Terephthalonitrile reductive alkylation
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 10, October, 2016
2435
8 : 2, sevenfold eluation). IR (film), ν/cm–1: 2227 (C≡N), 2247
(C≡N). 1H NMR (500.13 MHz) δ: 1.69—1.72 (m, 2 Н, C(3´)H2);
1.78—1.84 (m, 2Н, C(2´)H2); 2.37 (t, 2 Н, C(4´)H2, J = 7.2 Hz);
2.72 (t, 2 Н, C(1´)H2, J =7.5); 7.28 (d, 2 H, С(3)H, С(5)H, J =
= 8.0 Hz); 7.58 (d, 2 H, С(2)H, С(6)H, J = 8.0 Hz). 13C NMR
(125.77 MHz) δ: 17.9 (C(4´)); 25.7 (C(2´)); 30.6 (C(3´)); 36.0
(C(1´)); 111.0 (C(1)); 119.7 (CCN(1)); 120.1 (CCN(5´)); 130.0
(С(3), C(5)); 133.2 (C(2), C(6)); 147.7 (C(4)). Massꢀspectrum
(EI, 70 eV), m/z (Irel (%)): 184 [M]+ (32), 183 (28), 130 (52), 116
(100), 89 (22). Found: m/z 184.0998 [M]+. С12H12N2. Calcuꢀ
lated: M = 184.1000.
tially benzonitrile 8 (0.3 mL, 3.0 mmol) and sodium metal (0.068 g,
2.96 mmol) were added at temperature –(33—50) °C affording
–
thus darkꢀred solution of benzonitrile radical anion [8]•
.
ωꢀXꢀAlkyl bromide 5a—c (0.6 eq in respect to nitrile 8) was added
to this solution and the stirring was continued for 1.5 h at –33 °C in
the atmosphere of evaporating NH3. Following processing was
performed similarly to described above. The composition of obꢀ
tained in this way reaction mixtures was analyzed by 1Н NMR and
GC/MS methods.
The authors acknowledge the MultiꢀAccess Chemiꢀ
cal Service Center SB RAS for spectral and analytical
measurements. The work was performed with financial
support of Russian Foundation for Basic Research
(Project No 14ꢀ03ꢀ00108) and Federal Agency of Scienꢀ
tific Organizations (Project No 0302ꢀ2016ꢀ0007).
Ethyl 6ꢀ(4ꢀcyanophenyl)hexanоate (6c),30 CAS No. 1888410ꢀ
56ꢀ7, was separated from the reaction mixture of [1]2– and 5c
(0.593 g) as colorless oil (0.258 g, 1.05 mmol, 45%), Rf ≈ 0.42
(hexane—Et2O, 8 : 2, fourfold eluation). IR (film), ν/cm–1: 2227
1
(C≡N), 1732 (C=O). H NMR (400.13 MHz) δ: 1.22 (t, 3 Н,
C(8´)H3, J = 7.2 Hz); 1.33 (quint, 2 Н, C(3´)H2, J = 7.6 Hz);
1.58—1.66 (m, 4 Н, C(2´)H2, C(4´)H2); 2.26 (t, 2 Н, C(5´)H2, J =
= 7.6 Hz); 2.64 (t, 2 Н, C(1´)H2, J = 7.7); 4.09 (q, 2 H, С(7´)Н2,
J = 7.2 Hz); 7.24 (d, 2 H, H(3), H(5), J = 8.2 Hz); 7.53 (d, 2 H,
H(2), H(6), J = 8.2). 13C NMR (125.77 MHz) δ: 14.1 (C(8´));
24.5 (C(3´)); 28.4 (C(4´)); 30.4 (C(2´)); 34.0 (C(5´)); 35.7 (C(1´));
60.1 (C(7´)); 109.5 (C(1)); 118.9 (CCN); 129.0 (С(3), C(5)); 131.9
(C(2), C(6)); 148.0 (C(4)); 173.5 (C(6´)). Massꢀspectrum (EI,
70 eV), m/z (Irel (%)): 245 [M]+ (24), 200 (24), 158 (39), 155 (54),
130 (65), 116 (100), 101 (39), 88 (52). Found: m/z 245.1410 [M]+.
С15H19NO2. Calculated: M = 245.1406.
2ꢀ(2ꢀPhenylethyl)ꢀ1,3ꢀdioxane (7a),31 CAS No. 5663ꢀ30ꢀ9,
was separated from the reaction mixture of [1]2– and 5a (0.530 g) as
colorless oil (103 mg, 0.54 mmol, 23%), Rf ≈ 0.3 (hexane—Et2O,
9 : 1, fivefold eluation). 1H NMR (400.13 MHz) δ: 1.32 (dm, 1 Н,
C(5″)H, J = 13.4 Hz); 1.87—1.92 (m, 2 Н, C(2´)H2); 2.01—2.15
(m, 1 Н, C(5″)H); 2.70 (t, 2 Н, C(1´)H2, J = 7.9 Hz); 3.74 (td, 2 Н,
C(4″)H and С(6″)H, J = 12.0 Hz, J = 2.4 Hz); 4.06—4.12 (m, 2 H,
С(4″)Н and C(6″)Н); 4.49 (t, 1 Н, C(2″)H, J = 5.2 Hz); 7.13—7.18
(m, 3 H, H(2), H(4), H(6)); 7.26 (t, 2 H, H(3), H(5), J = 8.1 Hz).
Massꢀspectrum (EI, 70 eV), m/z (Irel (%)): 192 [M]+ (2), 133 (15),
114 (33), 105 (17), 91 (37), 87 (100), 59 (17).
5ꢀPhenylvaleronitrile (7b),32 CAS No. 7726ꢀ45ꢀ6, was sepaꢀ
rated from the reaction mixture of [1]2– and 5b (0.432 g) as
colorless oil (0.060 g, 0.38 mmol, 16%), Rf ≈ 0.4 (hexane—Et2O,
8 : 2, sevenfold eluation). 1H NMR (400.13 MHz) δ: 1.62—1.70
(m, 2 Н, C(3´)H2); 1.74—1.81 (m, 2 Н, C(2´)H2); 2.33 (t, 2 Н,
C(4´)H2, J = 7.1 Hz); 2.64 (t, 2 Н, C(1´)H2, J = 7.2 Hz); 7.14—
7.20 (m, 3 H, H(2), H(6), H(4)); 7.28 (t, 2 H, H(3), H(5), J =
= 7.0 Hz). Massꢀspectrum (EI, 70 eV), m/z (Irel (%)): 159 [M]+
(24), 158 (20), 91 (100).
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Ethyl 6ꢀphenylhexanoate (7c),33 CAS No. 52692ꢀ51ꢀ0, was
separated from the reaction mixture of [1]2– and 1b (0.593 g) as
colorless oil (0.129 g, 0.58 mmol, 25%), Rf ≈ 0.7 (hexane—Et2O,
8 : 2, fourfold eluation). 1H NMR (400.13 MHz) δ: 1.23 (t, 3 Н,
C(8´)H3, J = 7.1 Hz); 1.35 (quint, 2 Н, C(3´)H2, J = 7.4 Hz);
1.59—1.68 (m, 4 Н, C(2´)H2 and C(4´)H2); 2.27 (t, 2 Н, C(5´)H2,
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then under stirring in the atmosphere of evaporating NH3 sequenꢀ
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