Itoh et al.
135 (100). Anal. Calcd for C18H15NO3: C, 73.71; H, 5.15; N,
4.78. Found: C, 73.51; H, 5.06; N, 4.68.
1.39 (t, J ) 7.1 Hz, 3H), 2.07 (s, 3H), 4.37 (q, J ) 7.1 Hz, 2H),
7.02 (d, J ) 8.1 Hz, 2H), 7.41-7.51 (m, 2H), 7.69 (d, J ) 8.1
Hz, 2H), 7.90 (s, 1H), 7.86-8.03 (m, 1H);13C NMR (CDCl3) δ
14.3, 23.8, 61.3, 91.2, 119.0, 127.7, 128.3, 129.2, 131.1, 132.4,
138.3, 142.4, 142.6, 165.5, 170.1; EI-MS m/z 409 (M+, 44.7),
367 (100); HR-MS m/z for C17H16INO3 calcd 409.0175, found
409.0159.
Typ ica l P r oced u r e for th e P r ep a r a tion of 5c. To a
solution of refluxing TFA (4 mL) containing 4c (100 mg, 0.74
mmol) was added a TFA solution (2 mL) of PIFA (382 mg, 0.89
mmol) in one portion. After refluxing the reaction mixture for
3 min, the solvent was concentrated. To the residue was added
5% NaHCO3 (30 mL) under cooling. The aqueous layer was
extracted with AcOEt (50 mL × 2), and the combined organic
layer was washed with brine (30 mL), dried over Na2SO4, and
concentrated. Purification by column chromatography over
silica gel (AcOEt/n-hexane ) 1:1) afforded 5c (81 mg, 72%).
Typ ica l P r oced u r e for th e P r ep a r a tion of 3g. To 1g
(100 mg, 0.59 mmol) in HFIP (5 mL) was added PIFA (330
mg, 0.77 mmol). After stirring the reaction mixture for 30 min
at room temperature, HFIP was removed under reduced
pressure. To the residue was added 5% NaHCO3 (30 mL) under
cooling. The aqueous layer was extracted with AcOEt (40 mL
× 2), and the combined organic layer was washed with brine
(30 mL), dried over Na2SO4, and concentrated. Purification by
column chromatography over silica gel (AcOEt/n-hexane ) 1:3)
afforded 3g (173 mg, 79%).
4-[Acetyl(4-iod op h en yl)a m in o]ben zoic a cid eth yl ester
(3s): oil; IR (neat) 1720, 1690, 1610, 1490, 1370, 1280 cm-1
;
1H NMR (CDCl3) δ 1.38 (t, J ) 7.1 Hz, 3H), 2.08 (s, 3H), 4.37
(q, J ) 7.1 Hz, 2H), 7.00 (d, J ) 8.6 Hz, 2H), 7.29 (d, J ) 8.6
Hz, 2H), 7.72 (d, J ) 8.6 Hz, 2H), 8.04 (d, J ) 8.6 Hz, 2H); 13
C
NMR (CDCl3) δ 14.3, 24.0, 61.2, 92.4, 118.6, 126.6, 129.6, 130.7,
138.7, 142.3, 146.4, 165.7, 170.0; EI-MS m/z 409 (M+, 38.1),
367 (100); HR-MS m/z for C17H16INO3 calcd 409.0175, found
409.0174.
Typ ica l P r oced u r e for th e P r ep a r a tion of 3t. To 1t (100
mg, 0.53 mmol) in HFIP-TFA (10:1) (5 mL) was added PIFA
(296 mg, 0.69 mmol). After stirring the reaction mixture for
16 h at room temperature, the solvent was concentrated. To
the residue was added 5% NaHCO3 (30 mL) under cooling.
The aqueous layer was extracted with AcOEt (50 mL × 2),
and the combined organic layer was washed with brine (30
mL), dried over Na2SO4, and concentrated. Purification by
column chromatography over silica gel (AcOEt/n-hexane )
1:10) afforded 3t (171 mg, 83%).
N-(2-Ch lor op h en yl)-N-(4-iod op h en yl)a ceta m id e (3g):
oil; IR (neat) 1690, 1490, 1370, 1320, 1310 cm-1 1H NMR
;
(CDCl3) δ 2.01 (s, 3H), 7.09 (d, J ) 8.6 Hz, 2H), 7.18-7.45 (m,
3H), 7.45-7.57 (m, 1H), 7.57-7.74 (m, 2H); 13C NMR (CDCl3)
δ 23.2, 90.5, 127.4, 128.3, 129.9, 130.8, 133.3, 137.6, 138.5,
139.7, 140.8, 169.8; EI-MS m/z 373 (M+ + 2, 5.7), 371 (M+,
16.9), 329 (100); HR-MS m/z for C14H11ClINO calcd 370.9574,
found 370.9557.
N-(3-Ch lor op h en yl)-N-(4-iod op h en yl)a ceta m id e (3o):
colorless crystals; mp 97-99 °C (n-hexane); IR (KBr) 1670,
1370, 1320 cm-1; 1H NMR (CDCl3) δ 2.07 (s, 3H), 7.00 (d, J )
8.6 Hz, 2H), 7.14 (d, J ) 7.4 Hz, 1H), 7.22-7.36 (m, 2H), 7.25
(t, J ) 1.9 Hz, 1H), 7.67-7.76 (m, 2H); 13C NMR (DMSO-d6) δ
23.3, 91.8, 125.7, 126.4, 127.1, 129.6, 130.7, 133.1, 138.2, 142.4,
144.0, 169.1; EI-MS m/z 373 (M+ + 2, 10.4), 371 (M+, 32.3),
329 (100). Anal. Calcd for C14H11ClINO: C, 45.25; H, 2.98; N,
3.77. Found: C, 45.22; H, 2.75; N, 3.63.
N-(4-Ch lor op h en yl)-N-(4-iod op h en yl)a ceta m id e (3p ):
oil; IR (neat) 1680, 1490 cm-1; 1H NMR (CDCl3) δ 2.06 (s, 3H),
6.99 (d, J ) 8.6 Hz, 2H), 7.17 (d, J ) 8.7 Hz, 2H), 7.29-7.40
(m, 2H), 7.62-7.74 (m, 2H); 13C NMR (CDCl3) δ 23.8, 91.0,
127.9, 129.8, 131.8, 133.9, 138.3, 141.0, 142.3, 170.1; EI-MS
m/z 373 (M+ + 2, 9.80), 371 (M+, 30.2), 329 (100); HR-MS m/z
for C14H11ClINO calcd 370.9574, found 370.9576.
N-(4-Iod op h en yl)-N-p h en yl-2,2,2-t r iflu or oa cet a m id e
(3t): colorless crystals; mp 62-63 °C (n-hexane); IR (KBr)
1710, 1600, 1500, 1400, 1240, 1220, 1140 cm-1 1H NMR
;
(CDCl3) δ 7.05 (d, J ) 8.3 Hz, 2H), 7.28 (d, J ) 9.7 Hz, 2H),
7.40-7.43 (m, 3H), 7.72 (d, J ) 8.3 Hz, 2H); 13C NMR (CDCl3)
δ 92.6, 116.4 (q, J ) 288.6 Hz, CF3), 126.0, 127.7, 128.6, 129.6,
138.6, 141.2, 156.7 (q, J ) 36.6 Hz, CO); EI-MS m/z 391 (M+,
100), 167 (75.9). Anal. Calcd for C14H9F3INO: C, 42.99; H, 2.32;
N, 3.58. Found: C, 42.84; H, 2.24; N, 3.55.
N-(3-Met h ylp h en yl)-N-(4-iod op h en yl)-2,2,2-t r iflu or o-
a ceta m id e (3u ): oil; IR (neat) 1710, 1490, 1390, 1210, 1155
cm-1; 1H NMR (CDCl3) δ 2.36 (s, 3H), 6.99-7.24 (m, 5H), 7.31
(t, J ) 8.3 Hz, 1H), 7.71 (d, J ) 8.2 Hz, 2H); 13C NMR (CDCl3)
δ 21.2, 92.5, 116.4 (q, J ) 288.8 Hz, CF3), 122.9, 125.5, 127.7,
128.9, 129.3, 130.0, 138.5, 139.8, 141.1, 156.6 (q, J ) 36.4 Hz,
CO); EI-MS m/z 405 (M+, 100), 298 (20.0), 186 (44.9), 181
(36.7), 181 (37.9); HR-MS for C15H11F3INO calcd 404.9837,
found 404.9813.
N-(4-Ch lor op h en yl)-N-(4-iod op h en yl)-2,2,2-t r iflu or o-
a ceta m id e (3v): oil; IR (neat) 1710, 1500 cm-1 1H NMR
;
N-(2,6-Dich lor oph en yl)-N-(4-iodoph en yl)acetam ide (3q):
colorless crystals; mp 165-167 °C (benzene/n-hexane); IR
(CDCl3) δ 7.03 (d, J ) 8.1 Hz, 2H), 7.22 (d, J ) 8.2 Hz, 2H),
7.39 (d, J ) 8.2 Hz, 2H), 7.74 (d, J ) 8.1 Hz, 2H); 13C NMR
(CDCl3) δ 92.8, 116.3 (q, J ) 288.6 Hz, CF3), 127.6, 129.8,
133.5, 135.4, 137.5, 138.8, 141.0, 156.5 (q, J ) 36.6 Hz, CO);
EI-MS m/z 427 (M+ + 2, 32.3), 425 (M+, 100); HR-MS m/z for
(KBr) 1670, 1490, 1320, 1300 cm-1 1H NMR (DMSO-d6) δ
;
(major/minor ) 63:37) 1.88 (s, 1.9H), 2.15 (s, 1.1H), 7.03 (d, J
) 8.0 Hz, 1.3H), 7.22 (d, J ) 8.0 Hz, 0.7H), 7.37-7.50 (m,
0.4H), 7.50-7.85 (m, 4.6H); 13C NMR (DMSO-d6) δ (major)
22.8, 90.6, 126.4, 129.9, 131.6, 134.6, 136.7, 137.3, 139.3, 168.7;
(minor) 22.0, 93.0, 128.7, 129.2, 130.4, 134.1, 137.6, 138.0,
140.3, 169.1; EI-MS m/z 409 (M+ + 4, 3.42), 407 (M+ + 2, 20.2),
405 (M+, 31.1), 363 (100). Anal. Calcd for C14H10Cl2INO: C,
41.41; H, 2.48; N, 3.45. Found: C, 41.67; H, 2.22; N, 3.25.
3-[Acetyl(4-iod op h en yl)a m in o]ben zoic a cid eth yl ester
C
14H8ClF3INO calcd 424.9291, found 424.9281.
Su p p or tin g In for m a tion Ava ila ble: Experimental and
literature melting points of known compounds 1c, 1d , 1j, 1k ,
1q-v, 2a -c, 2f-h , 2m , 3a , 4b, and 5a -d . This material is
1
(3r ): oil; IR (neat) 1720, 1680, 1490 cm-1; H NMR (CDCl3) δ
J O0260847
7428 J . Org. Chem., Vol. 67, No. 21, 2002