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P. Kukula, K. Koprivova / Journal of Catalysis 234 (2005) 161–171
Appendix A
intensity): 81(45), 80(17), 66(16), 54(100), 41(46), 39(42),
28(30).
trans-2-Pentenenitrile: rt 5.30 min, 1H NMR (500 MHz,
GC, MS, and NMR data for the reaction components.
trans-Cinnamonitrile 1: rt 8.5 min, 1H NMR (300 MHz,
CDCl3): 5.88 (d, =CH–C≡N, 1H), 7.35–7.47 (m, Ph–CH=,
6H). MS (EI) m/z (rel. intensity): 129(100), 102(40),
76(22), 63(18), 51(24).
CDCl3): 1.10 (t, CH3–, 3H), 2.44 (dq, CH2, 2H), 5.33 (d,
=CHCN, 1H), 6.79 (dt, CH2CH=, 1H), MS (EI) m/z (rel.
intensity): 81(74), 80(20), 66(42), 54(100), 41(67), 39(41),
28(26).
Hydrocinnamonitrile 2: rt 7.6 min, 1H NMR (300 MHz,
CDCl3): 2.61 (t, –CH2–C≡N, 2H), 2.96 (t, Ph–CH2–, 2H).
MS (EI) m/z (rel. intensity): 131(83), 91(100), 77(18),
65(23), 51(13), 39(15).
1
trans-Pent-3-enyl-amine 16: rt 2.95 min, H NMR (500
MHz, CDCl3): 1.43 (dd, CH3, 3H), 2.03–2.27 (m, =CHCH2,
2H), 2.81 (t, CH2NH2, 2H), 5.14–5.32 (m, =CHCH2CN,
1H), 5.33–5.61 (m, CH3CH=, 1H), MS (EI) m/z (rel. inten-
sity): 85(9), 67(11), 55(12), 41(17), 39(22), 30(100), 28(19).
cis-Pent-2-enyl-amine 17: rt 3.04 min.
3-Phenyl-propylamine 4: rt 7.2 min, 1H NMR (300 MHz,
CDCl3): 1.19 (brs, –NH2, 2H), 1.78 (m, –CH2CH2NH2,
2H), 2.65 (t, –CH2–NH2, 2H), 2.72 (t, Ph–CH2–, 2H), 7.11–
7.34 (m, Ph–, 5H). MS (EI) m/z (rel. intensity): 135(15),
118(100), 117(65), 91(61), 77(44), 65(53), 51(39), 42(19).
Valeronirile 18: rt 5.09 min, MS (EI) m/z (rel. intensity):
82(14), 55(23), 54(70), 43(100), 41(82), 39(16), 27(34).
Pentylamine 19: rt 2.56 min, MS (EI) m/z (rel. intensity):
87(17), 56(10), 55(11), 45(12), 41(16), 30(100), 27(16).
3,3-Dimethyl-acrylonitrile 20: rt 5.00 min, 1H NMR
(300 MHz, CDCl3): 1.94 (d, CH3, 3H), 2.06 (d, CH3, 3H),
5.10–5.13 (m, CH, 1H).
1
3-Phenyl-allylamine 6: rt 8.3 min, H NMR (300 MHz,
CDCl3): 1.49 (brs, –NH2, 2H), 3.48 (d, –CH2–NH2, 2H),
1
1
6.32 (dt, Ph–CH=CH–, H), 6.51 (d, Ph–CH=CH–, H),
7.18–7.41 (m, Ph–, 5H). MS (EI) m/z (rel. intensity):
133(100), 132(89), 115(67), 91(34), 77(21), 56(23), 51(17).
Other by-products, usually <2%, not fully characterized, but
probably including alkylated primary and secondary amines
formed by the reaction with the solvent, rt 9.0–11.0 min;
secondary amines such as bis-(3-phenyl-propyl)-amine, (3-
phenyl-allyl)-(3-phenyl-propyl)-amine and bis-(3-phenyl-
allyl)-amine), rt 16.0–20.0 min.
1
Iso-valeronitrile 21: rt 3.58 min, H NMR (300 MHz,
1
CDCl3): 1.07 (d, CH3, 6H), 2.00–2.10 (m, CH, H), 2.25
(d, CH2, 2H), MS (EI) m/z (rel. intensity): 82(13), 68(16),
52(11), 43(100), 41(74).
3-Methyl-2-butenyl-amine 22: rt 3.11 min, 1H NMR (300
MHz, CDCl3): 1.63 (d, CH3, 3H), 1.68 (d, CH3, 3H), 3.25
1
(d, CH2, 2H), 5.26 (t, CH, H), MS (EI) m/z (rel. inten-
Cyclohex-1-enyl-acetonitrile 7: rt 9.3 min, 1H NMR
(300 MHz, CDCl3): 1.43–1.77 (m, CH2, 4H), 1.94–2.11 (m,
CH2, 4H), 3.00 (s, CH2CN, 2H), 5.78 (t, >C=CH–, 1H), MS
(EI) m/z (rel. intensity): 121(22), 81(100), 55(60), 53(29),
41(45), 39(40), 27(32).
sity): 85(9), 84(15), 70(100), 57(12), 53(16), 43(22), 41(34),
39(19), 30(47), 28(33).
Iso-amylamine 23: rt 2.15 min, 1H NMR (300 MHz,
CDCl3): 0.88 (d, CH3, 3H), 0.91 (d, CH3, 3H), 1.12 (brs,
NH2, 2H), 1.33 (q, CH2CH2NH2, 2H), 1.58–1.68 (m, CH,
1H), 2.70 (t, CH2NH2, 2H), MS (EI) m/z (rel. intensity):
87(11), 70(9), 55(13), 41(22), 30(100), 28(22), 27(20).
Cyclohexylidene-acetonitrile 8: rt 9.2 min, 1H NMR
(300 MHz, CDCl3): 1.53–1.67 (m, CH2, 6H), 2.24 (t,
CH2C=, 2H), 2.48 (t, CH2C=, 2H), 5.04 (s, CHCN, 1H).
Cyclohexylacetonitrile 9: rt 8.92 min, 1H NMR (300 MHz,
CDCl3): 1.07–1.38 (m, CH2CH, 5H), 1.57–1.83 (m, CH2,
6H), 2.24 (d, CH2CN, 2H).
1
cis-Geranylnitrile 24: rt 9.40 min, H NMR (500 MHz,
CDCl3): 1.60 (d, CH3, 3H), 1.69 (d, CH3, 3H), 1.90 (d,
CH3C=CHCN, 3H, 4J = 1.1 Hz), 2.13–2.21 (m, CH2, 2H),
2.41 (t, CH2, 2H), 5.05 (dt, CH–CH2, 1H), 5.09 (d, CH–CN,
1H, 4J = 1.0 Hz), MS (EI) m/z (rel. intensity): 148(8),
134(14), 81(12), 69(100), 53(15), 41(53), 28(15).
1
2-Cyclohex-1-enyl-ethylamine 10: rt 8.56 min, H NMR
(300 MHz, CDCl3): 1.17–1.23 (brs, NH2, 2H), 1.43–1.66
(m, CH2, 4H), 1.89 (brs, CH2, 2H), 1.98 (brs, CH2, 2H),
2.06 (t, CH2CH2NH2, 2H), 2.75 (t, CH2NH2, 2H), 5.46
(t, >C=CH–, 1H).
trans-Geranylnitrile 24: rt 9.28 min, 1H NMR (500 MHz,
CDCl3): 1.60 (d, CH3, 3H), 1.69 (d, CH3, 3H), 2.04 (s,
CH3C=CHCN, 3H), 2.13–2.21 (m, CH2, 2H), 2.41 (t, CH2,
2-Cyclohexyl-ethylamine 12: rt 8.24 min, 1H NMR (300
MHz, CDCl3): 1.03–1.32 (m, CH2, 4H), 1.43–1.87 (m,
CH + CH2, 8H), 2.76 (t, CH2NH2, 2H).
1
1
2H), 5.05 (dt, CH–CH2, H), 5.09 (s, CH–CN, H), MS
(EI) m/z (rel. intensity): 148(12), 134(22), 81(19), 69(100),
53(10), 41(59), 27(11).
trans-3-Pentenenitrile 14: rt 5.52 min, 1H NMR (500
MHz, CDCl3): 1.73 (dd, CH3, 3H), 3.05 (d, CH2, 2H), 5.38
(dq, =CHCH2CN, 1H), 5.79–5.86 (m, CH3CH=, 1H), MS
(EI) m/z (rel. intensity): 81(56), 80(14), 66(10), 54(100),
41(84), 39(56), 27(24).
3,7-Dimethyl-6-octenyl-nitrile 25: rt 9.21 min, MS (EI)
m/z (rel. intensity): 151(8), 150(16), 136(28), 122(14),
108(27), 94(25), 69(100), 55(29), 41(68), 27(12).
3,7-Dimethyl-6-octenyl-amine 26: rt 8.80 min, MS (EI)
m/z (rel. intensity): 155(10), 138(16), 123(23), 109(14),
95(32), 81(37), 70(100), 56(22), 41(39), 30(88).
cis-Geranylamine 27: rt 9.09 min, MS (EI) m/z (rel. in-
tensity): 153(8), 138(27), 121(32), 107(14), 93(47), 84(70),
70(95), 57(69), 41(100), 30(35).
cis-3-Pentenenitrile: rt 4.80 min, MS (EI) m/z (rel. inten-
sity): 81(39), 66(11), 54(43), 41(100), 39(49), 28(26).
cis-2-Pentenenitrile 15: rt 3.74 min, 1H NMR (500 MHz,
CDCl3): 1.06 (t, CH3, 3H), 2.40 (dq, CH2, 2H), 5.25 (d,
=CHCN, 1H), 6.45 (dt, CH2CH=, 1H), MS (EI) m/z (rel.