Substituted homoallenyl aldehydes and their derivatives. Part 2: Azines

Article abstract of DOI:10.2478/s11696-012-0238-z

This paper deals with the preparation of a variously substituted non-symmetrical azine set. The starting molecule for their preparation was a protected hydrazone. The protection was performed applying Zwierzak's method. This procedure is based on the transfer of hydrazine to diethylhydrazidophosphate, which reacts with aldehydes to produce protected hydrazones. In the second step of the procedure, under the action of sodium hydride, the addition of another aldehyde affords non-symmetrical azines in the reaction with the protected hydrazine. The procedure was shown to be a useful and effective method. In this, the second part of our study, we present results devoted to the preparation and full identification of non-symmetrical azines.

Full text of DOI:10.2478/s11696-012-0238-z

Chemical Papers 67 (1) 40–50 (2013)
DOI: 10.2478/s11696-012-0238-z
ORIGINAL PAPER
Substituted homoallenyl aldehydes and their derivatives.
Part 2: Azines
Juraj Galeta, Stanislav Man, Aneta Valoušková, Milan Potáček*
Department of Chemistry, Faculty of Science, Masaryk University, Kotlářská 2, 611 37 Brno, Czech Republic
Received 21 March 2012; Revised 7 June 2012; Accepted 11 June 2012
Dedicated to Professor Štefan Toma on the occasion of his 75th birthday
This paper deals with the preparation of a variously substituted non-symmetrical azine set. The
starting molecule for their preparation was a protected hydrazone. The protection was performed
applying Zwierzak’s method. This procedure is based on the transfer of hydrazine to diethyl-
hydrazidophosphate, which reacts with aldehydes to produce protected hydrazones. In the second
step of the procedure, under the action of sodium hydride, the addition of another aldehyde affords
non-symmetrical azines in the reaction with the protected hydrazine. The procedure was shown to
be a useful and effective method. In this, the second part of our study, we present results devoted
to the preparation and full identification of non-symmetrical azines.
c
ꢀ 2012 Institute of Chemistry, Slovak Academy of Sciences
Keywords: allenyl, azine, aldehyde, hydrazone, deprotonation, non-symmetrical
Introduction
treated with electrophiles (Galeta & Potáček, 2012;
Zachová et al., 2006, 2009). Non-symmetrical azines
serve as educts for the preparation of fused tricyclic
heterocyclic systems by combined intra-intermolecular
criss-cross cycloaddition (Galeta et al., 2009, 2011;
Man et al., 2002, 2004, 2005).
The preparation of protected hydrazones is the
first part of azine synthesis by Zwierzak’s method
(Zwierzak & Sulewska, 1976; Koziara et al., 1986).
We used this method with some changes to the syn-
thetic pathway (Galeta et al., 2013) and we report
here on the success of the second step, in which pro-
tected hydrazones under the treatment of sodium hy-
dride react with the submitted aldehyde to produce
non-symmetrical azines. Our targets were azines con-
taining an allenyl skeleton (Schweizer & Lee, 1984;
Schweizer et al., 1987). Syntheses of numerous organic
compounds with biological activity have been based
on the allenyl synthon (Zimmer, 1993; Brandsma,
2001; Brandsma & Nedolya, 2004; Krause & Hashmi,
2004; Brandsma, 2004; Brasholz et al., 2009). In the
past, symmetrical azines were used in the preparation
of fused cyclic compounds in intra-molecular criss-
cross cycloaddition reactions (Zachová et al., 2005)
leading to four fused five-membered rings and for
research into their interesting transformations when
Experimental
Unless stated otherwise, all reagents were pur-
chased from commercial (Sigma–Aldrich, USA) sup-
plier and used as received. Diethyl ether and toluene
were distilled from sodium/benzophenone prior to use.
All reactions were carried out under a dry argon at-
mosphere and monitored by TLC (Merck F254 sil-
ica gel; Merck, Germany). Products were separated
by liquid chromatography with a Horizon HPFC Sys-
tem (Biotage, Sweden) fitted with Biotage Si 12+M
and Si 25+M columns. FTIR spectra were recorded
with a GENESIS ATI (Unicam, UK) spectrometer.
1H NMR and 13C NMR spectra were recorded with
a Bruker Avance 300 spectrometer (Bruker, USA) op-
*Corresponding author, e-mail: potacek@chemi.muni.cz

J. Galeta et al./Chemical Papers 67 (1) 40–50 (2013)
41
Fig. 1. Two synthetic approaches leading to non-symmetrical allenyl azines IV.
Table 1. Collection of non-symmetrical allenyl azines IVa–IVax
Compound
R1
R
Yield/%
Reaction time/h
IVa
IVb
IVc
IVd
IVe
IVf
IVg
IVh
IVi
IVj
1-Adamantyl
TMS
H
H
H
69
86
87
77
88
65
77
56
83
91
83
87
90
76
86
79
84
86
89
87
87
82
83
90
95
63
83
83
81
76
74
78
46
65
86
81
76
90
75
82
76
85
73
70
72
82
71
83
81
82
24
3
1
0.5
8
6.5
1
24
1
1
8.5
1
1
5
2
2
2
2
2
2
2
2
2
2
2
1
2
2
2
2
2
2
5
4
1
6.5
3
2
1-Adamantyl
1-Adamantyl
1-Adamantyl
1-Adamantyl
1-Adamantyl
1-Adamantyl
2-Furyl
Me
Pyrrol
Morph
1-Adamantyl
Phenyl
H
Me
TMS
H
Me
TMS
H
H
Me
Et
H
Me
Et
H
Me
Et
1-Adamantyl
Phenyl
H
Me
Et
H
Me
Et
Morph
H
2-Furyl
2-Furyl
IVk
IVl
2-Thiophenyl
2-Thiophenyl
2-Thiophenyl
p-Me2N-Ph
p-MeO-Ph
p-MeO-Ph
p-MeO-Ph
p-Tolyl
p-Tolyl
p-Tolyl
Phenyl
Phenyl
IVm
IVn
IVo
IVp
IVq
IVr
IVs
IVt
IVu
IVv
IVw
IVx
IVy
IVz
IVaa
IVab
IVac
IVad
IVae
IVaf
IVag
IVah
IVai
IVaj
IVak
IVal
IVam
IVan
IVao
IVap
IVaq
IVar
IVas
IVat
IVau
IVav
IVaw
IVax
Phenyl
Phenyl
Phenyl
p-Cl-Ph
p-Cl-Ph
p-Cl-Ph
p-NO2-Ph
p-NO2-Ph
p-NO2-Ph
p-NO2-Ph
1-Naphthyl
1-Naphthyl
1-Naphthyl
9-Anthryl
9-Anthryl
9-Anthryl
Et
Bn
Et
Pr
iPr
Bn
Et
Pr
iPr
Me
TMS
H
Me
TMS
p-MeO-Ph
p-MeO-Ph
p-Tolyl
p-Tolyl
p-Tolyl
p-Tolyl
Phenyl
Phenyl
Phenyl
p-O2N-Ph
p-O2N-Ph
10
1
1
1
5
2
2
2
4.5
4
iPr
Bn
2
2
Pyrrol – pyrrolidinomethyl; Morph – morpholinomethyl.

42
J. Galeta et al./Chemical Papers 67 (1) 40–50 (2013)
Fig. 2. ORTEP representation of allenyl azine IVag shown at 50 % probability level (blue – N, red – O).
Table 2. Characterisation data of five allenyl azines IV
wi(calc.)/%
wi(found)/%
M.p.
Compound
Formula
Mr
C
H
N
◦C
IVq
C16H20N2O
C16H20N2
256.34
240.34
226.32
260.76
271.31
74.97
74.82
79.96
80.13
79.61
79.92
69.09
69.27
66.40
66.39
7.86
7.81
8.39
8.67
8.02
7.92
6.57
6.82
6.32
6.29
10.93
11.20
11.66
11.44
12.38
12.20
10.74
10.56
15.49
15.17
44–48
IVt
–
IVw
IVab
IVae
C15H18N2
–
–
C15H17ClN2
C15H17N3O2
75–78
erating at frequencies of 300.13 MHz (for 1H NMR)
and 75.47 MHz (for 13C NMR) with CDCl3 as sol-
vent. Tetramethylsilane (δ 0.00) or CDCl3 (δ 7.27)
served as internal standards for 1H NMR spectra,
and CDCl3 (δ 77.23) for 13C NMR spectra. MS
data were obtained on a Fisons Instruments TRIO
1000 spectrometer (Fisons Instruments, UK) at 70 eV
in the electron impact (EI) mode. Elemental analy-
ses were performed with a Perkin–Elmer CHN 2400
apparatus (Perkin–Elmer, USA). X-ray diffraction
data were collected on a Kuma KM-4 four-circle
CCD (Kuma Diffraction, Poland) diffractometer and
corrected for Lorentz and polarisation effects. The
structures were resolved by direct methods and re-
fined by full-matrix least-squares methods using the
SHELXTL program package (Bruker AXS, 1997). Hy-
drogen atoms were placed in calculated idealised po-
sitions.
General procedures for preparation of non-
symmetrical allenyl azines IV from hydrazones
II and III
A mixture of protected allenyl hydrazone III
(2 mmol) and paraformaldehyde (4 mmol, eq. CH2O)
in toluene (10 mL) was slowly added to a suspension
of NaH (72 mg, 3 mmol) in diethyl ether (10 mL)
at 5–10◦C. Next, the reaction mixture was stirred at
laboratory temperature, the solution was filtered and
the residue washed with diethyl ether (3 × 10 mL).
The combined organic phases were pre-concentrated
in a vacuum and the crude product purified by liq-
uid chromatography (Et2O) to give a colourless solid
IVa (370 mg, 69 %). Azine IVb with trimethylsilyl
(TMS) group was purified by vacuum distillation us-
ing a Kugelrohr apparatus (≈ 35 Pa, 60◦C) to give a
colourless viscous oil (358 mg, 86 %).

J. Galeta et al./Chemical Papers 67 (1) 40–50 (2013)
Table 3. Spectral data of newly prepared compounds
43
Compound
Spectral data
—
—
), 2849, 2897, 2926, 2967
—
IVa
IR, ν˜/cm−1: 1092, 1183, 1216, 1359, 1382, 1449, 1683, 1936 (
C
—
1H NMR (CDCl3), δ: 1.35 (s, 6H, 2 × CH3), 1.60–1.68 (m, 6H, Ad), 1.70–1.78 (m, 6H, Ad), 1.94 (bs, 3H, Ad), 4.77
2
2
—
—
—
—
—
—
—
—
(s, 2H, CH2), 6.96 (d, 1H, J = 13.5 Hz, N CH2), 7.38 (d, 1H, J = 13.5 Hz, N CH2), 7.73 (s, 1H, HC N)
13C NMR (CDCl3), δ: 27.6 (2 × CH3), 29.1 (CH, Ad), 36.7 (CH2, Ad), 36.8 (C, Ad), 40.8 (C), 43.1 (CH2, Ad),
—
—
—
—
— —
78.1 ( CH2), 118.4 ( C—Ad), 149.2 (N CH2), 171.6 (HC N), 207.6 ( C )
— —
—
—
—
—
MS, m/z (%): 270 (M+, 1), 255 (28), 135 (100), 107 (10)
1
—
IVb
IVc
H NMR (CDCl3), δ: 0.14 (s, 9H, Si—CH3), 1.32 (s, 6H, 2 × CH3), 4.48 (s, 2H, CH2), 6.96 (d, 1H, 2J = 13.5 Hz,
—
2
—
—
—
—
—
N
CH2), 7.38 (d, 1H, J = 13.5 Hz, N CH2), 7.65 (s, 1H, HC N)
—
13
—
—
—
—
—
—
C NMR (CDCl3), δ: 0.9 (Si—CH3), 26.4 (2 × CH3), 41.0 (C), 71.4 ( CH2), 101.8 ( C—Si), 149.6 (N CH2),
—
—
— —
C )
— —
170.5 (HC N), 209.6 (
IR, ν˜/cm−1: 1045, 1218, 1452, 1643, 1954 (
—
—
—
), 2850, 2907, 2968, 3020
—
C
1H NMR (CDCl3), δ: 1.26 (s, 6H, 2 × CH3), 1.65–1.82 (m, 12H, Ad), 2.04 (bs, 3H, Ad), 4.82 (d, 2H, 4J = 6.7 Hz,
4
—
—
—
—
—
CH2), 5.25 (t, 1H, J = 6.7 Hz, HC C), 7.53 (s, 1H, HC—Ad), 7.67 (s, 1H, HC N)
—
13C NMR (CDCl3), δ: 25.6 (2 × CH3), 28.1 (CH, Ad), 36.9 (CH2, Ad), 38.0 (C, Ad), 39.7 (C), 39.8 (CH2, Ad),
—
—
—
—
—
—
— —
77.7 ( CH2), 97.5 (HC C), 168.4 (HC—Ad), 171.0 (HC N), 207.1 ( C
)
— —
MS, m/z (%): 270 (M+, 56), 255 (30), 213 (16), 135 (100), 108 (70), 94 (43), 79 (42), 67 (30), 41 (20)
—
—
IVd
IVe
IR, ν˜/cm−1: 1046, 1218, 1452, 1642, 1953 (
C
), 2850, 2906, 2976, 3017
—
—
5
1H NMR (CDCl3), δ: 1.28 (s, 6H, 2 × CH3), 1.71 (t, 3H, J = 3.1 Hz, C—CH3), 1.76–1.82 (m, 12H, Ad), 2.07
—
—
5
—
—
—
—
(bs, 3H, Ad), 4.73 (q, J = 3.1 Hz, 2H, CH2), 7.53 (s, 1H, HC—Ad), 7.61 (s, 1H, HC N)
13
—
—
C NMR (CDCl3), δ: 15.4 ( C—CH3), 24.4 (2 × CH3), 28.1 (CH, Ad), 36.9 (CH2, Ad), 39.6 (C, Ad), 39.8 (CH2,
—
—
—
—
—
—
— —
Ad), 40.1 (C), 76.0 ( CH2), 103.5 ( C—CH3), 167.9 (HC—Ad), 170.6 (HC N), 206.5 ( C )
— —
MS, m/z (%): 284 (M+, 2), 149 (98), 135 (95), 123 (73), 108 (100), 93 (51), 79 (61), 67 (66), 55 (24), 41 (30)
IR, ν˜/cm−1: 1048, 1116, 1220, 1321, 1345, 1385, 1452, 1519, 1642, 1954 (
C
—
—
—
), 2796, 2851, 2907, 2970, 3019
—
1H NMR (CDCl3), δ: 1.30 (s, 6H, 2 × CH3), 1.70–1.71 (m, 4H, pyrrol.), 1.74–1.81 (m, 12H, Ad), 2.05 (bs, 3H, Ad),
—
—
2.49–2.53 (m, 4H, N—CH2), 3.07–3.12 (m, 2H, N—CH2), 4.85–5.02 (m, 2H, CH2), 7.48 (s, 1H, HC—Ad), 7.64
—
(s, 1H, HC N)
—
13C NMR (CDCl3), δ: 23.8 (2 × CH2), 24.8 (2 × CH3), 28.1 (CH, Ad), 36.9 (CH2, Ad), 39.7 (C, Ad), 39.8 (CH2, Ad),
—
—
—
—
—
—
—
40.3 (C), 54.2 (2 × CH2), 55.2 ( C—CH2), 78.1 ( CH2), 107.4 ( C—CH2), 168.0 (HC—Ad), 169.9 (HC N),
—
—
—
—
)
—
206.6 (
C
MS, m/z (%): 354 (M+, 1), 191 (100), 122 (92), 84 (90), 70 (22), 42 (17)
—
—
), 2763, 2808, 2849, 2904, 2965
—
IVf
IR, ν˜/cm−1: 1005, 1117, 1218, 1308, 1346, 1384, 1454, 1643, 1953 (
C
—
1H NMR (CDCl3), δ: 1.29 (s, 6H, 2 × CH3), 1.68–1.81 (m, 12H, Ad), 2.04 (bs, 3H, Ad), 2.41 (m, 4H, N—CH2), 2.93
5
5
—
—
—
—
(t, 2H, J = 2.3 Hz, C—CH2), 3.69 (m, 4H, O—CH2), 4.85 (t, 2H, J = 2.3 Hz, CH2), 7.52 (s, 1H, HC—Ad),
—
7.74 (s, 1H, HC N)
—
13C NMR (CDCl3), δ: 25.0 (2 × CH3), 28.1 (CH, Ad), 36.9 (CH2, Ad), 39.7 (C, Ad), 39.9 (CH2, Ad), 40.1 (C), 53.6
—
—
—
—
—
—
—
(N—CH2), 58.5 ( C—CH2), 67.1 (O—CH2), 77.3 ( CH2), 105.4 ( C—CH2), 168.8 (HC—Ad), 170.4 (HC N),
—
—
—
)
—
207.5 (
C
—
MS, m/z (%): 369 (M+, 1), 207 (100), 122 (62), 100 (89), 79 (24), 56 (22)
—
—
), 2850, 2901
—
IVg
IVh
IVi
IR, ν˜/cm−1: 1044, 1100, 1314, 1360, 1451, 1642, 1937 (
C
—
1H NMR (CDCl3), δ: 1.39 (s, 6H, 2 × CH3), 1.63–1.96 (m, 24H, Ad), 1.99 (bs, 3H, Ad), 2.08 (bs, 3H, Ad), 4.80 (s,
—
—
—
—
2H, CH2), 7.55 (s, 1H, HC—Ad), 7.73 (s, 1H, HC N)
13C NMR (CDCl3), δ: 27.8 (2 × CH3), 28.1 (CH, Ad), 29.2 (CH, Ad), 36.5 (C, Ad), 36.9 (2 × CH2, Ad), 39.8 (C,
—
—
—
—
—
Ad), 39.9 (CH2, Ad), 40.8 (C), 43.1 (CH2, Ad), 78.0 ( CH2), 118.7 ( C—Ad), 169.8 (HC—Ad), 170.0 (HC N),
—
—
—
)
—
207.8 (
C
—
MS, m/z (%): 404 (M+, 1), 389 (26), 269 (42), 228 (10), 135 (100)
IR, ν˜/cm−1: 1032, 1127, 1220, 1362, 1451, 1600, 1641, 1942 (
C
—
—
—
), 2849, 2907, 2971
—
1H NMR (CDCl3), δ: 1.35 (s, 6H, 2 × CH3), 1.70–1.85 (m, 12H, Ad), 2.10 (bs, 3H, Ad), 4.96 (s, 2H,
CH2),
—
—
—
—
7.22–7.39 (m, 5H, Ph), 7.48 (s, 1H, HC—Ad), 7.80 (s, 1H, HC N)
13C NMR (CDCl3), δ: 25.6 (2 × CH3), 28.0 (CH, Ad), 36.8 (CH2, Ad), 36.9 (C, Ad), 39.7 (CH2, Ad), 40.4 (C),
—
—
—
— —
C )
— —
77.6 ( CH2), 111.3 ( C–Ph), 126.9 (CH), 128.0 (2 × CH), 128.7 (2 × CH), 136.0 (C), 168.3 (HC—Ad), 170.3
—
—
(HC N), 208.2 (
—
MS, m/z (%): 346 (M+, 100), 305 (13), 291 (78), 189 (18), 135 (35), 83 (16)
IR, ν˜/cm−1: 1018, 1082, 1150, 1272, 1306, 1363, 1385, 1475, 1635, 1644, 1955 (
—
—
—
), 2868, 2931, 2971, 3120
—
C
4
4
1H NMR (CDCl3), δ: 1.27 (s, 6H, 2 × CH3), 4.81 (d, 2H, J = 6.7 Hz, CH2), 5.26 (t, 1H, J = 6.7 Hz, HC C),
—
—
—
—
6.48 (dd, 1H, 3J = 3.4 Hz, 3J = 1.8 Hz, Ar), 6.81 (d, 1H, 3J = 3.4 Hz, Ar), 7.54 (d, 1H, 3J = 1.8 Hz, Ar), 7.92 (s,
—
1H, HC N), 8.33 (s, 1H, HC—Ar)
—
13
—
— —
C )
— —
—
—
C NMR (CDCl3), δ: 25.7 (2 × CH3), 38.3 (C), 77.9 ( CH2), 97.3 (HC C), 112.2 (CH), 116.0 (CH), 145.6 (CH),
—
—
—
149.6 (C), 150.3 (HC—Ar), 171.3 (HC N), 207.1 (

44
J. Galeta et al./Chemical Papers 67 (1) 40–50 (2013)
Table 3. (continued)
Compound
Spectral data
—
—
), 2869, 2930, 2973, 3119
—
IVj
IR, ν˜/cm−1: 1017, 1083, 1109, 1150, 1274, 1372, 1456, 1479, 1636, 1952 (
C
—
5
1H NMR (CDCl3), δ: 1.27 (s, 6H, 2 × CH3), 1.68 (t, 3H, 5J = 3.0 Hz, C—CH3), 4.70 (q, 2H, J = 3.0 Hz, CH2),
—
—
—
—
6.49 (dd, 1H, 3J = 3.3 Hz, 3J = 1.7 Hz, Ar), 6.82 (d, 1H, 3J = 3.3 Hz, Ar), 7.55 (d, 1H, 3J = 1.7 Hz, Ar), 7.88 (s,
—
1H, HC N), 8.34 (s, 1H, HC—Ar)
—
13
—
—
—
—
—
—
C NMR (CDCl3), δ: 15.3 ( C—CH3), 24.4 (2 × CH3), 40.4 (C), 76.1 ( CH2), 103.4 ( C—CH3), 112.2 (CH),
—
—
— —
C )
— —
116.0 (CH), 145.6 (CH), 149.6 (C), 150.1 (HC—Ar), 171.2 (HC N), 206.4 (
—
—
—
), 2870, 2898, 2936, 2963,
—
IVk
IR, ν˜/cm−1: 1018, 1083, 1155, 1250, 1306, 1362, 1383, 1465, 1480, 1636, 1896, 1923 (
C
3108
1
H NMR (CDCl3), δ: 0.13 (s, 9H, Si—CH3), 1.34 (s, 6H, 2 × CH3), 4.47 (s, 2H, CH2), 6.50 (dd, 1H, 3J = 3.4 Hz,
—
—
3J = 1.8 Hz, Ar), 6.82 (d, 1H, 3J = 3.4 Hz, Ar), 7.55 (d, 1H, J = 1.8 Hz, Ar), 7.91 (s, 1H, HC N), 8.34 (s, 1H,
3
—
—
HC—Ar)
13
—
— —
C )
— —
—
—
C NMR (CDCl3), δ: 0.9 (Si—CH3), 26.5 (2 × CH3), 41.0 (C), 71.4 ( CH2), 101.8 ( C—Si), 112.2 (CH), 115.9
—
—
—
(CH), 145.5 (CH), 149.7 (C), 150.0 (HC—Ar), 172.2 (HC N), 209.6 (
—
—
—
C
—
IVl
IR, ν˜/cm−1: 1046, 1143, 1213, 1363, 1426, 1457, 1583, 1614, 1630, 1954 (
), 2866, 2927, 2968, 3077
1H NMR (CDCl3), δ: 1.30 (s, 6H, 2 × CH3), 4.85 (d, 2H, J = 6.7 Hz, CH2), 5.29 (t, 1H, J = 6.7 Hz, HC C),
4
4
—
—
—
—
7.09 (dd, 1H, 3J = 5.0 Hz, 3J = 3.7 Hz, Ar), 7.37 (d, 1H, 3J = 3.7 Hz, Ar), 7.44 (d, 1H, 3J = 5.0 Hz, Ar), 7.89 (s,
—
1H, HC N), 8.64 (s, 1H, HC—Ar)
—
13
—
— —
C )
— —
—
—
C NMR (CDCl3), δ: 25.7 (2 × CH3), 38.3 (C), 77.9 ( CH2), 97.4 (HC C), 127.8 (CH), 129.8 (CH), 132.2 (CH),
—
—
—
139.0 (C), 155.3 (HC—Ar), 170.6 (HC N), 207.2 (
—
—
—
—
IVm
IR, ν˜/cm−1: 1046, 1108, 1214, 1427, 1454, 1581, 1630, 1952 (
C
), 2867, 2927, 2972
—
1H NMR (CDCl3), δ: 1.29 (s, 6H, 2 × CH3), 1.70 (t, 3H, 5J = 3.1 Hz,
C—CH3), 4.71 (q, 2H, 5J = 3.1 Hz,
—
—
—
—
—
CH2), 7.04–7.10 (m, 1H, Ar), 7.34–7.38 (m, 1H, Ar), 7.40–7.44 (m, 1H, Ar), 7.82 (s, 1H, HC N), 8.63 (s, 1H,
HC—Ar)
13
—
—
—
—
—
—
C NMR (CDCl3), δ: 15.4 ( C—CH3), 24.5 (2 × CH3), 40.4 (C), 76.1 ( CH2), 103.4 ( C—CH3), 127.8 (CH),
—
—
— —
C )
— —
129.7 (CH), 132.1 (CH), 139.1 (C), 155.1 (HC—Ar), 170.4 (HC N), 206.5 (
MS, m/z (%): 232 (M+, 1), 220 (100), 192 (35), 147 (24), 110 (46), 96 (32), 70 (29)
—
—
), 2869, 2897, 2933, 2965,
—
IVn
IVo
IVp
IVq
IVr
IR, ν˜/cm−1: 1046, 1173, 1213, 1250, 1362, 1383, 1427, 1462, 1583, 1632, 1897, 1922 (
C
—
3058, 3076
1
H NMR (CDCl3), δ: 0.16 (s, 9H, Si—CH3), 1.37 (s, 6H, 2 × CH3), 4.49 (s, 2H, CH2), 7.09 (dd, 1H, 3J = 4.9 Hz,
—
—
3
3J = 3.7 Hz, Ar), 7.38 (d, 1H, 3J = 3.7 Hz, Ar), 7.44 (d, 1H, J = 4.9 Hz, Ar), 7.87 (s, 1H, HC N), 8.64 (s, 1H,
—
—
HC—Ar)
13
—
— —
C )
— —
—
—
C NMR (CDCl3), δ: 0.8 (Si—CH3), 26.4 (2 × CH3), 40.9 (C), 71.2 ( CH2), 101.6 ( C—Si), 127.6 (CH), 129.5
—
—
—
(CH), 131.9 (CH), 139.0 (C), 154.8 (HC—Ar), 171.3 (HC N), 209.4 (
IR, ν˜/cm−1: 1180, 1366, 1527, 1610, 1953 (
—
—
—
), 2809, 2866, 2923, 2977, 3201
—
C
4
1H NMR (CDCl3), δ: 1.29 (s, 6H, 2 × CH3), 2.98 (s, 6H, N—CH3), 4.82 (d, 2H, J = 6.6 Hz, CH2), 5.30 (t, 1H,
—
—
4
3
J = 6.6 Hz, HC C), 6.66 (d, 2H, 3J = 8.8 Hz, Ar), 7.62 (d, 2H, J = 8.8 Hz, Ar), 7.88 (s, 1H, HC N), 8.41 (s,
—
—
—
—
1H, HC—Ar)
13
—
— —
C )
— —
—
—
C NMR (CDCl3), δ: 25.8 (2 × CH3), 38.1 (C), 40.2 (N—CH3), 77.7 ( CH2), 97.6 (HC C), 111.7 (CH), 121.7
—
—
(C), 130.1 (CH), 152.4 (C), 161.8 (HC—Ar), 168.6 (HC N), 207.1 (
—
MS, m/z (%): 255 (M+, 16), 254 (24), 240 (35), 146 (100), 94 (44)
IR, ν˜/cm−1: 1032, 1168, 1252, 1512, 1608, 1633, 1954 (
C
), 2837, 2868, 2931, 2966, 3035, 3072
—
—
—
—
4
1H NMR (CDCl3), δ: 1.31 (s, 6H, 2 × CH3), 3.83 (s, 3H, O—CH3), 4.84 (d, 2H, J = 6.7 Hz, CH2), 5.30 (t, 1H,
—
—
4
3
J = 6.7 Hz, HC C), 6.92 (d, 2H, 3J = 8.9 Hz, Ar), 7.71 (d, 2H, J = 8.9 Hz, Ar), 7.88 (s, 1H, HC N), 8.44 (s,
—
—
—
—
1H, HC—Ar)
13
—
— —
C )
— —
—
—
C NMR (CDCl3), δ: 25.8 (2 × CH3), 38.2 (C), 55.5 (O—CH3), 77.8 ( CH2), 97.6 (HC C), 114.4 (CH), 126.9
—
—
—
(C), 130.2 (CH), 160.9 (HC—Ar), 162.2 (C), 169.8 (HC N), 207.2 (
MS, m/z (%): 243 (M+ + 1, 45), 241 (67), 227 (100), 211 (25), 134 (50), 108 (56), 94 (58)
IR, ν˜/cm−1: 1030, 1254, 1512, 1608, 1628, 1954 (
C
—
—
—
), 2837, 2866, 2927, 2978, 3045, 3076
—
5
1H NMR (CDCl3), δ: 1.30 (s, 6H, 2 × CH3), 1.71 (t, 3H, J = 3.0 Hz, C—CH3), 3.84 (s, 3H, O—CH3), 4.72 (q,
—
—
5
3
2H, J = 3.0 Hz, CH2), 6.93 (d, 2H, 3J = 8.9 Hz, Ar), 7.71 (d, 2H, J = 8.9 Hz, Ar), 7.81 (s, 1H, HC N), 8.44
—
—
—
—
(s, 1H, HC—Ar)
13
—
—
—
— —
C )
— —
—
—
C NMR (CDCl3), δ: 15.5 ( C—CH3), 24.5 (2 × CH3), 40.4 (C), 55.5 (O—CH3), 76.1 ( CH2), 103.6 ( C—
—
—
—
CH3), 114.4 (CH), 127.0 (C), 130.2 (CH), 160.7 (HC—Ar), 162.2 (C), 169.6 (HC N), 206.6 (
MS, m/z (%): 257 (M+ + 1, 25), 255 (27), 241 (100), 225 (12), 211 (25), 134 (27), 122 (40), 108 (65)
IR, ν˜/cm−1: 1032, 1168, 1252, 1512, 1608, 1633, 1952 (
C
—
—
—
), 2839, 2872, 2931, 2968, 3035, 3072
—
1H NMR (CDCl3), δ: 1.00 (t, 3H, 3J = 7.3 Hz, H3C—CH2), 1.31 (s, 6H, 2 × CH3), 1.90–2.03 (m, 2H, H3C—CH2),
5
3.84 (s, 3H, O—CH3), 4.85 (t, 2H, J = 4.0 Hz, CH2), 6.93 (d, 2H, 3J = 8.9 Hz, Ar), 7.71 (d, 2H, 3J = 8.9 Hz,
—
—
—
Ar), 7.81 (s, 1H, HC N), 8.44 (s, 1H, HC—Ar)
—
13
—
C NMR (CDCl3), δ: 12.7 (H3C—CH2), 20.5 (H3C—CH2), 24.7 (2 × CH3), 40.6 (C), 55.5 (O—CH3), 78.9 ( CH2),
—
—
—
—
—
— —
110.7 ( C—Et), 114.4 (CH), 127.0 (C), 130.2 (CH), 160.7 (HC—Ar), 162.1 (C), 169.8 (HC N), 205.9 ( C
)
— —
MS, m/z (%): 271 (M+ + 1, 72), 255 (100), 241 (36), 227 (16), 134 (46), 122 (83), 107 (36)

J. Galeta et al./Chemical Papers 67 (1) 40–50 (2013)
45
Table 3. (continued)
Compound
Spectral data
—
—
), 2868, 2929, 2968, 3026, 3051
—
IVs
IVt
IVu
IR, ν˜/cm−1: 1109, 1176, 1306, 1458, 1635, 1954 (
C
—
1H NMR (CDCl3), δ: 1.31 (s, 6H, 2 × CH3), 2.38 (s, 3H, Ph—CH3), 4.84 (d, 2H, 4J = 6.7 Hz, CH2), 5.30 (t,
—
—
4
3
3
—
—
—
—
1H, J = 6.7 Hz, HC C), 7.21 (d, 2H, J = 8.1 Hz, Ar), 7.65 (d, 2H, J = 8.1 Hz, Ar), 7.88 (s, 1H, HC N), 8.45
(s, 1H, HC—Ar)
13
—
—
—
C NMR (CDCl3), δ: 21.8 (Ph—CH3), 25.8 (2 × CH3), 38.3 (C), 77.9 ( CH2), 97.5 (HC C), 128.6 (CH), 129.7
—
—
—
—
—
—
C
—
(CH), 131.5 (C), 141.6 (C), 161.3 (HC—Ar), 170.0 (HC N), 207.2 (
)
MS, m/z (%): 227 (M+ + 1, 100), 211 (72), 118 (13), 108 (37), 94 (39)
IR, ν˜/cm−1: 1109, 1176, 1306, 1454, 1635, 1954 (
C
), 2868, 2928, 2971, 3026, 3049
—
—
—
—
1H NMR (CDCl3), δ: 1.30 (s, 6H, 2 × CH3), 1.71 (t, 3H, J = 3.0 Hz, C—CH3), 2.38 (s, 3H, Ph—CH3), 4.72
5
—
—
5
3
(q, 2H, J = 3.0 Hz, CH2), 7.21 (d, 2H, 3J = 8.1 Hz, Ar), 7.66 (d, 2H, J = 8.1 Hz, Ar), 7.82 (s, 1H, HC N),
—
—
—
—
8.45 (s, 1H, HC—Ar)
13
—
—
—
—
—
—
C NMR (CDCl3), δ: 15.5 ( C—CH3), 21.8 (Ph—CH3), 24.5 (2 × CH3), 40.4 (C), 76.1 ( CH2), 103.5 ( C—
—
— —
C )
— —
CH3), 128.5 (CH), 129.7 (CH), 131.5 (C), 141.6 (C), 161.0 (HC—Ar), 169.8 (HC N), 206.5 (
—
MS, m/z (%): 240 (M+, 20), 225 (100), 122 (38), 108 (100), 91 (85)
IR, ν˜/cm−1: 1176, 1306, 1458, 1635, 1950 (
C
—
—
—
), 2873, 2931, 2970, 3026, 3049
—
1H NMR (CDCl3), δ: 1.00 (t, 3H, 3J = 7.4 Hz, H3C—CH2), 1.31 (s, 6H, 2 × CH3), 1.89–2.03 (m, 2H, H3C—CH2),
5
2.38 (s, 3H, Ph—CH3), 4.85 (t, 2H, J = 4.0 Hz, CH2), 7.21 (d, 2H, 3J = 7.9 Hz, Ar), 7.65 (d, 2H, 3J = 7.9 Hz,
—
—
—
Ar), 7.81 (s, 1H, HC N), 8.45 (s, 1H, HC—Ar)
—
13C NMR (CDCl3), δ: 12.7 (H3C—CH2), 20.5 (H3C—CH2), 21.8 (Ph—CH3), 24.7 (2 × CH3), 40.6 (C), 78.9
—
—
—
—
CH2), 110.7 ( C—Et), 128.6 (CH), 129.7 (CH), 131.6 (C), 141.6 (C), 161.0 (HC—Ar), 170.1 (HC N), 205.9
—
—
—
(
(
—
—
)
—
C
MS, m/z (%): 255 (M+ + 1, 84), 239 (100), 122 (91), 109 (46), 91 (63)
—
—
), 2868, 2929, 2968, 3028, 3060
—
IVv
IVw
IVx
IR, ν˜/cm−1: 1448, 1635, 1954 (
C
—
1
4
4
—
—
—
H NMR (CDCl3), δ: 1.31 (s, 6H, 2 × CH3), 4.84 (d, 2H, J = 6.6 Hz, CH2), 5.30 (t, 1H, J = 6.6 Hz, HC C),
—
—
7.35–7.47 (m, 3H, Ph), 7.72–7.82 (m, 2H, Ph), 7.88 (s, 1H, HC N), 8.47 (s, 1H, HC—Ph)
—
13
—
—
—
C NMR (CDCl3), δ: 25.8 (2 × CH3), 38.3 (C), 77.9 ( CH2), 97.5 (HC C), 128.6 (2 × CH), 128.9 (2 × CH),
—
—
— —
C )
— —
131.2 (CH), 134.2 (C), 161.1 (HC—Ph), 170.3 (HC N), 207.2 (
—
MS, m/z (%): 213 (M+ + 1, 100), 197 (35), 77 (48)
IR, ν˜/cm−1: 1109, 1448, 1637, 1955 (
C
—
—
—
), 2870, 2929, 3026, 3062
—
1H NMR (CDCl3), δ: 1.31 (s, 6H, 2 × CH3), 1.72 (t, 3H, 5J = 3.0 Hz,
C—CH3), 4.73 (q, 2H, 5J = 3.0 Hz,
—
—
—
—
—
—
CH2), 7.38–7.46 (m, 3H, Ph), 7.73–7.80 (m, 2H, Ph), 7.82 (s, 1H, HC N), 8.47 (s, 1H, HC—Ph)
13
—
—
—
—
— —
C )
— —
C NMR (CDCl3), δ: 15.5 ( C—CH3), 24.5 (2 × CH3), 40.4 (C), 76.1 ( CH2), 103.5 ( C—CH3), 128.6 (2 × CH),
—
—
—
—
128.9 (2 × CH), 131.2 (CH), 134.3 (C), 160.9 (HC—Ph), 170.0 (HC N), 206.5 (
MS, m/z (%): 225 (M+ + 1, 38), 211 (88), 122 (42), 108 (74), 77 (100)
IR, ν˜/cm−1: 1448, 1635, 1952 (
C
—
—
—
), 2870, 2933, 2968, 3062
—
1H NMR (CDCl3), δ: 1.00 (t, 3H, 3J = 7.4 Hz, H3C—CH2), 1.31 (s, 6H, 2 × CH3), 1.90–2.03 (m, 2H, H3C—CH2),
5
—
—
—
—
4.85 (t, 2H, J = 4.0 Hz, CH2), 7.34–7.47 (m, 3H, Ph), 7.71–7.79 (m, 2H, Ph), 7.81 (s, 1H, HC N), 8.47 (s, 1H,
HC—Ph)
13
—
—
—
)
C NMR (CDCl3), δ: 12.7 (H3C—CH2), 20.5 (H3C—CH2), 24.7 (2 × CH3), 40.7 (C), 79.0 ( CH2), 110.7 ( C—
—
—
—
— —
C
— —
Et), 128.6 (2 × CH), 128.9 (2 × CH), 131.2 (CH), 134.3 (C), 160.9 (HC—Ph), 170.4 (HC N), 205.9 (
MS, m/z (%): 240 (M+, 14), 225 (78), 211 (34), 122 (58), 77 (100)
—
—
), 2849, 2907, 2971
—
IVy
IR, ν˜/cm−1: 1032, 1127, 1220, 1362, 1451, 1600, 1641, 1942 (
C
—
1H NMR (CDCl3), δ: 1.35 (s, 6H, 2 × CH3), 1.70–1.85 (m, 12H, Ad), 2.10 (bs, 3H, Ad), 4.96 (s, 2H,
CH2),
—
—
—
7.22–7.39 (m, 5H, Ph), 7.48 (s, 1H, HC—Ad), 7.80 (s, 1H, HC N)
—
13C NMR (CDCl3), δ: 25.6 (2 × CH3), 28.0 (CH, Ad), 36.8 (CH2, Ad), 36.9 (C, Ad), 39.7 (CH2, Ad), 40.4 (C),
—
—
—
—
— —
C )
— —
77.6 ( CH2), 111.6 ( C—Ad), 126.9 (CH), 128.0 (2 × CH), 128.7 (2 × CH), 134.2 (C), 168.3 (HC—Ad), 170.3
—
(HC N), 208.2 (
—
MS, m/z (%): 346 (M+, 100), 305 (13), 291 (78), 189 (18), 135 (35), 83 (16)
—
—
IVz
IR, ν˜/cm−1: 1472, 1482, 1609, 1625, 1927 (
C
), 2932, 3037, 3057
—
—
—
1
H NMR (CDCl3), δ: 1.33 (s, 6H, 2 × CH3), 4.93 (s, 2H, CH2), 7.11–7.25 (m, 6H, Ph), 7.31–7.33 (m, 2H, Ph),
—
—
—
7.67–7.70 (m, 2H, Ph), 7.96 (s, 1H, HC N), 8.38 (s, 1H, HC—Ph)
13
—
—
—
—
C NMR (CDCl3), δ: 25.6 (2 × CH3), 40.6 (C), 77.7 ( CH2), 116.6 ( C—Ph), 126.9 (2 × CH), 128.0 (2 × CH),
—
128.3 (2 × CH), 128.6 (2 × CH), 130.9 (CH), 132.8 (CH), 134.0 (C), 135.9 (C), 160.6 (HC—Ph), 170.4 (HC N),
—
—
—
)
—
208.2 (
C
—
—
—
—
—
IVaa
IR, ν˜/cm−1: 1092, 1491, 1635, 1954 (
C
), 2868, 2929, 2970, 3030, 3055
4
4
1H NMR (CDCl3), δ: 1.31 (s, 6H, 2 × CH3), 4.85 (d, 2H, J = 6.6 Hz, CH2), 5.29 (t, 1H, J = 6.6 Hz, HC C),
—
—
—
—
3
7.39 (d, 2H, 3J = 8.3 Hz, Ar), 7.70 (d, 2H, J = 8.3 Hz, Ar), 7.87 (s, 1H, HC N), 8.43 (s, 1H, HC—Ar)
—
—
13
—
—
—
C NMR (CDCl3), δ: 25.7 (2 × CH3), 38.3 (C), 78.0 ( CH2), 97.4 (HC C), 129.3 (CH), 129.7 (CH), 132.7 (C),
—
—
—
—
—
C
—
—
137.2 (C), 159.8 (HC—Ar), 170.7 (HC N), 207.2 (
)
MS, m/z (%): 247 (M+, 16), 245 (20), 231 (21), 139 (28), 135 (26), 111 (61), 108 (95), 94 (100)

46
J. Galeta et al./Chemical Papers 67 (1) 40–50 (2013)
Table 3. (continued)
Compound
Spectral data
—
—
), 2868, 2931, 2974, 3029, 3051
—
IVab
IR, ν˜/cm−1: 1092, 1490, 1635, 1954 (
C
—
1H NMR (CDCl3), δ: 1.30 (s, 6H, 2 × CH3), 1.71 (t, 3H, 5J = 3.0 Hz,
C—CH3), 4.73 (q, 2H, 5J = 3.0 Hz,
—
—
CH2), 7.39 (d, 2H, 3J = 8.4 Hz, Ar), 7.70 (d, 2H, J = 8.4 Hz, Ar), 7.81 (s, 1H, HC N), 8.43 (s, 1H, HC—Ar)
3
—
—
—
—
13
—
—
—
—
C NMR (CDCl3), δ: 15.4 ( C—CH3), 24.4 (2 × CH3), 40.5 (C), 76.2 ( CH2), 103.4 ( C—CH3), 129.3 (CH),
—
—
—
—
— —
C )
— —
129.7 (CH), 132.8 (C), 137.2 (C), 159.6 (HC—Ar), 170.5 (HC N), 206.6 (
MS, m/z (%): 261 (M+, 100), 259 (22), 245 (76), 138 (24), 122 (62), 108 (100), 93 (36)
—
—
), 2872, 2931, 2970, 3030, 3051
—
IVac
IR, ν˜/cm−1: 1090, 1491, 1635, 1950 (
C
—
1H NMR (CDCl3), δ: 1.00 (t, 3H, 3J = 7.3 Hz, H3C—CH2), 1.31 (s, 6H, 2 × CH3), 1.89–2.02 (m, 2H, H3C—CH2),
5
3
4.86 (t, 2H, J = 4.0 Hz, CH2), 7.39 (d, 2H, 3J = 8.4 Hz, Ar), 7.70 (d, 2H, J = 8.4 Hz, Ar), 7.80 (s, 1H, HC N),
—
—
—
—
8.43 (s, 1H, HC—Ar)
13
—
— —
C )
— —
—
—
C NMR (CDCl3), δ: 12.7 (H3C—CH2), 20.5 (H3C—CH2), 24.7 (2 × CH3), 40.7 (C), 79.0 ( CH2), 110.6 ( C—
—
—
Et), 129.3 (CH), 129.7 (CH), 132.8 (C), 137.2 (C), 159.6 (HC—Ar), 170.8 (HC N), 205.9 (
—
MS, m/z (%): 275 (M+, 32), 248 (11), 165 (100), 138 (46), 111 (63), 89 (55)
—
—
), 2867, 2931, 2971, 3043, 3092, 3129
—
IVad
IVae
IVaf
IR, ν˜/cm−1: 1108, 1340, 1518, 1598, 1634, 1950 (
C
—
4
4
1H NMR (CDCl3), δ: 1.32 (s, 6H, 2 × CH3), 4.87 (d, 2H, J = 6.6 Hz, CH2), 5.29 (t, 1H, J = 6.6 Hz, HC C),
—
—
—
—
7.89 (s, 1H, HC N), 7.93 (d, 2H, 3J = 8.9 Hz, Ar), 8.27 (d, 2H, 3J = 8.9 Hz, Ar), 8.50 (s, 1H, HC—Ar)
—
—
13
—
—
—
—
—
C NMR (CDCl3), δ: 25.7 (2 × CH3), 38.5 (C), 78.1 ( CH2), 97.2 (HC C), 124.2 (CH), 129.1 (CH), 140.1 (C),
—
—
—
—
C
—
149.3 (C), 158.3 (HC—Ar), 171.6 (HC N), 207.3 (
)
MS, m/z (%): 256 (M+, 38), 242 (80), 195 (20), 108 (76), 94 (100), 79 (64)
IR, ν˜/cm−1: 1107, 1343, 1520, 1602, 1631, 1951 (
C
), 2865, 2927, 2971, 3051, 3081, 3108
—
—
—
—
—
1H NMR (CDCl3), δ: 1.32 (s, 6H, 2 × CH3), 1.72 (t, 3H, 5J = 3.0 Hz,
C—CH3), 4.74 (q, 2H, 5J = 3.0 Hz,
—
3
CH2), 7.83 (s, 1H, HC N), 7.93 (d, 2H, J = 8.8 Hz, Ar), 8.27 (d, 2H, 3J = 8.8 Hz, Ar), 8.50 (s, 1H, HC—Ar)
—
—
—
—
13
—
—
—
— —
C )
— —
—
—
C NMR (CDCl3), δ: 15.4 ( C—CH3), 24.3 (2 × CH3), 40.6 (C), 76.3 ( CH2), 103.2 ( C—CH3), 124.1 (CH),
—
—
—
129.1 (CH), 140.1 (C), 149.3 (C), 158.1 (HC—Ar), 171.4 (HC N), 206.5 (
MS, m/z (%): 271 (M+, 4), 270 (19), 256 (100), 210 (33), 122 (55), 108 (58)
IR, ν˜/cm−1: 1103, 1342, 1521, 1601, 1633, 1949 (
C
—
—
), 2856, 2871, 2931, 2969, 3046, 3103
—
—
1H NMR (CDCl3), δ: 1.01 (t, 3H, 3J = 7.3 Hz, H3C—CH2), 1.32 (s, 6H, 2 × CH3), 1.89–2.03 (m, 2H, H3C—CH2),
5
4.87 (t, 2H, J = 4.0 Hz, CH2), 7.83 (s, 1H, HC N), 7.93 (d, 2H, 3J = 8.6 Hz, Ar), 8.27 (d, 2H, 3J = 8.6 Hz,
—
—
—
—
Ar), 8.50 (s, 1H, HC—Ar)
13
—
— —
C )
— —
—
—
C NMR (CDCl3), δ: 12.7 (H3C—CH2), 20.5 (H3C—CH2), 24.6 (2 × CH3), 40.8 (C), 79.1 ( CH2), 110.4 ( C—
—
—
—
Et), 124.1 (CH), 129.1 (CH), 140.1 (C), 149.3 (C), 158.1 (HC—Ar), 171.7 (HC N), 205.9 (
MS, m/z (%): 285 (M+, 3), 284 (10), 270 (100), 256 (33), 224 (23), 136 (25), 122 (66), 107 (42)
1
—
—
—
IVag
IVah
H NMR (CDCl3), δ: 1.36 (s, 6H, 2 × CH3), 2.39–2.47 (m, 4H, N—CH2), 2.96–3.00 (m, 2H, C—CH2), 3.61–3.68
—
(m, 4H, O—CH2), 4.84–4.88 (m, 2H, CH2), 7.93 (d, 2H, J = 8.1 Hz, Ar), 7.96 (s, 1H, HC N), 8.28 (d, 2H, 3J
3
—
—
= 8.1 Hz, Ar), 8.50 (s, 1H, HC—Ar)
13
—
—
—
—
C NMR (CDCl3), δ: 24.9 (2 × CH3), 40.2 (C), 53.6 (N—CH2), 58.7 ( C—CH2), 67.2 (O—CH2), 77.5 ( CH2),
—
—
—
—
— —
105.3 ( C—CH2), 124.2 (CH), 129.0 (CH), 140.2 (C), 149.3 (C), 157.8 (HC—Ar), 172.5 (HC N), 207.6 ( C )
— —
IR, ν˜/cm−1: 1240, 1319, 1338, 1464, 1510, 1578, 1633, 1954 (
C
), 2868, 2927, 2970, 3053
—
—
—
—
—
1H NMR (CDCl3), δ: 1.44 (s, 6H, 2 × CH3), 4.94 (d, 2H, J = 6.8 Hz, CH2), 5.43 (t, 1H, J = 6.8 Hz, HC C),
4
4
—
—
—
—
—
7.47–7.67 (m, 3H, Ar), 7.84–8.00 (m, 2H, Ar), 8.00–8.09 (m, 1H, Ar), 8.10 (s, 1H, HC N), 8.85–8.97 (m, 1H, Ar),
9.21 (s, 1H, HC—Ar)
13
—
—
—
—
C NMR (CDCl3), δ: 25.8 (2 × CH3), 38.3 (C), 77.9 ( CH2), 97.5 (HC C), 124.7 (CH), 125.3 (CH), 126.3 (CH),
—
—
127.3 (CH), 128.8 (CH), 129.1 (CH), 129.7 (C), 131.5 (C), 131.7 (CH), 134.0 (C), 160.9 (HC—Ar), 170.3 (HC N),
—
—
)
—
207.2 (
C
—
MS, m/z (%): 262 (M+, 24), 247 (71), 234 (17), 192 (30), 153 (75), 139 (34), 127 (100), 108 (73), 94 (96), 79 (47),
67 (65), 53 (41), 41 (54)
—
—
), 2868, 2927, 2972, 3045
—
IVai
IR, ν˜/cm−1: 1109, 1240, 1317, 1338, 1371, 1456, 1512, 1576, 1633, 1951 (
C
—
1H NMR (CDCl3), δ: 1.36 (s, 6H, 2 × CH3), 1.75 (t, 3H, 5J = 3.1 Hz,
C—CH3), 4.74 (q, 2H, 5J = 3.1 Hz,
—
—
—
—
—
—
CH2), 7.45–7.65 (m, 3H, Ar), 7.81–7.94 (m, 2H, Ar), 7.95 (s, 1H, HC N), 7.95–8.02 (m, 1H, Ar), 8.78–8.89 (m,
1H, Ar), 9.14 (s, 1H, HC—Ar)
13
—
—
—
—
C NMR (CDCl3), δ: 15.5 ( C—CH3), 24.5 (2 × CH3), 40.5 (C), 76.2 ( CH2), 103.6 ( C—CH3), 124.8 (CH),
—
—
125.5 (CH), 126.3 (CH), 127.4 (CH), 128.9 (CH), 129.1 (CH), 129.8 (C), 131.6 (C), 131.7 (CH), 134.1 (C), 160.7
—
— —
C )
— —
(HC—Ar), 170.3 (HC N), 206.6 (
—
MS, m/z (%): 277 (M+ + 1, 30), 261 (35), 245 (31), 229 (39), 149 (17), 122 (87), 108 (100), 95 (27), 79 (24), 67
(50), 55 (32), 41 (25)
IR, ν˜/cm−1: 1022, 1173, 1214, 1249, 1315, 1339, 1362, 1383, 1406, 1461, 1511, 1577, 1633, 1896, 1924 (
C
—
—
—
), 2898,
—
IVaj
2932, 2965, 3053
1
—
H NMR (CDCl3), δ: 0.24 (s, 9H, Si—CH3), 1.48 (s, 6H, 2 × CH3), 4.56 (s, 2H, CH2), 7.50–7.67 (m, 3H, Ar),
—
7.87–7.99 (m, 2H, Ar), 8.00–8.04 (m, 1H, Ar), 8.05 (s, 1H, HC N), 8.89 (d, 1H, 3J = 8.4 Hz, Ar), 9.20 (s, 1H,
—
—
HC—Ar)
13
—
—
—
C NMR (CDCl3), δ: 1.0 (Si—CH3), 26.6 (2 × CH3), 41.1 (C), 71.5 ( CH2), 102.0 ( C—Si), 124.8 (CH), 125.5
—
(CH), 126.3 (CH), 127.4 (CH), 128.9 (CH), 129.1 (CH), 130.0 (C), 131.7 (CH), 134.1 (C), 160.6 (HC—Ar), 171.4
—
— —
C )
— —
(HC N), 209.6 (
—

J. Galeta et al./Chemical Papers 67 (1) 40–50 (2013)
47
Table 3. (continued)
Compound
Spectral data
IR, ν˜/cm−1: 1159, 1257, 1444, 1454, 1520, 1632, 1954 (
C
), 2867, 2929, 2970, 3051
—
—
—
—
IVak
—
4
4
1H NMR (CDCl3), δ: 1.45 (s, 6H, 2 × CH3), 4.94 (d, 2H, J = 6.6 Hz, CH2), 5.45 (t, 1H, J = 6.6 Hz, HC C),
—
—
—
—
—
7.45–7.65 (m, 4H, Ant), 7.98–8.10 (m, 2H, Ant), 8.13 (s, 1H, HC N), 8.53 (s, 1H, Ant), 8.64–8.75 (m, 2H, Ant),
9.72 (s, 1H, HC—Ant)
13
—
—
—
C NMR (CDCl3), δ: 25.9 (2 × CH3), 38.5 (C), 78.0 ( CH2), 97.6 (HC C), 125.4 (2 × CH), 125.6 (2 × CH),
—
—
—
— —
C )
— —
127.1 (2 × CH), 129.1 (2 × CH), 130.5 (CH), 130.7 (C), 131.5 (C), 160.7 (HC—Ant), 170.9 (HC N), 207.3 (
MS, m/z (%): 312 (M+, 64), 297 (27), 203 (100), 176 (27), 108 (15), 94 (90), 79 (18), 67 (14), 53 (14), 41 (22)
—
—
—
IVal
IR, ν˜/cm−1: 1109, 1215, 1444, 1632, 1952 (
C
), 2868, 2927, 2974, 3051, 3082
—
—
1H NMR (CDCl3), δ: 1.42 (s, 6H, 2 × CH3), 1.81 (t, 3H, 5J = 3.0 Hz,
C—CH3), 4.77 (q, 2H, 5J = 3.0 Hz,
—
—
—
—
—
CH2), 7.45–7.65 (m, 4H, Ant), 8.00–8.04 (m, 1H, Ant), 8.05 (s, 1H, HC N), 8.05–8.08 (m, 1H, Ant), 8.55 (s, 1H,
Ant), 8.64–8.71 (m, 2H, Ant), 9.71 (s, 1H, HC—Ant)
13
—
—
—
—
C NMR (CDCl3), δ: 15.6 ( C—CH3), 24.6 (2 × CH3), 40.6 (C), 76.2 ( CH2), 103.6 ( C—CH3), 125.4 (2 × CH),
—
—
—
—
125.6 (2 × CH), 127.2 (2 × CH), 129.2 (2 × CH), 130.5 (CH), 130.8 (C), 131.6 (C), 160.1 (HC—Ant), 170.7 (HC N),
—
—
)
—
206.6 (
C
—
MS, m/z (%): 327 (M+ + 1, 19), 312 (18), 203 (100), 176 (32), 108 (58), 67 (10)
IR, ν˜/cm−1: 1021, 1160, 1249, 1306, 1362, 1444, 1519, 1632, 1896, 1924 (
C
), 2869, 2898, 2930, 2965, 3029, 3052,
—
—
—
—
IVam
3082
1
—
H NMR (CDCl3), δ: 0.28 (s, 9H, Si—CH3), 1.52 (s, 6H, 2 × CH3), 4.58 (s, 2H, CH2), 7.49–7.54 (m, 2H, Ant),
—
3
—
—
7.55–7.61 (m, 2H, Ant), 8.04 (d, 2H, J = 8.3 Hz, Ant), 8.12 (s, 1H, HC N), 8.53 (bs, 1H, Ant), 8.65–8.69 (m, 2H,
Ant), 9.71 (s, 1H, HC—Ant)
13
—
—
—
C NMR (CDCl3), δ: 1.1 (Si—CH3), 26.6 (2 × CH3), 41.3 (C), 71.5 ( CH2), 102.0 ( C—Si), 125.4 (2 × CH),
—
125.5 (2 × CH), 127.1 (2 × CH), 129.1 (2 × CH), 130.3 (CH), 130.7 (C), 131.5 (C), 160.2 (HC—Ant), 171.9
—
—
— —
C )
— —
(HC N), 209.7 (
—
—
—
), 2836, 2935, 2969
—
IVan
IVao
IVap
IVaq
IVar
IR, ν˜/cm−1: 1035, 1180, 1245, 1290, 1384, 1461, 1509, 1606, 1646, 1940 (
C
1H NMR (CDCl3), δ: 1.14 (t, 3H, 3J = 7.6 Hz, CH2—CH3), 1.32 (s, 6H, 2 × CH3), 2.35 (dq, 2H, 3J = 7.6 Hz, 3J
= 5.1 Hz, CH2—CH3), 3.80 (s, 3H, OCH3), 4.98 (s, 2H, CH2), 6.97 (d, 2H, 3J = 8.7 Hz, Ar), 7.68 (d, 2H, 3J =
—
—
3
—
—
—
—
8.7 Hz, Ar), 7.72 (s, 1H, HC N), 7.80 (t, 1H, J = 5.1 Hz, CH—CH2)
13
—
C NMR (CDCl3), δ: 10.5 (CH2—CH3), 25.6 (2 × CH3), 26.1 (CH2—CH3), 39.9 (C), 55.4 (OCH3), 77.5 ( CH2),
—
—
—
—
—
—
—
109.5 ( C—Ar), 115.5 (2 × CH), 130.4 (2 × CH), 139.0 (C), 151.3 (C), 165.8 ( CH—CH2), 170.9 (HC N), 208.8
—
—
)
—
(
C
—
IR, ν˜/cm−1: 1035, 1180, 1245, 1288, 1454, 1509, 1606, 1643, 1941 (
C
), 2834, 2931, 2969, 3029
—
—
—
—
—
1H NMR (CDCl3), δ: 1.35 (s, 6H, 2 × CH3), 3.68 (d, 2H, 3J = 5.8 Hz, CH—CH2), 3.79 (s, 3H, OCH3), 4.99
—
(s, 2H, CH2), 7.07 (d, 2H, 3J = 8.1 Hz, Ar), 7.33–7.45 (m, 5H, Ph), 7.62 (d, 2H, 3J = 8.1 Hz, Ar), 7.75 (s, 1H,
—
—
3
—
—
—
HC N), 7.84 (t, 1H, J = 5.8 Hz, CH—CH2)
—
13
—
—
—
—
C NMR (CDCl3), δ: 24.3 (CH2), 25.2 (2 × CH3), 39.5 (C), 55.4 (OCH3), 77.6 ( CH2), 109.5 ( C—Ar), 114.9
—
—
(CH), 127.5 (C), 128.5 (CH), 128.9 (CH), 129.1 (CH), 129.5 (CH), 131.3 (C), 152.2 (C), 162.4 ( CH—CH2), 170.8
(HC N), 209.2 (
—
—
— —
C )
— —
IR, ν˜/cm−1: 1032, 1210, 1388, 1466, 1512, 1649, 1942 (
C
—
—
—
), 2878, 2922, 2966
—
1H NMR (CDCl3), δ: 1.15 (t, 3H, 3J = 7.2 Hz, CH2—CH3), 1.35 (s, 6H, 2 × CH3), 2.30 (dq, 2H, 3J = 7.2 Hz, 3J
= 5.2 Hz, CH2—CH3), 2.40 (s, 3H, Ph—CH3), 5.01 (s, 2H, CH2), 7.20 (d, 2H, 3J = 8.0 Hz, Ar), 7.67 (d, 2H, 3J
—
—
3
—
—
—
—
= 8.0 Hz, Ar), 7.70 (s, 1H, HC N), 7.76 (t, 1H, J = 5.1 Hz, CH—CH2)
13C NMR (CDCl3), δ: 10.4 (CH2—CH3), 22.0 (Ph—CH3), 25.3 (2 × CH3), 25.9 (CH2—CH3), 39.5 (C), 77.4
—
—
—
—
—
—
(
CH2), 111.8 ( C—Ar), 128.5 (2 × CH), 129.4 (2 × CH), 131.0 (C), 137.3 (C), 165.2 ( CH—CH2), 169.9
—
—
—
—
—
C )
—
(HC N), 207.8 (
IR, ν˜/cm−1: 1014, 1106, 1346, 1382, 1465, 1600, 1940 (
—
—
—
), 2873, 2933, 2967
—
C
1H NMR (CDCl3), δ: 1.20 (t, 3H, 3J = 7.1 Hz, CH2—CH3), 1.38 (s, 6H, 2 × CH3), 1.60–1.68 (m, 2H, CH2),
1.76–1.83 (m, 2H, CH2), 2.34 (s, 3H, Ph—CH3), 5.00 (s, 2H, CH2), 7.24 (d, 2H, 3J = 8.2 Hz, Ar), 7.63 (s, 1H,
—
—
HC N), 7.65 (d, 2H, 3J = 8.2 Hz, Ar), 7.81 (t, 1H, J = 5.3 Hz, CH—CH2)
3
—
—
—
—
13C NMR (CDCl3), δ: 13.9 (CH2—CH3), 19.8 (CH2—CH3), 21.7 (Ph—CH3), 23.0 (CH2), 25.4 (2 × CH3), 40.0
—
—
—
—
— —
C )
— —
—
—
(C), 77.4 ( CH2), 110.5 ( C—Ar), 128.3 (2 × CH), 129.5 (2 × CH), 131.0 (C), 137.4 (C), 165.7 ( CH—CH2),
—
—
169.9 (HC N), 207.4 (
IR, ν˜/cm−1: 1021, 1110, 1383, 1464, 1510, 1644, 1940 (
C
—
—
—
), 2870, 2928, 2967
—
1H NMR (CDCl3), δ: 1.09 (d, 6H, 3J = 7.0 Hz, 2 × CH3), 1.35 (s, 6H, 2 × CH3), 2.35 (s, 3H, Ph—CH3), 2.38–2.52
(m, 1H, CH), 4.99 (s, 2H, CH2), 7.22 (d, 2H, 3J = 8.1 Hz, Ar), 7.60 (d, 2H, 3J = 8.1 Hz, Ar), 7.64 (s, 1H, HC N),
—
—
—
—
—
—
3
7.70 (d, 1H, J = 5.7 Hz, CH—CH)
13
—
—
—
—
— —
C )
— —
C NMR (CDCl3), δ: 19.8 (2 × CH3), 25.6 (2 × CH3), 30.1 (CH), 40.9 (C), 77.4 ( CH2), 110.7 ( C—Ar), 128.3
—
—
—
—
(2 × CH), 129.7 (2 × CH), 130.8 (C), 136.7 (C), 165.8 ( CH—CH), 169.0 (HC N), 207.1 (

48
J. Galeta et al./Chemical Papers 67 (1) 40–50 (2013)
Table 3. (continued)
Compound
Spectral data
—
—
), 2872, 2936, 2969
—
IVas
IR, ν˜/cm−1: 1023, 1119, 1384, 1460, 1517, 1621, 1942 (
C
—
3
1H NMR (CDCl3), δ: 1.34 (s, 6H, 2 × CH3), 2.31 (s, 3H, Ph—CH3), 3.66 (d, 2H, J = 5.9 Hz, CH—CH2), 4.96
—
—
(s, 2H, CH2), 7.21 (d, 2H, 3J = 8.4 Hz, Ar), 7.30–7.42 (m, 5H, Ph), 7.58 (d, 2H, 3J = 8.4 Hz, Ar), 7.61 (s, 1H,
—
—
3
—
—
—
—
HC N), 7.88 (t, 1H, J = 5.9 Hz, CH—CH2)
13
—
—
—
—
C NMR (CDCl3), δ: 24.0 (CH2), 25.6 (2 × CH3), 39.3 (C), 77.9 ( CH2), 110.1 ( C—Ar), 127.5 (C), 128.5
—
—
—
—
(CH), 128.7 (CH), 128.9 (CH), 129.1 (CH), 129.5 (CH), 131.3 (C), 137.7 (C), 162.4 ( CH—CH2), 170.1 (HC N),
—
—
)
—
207.9 (
C
—
—
—
), 2880, 2934, 2974
—
IVat
IR, ν˜/cm−1: 1047, 1126, 1383, 1492, 1597, 1646, 1941 (
C
—
1H NMR (CDCl3), δ: 1.35 (s, 6H, 2 × CH3), 1.52 (t, 3H, 3J = 7.5 Hz, CH2—CH3), 2.36 (dq, 2H, 3J = 7.5 Hz,
3
J = 5.1 Hz, CH2—CH3), 4.99 (s, 2H, CH2), 7.25–7.30 (m, 2H, Ph), 7.79–7.83 (m, 3H, Ph), 7.84 (t, 1H, 3J =
—
—
—
—
—
—
5.1 Hz, CH—CH2), 7.87 (s, 1H, HC N)
13
—
—
—
—
C NMR (CDCl3), δ: 10.4 (CH2—CH3), 25.3 (2 × CH3), 25.9 (CH2—CH3), 40.1 (C), 77.4 ( CH2), 116.8 ( C—
—
—
—
—
— —
C )
— —
Ph), 127.7 (2 × CH), 127.8 (CH), 128.5 (2 × CH), 137.0 (C), 165.2 ( CH—CH2), 168.9 (HC N), 207.9 (
—
—
), 2877, 2939, 2964
—
IVau
IR, ν˜/cm−1: 1016, 1109, 1344, 1382, 1465, 1601, 1943 (
C
—
1H NMR (CDCl3), δ: 1.29 (t, 3H, 3J = 7.1 Hz, CH2—CH3), 1.36 (s, 6H, 2 × CH3), 1.59–1.65 (m, 2H, CH2), 1.68–
3
—
—
—
—
1.71 (m, 2H, CH2), 4.96 (s, 2H, CH2), 7.38 (t, 1H, J = 5.0 Hz, CH—CH2), 7.51–7.59 (m, 2H, Ph), 7.75–7.80
—
(m, 3H, Ph), 7.81 (s, 1H, HC N)
—
13
—
C NMR (CDCl3), δ: 13.9 (CH2—CH3), 19.8 (CH2—CH3), 23.0 (CH2), 25.2 (2 × CH3), 39.6 (C), 77.3 ( CH2),
—
—
—
—
—
—
111.8 ( C—Ph), 127.3 (CH), 128.5 (2 × CH), 128.8 (2 × CH), 137.3 (C), 164.5 ( CH—CH2), 169.3 (HC N),
—
—
—
)
—
207.8 (
C
—
—
—
—
), 2925, 2971
—
IVav
IVaw
IVax
IR, ν˜/cm−1: 1029, 1087, 1141, 1398, 1456, 1558, 1600, 1650, 1945 (
C
1H NMR (CDCl3), δ: 1.11 (d, 6H, 3J = 7.0 Hz, 2 × CH3), 1.38 (s, 6H, 2 × CH3), 2.40–2.55 (m, 1H, CH), 5.02
3
—
—
—
—
(s, 2H, CH2), 7.43–7.49 (m, 2H, Ph), 7.52 (d, 1H, J = 6.7 Hz, CH—CH), 7.69–7.74 (m, 3H, Ph), 7.85 (s, 1H,
—
HC N)
—
13
—
—
—
C NMR (CDCl3), δ: 19.8 (2 × CH3), 25.7 (2 × CH3), 29.9 (CH), 40.3 (C), 77.8 ( CH2), 111.7 ( C—Ph), 127.0
—
—
—
—
— —
C )
— —
(CH), 128.2 (2 × CH), 128.8 (2 × CH), 136.5 (C), 165.8 ( CH—CH), 169.0 (HC N), 207.1 (
—
IR, ν˜/cm−1: 1051, 1101, 1384, 1463, 1517, 1592, 1644, 1934 (
C
—
—
—
), 2871, 2921, 2960
—
3
1H NMR (CDCl3), δ: 1.16 (d, 6H, J = 7.1 Hz, 2 × CH3), 1.40 (s, 6H, 2 × CH3), 2.55–2.66 (m, 1H, CH—CH),
—
—
—
—
3
3
—
—
—
5.18 (s, 2H, CH2), 7.41 (d, 2H, J = 8.8 Hz, Ar), 7.70 (s, 1H, HC N), 7.84 (t, 1H, J = 5.3 Hz, CH—CH),
—
8.14 (d, 2H, 3J = 8.8 Hz, Ar)
13
—
—
—
—
C NMR (CDCl3), δ: 19.8 (2 × CH3), 26.7 (2 × CH3), 29.3 (CH), 42.9 (C), 79.8 ( CH2), 108.0 ( C—Ar), 123.2
—
—
—
—
— —
(CH), 128.8 (CH), 141.0 (C), 146.8 (C), 163.6 ( CH—CH), 170.9 (HC N), 209.9 ( C )
— —
IR, ν˜/cm−1: 1027, 1113, 1347, 1382, 1467, 1511, 1620, 1932 (
C
), 2873, 2937, 2968
—
—
—
—
—
3
1H NMR (CDCl3), δ: 1.37 (s, 6H, 2 × CH3), 3.68 (d, 2H, J = 5.5 Hz, CH—CH2), 5.21 (s, 2H, CH2), 7.31–7.38
—
—
—
3
3
—
—
—
—
(m, 5H, Ph), 7.39 (d, 2H, J = 8.9 Hz, Ar), 7.79 (s, 1H, HC N), 7.84 (t, 1H, J = 5.5 Hz, CH—CH2), 8.10 (d,
2H, 3J = 8.9 Hz, Ar)
13
—
—
—
C NMR (CDCl3), δ: 24.6 (CH2), 27.2 (2 × CH3), 42.5 (C), 80.1 ( CH2), 107.5 ( C—Ar), 123.8 (CH), 127.9
—
—
—
—
— —
(CH), 128.5 (CH), 129.3 (CH), 130.1 (CH), 141.3 (C), 146.9 (C), 162.9 ( CH—CH2), 171.3 (HC N), 210.2 ( C )
— —
—
Ad – 1-Adamantyl; Ant – 9-anthryl; Ph – phenyl.
The procedure for the preparation of other azines
IVc–IVax differed only in the amounts of reactants
used. The reaction mixture contained 10.5 mmol of
protected hydrazone II and 10 mmol of allenyl alde-
hyde. The desired azines were purified by filtering the
crude product in petroleum ether through a short col-
umn of neutral alumina or by liquid chromatography
(DCM).
presence of a strong base with a second aldehyde af-
forded the expected azines IV. Two reaction pathways
(A and B) could be utilised (Fig. 1). The second path-
way (B) served for derivatives with a hydrogen atom
(R = H) because it was not possible to prepare hy-
drazone II after reaction with formaldehyde. Thus, we
collected very differently substituted azines IV in high
yields using a relatively easy and rapid procedure (Ta-
ble 1).
Results and discussion
For structural studies, we were able to prepare a
crystal suitable for X-ray analysis. It clearly shows
that the stereochemical arrangement in a heterodiene
system is trans – s-trans – trans and that the allenyl
group lies approximately in the extended plane de-
fined by the heterodiene and p-nitrophenyl ring but is
oriented in the opposite direction (Fig. 2).
Since thermal stress can initiate slow decompo-
sition of compounds IV, elemental analyses of just
five representatives were carried out (Table 2). It is
The investigation and preparation of non-symme-
trical allenyl azines IV represents a major part of
the work undertaken in our laboratory. The starting
compounds II and III for their preparation were pub-
lished in Part 1 (Galeta et al., 2013). Their prepara-
tion follows Zwierzak’s procedure, in which protected
hydrazine I reacts with carbonyl compounds forming
protected hydrazones II or III. Their reaction in the

J. Galeta et al./Chemical Papers 67 (1) 40–50 (2013)
49
Fig. 3. Decomposition of aromatic aldazines.
worth noting here that aliphatic aldazines are some of
the most stable derivatives. The stability of aromatic
derivatives decreases with their increasing aromatic-
ity. It was observed that decomposition mainly pro-
duced their symmetrical counterparts (Fig. 3) consist-
ing of the same aldehyde segments bound to nitrogen
atoms of the azine moiety. For this reason, handling
them at ambient temperature was limited to the short-
est time necessary. Spectral data of all newly prepared
compounds are summarized in Table 3.
DOI: 10.1002/1099-0690(200112)2001:24<4569::aid-ejoc
4569>3.0.CO;2-w.
Brandsma, L. (2004). Synthesis of acetylenes, allenes and cu-
mulenes: Methods and techniques. Oxford, UK: Elsevier.
Brandsma, L., & Nedolya, N. A. (2004). Allenic compounds
and isothiocyanates as key building units in the synthesis of
heterocycles. Synthesis, 2004, 735–745. DOI: 10.1055/s-2004-
816005.
Brasholz, M., Reissig, H. U., & Zimmer, R. (2009). Sugars, alka-
loids, and heteroaromatics: exploring heterocyclic chemistry
with alkoxyallenes. Accounts of Chemical Research, 42, 45–
56. DOI: 10.1021/ar800011h.
Bruker AXS (1997). SHELXTL, Version 5.10. An integrated
system for solving and refining crystal structures from diffrac-
tion data. Madison, WI, USA: Bruker AXS.
Conclusions
Galeta, J., Man, S., & Potáček, M. (2009). Non-symmetrical
allenyl azines and their transformations leading to new het-
erocyclic skeletons. ARKIVOC, 2009, 6, 245–259.
Galeta, J., Man, S., Bouillon, J. P., & Potáček, M. (2011). Un-
expected heterocyclic products from cycloaddition reactions
of nonsymmetrical allenyl aldoketazines with substituted
alkynes. European Journal of Organic Chemistry, 2011, 392–
398. DOI: 10.1002/ejoc.201001044.
Galeta, J., & Potáček, M. (2012). Substituted diazatetracyclo
[4.4.0.13,10.15,8]dodecanes as stable caged proton sponges.
The Journal of Organic Chemistry, 77, 1010–1017. DOI:
10.1021/jo202235f.
Galeta, J., Man, S., & Potáček, M. (2013). Substituted homoal-
lenyl aldehydes and their derivatives. Part 1: Homoallenyl
aldehydes and protected hydrazones. Chemical Papers, 67,
29–39. DOI: 10.2478/s11696-012-0215-6.
Koziara, A., Turski, K., & Zwierzak, A. (1986). A general syn-
thesis of unsymmetrical azines via N-(diethoxyphosphinyl)-
hydrazones. Synthesis, 1986, 298–301. DOI: 10.1055/s-1986-
31589.
Detailed investigation of scope of preparation of
non-symmetrical allenyl azines afforded 50 new deriva-
tives, which can serve as very potent systems for
subsequent cycloaddition reaction steps. Two possi-
ble pathways for their preparation and, alternatively,
the degradation products of aromatic aldazines were
discussed. The crystal structure of one product was
also obtained and discussed.
Acknowledgements. The authors are grateful to Marek
Nečas for crystallographic measurements. The research was
supported by the Grant Agency of the Czech Republic, project
No. 203/09/1345.
Supplementary data
Crystallographic data on the structure of azine
IVag have been deposited in the Cambridge Crystal-
lographic Data Centre, CCDC No. 871315. Copies of
this information may be obtained free of charge from
The Director, CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK (Tel: +44 (0)1223 762911; e-mail:
kamila@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.
uk).
Krause, N., & Hashmi, A. S. K. (2004). Modern allene chem-
istry. Weinheim, Germany: Wiley–VCH.
Man, S., Kulhánek, P., Potáček, M., & Nečas, M. (2002). New
fused heterocycles by combined intra-intermolecular criss-
cross cycloaddition of nonsymmetrical azines. Tetrahedron
Letters, 43, 6431–6433. DOI: 10.1016/s0040-4039(02)01378-
3.
Man, S., Bouillon, J. P., Nečas, M., & Potáček, M. (2004). Com-
bined intra-intermolecular criss-cross cycloaddition of a new
fluorinated unsymmetrical allenylazine with alkynes. Tetra-
hedron Letters, 45, 9419–9421. DOI: 10.1016/j.tetlet.2004.10.
107.
References
Brandsma, L. (2001). Unsaturated carbanions, heterocumulenes
and thiocarbonyl compounds – new routes to heterocycles.
European Journal of Organic Chemistry, 2001, 4569–4581.
Man, S., Nečas, M., Bouillon, J. P., Baillia, H., Harakat, D., &
Potáček, M. (2005). New intra-intermolecular criss-cross cy-
cloaddition of unsymmetrical allenylazines with alkynes lead-

50
J. Galeta et al./Chemical Papers 67 (1) 40–50 (2013)
ing to three fused five-membered heterocycles. Tetrahedron,
61, 2387–2393. DOI: 10.1016/j.tet.2005.01.020.
Zachová, H., Marek, R., Man, S., Taraba, J., & Potáček, M.
(2006). A new rearrangement of fused tetracyclic heterocy-
cles in an acidic medium in the presence of NaBH3CN. Tetra-
hedron Letters, 47, 8157–8159. DOI: 10.1016/j.tetlet.2006.09.
030.
Zachová, H., Man, S., Taraba, J., & Potáček, M. (2009). Rear-
rangement of fused tetracyclic heterocycles induced by alkyl
halides and formation of a new type of ‘proton sponge’. Tetra-
hedron, 65, 792–797. DOI: 10.1016/j.tet.2008.11.057.
Zimmer, R. (1993). Alkoxyallenes – building blocks in organic
synthesis. Synthesis, 1993, 165–178. DOI: 10.1055/s-1993-
25823.
Schweizer, E. E., & Lee, K. J. (1984). Reactions of azines.
8. Synthesis and thermal rearrangement of 1-oxo-3,4-diaza-
2,4,6-heptatrienes and 1-oxo-3,4-diaza-2,4,6,7-octatetraenes
(allenyl azines). The Journal of Organic Chemistry, 49,
1959–1964. DOI: 10.1021/jo00185a025.
Schweizer, E. E., Hayes, J. E., Hirwe, S. N.,
& Rhein-
gold, A. L. (1987). Reactions of azines. 9. Preparation of
4,5-dihydropyrazolo[1,5-a]pyridines, 6,7-dihydropyrazolo[1,5-
a]pyridines, and pyrazolo[1,5-a]pyridines. The Journal of Or-
ganic Chemistry, 52, 1319–1324. DOI: 10.1021/jo00383a028.
Zachová, H., Man, S., Nečas, M., & Potáček, M. (2005). Fused
tetracyclic heterocycles by thermally initiated intramolec-
ular criss-cross cycloaddition of 3-substituted homoalleny-
laldazines. European Journal of Organic Chemistry, 2005,
2548–2557. DOI: 10.1002/ejoc.200400814.
Zwierzak, A.,
& Sulewska, A. (1976). Solid-liquid phase-
transfer-catalysed phosphorylation of hydrazine. Prepara-
tion of dialkyl phosphorohydrazidates and N,Nꢀ-bis[dialk-
oxyphosphoryl]hydrazines. Synthesis, 1976, 835–837. DOI:
10.1055/s-1976-25385.