Effect of ortho substituents on carbonyl carbon 13C NMR
chemical shifts in substituted phenyl benzoates
Vilve Nummert1, Mare Piirsalu2, Vahur Mäemets3, Signe Vahur4 and Ilmar A. Koppel5
Institute of Chemistry, University of Tartu, Jacobi 2, 51014 Tartu, Estonia
e-mail: 1vilve.nummert@ut.ee, 2mare.piirsalu@ut.ee, 3vahur.maemets@ut.ee,
4
signe.vahur@ut.ee, 5ilmar.koppel@ut.ee
Supplementary material
Table S1. 13C NMR spectra for ortho-, meta- and para-substituted phenyl benzoates
(X-C6H4CO2C6H5, C6H5CO2C6H4-X), methyl benzoates and ethyl benzoates.
1
H and proton-decoupled 13C NMR spectra of compounds were measured in CDCl3 at
300 K on a Bruker AC-200 spectrometer. The chemical shifts are referenced to an
internal TMS, which = 0 ppm.
1
H NMR: 8.19 m, 2H (H-2,6); 7.14-7.30 m,
1. Phenyl benzoate
O
3H (H-9,11,13); 7.31-7.65 m, 5H (H9
10
6
5
3,4,5,10,12). 13C NMR: 129.72 (C-1);
1
8
11
O
4
130.13 (C-2,6); 128.54 (C-3,5); 133.48 (C7
4); 165.04 (C-7); 151.09 (C-8); 121.69 (C13
3
12
2
9,13); 129.45 (C-10,12); 125.80 (C-11).
1
H NMR: 7.97 m, 1H (H-3); 7.58-7.77 m,
2. Phenyl 2-nitrobenzoate
O
9
2H (H-4,5); 7.84 m, 1H (H-6); 7.19-7.34 m,
10
6
5
3H (H-9,11,13); 7.35-7.49 m, 2H (H1
8
11
O
4
10,12). 13C NMR: 127.37 (C-1); 148.18 (C7
2
13
3
12
2); 124.15 (C-3); 132.18 (C-4); 133.23 (CNO2
5); 130.08 (C-6); 164.03 (C-7); 150.56 (C8); 121.27 (C-9,13); 129.61 (C-10,12);
126.43 (C-11).
1
H NMR: 7.63-7.90 m, 3H (H-3,4,5); 8.30
3. Phenyl 2-cyanobenzoate
O
m,
1H (H-6); 7.22-7.34 m, 3H (H-9,11,13);
9
10
6
5
7.37-7.50 m, 2H (H-10,12). 13C NMR:
1
8
11
O
4
131.83 (C-1); 113.37 (C-2); 132.67 (C-3);
7
2
13
3
12
134.98 (C-4); 133.29 (C-5); 131.64 (C-6);
CN
14
162.49 (C-7); 150.52 (C-8); 121.41 (C9,13); 129.55 (C-10,12); 126.32 (C-11);
117.23 (C-14).
1
H NMR: 7.1-7.3 m, 5H (H-3,5,9,11,13);
4. Phenyl 2-fluorobenzoate
O
7.56
m, 1H (H-4); 8.09 m, 1H (H-6); 7.41
9
10
6
5
m, 2H (H-10,12). 13C NMR: 118.34 (C-1),
1
8
11
4
O
2
JC-F = 9.7; 162.34, (C-2), 1JC-F = 261.7;
7
2
13
3
12
117.20 (C-3), 2JC-F = 22.5; 135.13 (C-4),
F
3
JC-F = 9.1; 124.14 (C-5), 4JC-F = 4.0;
132.50 (C-6); 162.71 (C-7), 3JC-F = 3.9;
150.82 (C-8); 121.68 (C-9.13); 129.48 (C-
1
5. Phenyl 2-methoxybenzoate
O
6
5
9
1
8
O
4
10
11
7
2
3
13
O
12
CH3
14
6. Phenyl 2-aminobenzoate
O
6
5
9
1
8
O
4
10
11
7
2
3
13
12
9
10
NH2
7. Phenyl 4-nitrobenzoate
O
6
5
1
O2N
O
4
8
11
7
2
3
13
12
9
10
8. Phenyl 4-fluorobenzoate
F
O
6
5
1
4
O
8
11
7
2
3
13
12
9
10
9. Phenyl 4-chlorobenzoate
5
Cl
O
6
1
4
O
8
11
7
3
13
2
12
10. Phenyl 4-bromobenzoate
5
Br
O
6
1
4
9
O
10
8
11
7
3
2
13
11. Phenyl 4-methylbenzoate
12
10,12); 126.00 (C-11).
1
H NMR: 6.94-7.05 m, 2H (H-3,5); 8.00
ddd, 1H (H-6), 3J = 7.4 4J = 1.9 5J = 0.5;
7.32-7.54 m, 3H (H-4,10,12); 7.15-7.27 m,
3H (H-9,11,13); 3.86 s, 3H (H-14). 13C
NMR: 119.51 (C-1); 159.84 (C-2); 112.41
(C-3); 134.17 (C-4); 120.24 (C-5); 132.05
(C-6); 164.38 (C-7); 151.17 (C-8); 121.84
(C-9,13); 129.34 (C-10,12); 126.46 (C-11);
56.04 (C-14).
1
H NMR: 6.60-6.76 m, 2H (H-3,5); 7.1-7.5
m, 6H (H-4,9,10,11,12,13); 8.08 dd, 1H (H6), 3J = 8.0 4J = 1.6; 5.75 s, 2H (-NH2). 13C
NMR: 109.81 (C-1); 151.32 (C-2); 116.40
(C-3); 134.80 (C-4); 116.79 (C-5); 131.62
(C-6); 166.77 (C-7); 150.94 (C-8); 122.00
(C-9,13); 129.43 (C-10,12); 125.73 (C-11).
1
H NMR: 8.29-8.43 m, 4H (H-2,3,5,6);
7.18-7.36 m, 3H (H-9,11,13); 7.46 m, 2H
(H-10,12). 13C NMR: 135.09 (C-1); 131.27
(C-2,6); 123.70 (C-3,5); 151.03 (C-4);
163.27 (C-7); 150.68 (C-8); 121.43 (C9,13); 129.67 (C-10,12); 126.38 (C-11).
1
H NMR: 8.22 dd, 2H (H-2,6), 3J = 9.1, 4JHF = 5.5; 7.10-7.33 m, 5H (H-3,5,9,11,13);
7.43 m, 2H (H-10,12). 13C NMR: 126.04
(C-1); 132.80 d, (C-2,6), 3JC-F = 9.5; 115.78
d, (C-3,5), 2JC-F = 22.1; 166.24 d, (C-4), 1JCF = 255.1; 164.15 (C-7); 151.02 d, (C-8),
7
JC-F = 0.7; 121.67 (C-9,13); 129.52 (C10,12); 125.96 (C-11).
1
H NMR: 8.13 d, 2H (H-2,6), 3J = 8.9;
7.36-7.52 m, 4H (H-3,5,10,12); 7.15-7.32
m, 3H (H-9,11,13). 13C NMR: 128.20 (C1); 131.54 (C-2,6); 128.95 (C-3,5); 140.13
(C-4); 164.25 (C-7); 150.92 (C-8); 121.61
(C-9,13); 129.52 (C-10,12); 126.00 (C-11).
1
H NMR: 8.06 d, 2H (H-2,6), 3J = 8.8; 7.64
2H (H-3,5), 3J = 8.8; 7.13-7.33 m, 3H (H9,11,13); 7.43 m, 2H (10,12). 13C NMR:
128.83 (C-1); 131.66 (C-2,6); 131.99 (C3,5); 128.66 (C-4); 164.44 (C-7); 150.91
(C-8); 121.61 (C-9,13); 129.54 (C-10,12);
126.04 (C-11).
1
H NMR: 8.08 d, 1H (H-2,6), 3J = 8.3; 7.157.48 m, 7H (H-3,5,9,10,11,12,13); 2.42 s,
3H (H-14). 13C NMR: 127.05 (C-1); 130.24
(C-2,6); 129.30 (C-3,5); 144.33 (C-4);
2
O
6
5
14
9
1
H3C
8
O
4
10
11
7
3
13
2
12
1
12. Phenyl 4-methoxybenzoate
O
6
5
14
9
1
H3C O
10
8
O
4
11
7
2
3
13
12
9
10
13. Phenyl 4-aminobenzoate
O
6
5
1
H2N
8
O
4
11
7
3
13
2
12
14. Phenyl 3-nitrobenzoate
O
6
5
9
1
10
8
O
4
11
7
13
2
3
O2N
12
15. Phenyl 3-chlorobenzoate
O
6
5
1
9
10
8
O
4
11
7
13
2
3
Cl
12
16. Phenyl 3-methylbenzoate
O
6
5
1
9
10
8
O
4
11
7
13
2
3
12
H3C
14
17. 2-Nitrophenyl benzoate
5
1
4
O2N
O
6
O
9
10
8
11
7
3
2
13
165.16 (C-7); 151.21 (C-8); 121.78 (C9,13); 129.43 (C-10,12); 125.73 (C-11);
21.70 (C-14).
12
H NMR: 8.16 d, 2H (H-2,6), 3J = 9.1; 6.97
d, 2H (H-3,5), 3J = 9.1; 7.15-7.31 m, 3H (H9,11,13); 7.42 m 2H (H-10,12); 3.87 s, 3H
(H-14). 13C NMR: 122.00 (C-1); 132.25 (C2,6); 113.86 (C-3,5); 163.94 (C-4); 164.81
(C-7); 151.18 (C-8); 121.77 (C-9,13);
129.37 (C-10,12); 125.64 (C-11); 55.46 (C14).
1
H NMR: 8.00 d, 2H (H-2,6), 3J = 8.9; 6.67
d, 2H (H-3,5), 3J = 8.9; 7.15-7.30 m, 3H
(H-9,11,13); 7.41 m, 2H (H-10,12); 4.14 s,
2H (-NH2). 13C NMR: 119.03 (C-1); 132.37
(C-2,6); 113.92 (C-3,5); 151.52 (C-4);
165.18 (C-7); 151.42 (C-8); 121.92 (C9,13); 129.35 (C-10,12); 125.49 (C-11).
1
H NMR: 9.01 ddd, 1H (H-2), 4J = 2.3 4J =
1.7 5J = 0.5; 8.43-8.55 m, 2H (H-4,6); 7.72
ddd, 1H (H-5), 3J = 7.8 3J = 8.2 5J = 0.5;
7.15-7.35 m, 3H (H-9,11,13); 7.45 m, 2H
(H-10,12). 13C NMR: 131.53 (C-1); 125.04
(C-2); 148.53 (C-3); 127.92 (C-4); 129.89
(C-5); 135.69 (C-6); 163.05 (C-7); 150.65
(C-8); 121.45 (C-9,13); 129.65 (C-10,12);
126.37 (C-11).
1
H NMR: 8.18 ddd, 1H (H-2), 4J = 2.2 4J =
1.6 5J = 0.5; 7.60 ddd, 1H (H-4), 3J = 8.0 4J
= 2.2 4J = 1.2; 7.35-7.51 m, 3H (H5,10,12); 7.13-7.33 m, 3H (H-9,11,13). 13C
NMR: 131.53 (C-1); 130.22 (C-2); 134.86
(C-3); 133.58 (C-4); 129.90 (C-5); 128.89
(C-6); 163.93 (C-7); 150.88 (C-8); 121.58
(C-9,13); 129.56 (C-10,12); 126.09 (C-11).
1
H NMR: 7.97- 8.04 m, 2H (H-2,6); 7.367.47 m, 4H (H-4,5,10,12); 7.15- 7.30 m, 3H
(H-9,11,13); 2.42 s, 3H (H-14). 13C NMR:
129.76 (C-1); 127.40 (C-2); 128.51 (C-3);
134.33 (C-4); 138.46 (C-5); 130.75 (C-6);
165.33 (C-7); 151.23 (C-8); 121.78 (C9,13); 129.49 (C-10,12); 125.83 (C-11).
1
H NMR: 8.10 ddd, 1H (H-10), 3J = 8.0 4J
= 1.7 4J = 0.5; 8.19 m, 2H (H-2,6); 7.297.73 m, 6H (H-3,4,5,11,12,13). 13C NMR:
128.61 (C-1); 130.50 (C-2,6); 128.72 (C3,5); 134.11 (C-4); 164.32 (C-7); 144.39
3
18. 2-Cyanophenyl benzoate
14
O
6
5
NC
9
1
O
4
7
3
10
8
11
2
13
12
19. 2-Fluorophenyl benzoate
F
O
6
5
1
8
O
4
10
9
11
7
13
2
3
12
20. 2-Chlorophenyl benzoate
Cl
O
6
5
8
O
4
10
9
1
11
7
13
2
3
12
21. 2-(trifluoromethyl)phenyl benzoate
14
5
CF3
O
6
O
4
1
3
9
10
8
11
7
2
13
12
9
10
22. 2-iodophenyl benzoate
I
O
6
5
1
8
O
4
11
7
2
3
13
12
23. 2-Methylphenyl benzoate
14
5
1
4
H3C
O
6
9
O
10
8
11
7
3
2
13
12
(C-8); 142.13 (C-9); 125.76 (C-10); 126.61
(C-11); 134.60 (C-12); 125.38 (C-13).
1
H NMR: 8.26 d, 2H (H-2,6); 7.3-7.8 m, 7H
(H-3,4,5,10,11,12,13). 13C NMR 128.51 (C1); 130.54 (C-2,6); 128.80 (C-3,5); 134.23
(C-4); 164.01 (C-7); 152.75 (C-8); 107.19
(C-9); 133.37 (C-10); 126.21 (C-11);
134.00 (C-12); 123.33 (C-13); 115.15 (C14).
1
H NMR: 8.22 m, 2H (H-2,6); 7.51 m, 2H
(H-3,5); 7.65 m, 1H (H-4); 7.12-7.32 m, 4H
(H-10,11,12,13). 13C NMR: 128.99 (C-1);
130.41 (C-2,6); 128.65 (C-3,5); 133.79 (C4); 164.18 (C-7); 138.59 d, (C-8) 2JC-F =
12.8; 154.43 d, (C-9) 1JC-F = 249.5; 116.81
d, (C-10) 2JC-F = 18.6; 127.09 d, (C-11) 3JC4
F = 7.2; 124.49 d, (C-12) JC-F = 3.9; 123.99
(C-13).
1
H NMR: 8.23 m, 2H (H-2,6); 7.49 m, 2H
(H-3,5); 7.62 m, 1H (H-4); 7.13-7.35 m, 4H
(H-10,11,12,13). 13C NMR: 129.06 (C-1);
130.4 (C-2,6,10); 128.64 (C-3,5); 133.78
(C-4); 164.19 (C-7); 147.38 (C-8); 127.11
(C-9); 126.99 (C-11); 127.74 (C-12);
123.92 (C-13).
1
H NMR: 7.2-7.7 m, 7H (H3,4,5,10,11,12,13); 8.21 m, 2H (H-2,6). 13C
NMR 148.64 q (C-8), 3JC-F =2.0; 123.10 q
(C-9), 2JC-F = 31.5, 127.00 q (C-10), 3JC-F =
4.9; 125.92 (11); 133.06 (C-12); 124.53 (C13); 123.22 q (C-14), 1JC-F = 273.0; 129.00
(C-1); 130.45 (C-2,6); 128.76 (C-3,5);
133.96 (C-4); 164.52 (C-7).
1
H NMR: 7.81 ddd, 1H (H-10), 3J = 7.9 4J
= 1.5 5J = 0.3; 6.94 ddd, 1H (H-11), 3J = 7.9
3
J = 7.3 4J = 1.7; 7.34 ddd, 1H (H-12), 3J =
8.1 3J = 7.3 4J = 1.5; 7.21 ddd, 1H (H-13),
3
J = 8.1 4J = 1.7 5J = 0.3. 13C NMR 151.25
(C-8); 90.30 (C-9); 139.32 (C-10); 127.47
(C-11); 129.30 (C-12); 123.09 (C-13);
129.13 (C-1); 130.31 (C-2,6); 128.53 (C3,5); 133.68 (C-4); 164.03 (C-7).
1
H NMR: 8.22 m, 2H (H-2,6); 7.47 m, 2H
(H-3,5); 7.60 m, 1H (H-4); 7.08-7.30 m, 4H
(H-10,11,12,13). 13C NMR: 129.68 (C-1);
130.14 (C-2,6); 128.61 (C-3,5); 133.49 (C4); 164.76 (C-7); 149.69 (C-8); 130.30 (C9); 131.15 (C-10); 126.03 (C-11); 126.96
4
24. 2-Methoxyphenyl benzoate
14
H3C
O
6
5
1
10
9
8
O
4
O
11
7
13
2
3
12
25. 2-tert-butylphenyl benzoate
14 15
O
5
C(CH3)3
6
O
4
1
11
7
2
3
10
9
8
12
13
26. 2-(Dimethylamino)phenyl benzoate
14
5
H3C
O
6
1
O
4
CH3
N
9
10
8
11
7
13
2
3
12
27. Methyl-2-benzoyloxybenzoate
O
5
14
O
6
1
15
9
O
4
O
10
8
11
7
13
2
3
12
28. 4-Nitrophenyl benzoate
5
O
6
1
4
9
O
10
11
8
NO2
7
3
13
2
12
29. 4-Cyanophenyl benzoate
5
O
6
9
10
14
1
4
7
3
2
O
8
11
13
30. 4-Fluorophenyl benzoate
12
CN
(C-12); 122.05 (C-13); 16.19 (C-14).
1
H NMR: 8.21 m, 2H (H-2,6); 7.46 m, 2H
(H-3,5); 7.59 m, 1H (H-4); 6.90-7.03 m, 2H
(H-10,12); 7.09-7.28 m, 2H (H-11,13); 3.76
s, 3H (H-14). 13C NMR: 129.67 (C-1);
130.26 (C-2,6); 128.50 (C-3,5); 133.56 (C4); 164.69 (C-7); 140.25 (C-8); 151.51 (C9); 112.77 (C-10); 126.88 (C-11); 120.85
(C-12); 123.00 (C-13); 55.93 (C-14).
1
H NMR: 7.1-7.3m, 3H (H-11,12,13); 7.47.7 m, 4H (H-3,4,5,11); 1.38 s, 9H (H-15);
8.24 m, 2H (H-2,6). 13C NMR 149.54 (C8); 141.44 (C-9); 126.96 (C-10); 125.82 (C11); 127.26 (C-12); 124.24 (C-13); 34.57
(C-14); 30.39 (C-15); 130.07 (C-1); 130.24
(C-2,6); 128.70 (C-3,5); 133.54 (C-4);
165.40 (C-7).
1
H NMR: 8.25 m, 2H (H-2,6); 7.46-7.70 m,
3H (H-3,4,5); 6.94-7.28 m, 4H (H10,11,12,13); 2.77 s, 6H (H-14). 13C NMR:
130.09 (C-1); 130.22 (C-2,6); 128.57 (C3,5); 133.36 (C-4); 164.84 (C-7); 143.55
(C-8); 145.70 (C-9); 119.05 (C-10); 126.63
(C-11); 121.68 (C-12); 123.57 (C-13);
43.34 (C-14).
1
H NMR: 8.27 m, 2H (H-2,6); 7.45-7.70 m,
4H (H-3,4,5,12); 8.07 dd, 1H (H-10), 3J =
7.9, 4J = 1.8; 7.34 dt, 1H (H-11), 3J = 7.6, 4J
= 1.2; 7.23 dd, 1H (H-13), 3J = 8.1, 4J = 1.2.
13
C NMR: 129.71 (C-1); 130.30 (C-2,6);
128.59 (C-3,5); 133.52 (C-4); 165.34 (C-7);
150.88 (C-8); 123.69 (C-9); 131.92 (C-10);
126.05 (C-11); 133.77 (C-12); 124.01 (C13); 165.06 (C-14); 52.10 (C-15).
1
H NMR: 8.20 m, 2H (H-2,6); 7.54 m, 2H
(H-3,5); 7.69 m, 1H (H-4); 7.42 d, 2H (H9,13), 3J = 9.3; 8.31 d, 2H (H-10,12), 3J =
9.3. 13C NMR: 128.73 (C-1); 130.34 (C2,6); 128.82 (C-3,5); 134.23 (C-4); 164.21
(C-7); 155.83 (C-8); 122.61 (C-9,13);
125.25 (C-10,12); 145.55 (C-11).
1
H NMR: 8.19 d, 2H (H-2,6); 7.5-7.8 m, 5H
(H-3,4,5,10,12); 7.36 d, 2H (H-9,13);. 13C
NMR: 130.28 (C-2,6); 128.77 (C-3,5);
134.13 (C-4); 164.58 (C-7); 154.33 (C-8);
122.90 (C-9,13); 133.68 (C-10,12); 109.86
(C-11); 118.20 (C-14).
1
H NMR: 8.19 m, 2H (H-2,6); 7.50 m, 2H
5
O
6
5
1
O
4
10
9
11
8
F
7
3
13
2
12
31. 4-Chlorophenyl benzoate
5
O
6
4
1
7
3
9
10
8
O
2
11
Cl
11
CH3
12
13
32. 4-methyphenyl benzoate
5
O
6
1
4
9
10
8
O
7
3
7
2
12
13
33. 4-Methoxyphenyl benzoate
5
O
6
1
4
9
10
8
O
11
7
3
12
13
O
6
1
4
9
O
NO2
10
8
11
7
3
13
2
12
35. 3-Chlorophenyl benzoate
5
O
6
Cl
9
10
1
4
O
8
11
7
3
13
2
12
36. 3-Methylphenyl benzoate
14
5
O
6
1
4
9
O
10
CH3
8
11
7
3
2
CH3
14
2
34. 3-Nitrophenyl benzoate
5
O
13
12
(H-3,5); 7.63 m, 1H (H-4); 7.03-7.25 m, 4H
(H-9,10,12,13). 13C NMR: 129.51 (C-1);
130.20 (C-2,6); 128.63 (C-3,5); 133.68 (C4); 165.14 (C-7); 146.94 (C-8), 4JC-F = 2.9;
123.12 (C-9,13), 3JC-F = 8.5; 116.13 (C10,12), 2JC-F = 23.6; 160.38 (C-11), 1JC-F =
244.5.
1
H NMR: 7.16 d, 2H (H-9,13), 3J = 9.0;
7.38 d, 2H (H-10,12), 3J = 9.0; 7.3-7.7 m,
3H (H-3,4,5); 8.19 m, 2H (H-2,6). 13C
NMR: 149.55 (C-8); 123.09 (C-9,13);
129.53 (C-10,12); 131.29 (C-11); 129.34
(C-1); 130.20 (C-2,6); 128.62 (C-3,5);
133.73 (C-4); 164.86 (C-7).
1
H NMR: 2.36 s, 3H (H-14); 7.08 d, 2H (H9,13), 3J = 8.6; 7.21 (H-10,12) 3J = 8.6;
7.4-7.7 m, 3H (H-3,4,5); 8.20 m, 2H (H2,6). 13C NMR: 148.88 (C-8); 121.39 (C9,13); 130.00 (C-10,12); 135.46 (C-11);
20.87 (C-14); 129.87 (C-1); 130.16 (C-2,6);
128.54 (C-3,5); 133.44 (C-4); 165.31 (C-7).
1
H NMR: 3.80 s, 3H (H-14); 7.13 d, 2H (H9,13), 3J = 9.2; 6.93 d, 2H (H-10,12), 3J =
9.2; 7.4-7.7 m, 3H (H-3,4,5); 8.19 m, 2H
(H-2,6). 13C NMR: 144.59 (C-8); 122.44
(C-9,13); 114.60 (C-10,12); 157.42 (C-11);
55.63 (C-14); 129.82 (C-1); 130.13 (C-2,6);
128.54 (C-3,5); 133.44 (C-4); 165.45 (C-7).
1
H NMR: 8.10-8.27 m, 4H (H-2,6,9,11);
7.48-7.75 m, 5H (H-3,4,5,12,13). 13C
NMR:131.53 (C-1); 130.35 (C-2,6); 128.80
(C-3,5); 134.18 (C-4); 164.53 (C-7); 151.44
(C-8); 117.58 (C-9); 149.06 (C-10); 120.82
(C-11); 130.07 (C-12); 128.18 (C-13).
1
H NMR: 8.18 m, 2H (H-2,6); 7.50 m, 2H
(H-3,5); 7.64 m, 1H (H-4); 7.22-7.29 m, 2H
(H-9,11); 7.35 m, 1H (H-12); 7.13 ddd, 1H
(H-13), 3J = 7.9 4J = 1.5 4J = 2.1. 13C NMR:
129.30 (C-1); 130.24 (C-2,6); 128.66 (C3,5); 133.79 (C-4); 164.71 (C-7); 151.60
(C-8); 122.46 (C-9); 134.85 (C-10); 126.17
(C-11); 130.18 (C-12); 120.14 (C-13).
1
H NMR: 8.19 m, 2H (H-2,6); 7.46 m, 2H
(H-3,5); 7.58 m, 1H (H-4); 6.97-7.09m, 3H
(H-9,12,13); 7.28 m, 1H (H-11). 13C NMR:
129.87 (C-1); 130.14 (C-2,6); 128.53 (C3,5); 133.44 (C-4); 165.16 (C-7); 151.08
(C-8); 122.30 (C-9); 139.61 (C-10); 126.63
6
37. 3-Aminophenyl benzoate
5
O
6
1
9
NH2
8
O
4
10
11
7
13
2
3
12
38. Cyanomethyl benzoate
O
6
5
9
1
8
O
4
CN
7
2
C
H2
3
1
39. Chloromethyl benzoate
O
6
5
1
4
8
Cl
O
7
2
3
40. 2,2,2-trichloroethyl benzoate
6
5
8
O
1
CCl3
O
4
7
9
2
3
41. 2,2,2-trifluoroethyl benzoate
5
8
O
6
1
CF3
O
4
7
9
2
3
42. 2,2-dichloroethylbenzoate
5
8
O
6
1
CHCl2
O
4
7
9
2
3
43. Propargyl benzoate
5
O
6
1
4
10
9
O
8
7
3
2
44. 2-Chloroethyl benzoate
(C-11); 129.17 (C-12); 118.66 (C-13);
21.28 (C-14).
1
H NMR: 8.18 m, 2H (H-2,6); 7.41-7.68 m,
3H (H-3,4,5); 6.47-6.64 m, 3H (H-9,11,13);
7.17 t, 1H (H-12); 3J = 7.9; 3.78 s, 2H (NH2). 13C NMR: 129.92 (C-1); 130.16 (C2,6); 128.54 (C-3,5); 133.44 (C-4); 165.14
(C-7); 152.13 (C-8); 108.44 (C-9); 147.86
(C-10); 112.68 (C-11); 130.05 (C-12);
111.48 (C-13).
1
H NMR: 8.07 m, 2H (H-2,6); 7.49 t, 2H
(H-3,5), 3Jav = 7.6; 7.64 t, 1H (H-4) 3J = 7.4;
4.97 s, 2H (H-8). 13C NMR: 128.07 (C-1);
130.10 (C-2,6); 128.80 (C-3,5); 134.16 (C4); 165.00 (C-7); 48.83 (C-8); 114.42 (C-9).
H NMR: 8.05 m, 2H (H-2,6); 7.42 m, 2H
(H-3,5); 7.57 m, 1H (H-4); 5.93 s, 2H (H8). 13C NMR: 128.79 (C-1); 130.06 (C-2,6);
128.61 (C-3,5); 133.91 (C-4); 164.52 (C-7);
69.36 (C-8).
1
H NMR: 8.13 m, 2H (H-2,6); 7.47 m, 2H
(H-3,5); 7.61 m, 1H (H-4); 4.96 s, 2H (H8). 13C NMR: 128.88 (C-1); 130.09 (C-2,6);
128.63 (C-3,5); 133.77 (C-4); 164.87 (C-7);
74.53 (C-8); 95.21 (C-9).
1
H NMR: 8.05 m, 2H (H-2,6); 7.42 m, 2H
(H-3,5); 7.57 m, 1H (H-4); 4.67 q, 2H (H8), 3JF-H = 8.5; 13C NMR: 128.88 (C-1);
130.23 (C-2,6); 128.81 (C-3,5); 134.00 (C4); 165.14 (C-7); 61.02 q, (C-8), 2JF-C =
36.9; 123.54 q, (C-9), 1JF-C = 277.0.
1
H NMR: 8.07 m, 2H (H-2,6); 7.44 m, 2H
(H-3,5); 7.58 m, 1H (H-4); 4.66 d, 2H (H8), 3J = 6.0: 5.97 t, 1H (H-9), 3J = 6.0. 13C
NMR: 129.13 (C-1); 129.91 (C-2,6); 128.55
(C-3,5); 133.58 (C-4); 165.53 (C-7); 68.72
(C-8); 68.61 (C-9).
1
H NMR: 8.05 m, 2H (H-2,6); 7.41 m, 2H
(H-3,5); 7.55 m, 1H (H-4); 4.91 d, 2H (H8), 4J = 2.5; 2.54 d, 2H (H-10), 4J = 2.5. 13C
NMR: 129.60 (C-1); 129.81 (C-2,6); 128.43
(C-3,5); 133.25 (C-4); 165.69 (C-7); 52.42
(C-8); 77.88 (C-9); 75.07 (C-10).
1
H NMR: 8.06 m, 2H (H-2,6); 7.42 m, 2H
(H-3,5); 7.55 m, 1H (H-4); 3.79 t, 2H (H-8),
7
5
O
6
3
8
Cl
1
O
4
7
3
9
2
45. Benzyl benzoate
5
O
6
9
14
1
O
4
11
8
7
3
10
2
13
12
46. 2-Methoxyethyl benzoate
5
O
6
8
O
1
O
4
7
3
10
9
2
47. Methyl benzoate
5
O
6
8
1
4
O
7
3
2
1
H NMR: 7.27-7.50 m, 3H (H-3,4,5); 7.83
m 1H (H6); 3.94 s, 3H (H-8). 13C NMR:
130.33 (C-1); 133.78 (C-2); 131.10 (C-3);
132.49 (C-4); 126.56 (C-5); 131.39 (C-6);
166.19 (C-7); 52.36 (C-8).
48. Methyl 2-Chlorobenzoate
5
O
6
1
4
O
7
3
CH3
8
2
Cl
1
H NMR: 7.80 m, 1H (H-6); 7.66 m, 1H
(H-3); 7.78-7.42 m, 2H (H-4,5); 3.94 s, 3H
(H-8). 13C NMR: 132.46 (C-1);.121.70 (C2); 132.50 (C-3); 134.38 (C-4); 127.14 (C5); 131.30 (C-6); 166.66 (C-7); 52.40 (C-8).
49. Methyl 2-Bromobenzoate
5
O
6
1
4
O
7
3
CH3
8
2
Br
1
50. Methyl 2-Iodobenzoate
5
O
6
1
4
O
7
3
CH3
8
2
I
51. Ethyl benzoate
5
O
6
1
4
8
O
7
3
2
52. Ethyl 2-Nitrobenzoate
J = 5.7; 4.55 t, 2H (H-9), 3J = 5.7. 13C
NMR: 130.18 (C-1); 129.76 (C-2,6); 128.45
(C-3,5); 133.23 (C-4); 166.14 (C-7); 41.68
(C-8); 64.49 (C-9).
1
H NMR: 8.06 m, 2H (H-2,6); 7.22-7.53 m,
8H (H-3,4,5,9,10,11,12,13); 5.32 s, 2H (H14). 13C NMR: 130.26 (C-1); 129.67 (C2,6); 128.32 (C-3,5); 132.91 (C-4); 166.26
(C-7); 136.17 (C-8); 128.11 (C-9,13);
128.55 (C-10,12); 128.17 (C-11); 66.60 (C14).
1
H NMR: 8.06 m, 2H (H-2,6); 7.41 m, 2H
(H-3,5); 7.54 m, 1H (H-4); 3.71 t, 2H (H8); 4.47 t, 2H (H-9); 3.41 s, 3H (H-10). 13C
NMR: 130.29 (C-1); 129.73 (C-2,6); 128.35
(C-3,5); 132.96 (C-4); 166.54 (C-7); 64.02
(C-8); 70.63 (C-9); 58.95 (C-10).
1
H NMR: 8.03 m, 2H (H-2,6); 7.40 m, 2H
(H-3,5); 7.52 m 1H (H-4); 3.88 s 3H (H-8).
13
C NMR: 130.38 (C-1); 129.62 (C-2,6);
128.37 (C-3,5); 132.87 (C-4); 167.03 (C-7);
51.96 (C-8).
9
H NMR: 8.00 dd, 1H (H-3), 3J = 7.9, 4J =
1.8; 7.15 dt, 1H (H-4), 3Jav = 7.7, 4J = 1.8;
7.40 dt, 1H (H-5), 3Jav = 7.7, 4J = 1.2; 7.80
dd, 1H (H-6), 3J = 7.8, 4J = 1.2; 3.94 s, 3H
(H-8). 13C NMR: 135.45 (C-1); 93.99 (C2); 141.36 (C-3); 132.58 (C-4); 127.89 (C5); 130.93 (C-6); 167.00 (C-7); 52.41 (C-8).
1
H NMR: 8.05 m, 2H (H-2,6); 7.40 m, 2H
(H-3,5); 7.52 m, 1H (H-4); 4.36 q, 2H (H8), 3J = 7.1; 1.37 t, 3H (H-9). 13C NMR:
130.72 (C-1); 129.58 (C-2,6); 128.32 (C3,5); 132.76 (C-4); 166.55 (C-7); 60.89 (C8); 14.34 (C-9).
1
H NMR: 7.92 m, 1H (H-3); 7.58-7.78 m,
8
5
O
6
1
4
8
2
3
9
O
7
C
H2
NO2
53. Ethyl 2-cyanobenzoate
5
O
6
1
4
8
2
3
9
O
7
C
H2
CN
10
54. Ethyl 2-chlorobenzoate
5
O
6
1
4
8
2
3
9
O
7
C
H2
Cl
55. Ethyl 2-(trifluoromethyl)benzoate
5
O
6
1
4
2
3
10
CF3
9
O
7
8
C
H2
3H (H-4,5,6); 4.40 q, 2H (H-8), 3J = 7.2;
1.37 t, 3H (H-9) , 3J = 7.2. 13C NMR:
128.05 (C-1); 148.58 (C-2); 123.89 (C-3);
131.62 (C-4); 132.74 (C-5); 129.97 (C-6);
165.32 (C-7); 62.51 (C-8); 13.81 (C-9).
1
H NMR: 7.61-7.74 m, 2H (H-4,5); 7.82 m,
1H (H-3); 8.15 m, 1H (H-6); 4.48 q, 2H (H8), 3J = 7.2; 1.46 t, 3H (H-9), 3J = 7.2. 13C
NMR: 133.03 (C-1); 113.17 (C-2); 134.76
(C-3); 132.48 (C-4); 132.38 (C-5); 131.20
(C-6); 164.11 (C-7); 62.26 (C-8); 14.11 (C9); 117.47 (C-10).
1
H NMR: 7.25-7.50 m, 4H (H-2,3,4,5); 7.81
d, 1H (H-6), 3J = 7.5; 4.40 q, 2H (H-8), 3J =
7.2; 1.41 t, 3H (H-9), 3J = 7.2. 13C NMR:
130.97 (C-1); 133.73 (C-2); 131.06 (C-3);
132.28 (C-4); 126.54 (C-5); 131.27 (C-6);
165.84 (C-7); 61.53 (C-8); 14.24 (C-9).
1
H NMR: 7.70-7.82 m, 2H (H-3,6); 7.547.66 m, 2H (H-4,5); 4.40 q, 2H (H-8), 3J =
7.2; 1.39 t, 3H (H-9) , 3J = 7.2. 13C NMR:
128,87 (C-1), 3JC-F =32.5; 131.88(C-2), 2JC3
F =2.0; 126.70 (C-3), JC-F =5.3; 131.70 (C4
4), JC-F =1.1; 130.96 (C-5); 130.15 (C-6);
166.94 (C-7); 62.03 (C-8); 13.95 (C-9);
123.53 (C-10), 1JC-F =273.5.
9
Table S2. The ortho, meta and para substituent constants used in the correlations
X
Ia
Rb
H
2-NO2
2-CN
2-F
2-Cl
2-Br
2-I
2-CF3
2-CO2CH3
2-OCH3
2-NH2
2-N(CH3)2
2-CH3
2-CH2CH3
2-CH(CH3)2
2-C(CH3)3
3-NO2
3-SO2CH3
3-CN
3-F
3-Cl
3-Br
3-CF3
3-I
3-CO2CH3
3-CO2CH2CH3
3-COCH3
3-COC6H5
3-OCH3
3-SCH3
3-NH2
3-N(CH3)2
3-C6H5
3-CH3
3-CH2CH3
3-CH(CH3)2
3-C(CH3)3
4-NO2
4-SO2CH3
4-CN
4-F
4-Cl
4-Br
4-CF3
0
0.63
0.58
0.52
0.47
0.45
0.39
0.41
0.3
0.25
0.1
0.1
–0.05
–0.05
–0.05p
–0.07
0.63
0.59
0.58
0.52
0.47
0.45
0.41
0.39
0.3
0.3
0.28
0.28q
0.25
0.25
0.1
0.1
0.1
–0.05
–0.05
–0.05p
–0.07
0.63
0.59
0.58
0.52
0.47
0.45
0.41
0
0.19i
0.11i
–0.35
–0.2
–0.19
–0.12
0.1i
0.16i
–0.41
–0.48
–0.54
–0.1
–0.08i
–0.08i
–0.08i
0.19i
0.1i
0.11i
–0.35
–0.2
–0.19i
0.1i
–0.12
0.16i
0.16i
0.21i
0.14i
–0.41
–0.24
–0.48
–0.54
–0.1
–0.1
–0.08i
–0.08i
–0.08i
0.19i
0.1i
0.11i
–0.35
–0.2
–0.19
0.1
EsB c
0
–0.374
–0.03
–0.155
–0.243
–0.27
–0.3
–0.46l
–1.034m, –0.728v
–0.308
–0.425
–0.425
–0.264
–0.297o
–0.341o
–0.604
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
10
d
0
0.76
0
0.27
0.55
0.65
0.78
0.91
1.51
0.56
0.76
0.76
0.52
0.56
0.76
1.24
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
Re ΔR+f
COg
0
0
0
–
–
–0.85
–
–
–1.16
–
–
–0.99
–
–
–0.98
–
–
–
–
–
–0.70k
–
–
–0.65
–
–
–
–
–
–0.48
–
–
–
–
–
–0.33
–
–
–0.27n
–
–
–
–
–
–
–
–
0.23
0.19i
–
–0.64
0.1i
–
–
i
0.11
–
–0.67
–0.35 –
–0.44
–0.2
–
–0.46
–0.19i –
–0.41u
0.1i
–
–
–0.12 –
–
i
0.16
–
–
0.16i
–
–
0.21i
–
–
i
0.14
–
–
–0.41 –
–0.09u
–0.24 –
–
–0.48 –
–0.03
–0.54 –
–
–0.1
–
–
–0.1
– –0.01, 0.12u
–0.08i –
–
–0.08i –
–
i
–0.08
–
–
0.19i
0
–0.96
0.1i
0
–
0.11i
0
–0.84s
–0.45 –0.26
–0.03
–0.23 –0.19
–0.31
–0.19 –0.16
–0.32s
0.1
0
–
COh
0
–1.14
–2.68
–2.46
–1.12
–1.05j
–0.60j
0.06
–
–0.79
1.6
–
0.59
–
–
–
–2.12
–
–
–
–1.26
–
–
–
–
–
–
–
–0.1r
–
–
0.63
–
0.16
–
–
–
–1.9
–
–
–1.02
–0.92
–0.73
–
4-I
4-CO2CH3
4-CO2CH2CH3
4-COC6H5
4-COCH3
4-OCH3
4-SCH3
4-NH2
4-N(CH3)2
4-C6H5
4-CH3
4-CH2CH3
4-CH(CH3)2
4-C(CH3)3
0.39
0.3
0.3
0.28p
0.28
0.25
0.25
0.1
0.1
0.1
–0.05
–0.05
–0.05o
–0.07
–0.12
0.16i
0.16i
0.14i
0.21i
–0.41
–0.24
–0.48
–0.54
–0.1
–0.1
–0.08i
–0.08i
–0.08i
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–0.16
0.16i
0.16i
0.14i
0.21i
–0.61
–0.32
–0.82
–0.83
–0.11
–0.11
–0.1
–0.1
–0.13
–0.18
0
0
0
0
–0.71
–0.71
–1.23
–1.45
–0.26
–0.22
–0.17t
–0.15t
–0.11s
–
–
–
–
–
0.28
–
–
–
–
0.14
–
–
0.16r
–
–
–
–
–
–0.36
–
0.01
–
–
–0.01
–
–
–0.04
The inductive constants, I.[1] bThe resonance constants, 0R.[2] cThe steric constants,
EsB.[3-5] dThe modified Charton steric constants, .[3,6] eThe resonance constants, R.[7]
f
The resonance constants, ΔR+ = +para – 0para.[8] gThe CO for substituted phenyl
benzoates, C6H5CO2C6H4-X, were calculated as: CO = (CO)X – 165.17. The arithmetic
mean value of available in litarature CO for H substituent was used. hThe CO for
phenyl esters of substituted benzoic acids, X-C6H4CO2C6H5, were determined as CO =
(CO)X – 165.17. iThe 0R = 0para – I were calculated using 0para values.[8-10] jFor 2bromo and 2-iodo substituents[11] CO = 164.12 and CO = 164.57 were used. kFor 2-iodo
substituent CO = 164.47 – 165.17 = –0.70, using calculated CO = 164.47 with relation:
CO = (164.90  0.07) – (1.56  0.13)I + (0.33  0.14)R0 – (0.72  0.11)EsB (Table 4).
l
Calculated using log k = –0.153[3] with relation: log kortho= –0.377 + 1.54I + 0.95R +
1.09EsB.[12] mThe EsB = –1.034 for 2-CO2CH3 substituent was calculated using log k =
0.54[13] for alkaline hydrolysis of ortho-substituted phenyl esters of 2,4dichlorophenoxyacetic acids with equation: log kortho = (0.941 ± 0.121) + (1.25 ± 0.17)I
+ (1.30 ± 0.18)R0 + (0.952 ± 0.349)EsB. nFor 2-methyl substituent CO = 164.9[14] was
used. oThe EsB = –0.297 for 2-CH2CH3 and EsB = –0.341 for 2-CH(CH3)2 substituents
were calculated using relation: log kortho = (0.470 ± 0.047) + (1.64 ± 0.68)I + (0.864 ±
0.095)R0 + (0.908 ± 0.106)EsB, for alkaline hydrolysis of ortho-substituted phenyl
acetates.[15] pThe inductive constant[16] for isopropyl substituent. qThe inductive
constant[17] for benzoyl substituent. rFor 3-methoxy and 4-tertbutyl substituents[18] CO =
165.07 and CO = 165.33 were used. sFor 4-cyano and 4-bromo substituents[19] CO =
164.33 – 165.17 = –0.84 and CO = 164.85 – 165.17 = –0.32 were used. tThe resonance
constants, ΔR = +para – 0para were calculated using +para constants[17, 20] and 0para
constants.[10] uThe CO = 165.29 – 165.17 = 0.12, CO = 164.76 – 165.17 = –0.41, CO
= 165.08 – 165.17 = –0.09 for 3-CH3, 3-Br and 3-OCH3 derivatives,[21] respectively.
v
The steric constants, EsB, was calculated with equation:[12] log kortho = –(0.727 ± 0.066) +
(1.61 ± 0.10)I + (1.37 ± 0.11)R + (1.38 ± 0.14) EsB, R = 0.995, s = 0.076, n = 11 using
kinetic data from Table S5.
a
References
[1]
R.W. Taft, I.C. Lewis, J. Am. Chem. Soc. 1958, 80, 2435-2443.
11
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
R.W. Taft, Jr., S. Ehrenson, I.C. Lewis, R.E. Glick, J. Am. Chem. Soc. 1959, 81,
5352-5361.
V. Nummert, M. Piirsalu, V. Mäemets, I. Koppel, Collect. Czech. Chem.
Commun. 2006, 71, 107-128.
V.M. Nummert, M.V. Piirsalu, Reakts. Sposobnost Organ. Soedin. (Tartu) 1975,
11, 921-932.
V. Nummert, M. Piirsalu, J. Chem. Soc., Perkin Trans. 2 2000, 583-594.
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Soc., Perkin Trans. 2 1981, 500-508.
S. Ehrenson, R.T.C. Brownlee, R.W. Taft, (Eds: A. Streitwieser, Jr., R.W. Taft),
John Wiley & Sons, New York, London, Sydney, Toronto, 1973, 10, 1-80.
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V.A. Palm), Publishing House of VINITI, Moscow, 1979, 5(2), 164-165.
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New York, 1988.
I. Bauerová, M. Ludwig, Collect. Czech. Chem. Commun. 2001, 66, 770-784.
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12
Table S3. Carbonyl carbon 13C NMR chemical shifts, CO, in CDCl3 for phenyl
X-benzoates, methyl X-benzoates, ethyl X-benzoates, X-phenyl benzoates, and
X-phenyl acetates from literature used in correlations
CO/ppm
X
2-NO2
Phenyl Xbenzoates
165.18[1],
165.4[2],
165.19[3],
165.19[4],
165.18[5],
165.1[6],
165.08[7]
163.98[8]
2-CN
–
2-F
2-Cl
162.72[8]
163.79[8]
2-Br
2-I
164.12[8]
165.1[2],
164.57[8],
164.5[9],
164.7[10]
165.09[8]
165.78[1],
165.44[8]
H
2-CF3
2-CH3
2-CH2CH3
2-OCH3
2-NH2
–
164.39[1],
164.15[8],
164.6[11]
166.65[8]
2-CH(CH3)2
2-C(CH3)3
2-CO2CH3
4-NO2
–
–
–
163.5[2],
163.33[3],
163.32[4],
163.06[27]
3-NO2
–
4-CN
163.43[27]
Methyl Xbenzoates
167.04[7],
167.05[13],
167.07[16],
167.23[17],
166.9[18],
167.4[21],
166.96[22]
165.83[7];
166.03[17],
166.09[20]
164.4[15],
164.7[21]
164.96[12]
166.1[19]
Ethyl Xbenzoates
166.54[7];
166.4[18],
166.9[23],
166.6[24],
166.56[25]
X-phenyl X-phenyl
benzoates acetates
169.25[7],
169.33[31],
169.50[32],
169.49[33],
169.6[34]
–
–
168.63[7],
168.51[31]
164.1[23]
–
–
164.44[7]
–
–
–
166.43[7]
166.7[9]
166.15[7]
166.4[9]
–
–
168.3[29]
168.47[7],
168.36[31]
–
–
167.36[12]
167.95[1],
167.7[14],
168.0[13,19]
–
166.57[1],
166.67[7],
166.6[37]
168.6[7],
168.5[37]
–
–
–
165.17[16],
165.32[17],
165.1[18],
165.4[21],
165.01[22]
164.93[16],
165.12[17]
165.41[16],
–
167.59[8],
167.9[23]
–
164.9[28]
–
166.4[23],
166.1[26]
–
–
–
169.04[7],
169.1[17],
169.23[31]
169.49[7]
168.98[7]
168.18[7],
–
–
–
–
–
164.7[7],
164.5[18],
164.66[25],
164.5[35],
164.6[36]
164.49[7],
164.42[25]
164.86[25]
–
–
–
164.24[3],
164.23[4],
164.22[5]
169.33[7]
169.5[30]
169.56[7]
168.42[7],
168.36[32],
168.38[33]
13
164.54[5] 168.71[32],
168.7[33]
[3]
164.33
168.46[33]
3-CF3
4-COCH3
–
164.01[4],
163.86[27]
–
164.32[4]
3-COCH3
4-COPh
3-COPh
4-CO2CH3
–
–
–
–
165.7[21]
165.08[16]
165.9[16],
165.69[22]
165.816]
166.21[1],
166.2[16],
166.06[22]
166.24[16]
166.26[16]
166.21[16]
166.18[16]
3-CO2CH3
4-CO2Et
3-CO2Et
4-F
–
–
–
164.20[4],
164.63[27]
166.22[16]
–
–
166.11[16],
165.98[22]
3-F
4-Cl
3-Cl
–
164.34[1],
164.34[3],
164.21[27]
–
4-Br
164.37[27]
3-Br
–
165.95[16]
166.14[1],
166.18[16],
166.5[21]
165.83[16],
165.5[35]
166.32[16],
166.5[21],
166.19[22]
165.7[16]
4-I
164.62[27]
3-I
–
4-CH3
165.25[1],
165,25[3],
165.24[4],
165.07[27]
3-CH3
–
4-OCH3
164.90[1],
165.1[2],
164,92[3],
164.91[4],
164.77[27]
3-OCH3
165.07[1]
3-CN
4-CF3
166.57[16],
166.0[35]
165.43[16],
165.2[35]
167.14[1],
164.12[13],
167.14[16],
167.4[21],
167.06[22]
167.27[13],
167.25[16]
166.83[1],
166.84[16],
166.8[19],
167.1[21],
166.69[22],
166.7[37]
166.79[1],
164.42[25]
165.34[25]
–
–
–
–
165.2[25]
165.65[7],
165.9[23],
165.64[25]
165.64[25]
–
–
165.73[25] (4CO2R)
–
166.0[23]
165.69[25]
165.63[7],
165.8[23],
165.59[25]
165.3[25]
165.9[23],
165.69[25]
–
–
–
–
–
–
–
–
–
–
–
168.7[7]
–
–
–
–
–
–
–
–
165.72[7],
165.53[25],
165.4[35]
165.17[7],
165.15[25]
–
–
169.06[7],
169.2[32],
169.17[33]
169.0[32],
168.97[33]
164.85[3], 169.19[32],
164.85[5], 169.07[33]
164.9[28]
164.76[5], 168.98[32]
164.8[28]
–
–
–
–
166.61[7],
166.8[23],
166.66[25]
165.37[1], 169.62[7],
165.38[3], 169.74[32],
165.37[5], 169.69[33]
165.4[28]
166.74[7],
166.7[25]
166.31[7],
166.6[23],
166.32[25]
165.24[1],
165.29[5]
165.54[1],
165.55[3],
165.53[5],
165.6[28]
166.37[25]
165.08[5] 169.38[32]
165.3[25]
14
–
164.95[1],
164.95[3],
164.93[5]
164.76[5]
–
169.61[32]
169.85[7],
169.9[32],
169.87[33]
4-NH2
165.10[27]
3-NH2
–
165,50[3],
165.47[4],
165.35[27]
3-N(CH3)2 –
4-CH(CH3)2 –
4-C(CH3)3 –
4-N(CH3)2
3-C(CH3)3
4-C6H5
3-C6H5
4-SCH3
3-SCH3
4-SO2CH3
3-SO2CH3
–
–
–
–
–
163.58[27]
–
166.92[16]
167.17[16],
166.98[22]
167.35[16],
167.4[35],
167.2[37]
167.46[16],
167.31[22]
167.72[16]
–
–
–
166.96[16]
166.99[16]
166.83[16]
166.61[16]
165.42[16]
165.20[16]
166.93[7],
166.66[25],
166.6[35]
166.93[7],
166.71[25],
167.2[35]
167.0[25],
166.9[35]
–
–
–
–
–
–
167.19[25]
–
166.6[30],
166.2[35]
166.8[30]
–
–
–
–
–
–
–
–
–
169.37[7]
165.33[1] 169.3[30]
–
–
–
–
–
–
–
–
–
–
–
–
–
–
References
[1]
J. Liu, J. Chen, C. Xia, J. Catal. 2008, 253, 50-56.
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Z. Liu, R.C. Larock, Org. Lett. 2004, 6, 99-102.
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H. Neuvonen, K. Neuvonen, P. Pasanen, J. Org. Chem. 2004, 69, 3794-3800.
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C. Dell’Erba, G. Sancassan, G. Leandri, M. Novi, G. Petrillo, A. Mele, D.
Spinelli, G. Consiglio, Gass. Chim. Ital. 1989, 119, 643-647.
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D. Crich, J.T. Hwang, J. Org. Chem. 1998, 63, 2765-2770.
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Spectral Data Base System (SDBS) (http://www.aist.go.jp./RIOD/SDBS/).
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I. Bauerová, M. Ludwig, Collect. Czech. Chem. Commun. 2001, 66, 770-784.
[9]
R.J. Perry, B.D. Wilson, S.R. Turner, R.W. Blevins, Macromolecules 1995, 28,
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2004, 42, 844-851.
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16
Table S4. The alkyl substituent constants and the carbonyl carbon 13C NMR chemical
shifts, CO, for alkyl benzoates (C6H5CO2R) in CDCl3 from literature used in the data
analysis
R
CH3
NCCH2
ClCH2
F3CCH2
Cl3CCH2
Cl2CHCH2
CHCCH2
ClCH2CH2
C6H5CH2
CH3OCH2CH2
CH2=CHCH2
Ia
EsB b
c
COd
COe
0
0.58
0.47
0.41
0.43h
0.31h
0.27
0.17
0.11
0.098k
0.06l
0
–0.55
–0.17
–0.231f, –0.208g
–0.329i, –0.532g
–0.218i, –0.322g
–0.27j
–0.23
–0.24
–0.2
–0.15m
0
0.37
0.08
–
–
–
0.17
0.16
0.18
0.16
0.17
0
–2.00
–2.38
–1.76
–2.00
–1.37
–1.21
–0.74
–0.50
–0.36
166.9
164.9
–
–
164.9
–
–
166.17
166.4; 166.4
–
166.6n
a
The inductive[1] constants. bThe steric[2] constants. cThe Charton steric[3,4] constants.
For R = CH2CH2Cl and R = CH2CH2OCH3 isosteric constants of propyl and butyl
substituents, respectively, were used. For R = CH2CCH isosteric constant of allyl
substituent was used. dThe substituent chemical shifts, CO, were calculated as
difference: CO)R – CO)CH3. eThe CO values from Refs [5-9]. fThe steric constant was
calculated with equation: log k = –(0.780 ± 0.060) + (3.72 ± 0.17)I + (1.063 ±
0.214)EsB, R = 0.993, s = 0.066, s0 = 0.118, n = 8 (R = CH3, CH2CH3, CH2Cl,
CH2CH2Cl (2 values), CH2CCH, CH2OCH3, CH2CH2OCH3) using kinetic data of
alkaline hydrolysis of alkyl acetates,[10] (CH3CO2R). gThe steric constants, EsB, were
calculated with equation: log k = –(1.605 ± 0.150) + (4.25 ± 0.33)I + (1.39 ± 0.44)
EsB, R = 0.988, s = 0.120, s0 = 0.152, n = 8 using kinetic data from Table S5. hThe
inductive[11] constants. iThe steric conatant was calculated with equation: CO =
(1743.8 ± 0.6) + (73.8 ± 1.6)I + (46.64 ± 2.5)EsB, R = 0.999, s = 0.415, s0 = 0.046, n =
6 (R = CH3, CH2CH3, CH2CF3, CH2CH2Cl, CH2C6H5, CH2CH2OCH3,) using infrared
stretching frequencies of carbonyl group for alkyl 3-phenylpropionates.[12] jThe steric
constant was calculated as difference: log kH+(HCCCH2) – log kH+(CH3) for acid
hydrolysis of alkyl 4-nitrobenzoates.[13] kThe inductive constant was calculated using
equation: pK = (15.59 ± 0.08) – (7.89 ± 0.29)I, R = 0.996, s = 0.136, s0 = 0.091, n = 7
(R = CH3, CH2CH3, CH2CCl3, CH2CF3, CH2CHCl2, CH2CCH, CH2CH2Cl) for
aliphatic alcohols.[12, 14] lRef.[15] mThe steric constant was calculated as difference: (log
kH+)R – (log kH+)CH3 using acid hydrolysis rate constants of allyl[16] and methyl[17]
acetates , respectively. nRef.[18]
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R.W. Taft, I.C. Lewis, J. Am. Chem. Soc. 1958, 80, 2435-2443.
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M. Charton, J. Am. Chem. Soc. 1975, 97, 1552-1556.
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[6]
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[11]
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[17]
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Table S5. The second-order rate constants k (dm3 mol–1 s–1) for alkaline hydrolysis of
esters of benzoic acid, C6H5CO2R, in aqueous 0.5 M Bu4NBr at 25 Ca
R
F3CCH2
Cl3CCH2
Cl2CHCH2
CH3
2-CO2CH3-C6H4
103k1 (s–1)
27.15  0.15
25.38  0.17
26.54  0.16
12.17  0.05
10.91  0.05
11.02  0.06
7.098  0.065
7.043  0.049
6.469  0.078
1.246  0.015
1.261  0.017
1.311  0.020
3.537  0.037
3.463  0.089
3.475  0.147
kb (dm3mol–1s–1)
kc(dm3mol–1s–1)
log k2
nd
0.726  0.004
0.705  0.014
0.679  0.005
0.710  0.004
0.325  0.001
0.304  0.011
0.292  0.001
0.295  0.002
0.190  0.002
0.184  0.005
0.188  0.001
0.173  0.002
0.0333  0.0004 0.0340  0.0005
0.0337  0.0005
0.0351  0.0005
0.0946  0.0010 0.0934  0.0006
0.0926  0.0024
0.0929  0.0039
–0.152
3
–0.517
3
–0.735
3
–1.469
3
–1.030
3
a
The wavelength of UV spectra used in kinetic measurements is equal to 240 nm. bThe
second-order rate constants, k, were calculated by dividing the pseudo-first-order rate
constants, k1, by the alkali concentration, cOH- = 0.0374 M. cThe arithmetic mean value
of the second-order rate constants. dn equals to the total number of the k values used in
determination of the arithmetic mean value of the second-order rate constants.
19