Notes
CDCl
6
1
J . Org. Chem., Vol. 61, No. 3, 1996 1135
(
3
, 300 MHz) δ 0.8-1.6 (m, br, 14H), 3.33-3.5 (m, br, 4H),
.87-7.4 (m, 9H); 13C NMR (CDCl
, 300 MHz) δ171.7, 149.5,
48.1, 129.3, 127.9, 127.7, 123.1, 116.6, 40.0, 30.1 (br), 19.1, 13.6;
14.0; IR (KBr, cm-1) 3413, 2927, 2858, 1618, 1522, 1458, 806;
GC-MS (m/z) 191, 120. Anal. calcd for C13H21N: C, 81.61; H,
11.06. Found: C, 81.82; H, 10.83.
3
-
1
IR (neat, cm ) 3036, 2957, 2930, 2871, 1627, 1593, 1561, 1514,
N,N-Dieth yl-p-(h exyla m in o)ben za m id e (16). To a solu-
tion of N,N-diethyl-p-iodobenzamide (303 mg, 1.0 mmol), n-
hexylamine (0.15 mL, 1.1 mmol), and sodium tert-butoxide (270
mg, 2.78 mmol) in dioxane (9 mL) were added tris(dibenzyl-
ideneacetone)dipalladium(0) (5 mg, 0.005 mmol) and tri-o-
tolylphosphine (6 mg, 0.02 mmol). The solution was heated to
100 °C with stirring. Additional portions of the palladium
complex and phosphine were added after 16 h and after 22 h.
Complete consumption of starting material occurred after 40 h
(as judged by GC analysis). The solution was then cooled to
room temperature, taken up in ether (30 mL), filtered, and
concentrated. The crude product was then purified by flash
chromatography on silica gel using 4/1 hexane/ethyl acetate as
the eluant. Fractions containing product were concentrated to
1
7
7
496, 1465, 1422, 1345, 1295, 1256, 1191, 1132, 1103, 830, 762,
00. Anal. Calcd for C22
7.87; H, 9.16.
30 2
H N O: C, 78.06; H, 8.93. Found: C,
N-(3-Met h oxyp h en yl)-1,4-d ioxa -8-a za sp ir o[4.5]d eca n e
4
b
(
12). The general procedure gave 147 mg (59%) of a colorless
1
oil: H NMR (CDCl
3
, 300 MHz) δ 1.83 (t, 4H, J ) 6 Hz), 3.32 (t,
H, J ) 6 Hz), 3.79 (s, 3H), 3.99 (s, 4H), 6.37-6.58 (m, 3H),
.15 (t, 1H, J ) 8.1 Hz); 13C NMR (CDCl
, 300 MHz) δ 160.5,
52.1, 129.6, 109.2, 107.1, 104.0, 102.8, 64.2, 55.0, 47.5, 34.3;
4
7
1
3
-
1
IR (neat, cm ) 2956, 2884, 2833, 1602, 1579, 1496, 1466, 1438,
1
9
365, 1341, 1294, 1251, 1228, 1202, 1168, 1143, 1103, 1053, 965,
46, 912, 833, 761, 690.
Gen er a l P r oced u r e for th e Ca ta lytic Am in a tion of Ar yl
Iod id es w ith P r im a r y Am in es or An ilin es. To a solution of
aryl iodide (1 mmol), amine (1.1 mmol), and sodium tert-butoxide
give 52 mg (19%) of a colorless oil: 1H NMR (CDCl
, 300 MHz)
3
δ 0.90 (m, 3H), 1.18 (t, 6H, J ) 6.9 Hz), 1.29-1.42 (m, 6H), 1.61
(p, 2H, J ) 6.9 Hz), 3.11 (t, 2H, J ) 7.2 Hz), 3.43 (q, 4H, J ) 6.9
(
2.8 mmol) in dioxane (9 mL) were added tris(dibenzylidene-
1
3
acetone)dipalladium (0) (0.005 mmol, 1 mol% Pd) and tri-o-
tolylphosphine (0.02 mmol). The solution was heated to 100 °C
with stirring until the aryl halide had been completely consumed
as judged by GC analysis. The solution was then cooled to room
temperature, taken up in ether (30 mL), and washed with brine
Hz), 3.87 (s, br, 1H), 6.53-6.56 (m, 2H), 7.23-2.27 (m, 2H);
NMR (CDCl
C
3
, 300 MHz) δ 172.8, 149.4, 128.4, 125.1, 111.6, 43.6,
31.5, 29.3, 26.7, 22.5, 14.0; IR (neat, cm ) 3333, 2958, 2930,
2858, 1614, 1531, 1470, 1456, 1425, 1380, 1335, 1314, 1285,
-
1
1176, 1098, 831, 764. Anal. calcd for C17
10.21. Found: C, 74.12; H, 10.26.
28 2
H N O: C, 73.87; H,
(15 mL). The organic layer was dried over anhydrous magne-
sium sulfate, filtered, and concentrated. The crude product was
then purified further by flash chromatography on silica gel.
Fractions containing product were concentrated to give the pure
compound.
N,N-Dibu t yl-p-iod oben za m id e. To a solution of di-n-
butylamine (1.7 mL, 10.0 mmol) in dichloromethane (2 mL) in
an oven-dried Schlenk tube at 0 °C was added slowly 4-iodo-
benzoyl chloride (1.066 g, 4.0 mmol) in dichloromethane (2 mL).
The solution was stirred at 0 °C for 10 min and then warmed to
rt and stirred for 5 h. The reaction mixture was then diluted
N-(2,5-Xylyl)-h exyla m in e (13). The general procedure gave
41 mg (69%) of a pale yellow oil: 1H NMR (CDCl
1
3
, 300 MHz)
δ 0.91 (m, 3H), 1.30-1.45 (m, 6H), 1.66 (p, 2H, J ) 7.8 Hz), 2.09
s, 3H), 2.29 (s, 3H), 3.13 (t, 2H, J ) 7.2 Hz), 3.38 (s, 1H, br),
with ether (30 mL), washed with saturated aqueous NaHCO
10 mL), and washed with brine (10 mL). The organic layer was
then dried over anhydrous MgSO , filtered, and concentrated
3
(
(
6
3
2
2
1
.43-6.47 (m, 2H), 6.92 (d, 1H, J ) 7.5 Hz); 13C NMR (CDCl
00 MHz) δ 146.2, 136.6, 129.8, 118.6, 117.2, 110.5, 43.9, 31.6,
3
,
4
to give 1.29 g (90%) of a colorless oil: 1H NMR (CDCl
δ 0.7-1.7 (m, 14 H), 3.1-3.6 (m, br, 4H), 7.1 (m, 2H), 7.75 (m,
, 300 MHz)
3
-1
9.6, 26.9, 22.6, 21.5, 16.9, 14.0; IR (neat, cm ) 3428, 3014, 2956,
926, 2856, 1615, 1584, 1523, 1466, 1426, 1376, 1312, 1298,
2
9
2
1
3
H); 13C NMR (CDCl
4.8, 48.5, 44.3, 30.6, 29.3, 20.0, 19.5, 13.6, 13.4; IR (neat, cm
957, 2930, 2871, 1632, 1586, 1558, 1487, 1465, 1425, 1379,
296, 1265, 1234, 1182, 1101, 1007, 830, 754; GC-MS (m/z) 359,
58, 316, 231, 203, 104, 76. Anal. Calcd for C15H22INO: C,
3
, 300 MHz) δ 170.3, 137.2, 136.5, 128.0,
-
1
)
266, 792; GC-MS (m/z) 205, 134. Anal. Calcd for C14H23N:
C, 81.88; H, 11.30. Found: C, 82.07; H, 11.22.
Z)-N-(5-Hexen yl)-2,5-xylid in e (14). The general procedure
gave 155 mg of a yellow oil which was Kugelrohr distilled to
(
1
50.15; H, 6.17. Found: C, 50.38; H, 6.07.
give 147 mg (68%) of a colorless oil: H NMR (CDCl
3
, 300 MHz)
N,N-Dieth yl-p-iod oben za m id e.14 To a solution of diethyl-
amine (1.05 mL, 10.0 mmol) in dichloromethane (2 mL) in an
oven-dried flask at 0 °C was added slowly 4-iodobenzoyl chloride
δ 1.49 (p, 2H, J ) 7.2 Hz), 1.6-1.72 (m, 5H) 2.07-2.29 (m, 5H),
2
.29 (s, 3H), 3.14 (t, 2H, J ) 6.9 Hz), 3.38 (s, 1H, br), 5.35-5.51
13
(
(
1
m, 2H), 6.42-6.47 (m, 2H), 6.92 (d, 1H, J )7.5 Hz); C NMR
CDCl , 300 MHz) δ 146.2, 136.7, 130.2, 129.8, 124.2, 118.7,
17.2, 110.5, 43.8, 29.2, 27.1, 26.5, 21.5, 17.0, 12.8; IR (neat,
(1.066 g, 4.0 mmol) in dichloromethane (2 mL). The solution
3
was stirred at 0 °C for 10 min and then warmed to rt and stirred
for 15 h. The reaction mixture was then diluted with ether (30
-
1
cm ) 3426, 3012, 2927, 2856, 1615, 1583, 1523, 1444, 1298,
267, 793, 701; GC-MS (m/z) 217, 160, 134, 105, 91, 77. Anal.
Calcd for C15 23N: C, 82.88; H, 10.67. Found: C, 83.10, H,
mL), washed with saturated aqueous NaHCO
washed with brine (10 mL). The organic layer was then dried
over anhydrous MgSO , filtered, and concentrated to give 1.190
g (98%) of a colorless oil: H NMR (CDCl
.35 (m, br, 6H), 3.1-3.6 (m, br, 4H), 7.08-7.15 (m, 2H), 7.7-
3
(10 mL), and
1
H
1
0.45.
4
1
N-P h en yl-2,5-xylid in e (15).13 The general procedure gave
3
, 300 MHz) δ 1.0-
1
1
37 mg of a yellow oil which was Kugelrohr distilled to give 128
1
3
1
7.8 (m, 2H); C NMR (CDCl , 250 MHz) δ 170.2, 137.5, 136.6,
128.0; IR (neat, cm ) 2972, 2933, 1632, 1586, 1488, 1470, 1458,
3
mg (64%) of a colorless oil: H NMR (CDCl
3
, 300 MHz) δ 2.19
-1
1
3
(
s, 3H), 2.26 (s, 3H), 5.31 (s, 1H, br), 6.73-7.26 (m, 8H); C NMR
1
427, 1383, 1363, 1347, 1315, 1288, 1095, 1008.
(CDCl , 300 MHz) δ 144.1, 140.9, 136.4, 130.7, 129.2, 125.3,
3
-1
1
3
1
22.8, 120.2, 119.5, 117.3, 21.1, 17.4; IR (neat, cm ) 3386, 3048,
018, 2920, 2858, 1600, 1578, 1518, 1497, 1464, 1412, 1377,
311, 1000, 805, 747, 694.
Ack n ow led gm en t. We thank the National Science
Foundation and the National Institutes of Health for
their support of this work. Helpful conversations with
Dr. Ross Widenhoefer are gratefully acknowledged.
Preliminary experiments were carried out by Dr. Anil
Guram.
N-(4-Meth ylp h en yl)h exyla m in e (7). The general proce-
dure gave 75 mg (39%) of a yellow oil which was Kugelrohr
distilled to give 35 mg (18%) of a white solid, mp ) 37.1-37.3
°
8
8
C: 1H NMR (CDCl
H), 3.07 (t, 2H, J ) 7.5 Hz), 3.45 (s, br, 1H), 6.54 (d, 2H, J )
.7 Hz), 6.97 (d, 2H, J ) 8.89 Hz); 13C NMR (CDCl
, 300 MHz)
3
, 300 MHz) δ 0.89 (m, 3H), 1.26-1.64 (m,
3
J O951844H
δ 146.3, 129.7, 126.3, 112.9, 44.4, 31.6, 29.6, 26.8, 22.6, 20.3,
(
14) Amatore, C.; J utand, A.; Negri, S.; Fauvarque, J . F. J . Organo-
(13) Kricka, L. J .; Vernon, J . M. Can. J . Chem. 1974, 52, 299-302.
met. Chem. 1990, 390, 389-398.