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Catalysis Science & Technology
ν = 3266 (m, νN–H), 1698, 1659, 1602 (s, νCO; νCN) cm−1. Anal.
calcd. for C14H26N2O8: C, 53.99; H, 7.05; N, 7.00; found: C,
53.82; H, 7.27; N, 6.98. UV/Vis (CH2Cl2): λmax (ε) = 274 (25 040),
293 (27 220) nm (mol−1 dm3 cm−1).
6b. Propanedioic acid, 2,2′-[1,3-propanediylbis(imino
methylidyne)]bis-, 1,1′,3,3′-tetraethyl ester [CAS 1415327-35-3]:
procedure L-a with diethyl (ethoxymethylene)malonate
(22.37 g, 20.9 ml, 103.5 mmol) and 1,4-diaminobutane (4.56
g, 51.7 mmol). Yield: white solid (18.89 g, 44.09 mmol, 85%).
5a. 2-Propenoic acid, 3,3′-(1,2-ethanediyldiimino)bis[2-
cyano-, 1,1′-diethyl ester] [CAS 92325-24-1]: procedure L-a with
ethyl 2-cyano-3-ethoxyacrylate (21.14 g, 125 mmol) and 1,3-
diaminopropane (5.2 ml, 62 mmol). Yield: white solid (15.58 g,
1
3
Te = 136.3 °C. H-NMR (400 MHz, CDCl3): δ = 1.23 (t, JHH
=
3
7.1 Hz, 6H, CH3), 1.28 (t, JHH = 7.1 Hz, 6H, CH3), 1.62 (s, 4H,
3
CH2–CH2–CH2), 3.32 (d, JHH = 5.4 Hz, 4H, N–CH2), 4.12 (dd,
1
4
3
48.62 mmol, 74%). Mp = 108.5 °C. Te = 110.9 °C. H-NMR (400
3JHH = 7.2 Hz, JHH = 14.3 Hz, 4H, CH2), 4.18 (dd, JHH
=
MHz, CDCl3): δ = 1.30 (m, 6H, CH3), 1.94 (p, 3JHH = 6.6 Hz, 2H,
CH2–CH2–CH2), 3.43 (m, 4H, N–CH2), 4.20 (m, 2H, CH2), 7.07
(m, 1H, NH), 7.37 (m, 1H, CH), 7.84 (m, 1H, CH), 8.93 (m, 1H,
NH). 13C{1H}-NMR (100 MHz, CDCl3): δ = 14.29, 14.40 (CH3),
31.25 (–CH2–CH2–CH2), 46.25, 46.47 (–N–CH2), 60.71, 60.80
(CH2), 71.92, 72.25, 72.66, 72.72 (Cq), 116.72, 116.76, 118.38,
118.54 (CN), 159.15, 159.31 (CH), 165.02 (CO), 167.90
(CO). MS (ESI+) m/z (%): 321 (36) [M + H]+, 343 (100) [M +
Na]+. IR (KBr): ν = 3280 (m, νN–H), 2208 (s, νCN), 1689, 1635 (s,
νCO; νCN) cm−1. Anal. calcd. for C15H20N4O4: C, 55.92; H,
6.38; N, 17.64; found: C, 56.24; H, 6.29; N, 17.49. UV/Vis
(CH2Cl2): λmax (ε) = 288 (30 760) nm (mol−1 dm3 cm−1).
7.2 Hz, JHH = 14.3 Hz, 4H, CH2), 7.92 (d, JHH = 14.0 Hz, 2H,
CH), 9.18 (m, 2H, NH). 13C{1H}-NMR (100 MHz, CDCl3): δ =
14.19, 14.29 (CH3), 27.69 (CH2–CH2–CH2), 49.10 (N–CH),
59.49, 59.73 (CH2), 89.67 (Cq), 159.74 (CH), 165.81, 169.28
(CO). MS (ESI+) m/z (%): 429 (100) [M + H]+, 451 (42) [M +
4
3
Na]+. IR (KBr): ν = 3303 (m, νN–H), 1597, 1629, 1678 (s, νCO
;
νCN) cm−1. Anal. calcd. for C20H32N2O8: C, 56.06; H, 7.53; N,
6.54; found: C, 55.99; H, 7.50; N, 6.60. UV/Vis (CH2Cl2): λmax
(ε) = 284 (35 560) nm (mol−1 dm3 cm−1).
7a. 2-Propenoic acid, 3,3′-(1,2-cyclohexanediyldiimino)bis[2-
cyano-, diethyl ester, trans-] [CAS 156996-20-2]: procedure L-a
with ethyl 2-cyano-3-ethoxyacrylate (4.06 g, 24 mmol) and 1,2-
diaminocyclohexane (1.4 ml, 12 mmol). Yield: white solid (3.37
g, 9.35 mmol, 78%). Mp = 167.8 °C. Te = 171.9 °C. 1H-NMR (400
MHz, CDCl3): δ = 1.27 (t, 3JHH = 7.1 Hz, 6H, CH3), 1.37 (m, 4H,
5b. Propanedioic acid, 2,2′-[(1,2-ethanediyl)bis(iminomethylidyne)]bis-,
1,1′,3,3′-tetraethyl ester [CAS 14452-46-1] (malonic acid,
[ethylenebis(iminomethylidyne)]di-,tetraethyl ester): procedure L-a
with diethyl (ethoxymethylene)malonate (10.43 g, 48.2 mmol)
and 1,3-diaminopropane (1.79 g, 24.1 mmol). Yield: white solid
(6.38 g, 15.4 mmol, 64%). Te = 97.0 °C. 1H-NMR (400 MHz,
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CHcyclo, CH2,cyclo), 1.81 (d, JHH = 7.92 Hz, 2H, CH2,cyclo), 2.06
3
(d, JHH = 12.6 Hz, 2H, CH2,cyclo), 3.00 (m, 2H, CHcyclo), 4.17 (q,
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3JHH = 7.0 Hz, 4H, CH2), 7.20 (d, JHH = 13.6 Hz, 2H, CH), 8.81
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3
4
CDCl3): δ = 1.24 (t, JHH = 7.1 Hz, 6H, CH3), 1.30 (t, JHH = 7.1
(dd, 3JHH = 6.5 Hz, JHH = 11.8 Hz, 2H, NH). 13C{1H}-NMR (100
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Hz, 6H, CH3), 1.90 (q, JHH = 6.92 Hz, 2H, CH2–CH2–CH2), 3.39
(q, JHH = 6.7 Hz, 4H, N–CH2), 4.14 (q, JHH = 7.1 Hz, 4H, CH2),
MHz, CDCl3): δ = 14.5 (CH3), 24.3 (CH2,cyclo), 32.4 (CH2,cyclo),
61.2 (CH2), 64.0 (CHcyclo), 72.9 (Cq), 118.3 (CN), 158.3 (CH),
168.1 (CO). MS (ESI+) m/z (%): 361 (100) [M + H]+, 383 (97)
[M + Na]+, 743 [2M + H]+. IR (KBr): ν = 3274 (m, νN–H), 2210 (s,
νCN), 1683, 1630 (s, νCO; νCN) cm−1. Anal. calcd. for
C18H24N4O4: C, 59.99; H, 6.71; N, 15.55; found: C, 60.38; H,
6.583; N, 15.53. UV/Vis (CH2Cl2): λmax (ε) = 277 (30750) nm
(mol−1 dm3 cm−1). UV/Vis (MeCN): λmax (ε) = 203 (20740), 275
(38 180) nm (mol−1 dm3 cm−1).
7b. Procedure L-a with diethyl (ethoxymethylene)malonate
(9.56 g, 44.2 mmol) and 1,2-diaminocyclohexane (2.52 g,
2.1 mmol). Yield: orange-white solid (7.75 g, 17.13 mmol,
78%). Te = 109.6 °C. 1H-NMR (400 MHz, CDCl3): δ = 1.17
3
3
3
3
4.19 (q, JHH = 7.1 Hz, 4H, CH2), 7.93 (d, JHH = 13.9 Hz, 2H,
CH), 9.19 (m, 2H, NH). 13C{1H}-NMR (100 MHz, CDCl3): δ =
14.21, 14.30 (CH3), 31.54 (N–CH2), 46.34 (CH2–CH2–CH2), 59.59,
59.86 (CH2), 90.26 (Cq), 159.66 (CH), 165.63, 169.29 (CO).
MS (ESI+) m/z (%): 415 (100) [M + H]+, 437 (17) [M + Na]+, 851
(13) [2M + Na]+. IR (KBr): ν = 3266 (m, νN–H), 1697, 1663, 1605 (s,
νCO; νCN) cm−1. Anal. calcd. for C19H30N2O8: C, 55.06; H, 7.30;
N, 6.76; found: C, 55.12; H, 7.42; N, 6.90. UV/Vis (CH2Cl2): λmax
(ε) = 288 (31 510) nm (mol−1 dm3 cm−1).
6a. 2-Propenoic acid, 3,3′-(1,3-propanediyldiimino)bis[2-
cyano-, diethyl ester] [CAS 157737-86-5]: procedure L-a with
ethyl 2-cyano-3-ethoxyacrylate (8.12 g, 48 mmol) and 1,4-
diaminobutane (2.4 ml, 24 mmol). Yield: white solid (6.05 g,
18.09 mmol, 75%). Te = 166.7 °C. 1H-NMR (400 MHz,
SO(CH3)2): δ = 1.15 (m, 6H, CH3), 1.43 (m, 4H, CH2–CH2–CH2),
3
3
(t, JHH = 7.1 Hz, 6H, CH3), 1.25 (t, JHH = 7.1 Hz, 6H, CH3),
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1.29 (d, JHH = 10.6 Hz, 2H, CH2,cyclo), 1.38 (m, 2H, CH2,cyclo),
1.78 (d, JHH = 8.3 Hz, 2H, CH2,cyclo), 2.06 (d, JHH = 13.1 Hz,
2H, CH2,cyclo), 2.97 (m, 2H, CHcyclo), 4.05 (q, JHH = 7.1 Hz, 4H,
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3
3
3
3
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3.26 (m, 4H, N–CH2), 4.06 (m, 4H, CH2), 7.73 (d, JHH = 14.5
CH2), 4.14 (q, JHH = 7.1 Hz, 4H, CH2), 7.82 (t, JHH = 13.8 Hz,
2H, CH), 9.14 (m, 2H, NH). 13C{1H}-NMR (100 MHz, CDCl3): δ
= 14.18, 14.21 (CH3), 24.12 (CH2,cyclo), 32.19 (CH2,cyclo), 59.43,
59.78 (CH2), 63.51 (CHcyclo), 90.36 (Cq), 158.70 (CH), 165.31,
169.31 (CO). MS (ESI+) m/z (%): 455 (100) [M + H]+, 932 (15)
[2M + H]+. IR (KBr): ν = 3258 (m, νN–H), 1717, 1681, 1640, 1613
(s, νCO; νCN) cm−1. Anal. calcd. for C22H34N2O8: C, 58.14; H,
7.54; N, 6.16; found: C, 58.12; H, 7.55; N, 6.15. UV/Vis (CH2Cl2):
λmax (ε) = 274 (31120), 290 (19760) nm (mol−1 dm3 cm−1).
8a. Procedure L-b with ethyl 2-cyano-3-ethoxyacrylate
(27.70 g, 163.7 mmol) and 2-aminobenzylamine (10.00 g,
3
3
Hz, 6H, CH), 7.91 (d, JHH = 15.0 Hz, 6H, CH), 8.63 (d, JHH
=
14.7 Hz, 6H, NH), 9.07 (d, JHH = 14.3 Hz, 6H, NH). 13C{1H}-
NMR (100 MHz, SO(CH3)2): δ = 14.24, 14.34 (CH3), 26.85 (CH2–
CH2–CH2), 48.35 (N–CH2), 59.46 (CH2), 68.13, 68.86 (Cq),
116.82, 119.15 (CN), 159.50, 159.96 (CH), 165.09, 166.60
(CO). MS (ESI+) m/z (%): 335 (38) [M + H]+, 357 (100) [M +
Na]+. IR (KBr): ν = 3273, 3227 (s, νN–H), 2205 (s, νCN), 1690,
1623, 1540 (s, νCO; νCN) cm−1. Anal. calcd. for C16H22N4O4:
C, 57.47; H, 6.63; N, 16.76; found: C, 57.32; H, 6.83; N, 16.94.
UV/Vis (CH2Cl2): λmax (ε) = 284 (32 900) nm (mol−1 dm3 cm−1).
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1668 | Catal. Sci. Technol., 2014, 4, 1658–1673
This journal is © The Royal Society of Chemistry 2014