176
M. Bellassoued et al. / Journal of Organometallic Chemistry 662 (2002) 172ꢀ177
/
4.5.3. [(4-Methoxyphenylamino)-phenyl-methyl]-but-3-
enoic acid (6c)
13C-NMR (62.9 MHz, CDCl3) d 178.4, 147.4, 147.3,
137.1, 133.8, 129.7, 129.6, 128.9, 128.6, 127.9, 126.9,
126.8, 118.5, 115.7, 114.6, 58.3, 57.2.
White solid; m.p.ꢁ
1H-NMR (250 MHz, acetone-d6) d 7.50ꢀ
Ar), 7.32ꢀ7.17 (m, 3H, Ar), 6.67ꢀ6.57 (m, 4H, Ar), 6.06
(dt, 1H, Jꢁ17.6, 9.3 Hz, CHÄ), 5.24ꢀ5.17 (m, 2H,
CH2Ä), 4.76 (d, 1H, Jꢁ8.5 Hz, CHN), 3.63 (s, 3H,
OMe), 3.48 (t, 1H, Jꢁ8.5 Hz, CHCOOH).
/
137 8C.
/
7.46 (m, 2H,
IR (KBr, cmꢂ1) 3400 (NH), 3400ꢀ
(CÄO). MS (APCI-, MeCN) m/z 292 [Mꢂ
/
3200 (OH), 1720
Hꢂ]. Anal.
/
/
/
/
/
/
/
Calc. for C19H19NO2: C, 77.79; H, 6.53; N, 4.77. Found:
C, 77.91; H, 6.51; N, 4.75%.
/
/
/
¯
13C-NMR (62.9 MHz, acetone-d6) d 173.2, 153.3,
143.3, 142.9, 135.5, 129.3, 128.8, 128.3, 119.9, 116.1,
115.6, 61.1, 59.1, 56.1.
4.5.7. (Phenyl-phenylamino-methyl)-3-methylbut-3-
enoic acid (6g)
White solid; m.p.ꢁ
1H-NMR (250 MHz, acetone-d6) d 7.39ꢀ
Ph), 7.12ꢀ7.00 (m, 3H, Ph), 6.85ꢀ6.78 (m, 2H, Ph),
6.46ꢀ6.33 (m, 3H, Ph), 4.98 (s, 1H, CH2Ä), 4.88 (s, 1H,
CH2Ä), 4.65 (d, 1H, Jꢁ11.1 Hz, CHN), 3.42 (d, 1H,
Jꢁ11.1 Hz, CHCOOH), 1.68 (s, 3H, Me).
/
156 8C.
IR (KBr, cmꢂ1) 3390 (NH), 3400ꢀ
(CÄO). MS (APCI-, MeCN) m/z 296 [Mꢂ
Calc. for C18H19NO3: C, 72.71; H, 6.44; N, 4.71. Found:
/
3200 (OH), 1720
/
7.35 (m, 2H,
/
/
Hꢂ]. Anal.
/
/
/
/
C, 72.82; H, 6.42; N, 4.72%.
/
/
/
¯
13C-NMR (62.9 MHz, acetone-d6) d 172.5, 147.6,
142.6, 141.3, 128.8, 128.0, 127.9, 127.1, 116.7, 116.1,
113.1, 61.3, 56.4, 18.1.
4.5.4. [(4-Nitro-phenyl)-(4-nitro-phenylamino)-
methyl]-but-3-enoic acid (6d)
Yellow solid; m.p.ꢁ
1H-NMR (250 MHz, acetone-d6) d 8.17ꢀ
Ar), 7.93ꢀ7.90 (m, 2H, Ar), 7.79ꢀ7.74 (m, 2H, Ar),
6.79ꢀ6.72 (m, 3H, Ar, NH), 5.86ꢀ5.71 (m, 1H, CHÄ),
5.20ꢀ5.01 (m, 3H, CH2Ä, CHN), 3.59 (t, 1H, Jꢁ9.0 Hz,
CHCOOH).
/
167 8C.
IR (KBr, cmꢂ1) 3390 (NH), 3400ꢀ
(CÄO). MS (APCI-, MeCN) m/z 280 [Mꢂ
/
3200 (OH), 1720
Hꢂ]. Anal.
/
8.14 (m, 2H,
/
/
/
/
Calc. for C18H19NO2: C, 76.84; H, 6.81; N, 4.98. Found:
C, 76.84; H, 6.80; N, 4.98%.
/
/
/
/
/
/
¯
13C-NMR (62.9 MHz, acetone-d6) d 172.8, 153.6,
148.7, 148.4, 139.0, 133.6, 129.7, 126.6, 124.3, 120.6,
113.1, 59.0, 57.3.
4.5.8. [(3-Nitro-phenyl)-phenylamino-methyl]-3-
methylbut-3-enoic acid (6h)
Red solid; m.p.ꢁ
1H-NMR (250 MHz, acetone-d6) d 8.40ꢀ
Ar), 8.04ꢀ7.95 (m, 2H, Ar), 7.56ꢀ7.49 (m, 1H, Ar),
6.98ꢀ6.92 (m, 2H, Ar), 6.61ꢀ6.44 (m, 3H, Ar), 5.13 (s,
1H, CH2Ä), 5.03 (s, 1H, CH2Ä), 4.95 (d, 1H, Jꢁ11.1
Hz, CHÄ), 3.61 (d, 1H, Jꢁ11.1 Hz, CHCOOH), 1.81 (s,
3H, Me).
/
167 8C.
IR (KBr, cmꢂ1) 3390 (NH), 3400ꢀ
(CÄO). MS (APCI-, MeCN) m/z 356 [Mꢂ
/
3200 (OH), 1720
Hꢂ]. Anal.
/
8.39 (m, 1H,
/
/
/
/
/
/
Calc. for C17H15N3O6: C, 57.14; H, 4.23; N, 11.76.
Found: C, 57.16; H, 4.22; N, 11.77%.
/
/
/
/
/
¯
13C-NMR (62.9 MHz, acetone-d6) d 173.3, 149.7,
148.3, 146.6, 141.9, 136.0, 130.6, 130.2, 123.8, 123.5,
118.5, 117.9, 114.4, 62.0, 57.2, 19.4.
4.5.5. [Phenylamino-(2-thienyl)methyl]-but-3-enoic acid
(6e)
Orange liquid.
1H-NMR (250 MHz, acetone-d6) d 7.21ꢀ
/
6.58 (m, 9H,
16.9, 9.5 Hz, CHÄ), 5.34ꢀ
), 5.00 (d, 1H, Jꢁ8.3 Hz, CHN),
8.3 Hz, CHCOOH).
IR (KBr, cmꢂ1) 3390 (NH), 3400ꢀ
(CÄO). MS (APCI-, MeCN) m/z 325 [Mꢂ
/
3200 (OH), 1720
Hꢂ]. Anal.
Ar, NH), 5.83 (dt, 1H, Jꢁ
5.27 (m, 2H, CH2Ä
3.48 (t, 1H, Jꢁ
/
/
/
/
/
/
/
Calc. for C18H18N2O4: C, 66.25; H, 5.56; N, 8.58.
Found: C, 66.19; H, 5.55; N, 8.58%.
/
¯
13C-NMR (62.9 MHz, acetone-d6) d 176.8, 159.0,
146.8, 145.8, 132.4, 129.6, 127.3, 125.3, 121.8, 119.0,
114.7, 56.1, 52.5.
4.5.9. [(4-Nitro-phenyl)-(4-nitro-phenylamino)-
methyl]-3-methylbut-3-enoic acid (6i)
IR (KBr, cmꢂ1) 3390 (NH), 3400ꢀ
(CÄO). MS (APCI-, MeCN) m/z 272 [Mꢂ
Calc. for C15H15NO2S: C, 65.91; H, 5.53; N, 5.12.
/
3200 (OH), 1720
Yellow solid; m.p.ꢁ
1H-NMR (250 MHz, acetone-d6) d 8.06ꢀ
Ar), 7.84ꢀ7.80 (m, 2H, Ar), 7.74ꢀ7.71 (m, 2H, Ar),
6.71ꢀ6.68 (m, 2H, Ar), 5.18 (d, 1H, Jꢁ9.5 Hz, CHN),
4.82 (s, 1H, CH2Ä), 4.71 (s, 1H, CH2Ä), 3.60 (d, 1H, Jꢁ
9.5 Hz, CHCOOH), 1.58 (s, 3H, Me).
/
186 8C.
/
/
Hꢂ]. Anal.
/
8.02 (m, 2H,
/
/
Found: C, 65.86; H, 5.51; N, 5.12%.
/
/
/
/
/
4.5.6. Phenyl-3-phenylamino-2-vinyl-pent-4-enoic acid
(6f)
¯
13C-NMR (62.9 MHz, acetone-d6) d 173.4, 154.2,
149.8, 148.6, 141.3, 139.1, 130.2, 127.0, 124.6, 117.3,
113.2, 60.6, 58.5, 21.9.
Orange solid; m.p.ꢁ
1H-NMR (250 MHz, CDCl3) d 7.23ꢀ
Ph), 6.65ꢀ6.46 (m, 4H, Ph, PhCHÄ, NH), 6.10 (dd, 1H,
Jꢁ16.7, 6.7 Hz, CHÄ), 5.89 (m, 1H, CHÄ), 5.23ꢀ5.16
(m, 2H, CH2Ä), 4.40 (m, 1H, CHN), 3.30 (t, 1H, Jꢁ6.7
Hz, CHCOOH).
/
150 8C.
/7.00 (m, 8H,
/
/
IR (KBr, cmꢂ1) 3390 (NH), 3400ꢀ
(CÄO). MS (APCI-, MeCN) m/z 370 [Mꢂ
/
3200 (OH), 1720
Hꢂ]. Anal.
/
/
/
/
/
/
/
/
Calc. for C18H17N3O6: C, 58.22; H, 4.61; N, 11.32.
Found: C, 58.34; H, 4.60; N, 11.33%.
¯