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A. Takacs et al. / Tetrahedron 67 (2011) 2402e2406
2405
water and brine. The organic phase was dried over Na2SO4 and
evaporated. The carboxamides were isolated via column chroma-
tography by using chloroform/ethyl acetate mixtures as eluents (for
exact ratios see analytical characterization below).
IR (KBr, (cmꢁ1)): 3375 (NH); 1639 and 1659 (CON). FABMS:
434.2445 (MþH) (calcd 434.2444). Anal. Calcd for C26H31N3O3
(433.55): C, 72.03; H, 7.21; N, 9.69; found: C, 71.77; H, 7.40; N, 9.45;
Rf (15% EtOAc/CH2Cl2) 0.68; mp 59e61 ꢀC. Pale yellow solid. Yield:
172 mg (40%).
4.3. Analytical and spectroscopic data of compounds
4.3.6. 7-(N-tert-Butylcarboxamido)-5-(N-tert-butylglyoxylamido)-8-
4.3.1. 5-(N,N-(Penta-30-oxa-10,50-diyl)carboxamido)-7-iodo-8-benzy-
benzyloxyquinoline (2d00). 1H NMR (CDCl3)
d
: 8.97 (d, J¼2.0 Hz, 1H,
loxyquinoline (2a). 1H NMR (CDCl3)
d: 8.96 (d, J¼3.7 Hz, 1H, H-2);
H-2); 8.80 (d, J¼8.0 Hz, 1H, H-4); 7.69 (s, 1H, H-6); 7.50 (d,
J¼7.1 Hz, 2H, Ph), 7.54 (dd, J¼5.0 and 3.4 Hz, 1H, H-3); 7.31e7.38
(m, 3H, Ph); 6.01 (br s, 1H, NH); 6.42 (br s, 1H, NH); 5.75 (s, 2H,
OCH2); 1.51 (s, 9H, C(CH3)3); 1.34 (s, 9H, C(CH3)3). 13C NMR
8.20 (d, J¼8.3 Hz, 1H, H-4); 7.82 (s, 1H, H-6); 7.67 (d, J¼7.3 Hz, 2H,
Ph); 7.31e7.55 (m, 4H, PhþH-3); 5.51 (s, 2H, OCH2); 3.75e3.99 (m,
4H, O(CH2)2); 3.43e3.70 (m, 2H, NCH2); 3.19e3.35 (m, 2H, NCH2).
13C NMR (CDCl3)
d: 166.9; 157.1; 150.5; 142.6; 137.2; 134.2; 133.8;
(CDCl3) d: 193.0; 167.0; 161.4; 157.2; 149.8; 142.3; 137.5; 134.8;
132.3; 129.1 (double intensity); 128.5 (double intensity); 128.4;
127.1; 122.6; 91.2; 76.8; 67.2 (double intensity); 48.1; 42.7. IR (KBr,
(cmꢁ1)): 1628 (CON). MS m/z: 474 (Mþ), 347 (MþꢁI). Anal. Calcd for
C21H19N2O3I (474.30): C, 53.18; H, 4.04; N, 5.91; found: C, 53.41; H,
4.29; N, 5.64; Rf (50% EtOAc/CHCl3) 0.41; mp 120e121 ꢀC. Yellow
solid. Yield: 410 mg (87%).
130.8; 130.0; 128.3 and 128.2 (double intensity); 128.0; 126.5;
124.7; 123.3; 77.6; 52.3; 51.7; 28.8; 28.3. IR (KBr, (cmꢁ1)): 3278
(NH); 1658 and 1640 (CON). FABMS: 462.2398 (MþH) (calcd
462.2393); Rf (15% EtOAc/CH2Cl2) 0.50; mp 64e66 ꢀC. Green solid.
Yield: 37 mg (8%).
4.3.7. 5,7-Bis(N-tert-butyl-glyoxylamido)-8-hydroxyquinoline
4.3.2. 5-(N,N-(Penta-10,50-diyl)carboxamido)-7-iodo-8-benzylox-
(3). 1H NMR (CDCl3)
d
: 9.42 (s, 1H, H-6); 9.22 (d, J¼2.8 Hz, 1H, H-2);
yquinoline (2b). 1H NMR (CDCl3)
d
: 8.96 (d, J¼3.8 Hz, 1H, H-2); 8.19
8.69 (br s, 1H, H-4); 8.20 (br s, 1H, OH); 7.58 (dd,1H, H-3); 6.71 (br s,
(d, J¼8.0 Hz, 1H, H-4); 7.80 (s, 1H, H-6); 7.66 (d, J¼7.3 Hz, 2H, Ph);
7.51 (dd, J¼3.8, 8.0 Hz, 1H, H-3); 7.31e7.40 (m, 3H, Ph); 5.49 (s, 2H,
OCH2); 3.75e3.90 (m, 2H, (NCH2)2); 3.17 (br s, 2H, NCH2); 1.35e1.80
1H, NH); 6.66 (br s, 1H, NH); 1.50 (s, 18H, 2ꢂC(CH3)3). 13C NMR
(CDCl3) d: 189.8; 189.7; 163.7; 163.4; 155.3; 148.0; 142.3; 138.6;
135.0; 130.1; 126.3; 115.1; 107.9; 52.1; 52.0; 28.7. IR (KBr, (cmꢁ1)):
3307 (NH); 1677 (CON); 1628 (CON). MS m/z: 421 (MþꢁHþNa), 299
(MþꢁCONHtBu). Anal. Calcd for C21H25N3O5 (399.45): C, 63.15; H,
6.31; N, 10.52; found: C, 63.31; H, 6.42; N, 10.30; Rf (20% EtOAc/
CHCl3) 0.44; mp 104e105 ꢀC. Yellow solid. Yield: 188 mg (47%).
(m, 6H, (CH2)3). 13C NMR (CDCl3)
d: 166.7; 156.3; 150.4; 142.6;
137.3; 134.1; 133.6; 131.9; 129.0 (double intensity); 128.5 (double
intensity); 128.3; 127.1; 122.4; 91.4; 76.8; 48.8; 43.2; 27.0; 26.0;
24.7. IR (KBr, (cmꢁ1)): 1630 (CON). MS m/z: 472 (Mþ), 345 (MþꢁI).
Anal. Calcd for C22H21N2O2I (472.33): C, 55.94; H, 4.48; N, 5.93;
found: C, 55.71; H, 4.59; N, 5.66; Rf (40% EtOAc/CHCl3) 0.69. Highly
viscous yellow oil. Yield: 405 mg (86%).
4.3.8. 5-Iodo-8-hydroxy-quinoline (5). 1H NMR (CDCl3)
d: 8.75 (d,
J¼2.4 Hz, 1H, H-2); 8.10 (d, J¼8.2 Hz, 1H, H-4); 7.75 (d, J¼8.4 Hz, 1H,
H-7); 7.45 (dd, J¼4, 8.4 Hz,1H, H-3); 7.09 (d, J¼8.4 Hz,1H, H-6), 6.95
4.3.3. 5-(N-Phenylcarboxamido)-7-iodo-8-benzyloxyquinoline
(br s, 1H, OH). 13C NMR (CDCl3)
d: 153.2, 148.7, 137.7, 136.5, 136.4,
(2c). 1H NMR (CDCl3)
d
: 8.96 (d, J¼3.4 Hz, 1H, H-2); 8.75 (d,
128.3, 122.5, 119.4, 90.8. MS m/z: 271/100 (Mþ), 243/7, 144/6, 116/
33. Anal. Calcd for C9H6ION (271.06): C, 39.88; H, 2.23; N, 5.17;
found: C, 39.75; H, 2.47; N, 4.88. Highly viscous yellow oil. Yield:
122 mg (45%).
J¼8.2 Hz, 1H, H-4); 8.08 (s, 1H, H-6); 7.90 (br s, 1H, NH); 7.60e7.68
(m, 4H, Ph); 7.49 (dd, J¼3.4, 8.2 Hz, 1H, H-3); 7.28e7.40 (m, 6H, Ph);
5.54 (s, 2H, OCH2). 13C NMR (CDCl3)
d: 164.9; 157.8; 150.4; 142.6;
137.9; 137.1; 135.1; 134.9; 131.2; 129.4 (double intensity); 129.0
(double intensity); 128.5 (double intensity); 128.4; 127.8; 125.2;
122.8; 121.1; 120.4; 90.4; 76.9. IR (KBr, (cmꢁ1)): 3270 (NH); 1644
(CON). MS m/z: 480 (Mþ), 353 (MþꢁI). Anal. Calcd for C23H17N2O2I
(480.30): C, 57.52; H, 3.57; N, 5.83; found: C, 57.40; H, 3.69; N, 5.70;
Rf (10% EtOAc/CHCl3) 0.55; mp 178e179 ꢀC. Pale yellow solid. Yield:
390 mg (81%).
4.3.9. 7-Iodo-8-hydroxyquinoline (50). Compound 50 (isolated as
a 70/30 mixture of 5/50): MS m/z: 271/100 (Mþ), 243/10,144/5,116/30.
Acknowledgements
The authors thank the Hungarian Research Fund (OTKA
CK78553), the Joint Project of the European UniondHungarian
National Development Program (GVOP-3.2.1-2004-04-0168/3) and
Science, Please! Research Team on Innovation (SROP-4.2.2./08/1/
2008-0011) and Portuguese Foundation FCT (PTDC/QUI-QUI/
112913/2009) for the financial support and Johnson Matthey for the
generous gift of palladium(II) acetate. A.F. Peixoto also thanks FCT
for the Ph.D. grant SFRH/BD/29681/2006.
4.3.4. 5-(N-tert-Butylcarboxamido)-7-iodo-8-benzyloxyquinoline
(2d). 1H NMR (CDCl3)
d
: 8.95 (d, J¼3.9 Hz, 1H, H-2); 8.69 (d,
J¼8.4 Hz, 1H, H-4); 7.94 (s, 1H, H-6); 7.66 (d, J¼7.3 Hz, 2H, Ph); 7.51
(dd, J¼3.9, 8.4 Hz, 1H, H-3); 7.32e7.40 (m, 3H, Ph); 5.80 (br s, 1H,
NH); 5.53 (s, 2H, OCH2); 1.52 (s, 9H, C(CH3)3). 13C NMR (CDCl3)
d:
166.5; 157.1; 150.2; 142.6; 137.2; 134.9; 134.4; 132.7; 129.0 (double
intensity); 128.5 (double intensity); 128.4; 127.7; 122.5; 90.5; 76.7;
52.6; 29.1. IR (KBr, (cmꢁ1)): 3307 (NH); 1634 (CON). MS m/z: 460
(Mþ), 333 (MþꢁI). Anal. Calcd for C21H21N2O2I (460.31): C, 54.80; H,
4.60; N, 6.09; found: C, 54.61; H, 4.69; N, 5.84; Rf (10% EtOAc/CHCl3)
0.59; mp 125e126 ꢀC. Dark green crystals. Yield: 350 mg (76%).
References and notes
€
ꢀ
1. Skoda-Foldes, R.; Kollar, L. Curr. Org. Chem. 2002, 6, 1097e1119.
2. Arcadi, A. Carbonylation of Enolizable Ketones (Enol Triflates) and Iodoalkenes
ꢀ
(Chapter 9) In Modern Carbonylation Methods; Kollar, L., Ed.; Wiley-VCH:
4.3.5. 5,7-Bis(N-tert-butylcarboxamido)-8-benzyloxyquinoline
Weinheim, 2008; pp. 223e250.
3. Applied Homogeneous Catalysis with Organometallic Compounds; Cornils, B.,
Herrmann, W. A., Eds.; Wiley-VCH: Weinheim, 1996.
4. Transition Metals for Organic Synthesis; Beller, M., Bolm, C., Eds.; Wiley-VCH:
Weinheim, 1998; Vols. IeII.
5. Colquhoun, H. M.; Thompson, D. J.; Twigg, M. V. Carbonylation. Direct Synthesis
of Carbonyl Compounds; Plenum: New York, NY and London, 1991.
6. Kang, S. K.; Park, S. S.; Kim, S. S.; Choi, J.-K.; Yum, E. K. Tetrahedron Lett. 1999, 40,
4379e4382.
(2d0). 1H NMR (CDCl3)
d
: 9.02 (d, J¼4.0 Hz, 1H, H-2); 8.91 (d,
J¼8.0 Hz, 1H, H-4); 8.40 (s, 1H, H-6); 8.19 (br s, 1H, NH); 7.52 (d,
J¼5.8 Hz, 2H, Ph), 7.52e7.56 (m, 1H, H-3); 7.39e7.41 (m, 3H, Ph);
6.06 (br s, 1H, NH); 5.61 (s, 2H, OCH2); 1.52 (s, 9H, C(CH3)3); 1.23 (s,
9H, C(CH3)3). 13C NMR (CDCl3)
d: 167.2; 163.4; 155.3; 149.9; 142.7;
136.3; 135.0; 130.5; 129.3; 129.2 (double intensity); 129.0; 128.8
(double intensity); 126.1; 124.3; 123.0; 79.0; 52.2; 51.3; 28.8; 28.4.
7. Comins, D. L.; Nolan, J. M.; Bori, I. D. Tetrahedron Lett. 2005, 46, 6697e6699.