The Journal of Organic Chemistry
Note
1
29.8, 75.7, 52.8; HRMS (ESI-TOF) m/z [M + Na]+ calcd for
C H O Na 215.0313; found 215.0496.
2-Butenedioic acid (2E)-1,4-bis[(4-methylphenyl)methyl] ester
(4k): yield 76 mg (94%); white solid; mp 113−115 °C; eluent in
10
8
4
1
General Procedure for the Isomerization of Maleic Acid
Diesters to Fumaric Acid Diesters. Maleic acid diester 3 (1 equiv,
.25 mmol) was added to acetonitrile (1 mL, 0.25 M) in a resealable
chromatography, hexane/diethyl ether 20:1; H NMR (CDCl , 500
3
MHz) δ 7.27 (d, 4H, J = 7.8 Hz), 7.19 (d, 4H, J = 7.8 Hz), 6.91 (s,
1
3
1
0
2H), 5.19 (s, 4H), 2.36 (s, 6H); C{ H} NMR (CDCl , 125 MHz) δ
3
tube. Catalyst 1a (5 mol %, 0.0125 mmol) was added subsequently.
The resultant solution was stirred at 80 °C for 16 h (oil bath). After
the reaction, solvent was removed by rotary evaporation. The residue
was purified by silica gel column with hexane/diethyl ether = 20:1−
165.9, 138.5, 133.8, 132.3, 129.4, 128.6, 67.2, 21.3; HRMS (ESI-
+
TOF) m/z [M + Na] calcd for C H O Na 347.1253; found
2
0
20
4
347.1258.
2-Butenedioic acid (2E)-1,4-bis[(4-bromophenyl)methyl] ester
10:1, and the desired product was obtained after rotary evaporation.
(4l): yield 113 mg (99%); white solid; mp 115−117 °C; eluent in
1
Dibenzyl fumarate (4a): yield 73 mg (99%); white solid; eluent in
chromatography, hexane/diethyl ether 10:1; H NMR (CDCl , 500
3
1
chromatography, hexane/diethyl ether 20:1; H NMR (CDCl , 500
MHz) δ 7.49−7.50 (d, 4H, J = 7.7 Hz), 7.23−7.25 (d, 4H, J = 7.7
3
1
3
1
13
1
MHz) δ 7.32−7.46 (m, 10H), 6.93 (s, 2H), 5.23 (s, 4H); C{ H}
NMR (CDCl , 125 MHz) δ 164.1, 135.3, 133.9, 128.8, 128.7, 128.5,
7.3. The physical data are the same as those in the literature.
Hz), 6.90 (s, 2H), 5.17 (s, 4H); C{ H} NMR (CDCl , 125 MHz) δ
3
3
164.6, 134.3, 133.8, 132.0, 130.1, 122.8, 66.5; HRMS (ESI-TOF) m/z
29
+
6
[M + Na] calcd for C H Br O Na 476.9130; found 476.9132.
1
8
14
2
4
Dimethyl fumarate (4b): yield 35 mg (98%); white solid; eluent in
2-Butenedioic acid (2E)-1,4-bis[(3-chlorophenyl)methyl] ester
1
chromatography, hexane/diethyl ether 20:1; H NMR (CDCl , 500
(4m): yield 91 mg (99%); white solid; mp 90−92 °C; eluent in
3
1
3
1
1
MHz) δ 6.85 (s, 2H), 3.79 (s, 6H); C{ H} NMR (CDCl , 125
chromatography, hexane/diethyl ether 10:1; H NMR (CDCl , 500
3
3
MHz) δ 165.5, 133.5, 52.5. The physical data are the same as those in
MHz) δ 7.37 (s, 2H), 7.24−7.32 (m, 6H), 6.94 (s, 2H), 5.20 (s, 4H);
30
13
1
the literature.
C{ H} NMR (CDCl , 125 MHz) δ 164.6, 137.2, 134.7, 133.8,
3
+
Diethyl fumarate (4c): yield 43 mg (99%); white solid; eluent in
130.1, 128.8, 128.4, 126.4, 66.3; HRMS (ESI-TOF) m/z [M + Na]
1
chromatography, hexane/diethyl ether 20:1; H NMR (CDCl , 500
calcd for C H Cl O Na 387.0154; found 387.0161.
3
18 14
2
4
MHz) δ 6.84 (s, 2H), 4.25 (q, 4H, J = 7.1 Hz), 1.31 (t, 6H, J = 7.1
2-Butenedioic acid (2E)-1,4-bis[(4-trifluoromethylphenyl)methyl]
Hz); 13C{ H} NMR (CDCl , 125 MHz) δ 165.1, 133.8, 61.5, 14.2.
1
3
ester (4n): yield 108 mg (99%); white solid; mp 58−60 °C; eluent in
31
1
The physical data are the same as those in the literature.
chromatography, hexane/diethyl ether 20:1; H NMR (CDCl , 500
3
Di-n-propyl fumarate (4d): yield 50 mg (99%); colorless liquid;
MHz) δ 7.63−6.64 (d, 4H, J = 7.7 Hz), 7.48−7.49 (d, 4H, J = 7.8
1
13
1
eluent in chromatography, hexane/diethyl ether 20:1; H NMR
Hz), 6.95 (s, 2H), 5.29 (s, 4H); C{ H} NMR (CDCl , 125 MHz) δ
3
(
(
CDCl , 500 MHz) δ 6.85 (s, 2H), 4.14−4.17 (m, 4H), 1.63−1.72
164.5, 139.2, 133.9, 131.0, 130.7, 128.5, 125.8, 125.7, 125.1, 123.0,
3
1
3
1
19
p, 4H), 0.95−0.98 (t, 6H, J = 7.5 Hz); C{ H} NMR (CDCl , 125
120.8, 66.3, 31.1; F NMR (CDCl , 470 MHz) δ −62.7; HRMS
3
3
+
MHz) δ 165.2, 133.7, 67.0, 22.0, 10.5; HRMS (ESI-TOF) m/z [M +
H] calcd for C H O 201.1121; found 201.1121.
(ESI-TOF) m/z [M + Na] calcd for C H F O Na 455.0683; found
2
0
14
6
4
+
10
17
4
455.0689.
Di-n-octyl fumarate (4e): yield 85 mg (99%); colorless liquid;
2-Butenedioic acid (2E)-1,4-bis(2-naphthyl) ester (4o): yield 99
1
eluent in chromatography, hexane/diethyl ether 20:1; H NMR
mg (99%); white solid; mp 141−143 °C; eluent in chromatography,
1
(
CDCl , 500 MHz) δ 6.84 (s, 2H), 4.17−4.20 (t, 4H, J = 7.1 Hz),
hexane/diethyl ether 20:1; H NMR (CDCl , 500 MHz) δ 7.84−7.86
3
3
1
3
1
1
.60−1.69 (m, 4H), 1.25−1.37 (m, 24H), 0.86−0.89 (t, 6H, J = 7.1
(m, 8H), 7.46−7.51 (m, 6H), 6.99 (s, 2H), 5.40 (s, 4H); C{ H}
NMR (CDCl , 125 MHz) δ 164.9, 133.9, 133.3, 133.3, 132.7, 128.7,
13
1
Hz); C{ H} NMR (CDCl , 125 MHz) δ 165.3, 133.8, 65.7, 31.9,
3
3
2
9.3, 28.7, 26.0, 22.8, 14.2. The physical data are the same as those in
128.1, 127.9, 127.7, 126.6, 126.5, 126.0, 67.4; HRMS (ESI-TOF) m/z
32
+
the literature.
[M + Na] calcd for C H O Na 419.1250; found 419.1254.
2
6
20
4
Di-n-nonyl fumarate (4f): yield 92 mg (99%); white solid; eluent in
2-Butenedioic acid (2E)-1,4-bis(cyclopropylmethyl) ester (4p):
1
chromatography, hexane/diethyl ether 20:1; H NMR (CDCl , 500
yield 56 mg (99%); colorless liquid; eluent in chromatography,
3
1
MHz) δ 6.84 (s, 2H), 4.17−4.20 (t, 4H, J = 7.1 Hz), 1.62−1.70 (p,
hexane/diethyl ether 20:1; H NMR (CDCl , 500 MHz) δ 6.89 (s,
3
1
3
1
4
H), 1.26−1.36 (m, 28H), 0.86−0.89 (t, 6H, J = 7.2 Hz); C{ H}
2H), 4.03−4.04 (d, 4H, J = 7.6 Hz), 1.15−1.19 (m, 2H), 0.58−0.61
1
3
1
NMR (CDCl , 125 MHz) δ 164.3, 133.8, 65.7, 32.0, 29.6, 29.4, 28.6,
(m, 4H), 0.29−0.33 (m, 4H); C{ H} NMR (CDCl , 125 MHz) δ
3
3
+
2
6.0, 22.8, 14.2. The physical data are the same as those in the
165.3, 133.9, 70.3, 9.83, 3.46; HRMS (ESI-TOF) m/z [M + Na]
32
literature.
calcd for C H O Na 247.0939; found 247.0941.
1
2
16
4
Di-isopropyl fumarate (4g): yield 50 mg (99%); colorless liquid;
2-Butenedioic acid (2E)-1,4-bis(allyl) ester (4q): yield 47 mg
1
eluent in chromatography, hexane/diethyl ether 20:1; H NMR
(97%); colorless liquid; eluent in chromatography, hexane/diethyl
1
(
1
1
CDCl , 500 MHz) δ 6.80 (s, 2H), 5.07−5.12 (p, 2H, J = 6.7 Hz),
ether 20:1; H NMR (CDCl , 500 MHz) δ 6.89 (s, 2H), 5.90−5.97
3
3
1
3
1
13
1
.28−1.29 (d, 12H, J = 6.1 Hz); C{ H} NMR (CDCl , 125 MHz) δ
(m, 2H), 5.25−5.27 (m, 4H), 4.66−4.70 (m, 4H); C{ H} NMR
(CDCl , 125 MHz) δ 164.6, 133.7, 131.6, 119.0, 66.0. The physical
data are the same as those in the literature.
3
64.7, 134.4, 69.0, 21.9. The physical data are the same as those in the
3
32
34
literature.
Di-tert-butyl fumarate (4h): yield 57 mg (97%); white solid; eluent
2-Butenedioic acid (2E)-1,4-bis(3-phenyl-2-propenyl) ester (4r):
1
in chromatography, hexane/diethyl ether 20:1; mp 69−71 °C; H
yield 63 mg (73%); white solid; mp 70−72 °C; eluent in
1
3
1
1
NMR (CDCl , 500 MHz) δ 6.66 (s, 2H), 1.49 (s, 18H); C{ H}
chromatography, hexane/diethyl ether 20:1; H NMR (CDCl , 500
3
3
NMR (CDCl , 125 MHz) δ 164.6, 134.7, 81.8, 28.1; HRMS (ESI-
MHz) δ 7.27−7.41 (m, 10H), 6.94 (s, 2H), 6.68−6.71 (d, 2H), 6.28−
3
+
13
1
TOF) m/z [M + Na] calcd for C H O Na 251.1250; found
6.34 (m, 2H), 4.86−4.88 (m, 4H); C{ H} NMR (CDCl , 125
1
2
20
4
3
2
51.1254.
MHz) δ 168.8, 136.1, 135.0, 133.9, 128.8, 128.4, 126.8, 122.5, 66.0;
HRMS (ESI-TOF) m/z [M + Na] calcd for C H O Na 371.1250;
+
Dicyclohexyl fumarate (4i): yield 70 mg (93%); colorless liquid;
2
2
20
4
1
eluent in chromatography, hexane/diethyl ether 20:1; H NMR
found 371.1254.
(
(
(
CDCl , 500 MHz) δ 6.82 (s, 2H), 4.83−4.90 (m, 2H), 1.85−1.89
2-Butenedioic acid (2E)-1,4-bis[(3,3-dimethyl)allyl] ester (4s):
3
1
3
1
m, 4H), 1.72−1.76 (m, 4H), 1.35−1.58 (m, 12H); C{ H} NMR
yield 63 mg (99%); colorless liquid; eluent in chromatography,
1
CDCl , 125 MHz) δ 164.5, 134.1, 73.9, 31.6, 25.4, 23.8. The physical
hexane/diethyl ether 20:1; H NMR (CDCl , 500 MHz) δ 6.84 (s,
3
3
33
data are the same as those in the literature.
2H), 5.35−5.38 (m, 2H), 4.67−4.69 (d, 4H, J = 8.16 Hz), 1.72−1.76
1
3
1
Dicyclopentyl fumarate (4j): yield 57 mg (90%); colorless liquid;
(d, 12H, J = 22 Hz); C{ H} NMR (CDCl , 125 MHz) δ 165.2,
3
1
eluent in chromatography, hexane/diethyl ether 20:1; H NMR
140.1, 133.8, 118.1, 62.3, 25.9, 18.2; HRMS (ESI-TOF) m/z [M +
+
(
(
(
CDCl , 500 MHz) δ 6.78 (s, 2H), 5.25−5.28 (m, 2H), 1.88−1.91
Na] calcd for C H O Na 275.1251; found 275.1254.
3
14 20
4
1
3
1
m, 4H), 1.72−1.76 (m, 8H), 1.58−1.63 (m, 4H); C{ H} NMR
2-Butenedioic acid (2E)-1,4-bis(propagylic) ester (4t): yield 48 mg
CDCl , 125 MHz) δ 165.0, 134.0, 78.3, 32.8, 23.8; HRMS (ESI-
(99%); white solid; mp 87−88 °C; eluent in chromatography,
3
+
1
TOF) m/z [M + Na] calcd for C H O Na 275.1254; found
hexane/diethyl ether 20:1; H NMR (CDCl , 500 MHz) δ 6.92 (s,
1
4
20
4
3
275.1254.
2H), 4.81 (d, 4H, J = 2.62 Hz), 2.51−2.52 (t, 2H, J = 2.49 Hz);
E
J. Org. Chem. XXXX, XXX, XXX−XXX