-Bu (8.0 mg, 0.083 mmol) were
suspended in 2 mL of toluene in a small screw-capped vial.
The vial was sealed with a cap containing a Teflon-lined
septum and removed from the dry box. Piperidine (9.0 µL,
0.090 mmol) was added to the reaction mixture by syringe.
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(29) Spagnolo, P.; Zanirato, P. J . Chem. Soc., Perkin Trans. 1 1988,
2615-2620.