Substituted homoallenyl aldehydes and their derivatives. Part 1: Homoallenyl aldehydes and protected hydrazones

Article abstract of DOI:10.2478/s11696-012-0215-6

The paper presents a simple synthesis of substituted propargyl vinyl ethers and their subsequent thermally-initiated Claisen rearrangement leading to various 3-substituted homoallenyl aldehydes. Several methods, including Sonogashira coupling, base-promoted substitution on the triple bond by sodium amide or butyllithium, and the preparation of substituted propargyl alcohols, were used in the initial step. Phosphate-protected homoallenyl aldehyde hydrazone derivatives were synthesised and fully characterised. The stereochemistry of 9-anthracene carbaldehyde hydrazone, which, surprisingly, afforded both cis and trans isomers, was established using X-ray analysis.

Full text of DOI:10.2478/s11696-012-0215-6

Chemical Papers 67 (1) 29–39 (2013)
DOI: 10.2478/s11696-012-0215-6
ORIGINAL PAPER
Substituted homoallenyl aldehydes and their derivatives.
Part 1: Homoallenyl aldehydes and protected hydrazones
Juraj Galeta, Stanislav Man, Milan Potáček*
Department of Chemistry, Faculty of Science, Masaryk University, Kotlářská 2, 611 37 Brno, Czech Republic
Received 20 March 2012; Revised 22 April 2012; Accepted 30 April 2012
Dedicated to Professor Štefan Toma on the occasion of his 75th birthday
The paper presents a simple synthesis of substituted propargyl vinyl ethers and their subsequent
thermally-initiated Claisen rearrangement leading to various 3-substituted homoallenyl aldehydes.
Several methods, including Sonogashira coupling, base-promoted substitution on the triple bond by
sodium amide or butyllithium, and the preparation of substituted propargyl alcohols, were used in
the initial step. Phosphate-protected homoallenyl aldehyde hydrazone derivatives were synthesised
and fully characterised. The stereochemistry of 9-anthracene carbaldehyde hydrazone, which, sur-
prisingly, afforded both cis and trans isomers, was established using X-ray analysis.
c
ꢀ 2012 Institute of Chemistry, Slovak Academy of Sciences
Keywords: homoallenyl aldehyde, hydrazone, Claisen rearrangement, isomerisation
Introduction
lished papers describing further transformations of
these products (Zachová et al., 2006, 2009; Buchlovič
et al., 2010b, 2012; Galeta & Potáček, 2012). How-
ever, despite this accumulated work, the possibility
of performing experiments on the triple bond con-
tinues to play a key role and we have encountered
failure many times. For this reason, we also com-
ment briefly on some of our less successful reac-
tions.
The preparation of protected hydrazones is the first
part of azine synthesis following Zwierzak’s method
(Koziara et al., 1986). We utilise this method but with
some improvements to the procedure which have en-
abled us to contribute here with some new derivatives.
In the past, the chemistry of allenyl synthon was
neglected. In the early 1990s, we began experiments
which involved the preparation and exploitation of al-
lenyl compounds (Potáček et al., 1993). Homoallenyl
aldehyde and its various substituted derivatives be-
came the key starting molecule and substrate for sub-
sequent work. Finally, we found that Claisen rear-
rangement of propargyl vinyl ethers provided a gen-
eral method for their preparation (Black & Landor,
1965). We have published a number of papers dealing
with the chemistry of allenyl compounds (Marek et
al., 1994, 1995a, 1995b, 1997; Man et al., 2002, 2004,
2005, 2006a, 2006b; Buchlovič et al., 2008, 2010a;
Galeta et al., 2009, 2011) and also one which provides
the methodology for substituting the triple bond of
propargyl vinyl ether (Zachová et al., 2005). These se-
lected publications clearly indicate that allenyl syn-
thon serves as an intra-molecular dipolarophile or
centre, where the final products of reactions are al-
ways cyclic derivatives with one ring, or bicyclic, tri-
cyclic, and tetracyclic skeletons. We have also pub-
Experimental
Unless stated otherwise, all reagents were pur-
chased from commercial suppliers and used as re-
ceived. THF and benzene were distilled from sodium/
benzophenone before use. Dichloromethane (DCM)
was dried with calcium chloride, distilled from P2O5
˚
and stored over dry 3 A molecular sieves. All reactions
*Corresponding author, e-mail: potacek@chemi.muni.cz

30
J. Galeta et al./Chemical Papers 67 (1) 29–39 (2013)
Fig. 1. Preparation of substituted propargyl vinyl ethers Va–Vh; Ad = 1-adamantyl; Py = pyridine; TMSCl = trimethylsilyl
chloride; BuLi = butyllithium; Ar = aryl; TBAF = tetrabutylammonium fluoride.
were carried out under a dry argon atmosphere and
were monitored by TLC (Merck F254 silica gel). Prod-
ucts were separated by liquid chromatography with a
Horizon HPFC System (Biotage, Inc.) fitted with Bio-
tage Si 12+M and Si 25+M columns. Melting points
were determined in open capillaries with a MPM–
HV2 thermometer. FTIR spectra were recorded with
Butyllithium (1.28 g, 20 mmol) was added dropwise
and the mixture was allowed to warm up to 0◦C.
After a slow addition of paraformaldehyde (0.90 g,
30 mmol), the mixture was stirred for one day and
then the reaction was quenched with water (30 mL).
The organic layer was separated and the aqueous layer
extracted with diethyl ether (3 × 25 mL). The com-
bined organic phases were dried with MgSO4, filtered,
and evaporated to yield a colourless solid. Recrys-
tallisation from methanol gave colourless crystals of
I (2.30 g, 81 %).
1
a GENESIS ATI (Unicam) spectrometer. H and 13C
NMR spectra were recorded with a Bruker Avance 300
spectrometer operating at frequencies of 300.13 MHz
(1H) and 75.47 MHz (13C) with CDCl3 as solvent.
Tetramethylsilane or CHCl3 were used as internal
standards for 1H NMR and CDCl3 for 13C NMR
spectra, respectively. MS data were obtained with a
Fisons Instruments TRIO 1000 spectrometer at 70 eV
in the electron impact mode and GC–MS data with a
Shimadzu GCMS-QP2010 operating in EI mode. Ele-
mental analyses were performed with a Perkin–Elmer
CHN 2400 apparatus. High-resolution mass spectra
(HRMS) were recorded on a Micromass Q-Tof micro
instrument in the positive ESI (CV = 30 V) mode.
X-ray diffraction data were collected on a Kuma KM-
4 four-circle CCD diffractometer and corrected for
Lorentz and polarisation effects. The structures were
resolved by direct methods and refined by full-matrix
least-squares methods using the SHELXTL program
package (Bruker AXS, 1997). Hydrogen atoms were lo-
cated in calculated idealised positions. Ether IV (Za-
chová et al., 2005) and phosphate VII (Zwierzak &
Sulewska, 1976) were prepared according to the liter-
ature.
1-(3-(1-Chloro-2-methylpropoxy)prop-1-ynyl)
adamantane (II)
A mixture of compound I (0.951 g, 5 mmol) and
isobutyraldehyde (0.721 g, 10 mmol) in dichlorome-
thane (20 mL) was cooled to approximately –5◦C and
gaseous HCl was introduced over a period of 3 h main-
taining the temperature at approximately 0◦C. Then,
the mixture was dried with MgSO4, filtered, and the
solvent evaporated to give II (1.36 g, 97 %). No addi-
tional purification was needed.
1-(3-(2-Methylprop- 1-enyloxy)prop-1-
ynyl)adamantane (Va)
Chlorinated ether II (0.505 g, 1.8 mmol) and pyri-
dine (5 mL) were heated under reflux for 2 h. Then,
saturated aqueous NaCl (25 mL) was added and
the organic part was extracted with diethyl ether
(4 × 15 mL). Organic extracts were washed with a
5 mass % CuSO4 aqueous solution (4 × 15 mL) and
finally with water (2 × 15 mL). Drying with MgSO4
and solvent evaporation afforded Va (0.413 g, 94 %)
in sufficient purity.
3-(1-Adamantyl)prop-2-yn-1-ol (I)
1-Adamantylacetylene (2.40 g, 15 mmol) was dis-
solved in dry THF (20 mL) and cooled to –60◦C.

J. Galeta et al./Chemical Papers 67 (1) 29–39 (2013)
31
1-(2-Methylprop-1-enyloxy)but-2-yne (Vb) and
1-(2-methylprop-1-enyloxy)pent-2-yne (Vc)
Ether IV (55.08 g, 0.5 mol) was slowly added to a
suspension of NaNH2 (23.41 g, 0.6 mol) in liquid am-
monia (∼200 mL, –33◦C). After 30 min, iodomethane
(99.36 g, 0.7 mol) (for Vb) or bromoethane (76.28 g,
0.7 mol) (for Vc) was added dropwise (in ca. 30 min)
and the reaction mixture was stirred and warmed
to ambient temperature overnight. The reaction was
quenched with water (100 mL) and the product was
extracted with diethyl ether (5 × 50 mL). The com-
bined organic layers were dried with MgSO4, the sol-
vent was evaporated, and the product distilled under
diminished pressure (∼2 kPa) at 57–60◦C for Vb and
at 63–66◦C for Vc to give colourless liquids (69 % and
50 %, respectively).
Fig. 2. Propargyl Claisen rearrangement of ethers Va–Vh to
penta-3,4-dienals VIa–VIh. Substituent R (yield): 1-
adamantyl (91 %), methyl (88 %), ethyl (82 %),
trimethylsilyl (79 %), phenyl (82 %), 4-methylphenyl
(78 %), 4-methoxyphenyl (73 %), 4-nitrophenyl (75 %).
1-Methoxy-4-(3-(2-methylprop-1-enyloxy)
prop-1-ynyl)benzene (Vg) and 1-nitro-4-(3-(2-
methylprop-1-enyloxy)prop-1-ynyl)benzene
(Vh)
(3-(2-Methylprop-1-enyloxy)prop-1-
ynyl)trimethylsilane (Vd)
Ether IV (1.652 g, 18 mmol, 1.2 equiv.) was dis-
solved in benzene (degassed with argon for 30 min).
Then, 4-iodoanisole (3.511 g, 15 mmol, 1 equiv.) (for
Vg) or 1-iodo-4-nitrobenzene (3.735 g, 15 mmol, 1
equiv.) (for Vh), piperidine (3.065 g, 36 mmol, 2.4
equiv.), CuI (0.029 g, 0.15 mmol, 0.01 equiv.), and
PdCl2(PPh3)2 (0.316 g, 0.45 mmol, 0.03 equiv.) were
added and heated to 40◦C in an argon atmosphere for
2 h. The crude reaction mixture was filtered through
a thin layer of silica gel and the solvent was evap-
orated. Colourless oil Vg (2.630 g, 81 %) or yellow
solid Vh (3.024 g, 87 %, m.p. 42–44◦C) were ob-
tained by liquid chromatography using DCM as sol-
vent.
Ether IV (11.02 g, 0.10 mol) in THF (100 mL)
was cooled to –50◦C and then butyllithium (8.01 g,
0.125 mol; 78 mL of 1.6 M solution,) was added. The
reaction continued with the addition of trimethylsi-
lyl chloride (13.58 g, 0.125 mol) in several por-
tions and finally the mixture was allowed to warm
up to ambient temperature. After 24 h, the re-
action was quenched with saturated aqueous NaCl
(100 mL), the organic layer was separated, and
the aqueous layer was extracted with diethyl ether
(2 × 100 mL). The combined organic layers were
dried with MgSO4 and, after solvent evaporation, the
crude product was purified by distillation under di-
minished pressure using a Kugelrohr apparatus (∼20
Pa, 60–80◦C) to give Vd as a colourless oil (16.77 g,
92 %).
Claisen rearrangement of propargyl vinyl
ethers (Va–Vh) to 3-substituted-2,2-
dimethylpenta-3,4-dienals (VIa–Vh)
Ether V (1 g) was refluxed for 4 h (compounds
Va–Vd) or 15 min (compounds Ve–Vh) in an argon
atmosphere. The crude products were distilled under
normal pressure (aldehydes VIb and VIc, b.p. 120–
140◦C and 164–167◦C, respectively; colourless oils) or
under vacuum (∼20 Pa) using a Kugelrohr apparatus
(aldehydes VId and VIe–VIg, b.p. 80–100◦C and 185–
205◦C, respectively). Aldehyde VIa was used without
purification and VIh was separated as a yellow solid
(m.p. 57–60◦C) by liquid chromatography using DCM
as solvent.
(3-(2-Methylprop-1-enyloxy)prop-1-
ynyl)benzene (Ve) and 1-methyl-4-(3-(2-
methylprop-1-enyloxy)prop-1-ynyl)benzene
(Vf)
A mixture of ether IV (1.652 g, 18 mmol, 1.2
equiv.), iodobenzene (3.060 g, 15 mmol, 1 equiv.) (for
Ve) or 1-iodo-4-methylbenzene (3.271 g, 15 mmol, 1
equiv.) (for Vf), tetrabutylammonium fluoride trihy-
drate (7.099 g, 22.5 mmol, 1.5 equiv.), and PdCl2
(PPh3)2 (0.105 g, 0.15 mmol, 0.01 equiv.) was heated
to 80◦C in an argon atmosphere for 2 h. Then, wa-
ter (10 mL) was added and the product was ex-
tracted with ether (3 × 10 mL). The combined or-
ganic layers were dried with MgSO4, filtered through
a thin layer of silica gel, and the solvent was evap-
orated. Pure colourless oils Ve (2.320 g, 83 %) or
Vf (2.249 g, 75 %) were obtained by distillation
under diminished pressure in a Kugelrohr appara-
tus.
Diethyl Nꢀ-(3-(1-adamantyl)-2,2-dimethyl-
penta-3,4-dienyliden)hydrazidophosphate (IXa)
Hydrazidophosphate VII (0.513 g, 3.05 mmol) and
penta-3,4-dienal VIa (0.730 g, 3 mmol) in toluene
(25 mL) were heated under reflux for 5 h. The sol-
vent was evaporated and the product was separated
by liquid chromatography using AcOEt as solvent to
afford IXa (0.380 g, 45 %).

32
J. Galeta et al./Chemical Papers 67 (1) 29–39 (2013)
Fig. 3. Condensation reactions of aldehydes with diethyl hydrazidophosphate VII.
Diethyl Nꢀ-(3-trimethylsilyl-2,2-dimethylpenta-
3,4-dienyliden)hydrazidophosphate (IXb)
Diethyl Nꢀ-(1-adamantylmethylidene)
hydrazidophosphate (Xc)
Hydrazidophosphate VII (4.287 g, 25.5 mmol) and
penta-3,4-dienal VId (4.558 g, 25 mmol) in DCM
(45 mL) were heated under reflux for 4 h with the
azeotropic removal of water. The solvent was evapo-
rated and the product separated by liquid chromatog-
raphy using AcOEt/petroleum ether (ϕr = 1 : 1) to
give IXb (7.145 g, 86 %).
1-Adamantanecarbaldehyde (VIIIc) was prepared
in situ by oxidation of 1-adamantyl methanol (8.212 g,
50 mmol) with pyridinium chlorochromate (PCC,
16.167 g, 75 mmol) in dry DCC (150 mL) for 3 h. The
resulting dark solution was filtered through a short
column of florisil followed by the addition of hydrazi-
dophosphate VII (8.407 g, 50 mmol) to the filtrate.
The mixture was heated under reflux for 12 h and
the product was recrystallised from petroleum ether
to give colourless crystals of Xc (12.574 g, 80 %).
Synthesis of diethyl Nꢀ-(R1ylidene)
hydrazidophosphates Xa, Xb, and Xd–Xl
Hydrazidophosphate VII (5.044 g, 30 mmol) and
the carbonyl compounds VIIIa–VIIIl (45 mmol of VI-
IIa, 36 mmol of VIIIb, and 30 mmol of VIIId–VIIIl)
in benzene (50 mL) were heated for 1–2 h (for Xa,
Xb, Xd–Xk, respectively) or 4 h (for Xl), respectively
with azeotropic distillation. After solvent evapora-
tion, the crude product was distilled under dimin-
ished pressure (∼20 Pa) using a Kugelrohr appara-
tus (Xa, b.p. 140–150◦C, 81 %; Xb, b.p. 200–210◦C,
76 %; Xe, 225–235◦C, 79 %; all colourless oils) or
recrystallised from petroleum ether (Xc, Xd), ace-
tone (Xf ), or benzene/hexane (ϕr = 2 : 1) (Xg–
Xl).
Results and discussion
1-Adamantylacetylene used for the synthesis of
substituted propargyl alcohol (I ) was prepared from
1-acetyladamantane and PCl5 in dry chloroform at
ambient temperature. A similar transformation with
SOCl2 is described in the literature (Burkhard et
al., 1988). Both procedures yield 1-(1ꢀ-chloroethenyl)
adamantane as the main product. During our pro-
cedure, we observed the formation of 1-adamantyl-
1,1-dichloroethane as a by-product. Both chlorinated
compounds in the following reaction with KOH in di-
ethylene glycol at gradually increasing temperature
(up to 180◦C) yielded the desired 1-adamantylacetyl-

J. Galeta et al./Chemical Papers 67 (1) 29–39 (2013)
Table 1. Characterisation data of crystalline hydrazones X
33
wi(calc.)/%
wi(found)/%
Yield
M.p.
Compound
R1
Formula
Mr
Appearance
C
H
N
%
80
88
88
72
75
74
70
76
89
◦C
Xc
Xd
Xf
Xg
Xh
Xi
Xj
Xk
Xl
1-adamantyl
C15H27N2O3P
314.36
57.31
56.97
41.22
41.11
52.17
51.89
50.35
50.70
53.33
53.68
45.45
45.20
43.86
44.02
58.82
59.04
64.04
63.55
8.66
8.63
5.76
5.69
7.41
7.37
6.69
6.72
7.09
7.14
5.55
5.54
5.35
5.37
6.25
6.28
5.94
6.14
8.91
8.43
85.6–90.0
67.9–68.2
151.6–151.9
73.1–73.4
80.4–80.7
61.2–61.5
120.2–120.5
72.7–73.0
colourless
yellowish
pale orange
colourless
colourless
colourless
pale yellow
colourless
yellow
2-thiophenyl C9H15N2O3PS 262.27
10.68
10.22
14.04
13.73
9.79
4-Me2N-Ph
4-MeO-Ph
4-Me-Ph
C13H22N3O3P
C12H19N2O4P
C12H19N2O3P
299.31
286.26
270.26
9.35
10.37
10.16
9.64
4-Cl-Ph
C11H16ClN2O3P 290.68
9.27
4-NO2-Ph
1-naphthyl
9-anthryl
C11H16N3O5P
C15H19N2O3P
C19H21N2O3P
301.24
306.30
356.36
13.95
13.65
9.15
8.81
7.86
7.34
114.5–114.9a
150.2–150.8b
a) cis isomer; b) trans isomer.
ene. Finally, the base-promoted reaction of acetylene
with paraformaldehyde yielded alcohol I. Chlorinated
ether II was obtained by the reaction of I with isobu-
tyraldehyde in the presence of gaseous HCl. The sub-
sequent elimination of HCl by pyridine yielded the de-
sired substituted ether Va.
Although the easy formation of acetylide could be
expected, it is important to note that deprotonation
was not successful with Grignard reagents, sodium hy-
dride, or KOH in various solvents. The only active
agents were butyllithium and sodium amide (Fig. 1).
The very powerful and potent Sonogashira coupling
method of introducing an aryl to the triple bond also
proved to be successful here. We tried two different
procedures and synthesised four derivatives Ve–Vh
with various p-substituted phenyl rings. However, to
date, Sonogashira coupling has not been successful in
transforming substrate IV into derivatives with het-
eroaryl or anthryl substitution.
Thermal stress of propargyl vinyl ethers Va–Vh led
to propargyl Claisen rearrangement, and the corre-
sponding substituted homoallenyl aldehydes VIa–VIh
were obtained in very good to excellent yields (Fig. 2).
These products are relatively stable at room temper-
ature, but over time some colour impurities appear.
For this reason we kept them in a freezer, where they
remain colourless or yellow even after several months.
The preparation of aldehyde VIe from phenylacetylene
was conducted according to the literature (Zachová et
al., 2005), as for the preparation of aldehyde VIa from
1-adamantylacetylene. Spectral data of ethers V and
aldehydes VI are summarised in Table 2.
tection of hydrazine by Zwierzak’s method in the syn-
thesis of asymmetrical azines in order to avoid the
formation of symmetrical azines (Fig. 3). Because of
the large number of compounds described and fully
characterised, we intend to publish the formation of
asymmetrical azines and their characterisation in a
subsequent paper entitled (Galeta et al., 2013).
We wish to note a very interesting observation con-
cerning the isolation of both cis and trans isomers of
the hydrazone Xl (Fig. 4). It is not surprising to ob-
serve the formation of isomers in the case of prod-
ucts Xa or Xb, where we clearly observe the decreas-
ing occurrence of one isomer and the increasing occur-
rence of another, depending upon the increasing bulk
of the substituents. Because isomers with naphthyl-
or even phenyl-substituted products have never been
observed, the existence of both stereoisomers with an-
thryl substitution was somewhat unexpected. In the
case of hydrazone Xl, the integral ratio of isomers was
about 3.5 : 1. Repeated NMR measurements showed
a slow inversion of the integral ratio to about 1 : 2.
It should be noted that the measured sample was ex-
posed to daylight and ambient temperature. To prove
that light is responsible for this isomerisation, we grew
crystals of both isomers after their chromatographic
separation for X-ray structure analysis (Fig. 4). One
of them was prepared from a sample of the primary
minor isomer. This crystal was obtained by the slow
evaporation of acetone at ambient temperature in the
presence of light (cis). The second crystal was ob-
tained without access to light by freezing the sample
with the primary major isomer in Et2O (trans).
The diethyl phosphate group was used for the pro-
It is obvious from the data obtained that the ma-

34
J. Galeta et al./Chemical Papers 67 (1) 29–39 (2013)
Table 2. Spectral data of newly prepared compounds
Compound
Spectral dataa
I
1H NMR (CDCl3), δ: 1.65 (bs, 1H, OH), 1.71 (bs, 6H, Ad), 1.89 (bs, 6H, Ad), 1.98 (bs, 3H, Ad), 4.28 (s, 2H, CH2)
13
—
C NMR (CDCl3), δ: 28.2 (CH, Ad), 32.7 (C, Ad), 36.6 (CH2, Ad), 43.0 (CH2, Ad), 51.6 (O—CH2), 77.5 (—C—
—
—
CH2), 94.7 (—C—Ad)
—
II
1H NMR (CDCl3), δ: 1.07 (d, 3J = 6.7 Hz, 6H, 2 × CH3), 1.71 (bs, 6H, Ad), 1.89 (bs, 6H, Ad), 1.97 (bs, 3H, Ad),
2.08–2.23 (m, 1H, HC—CH3), 4.23 (d, 2J = 15.5 Hz, 1H, CH2), 4.31 (d, 2J = 15.5 Hz, 1H, CH2), 5.71 (d, 3J =
3.9 Hz, 1H, HC—Cl)
13C NMR (CDCl3), δ: 17.6 (CH3), 17.9 (CH3), 28.1 (CH, Ad), 29.7 (C, Ad), 36.1 (C—CH3), 36.5 (CH2, Ad), 42.9
—
—
(CH2, Ad), 57.6 (O—CH2), 73.0 (—C—CH2), 96.5 (—C—Ad), 101.9 (HC—Cl)
—
—
Va
Vb
1H NMR (CDCl3), δ: 1.59 (s, 3H, CH3), 1.64 (s, 3H, CH3), 1.71 (bs, 6H, Ad), 1.89 (bs, 6H, Ad), 1.97 (bs, 3H, Ad),
—
4.31 (s, 2H, CH2), 5.91–5.94 (m, 1H, CH)
—
13C NMR (CDCl3), δ: 15.3 (CH3), 19.7 (CH3), 28.2 (CH, Ad), 29.8 (C, Ad), 36.6 (CH2, Ad), 42.9 (CH2, Ad), 57.6
—
—
—
—
—
—
(O—CH2), 73.0 (—C—CH2), 95.4 (—C—Ad), 112.3 ( C), 138.7 ( CH)
—
—
IR, ν˜/cm−1: 1015, 1150, 1279, 1364, 1447, 1692 (C C—O), 2226 (C—C), 2859, 2881, 2921, 2961
—
—
—
—
1
5
—
—
—
—
—
H NMR (CDCl3), δ: 1.56 (s, 3H, C—CH3), 1.61 (s, 3H, C—CH3), 1.85 (t, J = 2.3 Hz, 3H, —C—CH3), 4.25
(q, J = 2.3 Hz, 2H, CH2), 5.86–5.92 (m, 1H, CH)
C NMR (CDCl3), δ: 3.7 (—C—CH3), 15.2 ( C—CH3), 19.7 ( C—CH3), 59.3 (O—CH2), 75.1 (—C), 82.7
—
5
—
—
—
—
13
—
—
—
—
—
—
—
—
—
—
—
(—C), 112.0 ( C), 138.9 ( CH)
—
MS, m/z (%): 125 (M+, 35), 95 (17), 71 (33), 53 (57), 43 (100)
Vc
Vd
IR, ν˜/cm−1: 1016, 1149, 1275, 1363, 1450, 1693 (C C—O), 2229 (C—C), 2858, 2881, 2920, 2976
—
—
—
—
3
1H NMR (CDCl3), δ: 1.14 (t, J = 7.4 Hz, 3H, H3C—CH2), 1.56 (s, 3H, C—CH3), 1.61 (s, 3H, C—CH3), 2.23
—
—
—
—
5
(qt, 3J = 7.4 Hz, 5J = 2.1 Hz, 2H, H3C—CH2), 4.27 (q, J = 2.1 Hz, 2H, O—CH2), 5.85–5.94 (m, 1H, CH)
—
—
13
—
—
—
—
C NMR (CDCl3), δ: 12.6 (H3C—CH2), 13.9 (H3C—CH2), 15.2 ( C—CH3), 19.7 ( C—CH3), 59.4 (O—CH2),
—
—
—
—
75.2 (—C), 88.7 (—C), 112.3 ( C), 138.9 ( CH)
—
—
—
—
IR, ν˜/cm−1: 1030, 1145, 1254, 1633, 1691 (C C—O), 2177 (C—C), 2862, 2962
—
—
—
—
1H NMR (CDCl3), δ: 0.18 (s, 9H, Si—CH3), 1.57 (s, 3H, CH3), 1.62 (s, 3H, CH3), 4.29 (s, 2H, CH2), 5.90–5.95 (m,
—
1H, CH)
—
13
—
—
—
—
C NMR (CDCl3), δ: 0.0 (Si—CH3), 15.3 (CH3), 19.7 (CH3), 59.6 (CH2), 91.8 (—C), 101.4 (—C), 113.2 ( C),
—
—
—
138.8 ( CH)
—
MS, m/z (%): 182 (M+, 12), 167 (12), 111 (70), 83 (90), 73 (100), 55 (40)
1
—
Ve
Vf
Vg
H NMR (CDCl3), δ: 1.60 (s, 3H, CH3), 1.67 (s, 3H, CH3), 4.54 (s, 2H, CH2), 6.00–6.05 (m, 1H, CH), 7.09–7.15
—
(m, 1H, Ph), 7.32–7.35 (m, 2H, Ph), 7.45–7.48 (m, 2H, Ph)
MS, m/z (%): 185 (M+, 100), 157 (70), 142 (90), 128 (50), 115 (50), 91 (30), 77 (30), 43 (30)
1H NMR (CDCl3), δ: 1.57 (s, 3H, CH3), 1.67 (s, 3H, CH3), 2.33 (s, 3H, Ph—CH3), 4.50 (s, 2H, CH2), 5.93–5.98
—
(m, 1H, CH), 7.09–7.16 (m, 2H, Ph), 7.31–7.34 (m, 2H, Ph)
—
MS, m/z (%): 200 (M+, 10), 185 (100), 157 (60), 142 (98), 128 (50), 115 (50), 91 (20), 77 (30), 43 (30)
IR, ν˜/cm−1: 1032, 1142, 1249, 1508, 1606, 1691 (C C—O), 2226 (C—C), 2856, 2960, 3032
—
—
—
—
1H NMR (CDCl3), δ: 1.60 (s, 3H, CH3), 1.67 (s, 3H, CH3), 3.82 (s, 3H, O—CH3), 4.53 (s, 2H, CH2), 5.97–6.02 (m,
1H, CH), 6.83 (d, 3J = 8.1 Hz, 2H, Ph), 7.40 (d, 3J = 8.1 Hz, 2H, Ph)
—
—
13
—
—
—
—
—
C NMR (CDCl3), δ: 15.3 (CH3), 19.8 (CH3), 55.5 (O—CH3), 59.7 (CH2), 83.7 (—C), 86.5 (—C), 112.8 ( C),
—
—
—
114.1 (2 × CH, Ph), 114.9 (C, Ph), 133.5 (2 × CH, Ph), 138.9 ( CH), 160.0 (C)
MS, m/z (%): 216 (M+, 55), 201 (100), 173 (33), 145 (12)
Vh
IR, ν˜/cm−1: 1018, 1142, 1342, 1691 (C C—O), 2447 (C—C), 2856, 2918, 3107
—
—
—
—
1
—
H NMR (CDCl3), δ: 1.60 (s, 3H, CH3), 1.67 (s, 3H, CH3), 4.56 (s, 2H, CH2), 5.93–5.97 (m, 1H, CH), 7.59 (d,
—
3J = 8.2 Hz, 2H, Ph), 8.19 (d, 3J = 8.2 Hz, 2H, Ph)
13
—
—
—
—
—
C NMR (CDCl3), δ: 15.2 (CH3), 19.6 (CH3), 59.3 (CH2), 84.5 (—C), 90.5 (—C), 113.7 ( C), 123.7 (2 × CH,
—
—
Ph), 129.5 (2 × CH, Ph), 132.7 (C, Ph), 138.7 ( CH), 147.5 (C)
—
MS, m/z (%): 231 (M+, 12), 214 (20), 160 (100), 114 (45), 102 (55), 43 (30)
VIa
VIb
1H NMR (CDCl3), δ: 1.19 (s, 6H, 2 × CH3), 1.54–1.67 (m, 6H, Ad), 1.77–1.82 (m, 6H, Ad), 1.90 (bs, 3H, Ad), 4.78
—
—
—
(s, 2H, CH2), 9.39 (s, 1H, HC O)
—
13C NMR (CDCl3), δ: 24.0 (2 × CH3), 29.1 (CH, Ad), 36.8 (CH2, Ad), 42.9 (C, Ad), 43.0 (CH2, Ad), 49.0 (C),
—
—
— —
78.4 ( CH2), 115.7 (C-Ad), 203.8 (HC O), 208.4 ( C )
— —
—
—
IR, ν˜/cm−1: 1112, 1372, 1452, 1726 (C O), 1953 (
), 2780, 2871, 2926, 2967
—
—
—
— —
C
— —
1H NMR (CDCl3), δ: 1.18 (s, 6H, 2 × CH3), 1.64 (t, 5J = 3.2 Hz, 3H,
C—CH3), 4.77 (q, 5J = 3.2 Hz, 2H,
—
—
—
—
—
CH2), 9.35 (s, 1H, HC O)
13
—
—
—
—
—
—
—
C NMR (CDCl3), δ: 15.2 ( C—CH3), 20.6 (2 × CH3), 48.2 (C), 76.3 ( CH2), 100.0 ( C—CH3), 202.4 (HC O),
—
—
—
)
—
207.2 (
C
—
GC-MS, m/z (%): 124 (M+, 2), 109 (100), 67 (44)

J. Galeta et al./Chemical Papers 67 (1) 29–39 (2013)
35
Table 2. (continued)
Compound
Spectral dataa
—
— —
C ), 2692, 2798, 2875, 2935, 2972
— —
VIc
IR, ν˜/cm−1: 1149, 1444, 1734 (C O), 1949 (
—
1H NMR (CDCl3), δ: 0.97 (t, 3J = 7.1 Hz, 3H, H3C—CH2), 1.16 (s, 6H, 2 × CH3), 1.76–1.93 (m, 2H, H3C—CH2),
5
—
—
—
—
4.88 (t, J = 4.0 Hz, 2H, CH2), 9.32 (s, 1H, HC O)
13
—
—
—
C NMR (CDCl3), δ: 12.5 (H3C—CH2), 20.5 (H3C—CH2), 20.8 (2 × CH3), 48.5 (C), 79.1 ( CH2), 107.2 ( C—
—
—
— —
C )
— —
Et), 202.7 (HC O), 206.7 (
—
GC-MS, m/z (%): 138 (M+, 1), 123 (49), 109 (100), 79 (31), 67 (92)
—
— —
C ), 2825, 2932, 3011
— —
VId
VIe
VIf
IR, ν˜/cm−1: 1345, 1728 (C O), 1925 (
—
1
—
—
—
—
H NMR (CDCl3), δ: 0.13 (s, 9H, Si—CH3), 1.22 (s, 6H, 2 × CH3), 4.51 (s, 2H, CH2), 9.36 (s, 1H, HC O)
13
—
—
—
—
C NMR (CDCl3), δ: 0.6 (Si—CH3), 22.8 (2 × CH3), 48.6 (C), 71.4 ( CH2), 98.5 ( C—Si), 203.0 (HC O),
—
—
—
—
)
—
210.6 (
C
—
GC-MS, m/z (%): 182 (M+, 18), 167 (75), 155 (40), 97 (30), 73 (100), 43 (50)
IR, ν˜/cm−1: 1030, 1140, 1455, 1730 (C O), 1941 (
—
—
— —
C
— —
), 2701, 2802, 2932, 3052
—
1
—
—
H NMR (CDCl3), δ: 1.27 (s, 6H, 2 × CH3), 5.10 (s, 2H, CH2), 7.15–7.35 (m, 5H, Ph), 9.60 (s, 1H, HC O)
—
13
—
—
—
—
C NMR (CDCl3), δ: 22.1 (2 × CH3), 48.7 (C), 78.6 ( CH2), 108.5 ( C—Ph), 127.9 (CH, Ph), 128.6 (2 × CH,
—
—
— —
C )
— —
Ph), 130.1 (2 × CH, Ph), 135.4 (C), 203.4 (HC O), 209.2 (
GC-MS, m/z (%): 186 (M+, 33), 171 (96), 143 (40), 128 (55), 115 (100), 91 (30), 77 (32), 43 (58)
IR, ν˜/cm−1: 1020, 1110, 1384, 1461, 1608, 1729 (C O), 1936 (
—
—
— —
C ), 2921, 2973
— —
1H NMR (CDCl3), δ: 1.25 (s, 6H, 2 × CH3), 2.42 (s, 3H, Ph—CH3), 5.24 (s, 2H, CH2), 7.03 (d, 3J = 8.3 Hz,
—
—
3
—
—
2H, Ph), 7.70 (d, J = 8.3 Hz, 2H, Ph), 9.66 (s, 1H, HC O)
13
—
—
—
C NMR (CDCl3), δ: 19.8 (2 × CH3), 20.6 (Ph—CH3), 48.6 (C), 77.0 ( CH2), 108.0 ( C—Ph), 126.6 (C), 127.8
—
—
—
— —
C )
— —
(2 × CH, Ph), 129.9 (2 × CH, Ph), 135.9 (C), 201.8 (HC O), 207.6 (
GC-MS, m/z (%): 200 (M+, 10), 185 (100), 157 (50), 142 (90), 128 (40), 115 (40), 91 (20), 77 (20), 43 (25)
—
— —
C
— —
VIg
VIh
IXa
IR, ν˜/cm−1: 1036, 1180, 1248, 1606, 1726 (C O), 1938 (
), 2704, 2837, 2933
—
—
1
H NMR (CDCl3), δ: 1.27 (s, 6H, 2 × CH3), 3.79 (s, 3H, O—CH3), 5.08 (s, 2H, CH2), 6.83 (d, 3J = 8.3 Hz, 2H,
—
3
—
—
Ph), 7.12 (d, J = 8.3 Hz, 2H, Ph), 9.59 (s, 1H, HC O)
13
—
—
—
C NMR (CDCl3), δ: 21.1 (2 × CH3), 49.4 (C), 55.6 (O—CH3), 73.2 ( CH2), 109.5 ( C—Ph), 115.5 (2 × CH,
—
—
—
— —
C )
— —
Ph), 130.7 (2 × CH, Ph), 140.5 (C), 150.3 (C), 201.8 (HC O), 209.1 (
GC-MS, m/z (%): 216 (M+, 10), 145 (100), 102 (13), 43 (13)
IR, ν˜/cm−1: 1344, 1520, 1595, 1729 (C O), 1932 (
1H NMR (CDCl3), δ: 1.30 (s, 6H, 2 × CH3), 5.27 (s, 2H, CH2), 7.37 (d, 3J = 8.9 Hz, 2H, Ph), 8.13 (d, 3J =
), 2831, 2930, 3100
—
—
—
— —
C
— —
—
—
8.9 Hz, 2H, Ph), 9.59 (s, 1H, HC O)
—
13
—
—
—
C NMR (CDCl3), δ: 22.1 (2 × CH3), 48.5 (C), 80.0 ( CH2), 107.5 ( C—Ph), 123.8 (2 × CH, Ph), 128.7
—
—
— —
C )
— —
(2 × CH, Ph), 142.4 (C), 146.8 (C), 202.8 (HC O), 210.2 (
—
GC-MS, m/z (%): 231 (M+ , 21), 216 (100), 170 (25), 155 (24), 141 (60), 115 (30)
IR, ν˜/cm−1: 1034, 1058, 1100, 1166, 1241 (P O), 1453, 1480, 1681, 1936 (
—
— —
C ), 2850, 2899, 2969, 3131 (NH)
— —
—
3
1H NMR (CDCl3), δ: 1.18 (s, 6H, C—CH3), 1.25 (t, JH,H = 7.0 Hz, 6H, CH2—CH3), 1.50–1.60 (m, 6H, Ad),
—
—
1.63–1.70 (m, 6H, Ad), 1.84 (bs, 3H, Ad), 3.95–4.13 (m, 4H, O—CH2), 4.64 (s, 2H, CH2), 7.04 (s, 1H, HC N),
—
—
2
8.28 (d, JH,P = 28.1 Hz, 1H, NH)
13C NMR (CDCl3), δ: 16.0 (d, JC,P = 6.9 Hz, CH2—CH3), 28.0 (2 × CH3), 29.1 (CH, Ad), 36.1 (C, Ad), 36.7
3
2
—
—
—
—
(CH2, Ad), 40.5 (C), 42.9 (CH2, Ad), 62.9 (d, JC,P = 5.7 Hz, O—CH2), 77.6 ( CH2), 118.5 ( C-Ad), 154.3 (d,
3
—
— —
C )
— —
JC,P = 18.1 Hz, HC N), 207.5 (
—
GC-MS, m/z (%): 394 (M+, 47), 259 (10), 242 (100), 135 (16), 98 (11)
—
—
—
IXb
Xa
IR, ν˜/cm−1: 1036, 1248 (P O), 1479, 1921 (
C
), 2906, 2931, 2968, 3145 (NH)
—
—
—
3
1H NMR (CDCl3), δ: 0.12 (s, 9H, Si—CH3), 1.24 (s, 6H, C—CH3), 1.34 (t, JH,H = 7.1 Hz, 6H, CH2—CH3),
2
—
—
—
—
4.05–4.25 (m, 4H, O—CH2), 4.43 (s, 2H, CH2), 6.97 (s, 1H, HC N), 7.29 (d, JH,P = 27.1 Hz, 1H, NH)
3
13C NMR (CDCl3), δ: 0.8 (Si—CH3), 16.3 (d, JC,P = 7.1 Hz, CH2—CH3), 26.8 (2 × CH3), 40.7 (C), 63.5 (d,
2
3
—
—
—
—
—
—
— —
JC,P = 5.1 Hz, O—CH2), 71.1 ( CH2), 102.2 ( C—Si), 154.2 (d, JC,P = 17.2 Hz, HC N), 209.4 ( C )
— —
GC-MS, m/z (%): 332 (M+, 30), 180 (100), 108 (11), 73 (15)
IR, ν˜/cm−1: 1028, 1167, 1238 (P O), 1392, 1443, 1479, 1631 (C N), 2872, 2931, 2983, 3153 (NH)
1H NMRb (CDCl3), δ: 1.26 (t, 3JH,H = 6.9 Hz, 6H, CH2—CH3), 1.80 (d, 3JH,H = 5.3 Hz, 3H, C—CH3), 3.95–4.15
(m, 4H, CH2), 7.15 (q, JH,H = 5.3 Hz, 1H, CH), 8.14 (d, JH,P = 26.8 Hz, 1H, NH)
13C NMRb (CDCl3), δ: 16.1 (d, JC,P = 7.0 Hz, CH2—CH3), 18.1 ( C—CH3), 63.0 (d, JC,P = 5.1 Hz, CH2),
144.5 (d, JC,P = 19.1 Hz, CH)
1H NMRc (CDCl3), δ: 1.26 (t, 3JH,H = 6.9 Hz, 6H, CH2—CH3), 1.76 (d, 3JH,H = 5.3 Hz, 3H, C—CH3), 3.95–4.15
(m, 4H, CH2), 6.69 (q, JH,H = 5.3 Hz, 1H, CH), 7.59 (d, JH,P = 27.1 Hz, 1H, NH)
13C NMRc (CDCl3), δ: 12.6 ( C—CH3), 16.1 (d, JC,P = 7.0 Hz, CH2—CH3), 63.2 (d, JC,P = 5.1 Hz, CH2),
—
—
—
—
—
—
3
2
3
2
—
—
3
—
—
3
2
3
2
—
—
3
142.6 (d, JC,P = 18.2 Hz, CH)
GC-MS, m/z (%): 194 (M+, 1), 126 (43), 98 (100), 81 (49)
HRMS, m/z (found/calc.): 195.0905/195.0893 (C6H16N2O3P+
)

36
J. Galeta et al./Chemical Papers 67 (1) 29–39 (2013)
Table 2. (continued)
Compound
Spectral dataa
—
—
Xb
IR, ν˜/cm−1: 1035, 1166, 1237 (P O), 1393, 1461, 1733 (C N), 2874, 2911, 2934, 2964, 3163 (NH)
—
—
3
3
1H NMRb (CDCl3), δ: 0.83 (t, JH,H = 7.4 Hz, 3H, CH2—CH2—CH3), 1.24 (t, JH,H = 7.1 Hz, 6H, O—CH2—
3
CH3), 1.41 (qm, JH,H = 7.4 Hz, 2H, CH2—CH2—CH3), 2.03–2.14 (m, 2H, CH2—CH2—CH3), 3.95–4.12 (m, 4H,
3
2
O—CH2), 7.12 (t, JH,H = 5.7 Hz, 1H, CH), 8.21 (d, JH,P = 27.2 Hz, 1H, NH)
3
13C NMRb (CDCl3), δ: 13.5 (CH2—CH2—CH3), 16.0 (d, JC,P = 6.9 Hz, O—CH2—CH3), 19.9 (CH2—CH2—
2
3
CH3), 34.0 (CH2—CH2—CH3), 62.9 (d, JC,P = 5.5 Hz, O—CH2), 148.5 (d, JC,P = 18.5 Hz, CH)
1H NMRc (CDCl3), δ: 0.89 (t, 3JH,H = 7.4 Hz, 3H, CH2—CH2—CH3), 1.26 (t, 3JH,H = 7.1 Hz, 6H, O—CH2—CH3),
1.47 (qm, 3JH,H = 7.4 Hz, 2H, CH2—CH2—CH3), 2.20 (td, 3JH,H = 7.4 Hz, 3JH,H = 1.2 Hz, 2H, CH2—CH2—CH3),
3
2
3.95–4.12 (m, 4H, O—CH2), 6.53 (t, JH,H = 5.3 Hz, 1H, CH), 8.36 (d, JH,P = 27.2 Hz, 1H, NH)
3
13C NMRc (CDCl3), δ: 13.6 (CH2—CH2—CH3), 16.1 (d, JC,P = 6.8 Hz, O—CH2—CH3), 19.3 (CH2—CH2—
2
3
CH3), 28.0 (CH2—CH2—CH3), 63.0 (d, JC,P = 5.5 Hz, O—CH2), 148.0 (d, JC,P = 17.8 Hz, CH)
GC-MS, m/z (%): 222 (M+, 10), 126 (40), 98 (30), 70 (100), 55 (20)
HRMS, m/z (found/calc.): 223.1221/223.1206 (C8H20N2O3P+
)
—
—
Xc
IR, ν˜/cm−1: 1041, 1083, 1160, 1247 (P O), 1391, 1451, 1478, 1631 (C N), 2848, 2906, 2982, 3129 (NH)
—
—
3
1H NMR (CDCl3), δ: 1.33 (t, JH,H = 6.7 Hz, 6H, CH3), 1.62–1.77 (m, 12H, Ad), 1.97–2.02 (m, 3H, Ad), 4.06–4.20
2
—
—
(m, 4H, O—CH2), 6.86 (s, 1H, HC N), 7.12 (d, JH,P = 26.6 Hz, 1H, NH)
13C NMR (CDCl3), δ: 16.4 (d, JC,P = 6.7 Hz, CH3), 28.2 (CH, Ad), 36.7 (C, Ad), 36.9 (CH2, Ad), 40.3 (CH2,
3
2
3
—
Ad), 63.4 (d, JC,P = 5.6 Hz, O—CH2), 155.5 (d, JC,P = 17.0 Hz, HC N)
—
GC-MS, m/z (%): 314 (M+, 1), 153 (44), 126 (100), 98 (58), 81 (24)
3
Xd
Xe
1H NMR (CDCl3), δ: 1.37 (t, JH,H = 6.9 Hz, 6H, CH3), 4.12–4.26 (m, 4H, CH2), 6.98–7.02 (m, 1H, CH), 7.11–7.16
2
—
—
(m, 1H, CH), 7.25–7.29 (m, 1H, CH), 8.00 (s, 1H, HC N), 8.28 (d, JH,P = 27.6 Hz, 1H, NH)
13C NMR (CDCl3), δ: 16.3 (d, JC,P = 6.8 Hz, CH3), 63.8 (d, JC,P = 5.9 Hz, CH2), 127.1 (CH), 127.4 (CH),
128.2 (CH), 139.6 (d, JC,P = 19.8 Hz, HC N), 139.8 (C)
GC-MS, m/z (%): 262 (M+, 15), 153 (16), 126 (83), 109 (22), 98 (100), 81 (53)
IR, ν˜/cm−1: 1030, 1242 (P O), 1317, 1456, 1660 (C N), 2941, 2981, 3012, 3138 (NH)
1H NMRb (CDCl3), δ: 1.29 (t, JH,H = 7.1 Hz, 6H, CH3), 3.50 (d, JH,H = 5.8 Hz, 2H, Ph—CH2), 4.02–4.16 (m,
4H, O—CH2), 7.12–7.30 (m, 5H, Ph), 7.31 (t, JH,H = 5.8 Hz, 1H, N CH), 8.78 (d, JH,P = 27.7 Hz, 1H, NH)
13C NMRb (CDCl3), δ: 15.9 (d, JC,P = 6.8 Hz, CH3), 38.6 (Ph—CH2), 62.7 (d, JC,P = 5.4 Hz, O—CH2), 126.4
3
2
3
—
—
—
—
—
—
3
3
3
2
—
—
3
2
3
—
—
(CH), 128.4 (2 × CH), 128.6 (2 × CH), 136.8 (C), 146.5 (d, JC,P = 19.0 Hz, N CH)
1H NMRc (CDCl3), δ: 1.11 (t, JH,H = 7.0 Hz, 6H, CH3), 3.64 (d, JH,H = 5.2 Hz, 2H, Ph—CH2), 3.86–3.96 (m,
3
3
3
2
—
—
4H, CH2), 6.76 (t, JH,H = 5.2 Hz, 1H, N CH), 7.12–7.30 (m, 5H, Ph), 8.93 (d, JH,P = 28.6 Hz, 1H, NH)
13C NMRc (CDCl3), δ: 15.7 (d, JC,P = 6.8 Hz, CH3), 35.0 (Ph—CH2), 63.2 (d, JC,P = 6.2 Hz, CH2), 126.0
3
2
3
—
—
(CH), 128.1 (2 × CH), 128.3 (2 × CH), 135.9 (C), 148.2 (d, JC,P = 19.6 Hz, N CH)
GC-MS, m/z (%): 270 (M+, 80), 242 (20), 153 (20), 126 (90), 98 (100), 81 (40)
—
—
Xf
Xg
Xh
Xi
IR, ν˜/cm−1: 1032, 1066, 1168, 1226 (P O), 1369, 1391, 1482, 1532, 1615 (C N), 2814, 2905, 2941, 2986, 3136
—
—
(NH)
3
1H NMR (CDCl3), δ: 1.33 (t, JH,H = 7.0 Hz, 6H, CH3), 2.99 (s, 6H, N—CH3), 4.13–4.26 (m, 4H, CH2), 6.68 (d,
3
JH,H = 8.7 Hz, 2H, Ph), 7.49 (d, 3JH,H = 8.7 Hz, 2H, Ph), 7.56 (d, 2JH,P = 27.0 Hz, 1H, NH), 7.71 (s, 1H, HC N)
—
—
3
2
13C NMR (CDCl3), δ: 16.4 (d, JC,P = 6.9 Hz, CH3), 40.5 (N—CH3), 63.4 (d, JC,P = 5.5 Hz, CH2), 112.1 (CH),
3
—
122.8 (C), 128.2 (CH), 145.6 (d, JC,P = 18.9 Hz, HC N), 151.4 (C)
—
GC-MS, m/z (%): 299 (M+, 38), 162 (12), 146 (100), 126 (24), 98 (35), 81 (15)
IR, ν˜/cm−1: 1032, 1236 (P O), 1479, 1610, 2818, 2837, 2931, 2958, 3116 (NH)
1H NMR (CDCl3), δ: 1.36 (t, JH,H = 7.1 Hz, 6H, CH3), 3.82 (s, 3H, O—CH3), 4.03–4.37 (m, 4H, CH2), 6.88 (d,
—
—
3
3
3
2
—
JH,H = 8.8 Hz, 2H, Ph), 7.55 (d, JH,H = 8.8 Hz, 2H, Ph), 7.82 (s, 1H, HC N), 8.43 (d, JH,P = 28.1 Hz, 1H,
—
NH)
3
2
13C NMR (CDCl3), δ: 16.3 (d, JC,P = 7.1 Hz, CH3), 55.5 (O—CH3), 63.5 (d, JC,P = 5.1 Hz, CH2), 114.1 (CH),
3
—
127.6 (C), 128.2 (CH), 144.8 (d, JC,P = 19.2 Hz, HC N), 160.7 (C)
—
GC-MS, m/z (%): 286 (M+, 17), 153 (19), 126 (100), 109 (21), 98 (87), 81 (44)
IR, ν˜/cm−1: 1036, 1092, 1240 (P O), 1485, 2827, 2866, 2943, 2980, 3149 (NH)
1H NMR (CDCl3), δ: 1.36 (t, JH,H = 7.1 Hz, 6H, CH3), 2.35 (s, 3H, Ph—CH3), 4.09–4.31 (m, 4H, CH2), 7.16 (d,
—
—
3
3
3
2
—
JH,H = 7.9 Hz, 2H, Ph), 7.50 (d, JH,H = 7.9 Hz, 2H, Ph), 7.81 (s, 1H, HC N), 8.22 (d, JH,P = 28.1 Hz, 1H,
—
NH)
3
2
13C NMR (CDCl3), δ: 16.3 (d, JC,P = 7.1 Hz, CH3), 21.6 (Ph—CH3), 63.6 (d, JC,P = 6.1 Hz, CH2), 126.8 (CH),
3
—
129.5 (CH), 132.1 (C), 139.6 (C), 145.1 (d, JC,P = 19.2 Hz, HC N)
—
GC-MS, m/z (%): 270 (M+, 8), 153 (16), 126 (67), 98 (100), 81 (55)
IR, ν˜/cm−1: 1034, 1087, 1242 (P O), 1483, 2846, 2866, 2939, 2983, 3128 (NH)
1H NMR (CDCl3), δ: 1.37 (t, JH,H = 7.1 Hz, 6H, CH3), 4.08–4.31 (m, 4H, CH2), 7.31 (d, JH,H = 8.4 Hz, 2H,
Ph), 7.54 (d, JH,H = 8.4 Hz, 2H, Ph), 7.86 (s, 1H, HC N), 8.97 (d, JH,P = 28.7 Hz, 1H, NH)
13C NMR (CDCl3), δ: 16.3 (d, JC,P = 6.1 Hz, CH3), 63.6 (d, JC,P = 6.1 Hz, CH2), 127.9 (CH), 128.9 (CH),
—
—
3
3
3
2
—
—
3
2
3
—
133.4 (C), 135.1 (C), 143.8 (d, JC,P = 20.2 Hz, HC N)
—
GC-MS, m/z (%): 290 (M+, 7), 153 (18), 126 (100), 109 (21), 98 (90), 89 (19), 81 (48)

J. Galeta et al./Chemical Papers 67 (1) 29–39 (2013)
37
Table 2. (continued)
Compound
Spectral dataa
—
Xj
IR, ν˜/cm−1: 1032, 1242 (P O), 1343, 1520, 1582, 2844, 2945, 2993, 3128 (NH)
—
3
3
1H NMR (CDCl3), δ: 1.39 (t, JH,H = 7.1 Hz, 6H, CH3), 4.12–4.35 (m, 4H, CH2), 7.77 (d, JH,H = 8.9 Hz, 2H,
3
2
—
—
Ph), 7.95 (s, 1H, HC N), 8.22 (d, JH,H = 8.9 Hz, 2H, Ph), 9.21 (d, JH,P = 29.4 Hz, 1H, NH)
13C NMR (CDCl3), δ: 16.3 (d, JC,P = 6.1 Hz, CH3), 63.9 (d, JC,P = 6.1 Hz, CH2), 124.1 (CH), 127.3 (CH),
140.9 (C), 142.5 (d, JC,P = 20.2 Hz, HC N), 148.1 (C)
GC-MS, m/z (%): 301 (M+, 2), 153 (8), 126 (70), 98 (100), 81 (64)
3
2
3
—
—
—
Xk
IR, ν˜/cm−1: 1001, 1074, 1169, 1225, 1248 (P O), 1394, 1477, 1511, 2910, 2933, 2985, 3159 (NH)
—
3
1H NMR (CDCl3), δ: 1.42 (t, JH,H = 7.0 Hz, 6H, CH3), 4.22–4.35 (m, 4H, CH2), 7.45–7.60 (m, 3H, Naph),
2
3
—
—
7.78–7.91 (m, 3H, Naph), 8.26 (d, JH,P = 28.0 Hz, 1H, NH), 8.49 (s, 1H, HC N), 8.71 (d, JH,H = 8.3 Hz, 1H,
Naph)
3
2
13C NMR (CDCl3), δ: 16.4 (d, JC,P = 6.9 Hz, CH3), 63.7 (d, JC,P = 5.6 Hz, CH2), 124.6 (CH), 125.5 (CH),
3
126.2 (CH), 127.1 (CH), 127.3 (CH), 128.9 (CH), 130.1 (CH), 130.2 (C), 130.8 (C), 134.1 (C), 144.7 (d, JC,P
=
—
19.3 Hz, HC N)
—
GC-MS, m/z (%): 306 (M+, 11), 154 (55), 126 (100), 98 (92), 81 (35)
IR, ν˜/cm−1: 1049, 1093, 1161, 1217, 1244 (P O), 1394, 1443, 1473, 1624 (C N), 2908, 2933, 2985, 3055, 3151
—
—
—
—
Xl
(NH)
3
2
1H NMR (CDCl3), δ: 1.39 (t, JH,H = 7.1 Hz, 6H, CH3), 4.05–4.25 (m, 4H, CH2), 6.50 (d, JH,P = 28.6 Hz,
1H, NH), 7.45–7.60 (m, 4H, Ant), 7.85–7.95 (m, 2H, Ant), 8.00–8.10 (m, 2H, Ant), 8.24 (s, 1H, Ant), 8.53 (s, 1H,
—
HC N)
—
13C NMR (CDCl3), δ: 16.4 (d, 3JC,P = 6.1 Hz, CH3), 63.5 (d, 2JC,P = 5.4 Hz, CH2), 123.6 (2 × C), 124.5 (2 × CH),
3
126.0 (2 × CH), 127.4 (2 × CH), 128.8 (2 × C), 129.4 (2 × CH), 129.6 (CH), 131.5 (C), 142.4 (d, JC,P = 17.5 Hz,
—
HC N)
—
GC-MS, m/z (%): 356 (M+, 5), 203 (100), 189 (13), 126 (13), 98 (27), 81 (20)
a) Ad = 1-adamantyl; Ant = 9-anthryl; Naph = 1-naphthyl; Ph = phenyl; b) data for the first isomer (yield of Xa, Xb, Xe: 70 %,
80 %, 85 %, respectively); c) data for the second isomer (yield of Xa, Xb, Xe: 30 %, 20 %, 15 %, respectively).
Fig. 4. ORTEP plots of cis (A) and trans (B) isomers of hydrazone Xl shown at the 50 % probability level (ethyl groups are
omitted for clarity; blue = N, orange = P, red = O).
jor trans compound slowly isomerises to the cis form
probably under the influence of light. We assume that
the hydrazone double bond enters a conjugation with
the double bonds in the central anthracene ring, en-
abling rotation to cis isomer (Fig. 5). The feasible for-
mation of such a resonance structure can be explained
by comparable resonance energies of anthracene moi-
ety (351 kJ mol−1) and two preserved benzene rings
(301 kJ mol−1). We have not observed this isomeri-
sation without light, hence the isomerisation may be
considered as photoisomerisation.
In conclusion, we can state that the isomerisation
can proceed in light in both directions, with the final
formation of an almost equimolar mixture of stereoiso-
mers as detected by TLC. This might provide clues
to the formation of fold crystals composed of both
stereoisomers.
Supplementary data
Crystallographic data for the structures of both
stereoisomers of Xl have been deposited with the

38
J. Galeta et al./Chemical Papers 67 (1) 29–39 (2013)
Fig. 5. Photoisomerisation of a trans anthracene-containing derivative to a cis form.
Cambridge Crystallographic Data Centre as supple-
mentary publication nos. CCDC 871267 and 871268.
Copies of the data can be obtained, free of charge,
on application to CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK (tel: +44-(0)1223-762911; e-mail: de-
posit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk).
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.
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.
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.
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-
ing to three fused five-membered heterocycles. Tetrahedron,
61, 2387–2393. DOI: 10.1016/j.tet.2005.01.020.
Man, S., Buchlovič, M., & Potáček, M. (2006a). Cyclization of
β-allenyloximes as a novel method for nitrone preparation.
Tetrahedron Letters, 47, 6961–6963. DOI: 10.1016/j.tetlet.
2006.07.130.
Man, S., Nečas, M., Bouillon, J. P., Portella, C., & Potáček,
M. (2006b). Intra–intermolecular criss-cross cycloaddition of
nonsymmetrical allenylazines with fluorinated enones as an
initial step in the synthesis of 4H-pyrrolo[1,2-b]pyrazoles.
European Journal of Organic Chemistry, 2006, 3473–3478.
DOI: 10.1002/ejoc.200600175.
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.
References
Black, D. K., & Landor, S. R. (1965). Allenes. Part X. The
Claisen–Cope rearrangement of propargyl vinyl systems.
Journal of the Chemical Society, 1965, 6784–6788. DOI:
10.1039/jr9650006784.
Bruker AXS (1997). SHELXTL, Version 5.10. An integrated
system for solving and refining crystal structures from
diffraction data. Madison, WI, USA: Bruker AXS Ltd.
Buchlovič, M., Man, S., & Potáček, M. (2008). Allenyloxime–
a new source of heterocyclizations to stable cyclic nitrones.
Tetrahedron, 64, 9953–9961. DOI: 10.1016/j.tet.2008.07.113.
Buchlovič, M., Man, S., Kislits˜on, K., Mathot, C., & Potáček,
M. (2010a). One-pot, three-component synthesis of five-
membered cyclic nitrones by addition/cyclization/condensa-
tion domino reaction. Tetrahedron, 66, 1821–1826. DOI:
10.1016/j.tet.2010.01.040.
Buchlovič, M., Man, S., & Potáček, M. (2010b). Diverse chem-
ical behaviour of 2-hydroxy-functionalized pyrroline-1-oxide.
Tetrahedron Letters, 51, 5801–5803. DOI: 10.1016/j.tetlet.
2010.08.103.
Marek, R., Potáček, M., Marek, J., & De Groot, A. (1994).
Novel tandem cyclization-oxidation reaction of 2,2-dimethyl-
penta-3,4-dienal hydrazones. Tetrahedron Letters, 35, 6909–
6912. DOI: 10.1016/0040-4039(94)85039-9.
Buchlovič, M., Hebanová, S.,
& Potáček, M. (2012). 1,3-
Dipolar cycloadditions of new 2,5-bifunctionalized five-
membered cyclic nitrones. Tetrahedron, 68, 3117–3122. DOI:
10.1016/j.tet.2012.01.043.
Marek, R., Potáček, M., Marek, J., De Groot, A., & Dommisse,
R. (1995a). 2,2-Dimethylpenta-3,4-dienal derivatives: Prepa-
ration, NMR spectra, and crystal structure. Monatshefte fu¨r
Chemie, 126, 1151–1159. DOI: 10.1007/bf00811384.
Marek, R., Potáček, M., & Sapík, M. (1995b). Thermal cy-
clization of homoallenylhydrazones. Tetrahedron Letters, 36,
8101–8102. DOI: 10.1016/0040-4039(95)01686-c.
Marek, R., Šťastná-Sedláčková, I., Toušek, J., Marek, J.,
& Potáček, M. (1997). Homoallenylazines – intramolecu-
lar ”criss-cross” addition substrates. Synthesis, structure
and conformational study. Bulletin des Sociétés Chimiques
Belges, 106, 645–649.
Burkhard, J., Janků J., & Vodička, L. (1988). Reaction of
1-acetyladamantane with thionyl chloride. Collection of
Czechoslovak Chemical Communications, 53, 110–113. DOI:
10.1135/cccc19880110.
Galeta, J., Man, S., & Potáček, M. (2009). Non-symmetrical
allenyl azines and their transformations leading to new het-
erocyclic skeletons. ARKIVOC, 2009(vi), 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.
Potáček, M., Marek, R., Žák, Z., Trottier, J., Janoušek, Z., &
Viehe, H. G. (1993). Novel thermal tetracyclization by in-
tramolecular azine “criss-cross” addition. Tetrahedron Let-
ters, 34, 8341–8344. DOI: 10.1016/s0040-4039(00)61426-0.
Galeta, J., Man, S., Valoušková, A., & Potáček, M. (2013). Sub-
stituted homoallenyl aldehydes and their derivatives. Part 2:
Azines. Chemical Papers, 67, 40–50. DOI: 10.2478/s11696-
012-0238-z.

J. Galeta et al./Chemical Papers 67 (1) 29–39 (2013)
39
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.
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.
Zwierzak, A.,
& Sulewska, A. (1976). Solid-liquid phase-
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.
transfer-catalysed phosphorylation of hydrazine. Preparation
of dialkyl phosphorohydrazidates and N,Nꢀ-bis[dialkoxyphos-
phoryl]hydrazines. Synthesis, 1976, 835–837.