(d, 1H, J = 7.6 Hz, Ar–H), 7.08 (d, 1H, J = 7.6 Hz, Ar–H). 13
NMR (100 MHz, CDCl3): d 15.68, 21.02 (2CH3), 51.88, 52.97
C
Diethyl (Z)-2-(2,6-dimethylphenoxy)-2-butenedioate (1o).
Yellow oil. H NMR (400 MHz, CDCl3): d 1.16 (t, 3H, J =
1
(2OCH3), 113.81, 115.09, 124.19, 124.68, 131.00, 136.61, 150.62,
7.2 Hz, CH3), 1.24 (t, 3H, J = 7.2 Hz, CH3), 2.26 (s, 3H, CH3),
2.28 (s, 3H, CH3), 4.05 (q, 2H, J = 7.2 Hz, OCH2), 4.16 (q, 2H,
J = 7.2 Hz, OCH2), 6.08 (s, 1H, HC C), 6.95–7.01 (m, 3H,
Ar–H). 13C NMR (100 MHz, CDCl3): d 13.76, 14.07, 15.89,
16.89 (4CH3), 60.61, 62.16 (2CH2), 105.35, 120.14, 124.99,
128.58, 129.90, 151.79, 152.42 (4C, 4CH), 162.258, 164.18
(2C O, ester). IR (neat, nmax, cm-1): 1727, 1662, 1205, 1131.
Elemental analysis for C16H20O5: Calc. C, 65.74; H, 6.90.
Found: C, 65.60; H, 6.95. EIMS: m/z 292.1 (M+).
154.75 (4CH, 4C), 162.79, 164.13 (2C O, ester). IR (KBr, nmax
,
cm-1): 1732, 1634, 1425, 1210. Elemental analysis for C14H16O5:
Calc. C, 63.63; H, 6.10. Found: C, 63.75; H, 6.23. EIMS: m/z
264.1 (M+).
Dimethyl (Z)-2-(2,6-dichlorophenoxy)-2-butenedioate (1h).
White solid. mp 40–42 ◦C. 1H NMR (400 MHz, CDCl3): d 3.72
(s, 3H, OCH3), 3.77 (s, 3H, OCH3), 6.68 (s, 1H, HC C), 6.76 (d,
1H, J = 8.8 Hz, Ar–H), 7.14 (dd, 1H, J = 7.6 Hz, J = 2.4 Hz, Ar–
H), 7.42 (d, 1H, J = 2.4 Hz, Ar–H). 13C NMR (100 MHz, CDCl3):
d 52.15, 53.27 (2OCH3), 115.89, 116.94, 124.40, 127.61, 128.77,
130.45, 149.01, 151.20 (4C, 4CH), 161.80, 163.40 (2C O, ester).
IR (KBr, nmax, cm-1): 1724, 1655, 1487, 1212, 1100. Elemental
analysis for C14H16O5: Calc. C, 47.24; H, 3.30. Found: C, 47.12;
H, 3.44. EIMS: m/z 303.8 (M+).
Diethyl (Z)-2-(3-methoxyphenoxy)-2-butenedioate (1p). Yel-
low oil. 1H NMR (400 MHz, CDCl3): d 1.19 (t, 3H, J = 7.2 Hz,
CH3), 1.23 (t, 3H, J = 7.2 Hz, CH3), 3.77 (s, 3H, OCH3), 4.19
(2q, 4H, J = 7.2 Hz, 2OCH2), 6.58 (s, 1H, HC C), 6.51–
7.20 (m, 4H, Ar–H). 13C NMR (100 MHz, CDCl3): d 13.87,
14.03, 55.35 (3CH3), 60.99, 62.29 (2CH2), 102.53, 108.09, 109.16,
115.18, 129.95 (5CH), 149.90, 157.72, 160.82 (3C), 162.18,
163.57 (2C O, ester). IR (neat, nmax, cm-1): 1738, 1636, 1220,
1145. Elemental analysis for C15H18O6: Calc. C, 61.22; H, 6.16.
Found: C, 61.13; H, 6.04. EIMS: m/z 294.1 (M+).
Dimethyl (Z)-2-(3-◦Methoxyphenoxy)-2-butenedioate (1i).
White solid. mp 56–57 C. 1H NMR (400 MHz, CDCl3): d 3.73
(s, 3H, OCH3), 3.77 (s, 3H, OCH3), 3.80 (s, 3H, OCH3), 6.61 (s,
1H, HC C), 6.50–7.22 (m, 4H, Ar–H). 13C NMR (100 MHz,
CDCl3): d 52.03, 53.06, 55.37 (3CH3), 102.49, 107.94, 109.21,
115.16, 130.04 (5CH), 149.68, 157.61, 160.87 (3C), 162.64,
163.85 (2C O, ester). IR (KBr, nmax, cm-1): 1747, 1645, 1460,
1223, 1155. Elemental analysis for C13H14O6: Calc. C, 58.64; H,
5.30. Found: C, 58.73; H, 5.19. EIMS: m/z 266 (M+).
Diethyl (Z)-2-(3-nitrophenoxy)-2-butenedioate (1q). Yellow
oil. 1H NMR (400 MHz, CDCl3): d 1.21 (t, 3H, J = 7.2 Hz, CH3),
1.25 (t, 3H, J = 7.2 Hz, CH3), 4.18 (q, 2H, J = 7.2 Hz, OCH2),
4.26 (q, 2H, J = 7.2 Hz, OCH2), 6.80 (s, 1H, HC C), 7.056 (d,
2H, J = 9.2 Hz, Ar–H); 8.24 (d, 2H, J = 9.2 Hz, Ar–H). 13C
NMR (100 MHz, CDCl3): d 13.95, 13.99 (2CH3), 61.36, 62.82
(2CH2), 116.03, 117.83, 120.27, 125.89, 148.33, 161.24 (5CH,
3C), 161.50, 162.82 (2C O, ester). IR (neat, nmax, cm-1): 1758,
1640, 1217, 1155. Elemental analysis for C14H15NO7: Calc. C,
54.37; H, 4.89. Found: C, 54.25; H, 4.97. EIMS: m/z 309 (M+).
1
Diethyl (Z)-2-(phenoxy)-2-butenedioate (1l). Yellow oil. H
NMR (400 MHz, CDCl3): d 0.91 (t, 3H, J = 7.2 Hz, CH3), 1.33 (t,
3H, J = 7.2 Hz, CH3), 3.81 (q, 2H, J = 7.2 Hz, OCH2), 4.27 (q, 2H,
J = 7.2 Hz, OCH2), 6.40 (s, 1H, HC C), 6.31–7.48 (m, 5H, Ar–
H). 13C NMR (100 MHz, CDCl3): d 13.50, 14.26 (2CH3), 60.95,
62.20 (2CH2), 119.46 ( CH), 128.81, 129.04, 132.35, 133.22
(CH, C-Ar), 149.46 ( C), 164.48, 165.19 (2C O, ester). IR
(neat, nmax, cm-1): 1737, 1654, 1221, 1196. Elemental analysis
for C14H16O5: Calc. C, 63.63; H, 6.10. Found: C, 63.75; H, 6.29.
EIMS: m/z 264.1 (M+).
Diethyl (Z)-2-(2-naphtoxy)-2-butenedioate (1r). Yellow oil.
1H NMR (400 MHz, CDCl3): d 1.15 (t, 3H, J = 7.2 Hz, CH3),
1.22 (t, 3H, J = 7.2 Hz, CH3), 4.19 (q, 4H, J = 7.2 Hz, 2OCH2),
6.70 (s, 1H, HC C), 7.23–7.85 (m, 6H, Ar–H). 13C NMR
(100 MHz, CDCl3): d 13.87, 14.05 (2CH3), 61.00, 62.32 (2CH2),
110.88, 115.58, 118.09, 124.72, 126.65, 127.11, 127.80, 129.91,
130.65 (5CH), 130.18, 133.99, 150.02, 154.64 (4C), 162.23,
163.57 (2C O, ester). IR (neat, nmax, cm-1): 1734, 1668, 1265,
1158. Elemental analysis for C18H18O5: Calc. C, 68.78; H, 5.77.
Found: C, 68.70; H, 5.64. EIMS: m/z 314.1 (M+).
Diethyl (Z)-2-(2-chlorophenoxy)-2-butenedioate (1m). Yel-
low oil. 1H NMR (400 MHz, CDCl3): d 1.17 (t, 3H, J = 7.2 Hz,
CH3), 1.20 (t, 3H, J = 7.2 Hz, CH3), 4.17 (q, 2H, J = 7.2 Hz,
OCH2), 4.19 (q, 2H, J = 7.2 Hz, OCH2), 6.65 (s, 1H, HC C),
6.82–7.42 (m, 4H, Ar–H). 13C NMR (100 MHz, CDCl3): d
13.79, 13.94 (2CH3), 61.07, 62.40 (2CH2), 115.64, 116.20, 123.48,
124.09, 127.52, 130.65, 149.46, 152.47 (5CH, 3C), 161.46, 163.28
(2C O, ester). IR (neat, nmax, cm-1): 1750, 1634, 1454, 1211,
1186. Elemental analysis for C14H15ClO5: Calc. C, 56.29; H, 5.06.
Found: C, 56.36; H, 4.95. EIMS: m/z 297.9 (M+).
Dimethyl 2-(4-brom◦o-2-formylphenoxy)-2-butenedioate (1t).
White solid. mp 88–90 C. 1H NMR (400 MHz, CDCl3): d 3.74,
3.81 (2 s, 6H, 2OCH3), 6.76 (d, 1H, J = 8 Hz, Ar–H), 6.79 (s,
1H, HC C), 7.59 (dd, 1H, J = 8 Hz, J = 4 Hz, Ar–H), 8.02 (d,
1H, J = 4 Hz, Ar–H), 10.47 (s, 1H, CHO). 13C NMR (100 MHz,
CDCl3): d 52.31, 53.43 (2CH3), 116.79, 117.32, 117.35, 131.25,
137.96, 148.66, 157.78 (CH, C), 161.80, 163.22 (2C O, ester),
187.56 (CHO). IR (KBr, nmax, cm-1): 2830, 1747, 1720, 1646,
1200, 1141. Elemental analysis for C13H11BrO6: Calc. C, 45.50;
H, 3.23. Found: C, 45.65; H, 3.31. EIMS: m/z 341.9 (M+).
Diethyl (Z)-2-(4-bromophenoxy)-2-butenedioate (1n). Yel-
1
low oil. H NMR (400 MHz, CDCl3): d 1.41 (2t, 6H, J = 7.2,
2CH3), 4.17 (q, 2H, J = 7.2 Hz, OCH2), 4.20 (q, 2H, J = 7.2 Hz,
CH2), 6.83 (s, 1H, HC C), 6.85 (d, 2H, J = 8.8 Hz, Ar–H),
7.39 (d, 2H, J = 8.8 Hz, Ar–H). 13C NMR (100 MHz, CDCl3): d
13.89, 14.02 (2CH3), 61.09, 62.44 (2CH2), 115.80, 116.00, 117.93,
132.48, 149.42, 155.83 (CH, C), 161.81, 163.34 (2C O, ester).
IR (neat, nmax, cm-1): 1744, 1619, 1222, 1169. Elemental analysis
for C14H15BrO5: Calc. C, 56.29; H, 5.06. Found: C, 56.36; H,
4.90. EIMS: m/z 342 (M+).
Dimethyl 2-(4-chloro-2-formylphenoxy)-2-butenedioate (1u).
White solid. mp 96–98 ◦C. 1H NMR (400 MHz, CDCl3): d 3.75,
3.80 (2 s, 6H, 2OCH3), 6.79 (s, 1H, HC C), 6.82 (d, J = 8.8 Hz,
1H, Ar–H), 7.45 (dd, J = 8.8 Hz, J = 2.6 Hz, 1H, Ar–H), 7.88 (d,
J = 2.8 Hz, 1H, Ar–H), 10.48 (s, 1H, CHO). 13C NMR (100 MHz,
2854 | Green Chem., 2011, 13, 2851–2858
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