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Vereshchagin et al.
CH3O); 3.92 (s, 3 H, CH3O); 4.41 (s, 1 H, CH); 7.35–7.50 (m,
5 H, Ph).
(Ref. 37: m.p. 126—127 °C). 1H NMR (CDCl3), δ: 3.79 (s, 3 H,
CH3O); 3.94 (s, 1 H, CH); 3.98 (s, 3 H, CH3O); 7.11 (t, 2 H,
Ar, J = 8.7); 7.38 (d.d, 2 H, Ar, J1 = 5.1, J2 = 8.7).
Dimethyl 2,2ꢀdicyanoꢀ3ꢀ(4ꢀmethylphenyl)cyclopropaneꢀ
1,1ꢀdicarboxylate (2b). The yield was 52%, m.p. 137—139 °C
(Ref. 34: m.p. 137—139 °C). 1H NMR (CDCl3), δ: 2.39 (s,
3 H, CH3); 3.79 (s, 3 H, CH3O); 3.96 (s, 1 H, CH); 3.98 (s, 3 H,
CH3O); 7.18—7.30 (m, 4 H, Ar).
Dimethyl 2,2ꢀdicyanoꢀ3ꢀ(4ꢀmethoxyphenyl)cyclopropaneꢀ
1,1ꢀdicarboxylate (2c). The yield was 47%, m.p. 108—109 °C
(Ref. 34: m.p. 108—109 °C). 1H NMR (CDCl3), δ: 3.78 (s, 3 H,
CH3O); 3.79 (s, 3 H, CH3O); 3.93 (s, 1 H, CH); 3.94 (s,
3 H, CH3O); 6.91 (d, 2 H, Ar, J = 8.0); 7.27 (d, 2 H, Ar,
J = 8.0).
Dimethyl 2,2ꢀdicyanoꢀ3ꢀ(2ꢀmethoxyphenyl)cyclopropaneꢀ
1,1ꢀdicarboxylate (2d). The yield was 45%, m.p. 114—115 °C
(Ref. 37: m.p. 114—151 °C). 1H NMR (CDCl3), δ: 3.80 (s,
3 H, CH3O); 3.84 (s, 1 H, CH); 3.93 (s, 3 H, CH3O); 3.96
(s, 3 H, CH3O); 6.90—7.00 (m, 2 H, Ar); 7.18—7.22 (m, 1 H,
Ar); 7.33—7.44 (m, 1 H, Ar).
Dimethyl 3ꢀ(4ꢀchlorophenyl)ꢀ2,2ꢀdicyanocyclopropaneꢀ
1,1ꢀdicarboxylate (2e). The yield was 58%, m.p. 108—110 °C
(Ref. 34: m.p. 108—110 °C). 1H NMR (CDCl3), δ: 3.79 (s, 3 H,
CH3O); 3.92 (s, 1 H, CH); 3.98 (s, 3 H, CH3O); 7.25—7.45 (m,
4 H, Ar).
Dimethyl 2,2ꢀdicyanoꢀ3ꢀ(3ꢀfluorophenyl)cyclopropaneꢀ
1,1ꢀdicarboxylate (2k). The yield was 48%, m.p. 87—88 °C.
Found (%): C, 59.52; H, 3.78; N, 9.20. C15H11FN2O4. Calcuꢀ
lated (%): C, 59.61; H, 3.67; N, 9.27. 1H NMR (CDCl3), δ:
3.80 (s, 3 H, CH3O); 3.95 (s, 1 H, CH); 3.97 (s, 3 H, CH3O);
7.05—7.21 (m, 3 H, Ar); 7.35—7.45 (m, 1 H, Ar). 13C NMR
4
(CDCl3), δ: 16.4 (C); 39.3 (d, CH, JCF = 2.0); 46.2 (C); 53.9
(CH3O); 54.8 (CH3O); 109.2 (CN); 111.4 (CN); 115.9 (d, CH,
2
2
Ar, JCF = 34.4); 116.8 (d, CH, Ar, JCF = 20.8); 124.4 (d, C,
Ar, 4JCF = 3.1); 129.3 (d, CH, Ar, 3JCF = 7.9); 130.8 (d, CH, Ar,
3JCF = 8.4); 161.1 (C=O); 162.5 (d, CF, JCF = 246.9); 163.1
1
(C=O). MS (EI), m/z (Irel(%)): 302 [M]+ (1), 271 (2), 243 (4),
198 (3), 185 (6), 158 (42), 139 (50), 109 (10), 75 (14), 59 (100).
IR, νmax/cm–1: 2252 (CN), 1756 (C=O), 1748 (C=O).
Dimethyl 2,2ꢀdicyanoꢀ3ꢀ(2ꢀfluorophenyl)cyclopropaneꢀ
1,1ꢀdicarboxylate (2l). The yield was 46%, m.p. > 350 °C
(Ref. 44: m.p. > 350 °C). 1H NMR (CDCl3), δ: 3.83 (s, 3 H,
CH3O); 3.96 (s, 1 H, CH); 4.00 (s, 3 H, CH3O); 7.17 (m, 2 H,
Ar); 7.41 (m, 2 H, Ar).
Dimethyl
2,2ꢀdicyanoꢀ3ꢀ(4ꢀnitrophenyl)cyclopropaneꢀ
1,1ꢀdicarboxylate (2m). The yield was 39%, m.p. 140—142 °C
(Ref. 34: m.p. 140—142 °C). 1H NMR (CDCl3), δ: 3.85 (s, 3 H,
CH3O); 4.02 (s, 3 H, CH3O); 4.05 (s, 1 H, CH); 7.62 (d, 2 H,
J = 7.7); 8.31 (d, 2 H, J = 7.7).
Dimethyl 3ꢀ(3ꢀchlorophenyl)ꢀ2,2ꢀdicyanocyclopropaneꢀ
1,1ꢀdicarboxylate (2f). The yield was 42%, m.p. 78—79 °C.
Found (%): C, 56.39; H, 3.58; N, 8.68. C H11ClN2O4. Calcuꢀ
115
lated (%): C, 56.53; H, 3.48; N, 8.79. H NMR (CDCl3), δ:
Dimethyl
2,2ꢀdicyanoꢀ3ꢀ(1ꢀnaphthyl)cyclopropaneꢀ
3.82 (s, 3 H, CH O); 3.94 (s, 1 H, CH); 3.99 (s, 3 H, CH3O);
1,1ꢀdicarboxylate (2n). The yield was 54%, m.p. 176—177 °C.
3
7.25—7.30 (m, 1 H, Ar); 7.34—7.44 (m, 3 H, Ar). 13C NMR
Found (%): C, 68.08; H, 4.38; N, 8.32. C19H14N2O4. Calculated
1
(CDCl3), δ: 16.4 (C); 39.3 (CH); 46.3 (C); 54.1 (CH O); 55.0
(%): C, 68.26; H, 4.22; N, 8.38. H NMR (CDCl3), δ: 3.50 (s,
3
(CH3O); 109.2 (CN); 111.4 (CN); 126.8, 129.0, 129.1, 130.0,
3 H, CH3O); 4.07 (s, 3 H, CH3O); 4.30 (s, 1 H, CH); 7.48 (t,
1 H, Ar, J = 7.7); 7.53—7.66 (m, 2 H, Ar); 7.69 (d, 1 H, Ar,
J = 7.0); 7.91 (d, 2 H, Ar, J = 8.1); 7.99 (d, 1 H, Ar, J = 8.1).
13C NMR (CDCl3), δ: 16.3 (C); 39.2 (CH); 46.6 (C); 53.7
(CH3O); 54.9 (CH3O); 109.5 (CN); 112.3 (CN); 122.6, 123.3,
125.0, 126.5, 126.6, 127.3, 129.1, 130.4, 131.5, 133.6 (all Ar);
161.5 (C=O); 163.7 (C=O). MS (EI), m/z (Irel(%)): 334 [M]+
(5), 275 (16), 270 (25), 248 (15), 215 (25), 190 (43), 189 (20),
188 (21), 152 (13), 59 (100). IR, νmax/cm–1: 2252 (CN), 1772
(C=O), 1752 (C=O).
130.5, 135.1 (all Ar); 161.2 (C=O); 163.2 (C=O). MS (EI), m/z
+
(Irel(%)): 318 [M] (2), 286 (4), 259 (5), 201 (9), 174 (45), 155
(39), 138 (17), 91 (12), 75 (29), 59 (100). IR, νmax/cm–1: 2252
(CN), 1756 (C=O), 1748 (C=O).
Dimethyl 3ꢀ(2ꢀchlorophenyl)ꢀ2,2ꢀdicyanocyclopropaneꢀ
1,1ꢀdicarboxylate (2g). The yield was 48%, m.p. 116—117 °C
(Ref. 34: m.p. 116—118 °C). 1H NMR (CDCl3), δ: 3.81 (s, 3 H,
CH3O); 3.96 (s, 1 H, CH); 3.99 (s, 3 H, CH3O); 7.25—7.55 (m,
4 H, Ar).
Dimethyl 3ꢀ(4ꢀbromophenyl)ꢀ2,2ꢀdicyanocyclopropaneꢀ1,1ꢀ
dicarboxylate (2h). The yield was 46%, m.p. 107—108 °C
(Ref. 37: m.p. 107—108 °C). 1H NMR (CDCl3), δ: 3.78 (s, 3 H,
CH3O); 3.93 (s, 1 H, CH); 3.97 (s, 3 H, CH3O); 7.23 (d, 2 H,
Ar, J = 8.4); 7.53 (d, 2 H, Ar, J = 8.4).
Dimethyl 2,2ꢀdicyanoꢀ3ꢀ(3,4ꢀdimethoxyphenyl)cyclopropaneꢀ
1,1ꢀdicarboxylate (2o). The yield was 52%, m.p. 161—162 °C.
Found (%): C, 59.28; H, 4.78; N, 8.08. C17H16N2O6. Calcuꢀ
lated (%): C, 59.30; H, 4.68; N, 8.14. 1H NMR (CDCl3), δ: 3.79
(s, 3 H, CH3O); 3.87 (s, 3 H, CH3O); 3.88 (s, 3 H, CH3O); 3.93
(s, 1 H, CH); 3.96 (s, 3 H, CH3O); 6.85 (d, 1 H, Ar, J = 2.2);
6.86 (d, 1 H, Ar, J = 7.7); 6.93 (d.d, 1 H, Ar, J1 = 2.2, J2 = 7.7).
13C NMR (CDCl3), δ: 16.7 (C); 40.4 (CH); 46.6 (C); 54.1
(CH3O); 55.0 (CH3O); 56.0 (CH3O); 56.0 (CH3O); 109.9 (CN);
111.4 (Ar); 111.5 (Ar); 111.9 (CN); 119.1, 121.6, 149.2, 150.1
(all Ar); 161.7 (C=O); 163.6 (C=O). MS (EI), m/z (Irel(%)):
344 [M]+ (5), 312 (17), 285 (21), 225 (16), 200 (13), 181 (15),
156 (13), 140 (12), 114 (12), 59 (100). IR, νmax/cm–1: 2252
(CN), 1748 (C=O), 1732 (C=O).
Dimethyl 2,2ꢀdicyanoꢀ3ꢀ(3ꢀfluorophenyl)cyclopropaneꢀ
1,1ꢀdicarboxylate (2p). The yield was 48%, m.p. 87—88 °C.
Found (%): C, 59.52; H, 3.78; N, 9.20. C15H11FN2O4. Calcuꢀ
lated (%): C, 59.61; H, 3.67; N, 9.27. 1H NMR (CDCl3), δ:
3.80 (s, 3 H, CH3O); 3.95 (s, 1 H, CH); 3.97 (s, 3 H, CH3O);
7.05—7.21 (m, 3 H, Ar); 7.35—7.45 (m, 1 H, Ar). 13C NMR
Dimethyl 3ꢀ(3ꢀbromophenyl)ꢀ2,2ꢀdicyanocyclopropaneꢀ
1,1ꢀdicarboxylate (2i). The yield was 52%, m.p. 110—111 °C.
Found (%): C, 49.45; H, 3.15; Br, 21.65; N, 7.68. C15H11BrN2O4.
Calculated (%): C, 49.61; H, 3.05; Br, 21.79; N, 7.53. 1H NMR
(CDCl3), δ: 3.80 (s, 3 H, CH3O); 3.95 (s, 1 H, CH); 3.97 (s,
3 H, CH3O); 7.26—7.35 (m, 2 H, Ar); 7.50 —7.55 (m, 2 H, Ar).
13C NMR (CDCl3), δ: 16.6 (C); 39.3 (CH); 46.3 (C); 54.3
(CH3O); 55.1 (CH3O); 109.4 (CN); 111.6 (CN); 123.0, 127.3,
129.5, 130.8, 132.5, 132.1 (all Ar); 161.34 (C=O); 163.28 (C=O).
MS (EI), m/z (Irel(%)): 364 [M]+ (8), 362 [M]+ (7), 332 (21),
330 (20), 305 (16), 303 (15), 220 (73), 218 (65), 201 (65), 199
(76), 165 (60), 59 (100). IR, νmax/cm–1: 2256 (CN), 1760 (C=O),
1752 (C=O).
Dimethyl 2,2ꢀdicyanoꢀ3ꢀ(4ꢀfluorophenyl)cyclopropaneꢀ
1,1ꢀdicarboxylate (2j). The yield was 63%, m.p. 126—127 °C