Interaction of Aryloxychlorocarbenes
Cl)/ 343 (18). Anal. Calcd for C14H8Cl4N2O2: C, 44.48; H, 2.13;
N, 7.41. Found: C, 44.46; H, 2.42; N, 7.26.
0.9H), 1.19 (t, J ) 7.1 Hz, 0.9H). 13C NMR δ (ppm) a mixture
of three isomers: 164.5, 164.0, 163.3, 157.0, 156.8, 156.6, 149.2,
148.5, 147.2, 129.4, 120.9, 120.7, 119.2, 118.8, 114.7, 114.6,
114.5, 114.4, 110.3, 61.3, 61.1, 61.2, 61.1, 55.6, 14.2, 14.1 (d).
HRMS (FAB) calcd for C24H25Cl2O8 511.0921 (M + 1), found
511.0917.
Diethyl 1,4-Dichloro-1,4-bis(4-fluorophenoxy)-1,3-buta-
diene-2,3-dicarboxylate (6d). Colorless oil; a mixture of
isomers, IR (film) v (cm-1) 1732, 1601, 1501, 1456; 1H NMR δ
(ppm): 6.98-7.39 (m, 8H), 4.37 (q, J ) 7.1 Hz, 0.2H), 4.33 (q,
J ) 7.1 Hz, 0.6H), 4.26 (q, J ) 7.1 Hz, 2.6H), 4.17 (q, J ) 7.1
Hz, 0.4H), 4.17 (q, J ) 7.1 Hz, 0.2H), 1.40 (t, J ) 7.2 Hz, 0.3H),
1.36 (t, J ) 6.9 Hz, 1.2H), 1.31 (t, J ) 7.1 Hz, 3.0H), 1.27 (t,
J ) 7.1 Hz, 0.3H), 1.25 (t, J ) 7.1 Hz, 1.2H), 1.17 (t, J ) 7.1
Hz, 0.6H); 13C NMR δ (ppm) 164.2, 163.6, 163.0, 162.4, 161.0,
160.9, 160.7, 151.6, 150.7, 149.4, 148.6, 142.7, 131.0, 129.5,
128.7, 128.4, 128.3, 127.2, 123.8, 122.9, 122.3, 121.2, 121.1,
121.0, 120.9, 119.3, 119.2, 119.0, 118.9, 116.5 (d), 116.4, 116.3,
116.2, 116.1, 114.9, 111.3, 62.8, 62.1, 61.5, 61.4, 61.3, 60.8, 14.2,
14.1, 14.0, 13.9. HRMS (FAB) calcd for C22H19Cl2F2O6 487.0521
(M + 1), found 487.0526.
1,4-Bis-4-bromophenoxy-1,4-dichloro-2,3-diazabuta-
1,3-dienes (5f). Colorless crystals; mp 176-178 °C; IR v (cm-1
)
1634, 1575; 1H NMR δ (ppm) 7.53 (d, J ) 8.9 Hz, 4H), 7.17 (d,
J ) 8.9 Hz, 4H); 13C NMR δ (ppm) 152.3, 147.3, 132.6, 122.3,
119.2; N-Maldi-TOF MS 463 (M+ - 1). Anal. Calcd for C14H8-
Br2Cl2N2O2: C, 36.01; H, 1.73; N, 6.00. Found: C, 36.12; H,
1.73; N, 5.96.
1,4-Bis-2,4-dichlorophenoxy-1,4-dichloro-2,3-diazabuta-
1,3-dienes (5g). Colorless crystals; mp 132-133 °C; IR v
(cm-1) 1615, 1581, 1473; 1H NMR δ (ppm) 7.49 (2H, d, J ) 2.3
Hz), 7.30 (2H, dd, J ) 8.7 and 2.3 Hz), 7.24 (2H, d, J ) 8.7
Hz); 13C NMR δ (ppm) 147.9, 147.1, 132.4, 130.4, 128.0, 127.4,
123.8; MS (EI) 133 (100)/135(65), 283 (25)/285 (35)/287 (15),
409 (20)/411(30)/413 (20), 444 (M+, 3)/446 (5)/448 (4). Anal.
Calcd for C14H6Cl6N2O2: C, 37.62; H, 1.35; N, 6.27. Found: C,
37.71; H, 1.44; N, 5.95.
1,4-Bis-(4-chloro-3,5-dimethylphenoxy)-1,4-dichloro-
2,3-diazabuta-1,3-dienes (5h). Colorless crystals; mp 142-
1
143 °C; IR v (cm-1) 1628, 1582, 1469; H NMR δ (ppm) 7.02
(s, 4H), 2.40 (s, 12H); 13C NMR δ (ppm) 150.9, 146.9, 137.7,
131.9, 120.1, 20.9; TOF MS 379, 433 (M+ + 1)/435/437. Anal.
Calcd for C18H16Cl4N2O2: C, 49.80; H, 3.71; N, 6.32. Found:
C, 49.84; H, 3.84; N, 6.32.
Diethyl 1,4-Dichloro-1,4-bis(4-chlorophenoxy)-1,3-buta-
diene-2,3-dicarboxylate (6e). Colorless oil; a mixture of
1
three isomers, IR (film) v (cm-1) 1725, 1612, 1584, 1485; H
NMR δ (ppm) major symmetric isomer: 7.31 (d, J ) 9.0 Hz,
4H), 6.95 (d, J ) 9.0 Hz, 4H), 4.23 (q, J ) 7.1 Hz, 4H), 1.29 (t,
J ) 7.1 Hz, 6H). A mixture of three isomers: 7.35 (d, J ) 9.1
Hz, 1.6H), 7.31 (d, J ) 9.0 Hz, 1.4H), 7.27 (d, J ) 9.0 Hz, 1H),
7.10 (d, J ) 9.0 Hz, 0.8H), 7.05 (d, J ) 9.0 Hz, 0.8H), 6.98 (d,
J ) 9.0 Hz, 1.0H), 6.95 (d, J ) 9.0 Hz, 1.4H), 4.32 (q, J ) 7.1
Hz, 0.8H), 4.21-4.25 (m, 2.4H), 4.13 (q, J ) 7.1 Hz, 0.8H),
1.35 (t, J ) 7.1 Hz, 1.5H), 1.29 (t, J ) 7.1 Hz, 2.1H), 1.22 (t,
J ) 7.1 Hz, 1.2H), 1.14 (t, J ) 7.1 Hz, 1.2H). 13C NMR δ (ppm)
a mixture of three isomers: 164.0, 163.5, 162.7, 162.2, 153.4,
153.3, 152.7, 152.0, 151.2, 148.2, 130.9, 130.7, 130.1, 129.9,
129.8, 129.7, 129.6, 129.0, 120.8, 120.6, 119.0, 118.6, 115.7,
115.3, 111.9, 61.6, 61.5 (d), 61.4, 14.2, 14.1, 14.0, 13.9. HRMS
(FAB) calcd for C22H19Cl4O6 518.9930 (M + 1), found 518.9935.
Diethyl 1,4-Dichloro-1,4-diphenoxy-1,3-butadiene-2,3-
dicarboxylate (6a). Colorless oil; a mixture of four isomers,
1
IR (film) v (cm-1) 1730, 1614, 1585; H NMR δ (ppm) major
asymmetric isomer: 7.36 (t, J ) 7.8 Hz, 4H), 7.22 (t, J ) 7.5
Hz, 2H), 7.04 (d, J ) 8.5 Hz, 4H), 4.25 (q, J ) 7.1 Hz, 4H),
1.32 (t, J ) 7.1 Hz, 6H). A mixture of four isomers: 7.31-
7.41 (m, 6.0H), 7.16-7.26 (m, 1.0H), 7.14 (t, J ) 8.0 Hz, 1.2H),
7.07 (t, J ) 8.5 Hz, 1.8H), 4.40 (q, J ) 7.1 Hz, 0.3H), 4.33-
4.35 (m, 1.2H), 4.23-4.27 (m, 1.6H), 4.15 (q, J ) 7.1 Hz, 0.9H),
1.38-1.42 (m, 2.05H), 1.35 (t, J ) 7.1 Hz, 1.35H), 1.24 (t, J )
7.1 Hz, 1.05H), 1.14(t, J ) 7.1 Hz, 1.35H). 13C NMR δ (ppm)
a mixture of four isomers: 164.3, 163.8, 163.0, 162.5, 154.9,
153.7, 153.2, 151.6, 150.8, 148.6, 130.9, 129.8, 129.7, 129.6,
129.5, 126.4, 125.4, 125.2, 124.7, 124.5, 121.4, 119.5, 119.4,
119.3, 117.7, 117.4, 115.0 111.5, 62.7, 62.0, 61.4, 61.35, 61.3,
61.2, 14.2 (d) 14.1, 14.0 (d). HRMS (FAB) calcd for C22H21Cl2O6
451.0710 (M + 1), found 451.0709.
Diethyl 1,4-Dichloro-1,4-bis(4-bromophenoxy)-1,3-buta-
diene-2,3-dicarboxylate (6f). Colorless oil; a mixture of three
isomers, IR (film) v (cm-1) 1732, 1615, 1579, 1482; 1H NMR δ
(ppm) major symmetric isomer: 7.47 (d, J ) 8.9 Hz, 4H), 6.91
(d, J ) 8.9 Hz, 4H), 4.25 (q, J ) 7.1 Hz, 4H), 1.31 (t, J ) 7.1
Hz, 6H). A mixture of the other two isomers: 7.52 (d, J ) 8.9
Hz, 6H), 7.45 (d, J ) 8.9 Hz, 2H), 7.06 (d, J ) 8.9 Hz, 4H),
7.01 (d, J ) 8.9 Hz, 2H), 6.93 (d, J ) 9.0 Hz, 2H), 4.34 (q, J )
7.2 Hz, 2H), 4.24 (q, J ) 7.1 Hz, 4H), 4.15 (q, J ) 7.1 Hz, 2H),
1.37 (t, J ) 7.1 Hz, 3H), 1.24 (t, J ) 7.1 Hz, 6H), 1.15 (t, J )
7.1 Hz, 3H). 13C NMR δ (ppm) a mixture of isomers: 163.4,
162.7, 153.9, 153.8, 152.7, 152.6, 151.1, 132.8, 132.8, 132.7,
124.6, 123.0, 121.2, 119.4, 119.2, 119.0, 117.6, 117.4, 115.8,
61.6, 61.5 (d), 14.2, 14.1, 14.0. HRMS (FAB) calcd for C22H19-
Br2Cl2O6 606.8921 (M + 1), found 606.8907
Diethyl 1,4-Dichloro-1,4-bis(4-methylphenoxy)-1,3-buta-
diene-2,3-dicarboxylate (6b). Colorless oil; a mixture of
three isomers, IR (film) v (cm-1) 1730, 1590; 1H NMR δ (ppm)
major symmetric isomer: 7.15 (d, J ) 8.3 Hz, 4H), 6.93 (d,
J ) 8.5 Hz, 4H), 4.25 (q, J ) 7.1 Hz, 4H), 2.37 (s, 6H), 1.31 (t,
J ) 7.1 Hz, 6H). A mixture of three isomers: 7.18-7.20 (m,
1.4H), 7.15 (d, J ) 8.3 Hz, 1.9H), 7.12 (d, J ) 8.4 Hz, 0.7H),
7.07 (d, J ) 8.6 Hz, 0.7H), 7.01 (d, J ) 8.6 Hz, 0.7H), 6.96 (d,
J ) 8.6 Hz, 0.7H), 6.93 (d, J ) 8.5 Hz, 1.9H), 4.31 (q, J ) 7.1
Hz, 0.7H), 4.25 (q, J ) 7.1 Hz, 2.6H), 4.16 (q, J ) 7.1 Hz, 0.7H),
2.39 (s, 1.05H), 2.37 (s, 3.9H), 2.27 (s, 1.05H), 1.37 (t, J ) 7.1
Hz, 1.05H), 1.31 (t, J ) 7.1 Hz, 3.9H), 1.25 (t, J ) 7.1 Hz,
1.05H), 1.17 (t, J ) 7.1 Hz, 1.05H). 13C NMR δ (ppm) a mixture
of three isomers: 164.4, 163.1, 162.6, 152.8, 151.9, 151.5, 151.1,
148.9, 135.1, 134.9, 134.5, 134.1, 130.3, 130.2, 130.0 129.7,
129.0, 128.8, 128.5, 128.3, 126.5, 119.5, 119.4, 119.3, 117.9,
117.7, 117.3, 111.6, 110.9, 61.3, 61.25, 61.2, 61.1, 20.9, 20.8,
20.7, 20.6, 14.2, 14.1, 14.0, 13.9. HRMS (FAB) calcd for C24H25-
Cl2O6 479.1023 (M + 1), found 479.1027.
Diethyl 1,4-Dichloro-1,4-bis(4-methoxyphenoxy)-1,3-
butadiene-2,3-dicarboxylate (6c). Colorless oil; a mixture
of three isomers, IR (film) v (cm-1) 1727, 1615, 1592. 1H NMR
δ (ppm) major symmetric isomer: 6.97 (d, J ) 9.0 Hz, 4H),
6.86 (d, J ) 9.0 Hz, 4H), 4.25 (q, J ) 7.1 Hz, 4H), 3.82 (s, 6H),
1.31 (t, J ) 7.1 Hz, 6H). A mixture of three isomers: 7.11 (d,
J ) 9.0 Hz, 0.4H), 7.02-7.05 (m, 1.2H), 6.97 (d, J ) 9.0 Hz,
1.2H), 6.88-6.92 (m, 1.2H), 6.85-6.87 (m, 3H), 4.31 (q, J )
7.1 Hz, 0.6H), 4.25 (q, J ) 7.1 Hz, 2.8H), 4.18 (q, J ) 7.1 Hz,
2.8H), 3.83 (s, 0.9H), 3.82 (s, 3.3H), 3.81 (s, 0.9H), 1.36 (t, J )
7.1 Hz, 0.9H), 1.31 (t, J ) 7.1 Hz, 3.3H). 1.26 (t, J ) 7.2 Hz,
Dimethyl 1,4-Dichloro-1,4-bis(2,4-dichlorophenoxy)-
1,3-butadiene-2,3-dicarboxylate (6g). Colorless oil; asym-
1
metric isomer, IR v (cm-1) 1734, 1658, 1608, 1580, 1474; H
NMR δ (ppm) 7.50 (d, J ) 2.4 Hz, 1H,), 7.31 (d, J ) 2.4 Hz,
1H), 7.08-7.13 (m, 4H), 3.85 (s, 3H), 3.70 (s, 3H). A mixture
of isomers: IR v (cm-1) 1734, 1604, 1577, 1473; 1H NMR δ
(ppm) 7.49 (d, J ) 2.4 Hz, 1H), 7.46-7.48 (m, 3H), 7.22-7.30
(m, 4H), 7.08 (d, J ) 8.5 Hz, 1H), 7.05 (d, J ) 8.7 Hz, 3H),
3.86 (s, 3H), 3.81 (s, 6H), 3.73 (s, 3H). 13C NMR δ (ppm) a
mixture of isomers: 164.3, 163.9, 162.9, 151.7, 150.6, 149.2,
149.0, 147.9, 147.7, 131.9, 131.7, 130.6, 130.5 (d), 128.0 (d),
127.9, 127.2, 127.1, 125.6, 122.5, 122.4, 120.2, 119.6, 113.6,
110.7, 110.0, 52.6, 52.5. HRMS (FAB) calcd for C20H13Cl6O6
558.8838 (M + 1), found 558.8835.
Dimethyl 1,4-Dichloro-1,4-bis(4-chloro-3,5-dimethylphe-
noxy)-1,3-butadiene-2,3-dicarboxylate (6h). Colorless crys-
tals; mp 179-180 °C; IR v (cm-1) 1730, 1628, 1598, 1583, 1468;
1H NMR δ (ppm) 7.21 (s, 4H), 3.79 (s, 6H), 2.34 (s, 12H); 13C
NMR δ (ppm) 164.6, 151.0, 148.7, 137.7, 131.0, 118.9, 111.0,
J. Org. Chem, Vol. 70, No. 12, 2005 4845