MICHAEL-MICHAEL ALDOL REACTION OF CHALCONES WITH CYANOACETYLUREA AND CYANOACETYLPIPERIDINE

Article abstract of DOI:10.1135/cccc19950594

Several highly substituted cyclohexane derivatives were synthesized by the one-pot condensation of chalcones and cyanoacetylurea (2:1) using sodium alkoxide in anhydrous alcohol at room temperature.The structure of the reaction products was established by

Full text of DOI:10.1135/cccc19950594

594
Tabba, Yousef, Al-Arab:
MICHAEL–MICHAEL ALDOL REACTION OF CHALCONES
WITH CYANOACETYLUREA AND CYANOACETYLPIPERIDINE
Hani D. TABBA, Nidal M. YOUSEF and Mohammad M. AL-ARAB*
Department of Chemistry, Yarmouk University, Irbid, Jordan
Received October 21, 1994
Accepted December 23, 1994
Several highly substituted cyclohexane derivatives were synthesized by the one-pot condensation of
chalcones and cyanoacetylurea (2 : 1) using sodium alkoxide in anhydrous alcohol at room tempera-
1
ture. The structure of the reaction products was established by infrared, H and 13C NMR spectros-
copy as well as by their elemental analysis. Single crystal X-ray crystallography shows the presence
of the cyclohexane moiety.
Until recently, many authors have published on the condensation reaction of chalcones
with active methylene compounds1–5, but less is known about the reaction of chalcones
with N-cyanoacetyl derivatives. For example, the reaction of chalcones with malononi-
trile6 and ethyl cyanoacetate7 in presence of ammonium acetate gives substituted py-
ridines. Chalcones also react with thioacetamide8 to give 2-pyridinethiones, with
cyanoacetamide9 to give 2-pyridones, with ethyl cyanoacetate10 in presence of sodium
ethoxide to give 8-oxaquinolines and with ethyl phenylacetate11 to give the correspond-
ing ethyl 3-aryl-4-benzoyl-2-phenylbutyrates. In addition, chalcones were also con-
densed with guanidine hydrochloride12 to give 4,6-diaryl-3,4-dihydro-1H-pyrimidine-
2-thione. Furthermore, the preparative value of one-pot multicomponent, sequential
Michael–Michael ring closure reactions followed by aromatization is illustrated by a
total synthesis of juncunol13, an unusual dihydrophenanthrene. Recently, we reported
that the base catalyzed reaction of chalcones with benzyl cyanides14 in 1 : 1 molar ratio
using a suspension of sodium ethoxide in ether affords a single diastereoisomer of 2,3-
diaryl-4-aroylbutyronitriles.
More recently, we reported15 that the base catalyzed condensation of benzyl cyanides
and chalcones in a 1 : 2 molar ratio using sodium ethoxide in anhydrous ether at room
temperature gives only 1,3,4,5-tetraaryl-2-aroyl-4-cyanocyclohexanols. An ambiguous
structural assignment was achieved from analytical and infrared, proton and 13C nuclear
* The author to whom correspondence should be addressed.
Collect. Czech. Chem. Commun. (Vol. 60) (1995)

Michael–Michael Aldol Reaction of Chalcones
595
magnetic resonance spectral data as well as single crystal X-ray crystallography. In
view of our continued interest in the chemistry of active methylene nitriles and other
related compounds16–22, we report herein the synthesis of a series of highly substituted
SCHEME 1
Collect. Czech. Chem. Commun. (Vol. 60) (1995)

596
Tabba, Yousef, Al-Arab:
TABLE I
Selected bond angles (°) for the compound Vd
Atoms
Angles
Atoms
Angles
C5−C1−C2
C6−C1−C5
109.3(7)
111.4(7)
108.1(8)
108.4(7)
115.2(7)
108.7(7)
109.5(7)
C6−C1−C2
106.0(17)
110.0(7)
111.9(8)
112.2(3)
109.2(6)
109.6(7)
110.4(7)
113.1(7)
112.2(2)
113.1(7)
121.8(9)
123.5(8)
173.0(11)
115.7(8)
117.5(9)
120.8(9)
119.3(12)
122.2(10)
121.6(8)
122.4(8)
118.9(8)
121.2(10)
122.1(11)
124.0(11)
117.7(9)
119.5(13)
119.3(16)
119.5(8)
118.5(9)
119.7(9)
120.2(10)
C9−C1−C2
C9−C1−C5
C9−C1−C6
C3−C2−C1
C21−C2−C1
C4−C3−C2
C21−C2−C3
C31−C3−C2
C31−C3−C4
O3−C4−C3
C10−C4−C3
5.3O(63)−C4−C1010 C41
C41−C4−C10
C10−C5−C1
−C4−C3
106.0(7)
109.0(6)
O1
C41−C4−O3
C51−C5−C1
−C6−C1
C51−C5−C10113.7(7)
O2−C6−C1
114.7(8)
116.2(12)
112.8(7)
125.9(8)
116.6(9)
121.6(11)
119.5(11)
119.6(8)
118.8(8)
118.7(8)
120.1(9)
117.8(10)
119.9(10)
118.2(10)
122.2(12)
121.3(14)
119.9(12)
121.9(7)
121.1(9)
120.1(10)
120.3(8)
O2−C6−O1
O2−C7−C8
N1−C9−C1
C5−C10−C4
C7−O2−C6
C22−C21−C2
C26−C21−C22
C24−C23−C22
C26−C25−C24
O4−C31−C3
C26−C21−C2
C23−C22−C21
C25−C24−C23
C25−C26−C21
C32−C31−C3
C33−C32−C31
C37−C32−C33
C35−C34−C33
C37−C36−C35
C42−C41−C4
C46−C41−C42
C44−C43−C42
C46−C45−C44
C52−C51−C5
C56−C51−C52
C54−C53−C52
C56−C55−C54
C32−C31−O4
C37−C32−C31
C34−C33−C32
C36−C35−C34
C36−C37−C32
C46−C41−C4
C43−C42−C41
C45−C44−C43
C45−C46−C41
C56−C51−C5
C53−C52−C51
C55−C54−C53
C55−C56−C51
Collect. Czech. Chem. Commun. (Vol. 60) (1995)

Michael–Michael Aldol Reaction of Chalcones
597
cyclohexanol derivatives by a base catalyzed cyclocondensation reaction of chalcones I
and N-cyanoacetylpiperidine II or chalcones I and cyanoacetylurea III in 2 : 1 molar
ratios (Scheme 1). This simple one-pot reaction is carried out by stirring a mixture of
chalcones and the cyanoacetyl derivatives using sodium alkoxide in anhydrous alcohol.
In each condensation, a heavy precipitate is formed which upon workup and recrystal-
lization from glacial acetic acid provides piperidine derivatives IV or the cyclohexanol
derivatives V. When cyanoacetylurea was used as a Michael donor, the cyclohexanol
derivatives V isolated as a result of this reaction indicated that the reaction could in-
volve double Michael addition of cyanoacetylurea carbanion to two moles of chalcones
TABLE II
Selected bond lengths (Å) for the compound Vd
Atoms
Distances
Atoms
Distances
C1−C2
1.553(12)
1.484(12)
1.518(11)
1.539(13)
1.508(11)
1.487(12)
1.489(12)
1.302(12)
1.440(14)
1.192(11)
1.358(14)
1.331(17)
1.360(17)
1.334(13)
1.354(13)
1.326(18)
1.337(16)
1.360(16)
1.344(25)
1.354(11)
1.367(14)
1.349(14)
C1−C5
1.534(13)
1.424(12)
1.486(13)
1.499(12)
1.412(10)
1.515(10)
1.188(11)
1.219(21)
1.138(12)
1.356(14)
1.347(16)
1.332(19)
1.470(12)
1.334(14)
1.337(16)
1.341(15)
1.361(17)
1.299(25)
1.376(17)
1.354(13)
1.328(16)
1.358(15)
C1−C6
C1−C9
C2−C3
C2−C21
C3−C31
C4−O3
C3−C4
C4−C10
C4−C41
C5−C51
C6−O2
C5−C10
C6−O1
C7−C8
C7−O2
C9−N1
O4−C31
C21−C26
C23−C24
C25−C26
C32−C33
C33−C34
C35−C36
C41−C42
C42−C43
C44−C45
C51−C52
C52−C53
C54−C55
C21−C22
C22−C23
C24−C25
C31−C32
C32−C37
C34−C35
C36−C37
C41−C46
C43−C44
C45−C46
C51−C56
C53−C54
C55−C56
Collect. Czech. Chem. Commun. (Vol. 60) (1995)

598
Tabba, Yousef, Al-Arab:
followed by cyclization with the elimination of urea molecule and then introduction of
ethoxy or methoxy group instead. However, when N-cyanoacetylpiperidine was used as
the Michael donor, a simple Michael adduct IV resulting from the addition of the ace-
tylpiperidine carbanion to the chalcone was obtained and none of the cyclohexanol
derivative analogs were isolated. The reason could also be that the cyanoacetylurea is
more acidic than the piperidine derivative and hence a second Michael addition is
possible.
The structural identification of the cyclohexanol derivatives Va – Vi was based on
the spectral data, elemental analysis and X-ray crystallography. The infrared spectra of
these cyclohexanol derivatives show a peak at 3 410 – 3 500 cm−1 corresponding to the
stretching frequency of the hydroxyl group in addition to a very intense band at about
1 650 cm−1 due to the benzoyl carbonyl stretching frequency and a band at around
2 220 cm−1 characteristic for the cyano group. The carbalkoxy carbonyl stretching fre-
quency shows a strong peak at around 1 735 cm−1. The nuclear magnetic resonance
spectral data of the cyclohexanol derivatives were also consistent with the suggested
1
structure. As a representative example, in the H NMR spectrum of the compound Vd
the hydroxyl proton signal is a doublet (J = 2.5 Hz) as a result of a long range coupling
with H-5. The intramolecular hydrogen bonding between OH and H-5 makes the mole-
cule rigid enough in a W geometry and this makes the long range coupling possible.
C44
C45
C43
C46
C42
C55
C41
C3
C10
C56
C51
C4
C54
C34
C33
C35
O3
C53
C31
N1
C5
C6
C52
C9
C2
C32
C36
C1
C37
O4
C22
C21
C26
O1
O2
C23
C7
C8
C25
C24
FIG. 1
The crystal structure of the compound Vd
Collect. Czech. Chem. Commun. (Vol. 60) (1995)

Michael–Michael Aldol Reaction of Chalcones
599
TABLE III
Atomic coordinates (. 104) and equivalent isotropic displacement parameters (Å2 . 103) for the com-
pound Vd
Atom
x
y
z
Ueq
C1
C2
C3
4219(9)
4698(8)
3536(8)
2575(9)
3271(8)
5396(9)
6891(14)
7673(15)
3551(9)
2147(8)
2903(8)
5999(6)
5677(6)
3197(6)
4468(6)
5696(9)
5762(10)
6839(12)
7966(11)
8033(11)
6952(10)
3996(9)
3856(8)
3451(9)
3340(10)
3595(11)
3988(12)
4132(10)
1370(10)
813(11)
−345(13)
−908(15)
−392(14)
773(12)
2865(9)
3466(9)
3098(10)
2139(12)
1503(11)
11304(8)
10045(3)
9038(7)
3897(3)
3941(3)
3807(3)
4240(4)
4331(3)
4008(4)
3659(5)
3335(8)
3355(4)
4225(3)
2946(3)
4459(3)
3581(3)
4788(2)
4270(3)
3609(4)
3046(4)
2792(4)
3079(6)
3632(5)
3892(4)
3834(4)
3338(4)
2826(4)
2382(4)
2447(5)
2959(5)
3404(4)
4126(5)
3613(5)
3525(6)
3952(9)
4480(8)
4560(5)
4360(4)
4758(4)
4806(5)
4451(5)
4057(5)
36(3)
39(4)
35(3)
39(4)
40(4)
46(4)
118(7)
357(18)
46(4)
42(4)
62(4)
56(3)
65(3)
55(3)
59(3)
39(4)
57(4)
73(5)
85(6)
95(6)
64(5)
45(4)
41(4)
56(4)
71(5)
82(6)
95(6)
74(5)
53(4)
73(5)
92(6)
115(9)
110(8)
73(5)
43(4)
52(4)
67(5)
73(6)
58(4)
C4
C5
C6
C7
9189(7)
11479(7)
12247(8)
13658(11)
13453(17)
11334(8)
10433(7)
11324(7)
12459(5)
12839(6)
9187(5)
C8
C9
C10
N1
O1
O2
O3
O4
7553(5)
C21
C22
C23
C24
C25
C26
C31
C32
C33
C34
C35
C36
C37
C41
C42
C43
C44
C45
C46
C51
C52
C53
C54
C55
9910(7)
9926(8)
9860(10)
9757(10)
9721(11)
9791(8)
7819(8)
6923(8)
7192(8)
6334(9)
5200(10)
4948(10)
5790(9)
8277(8)
7823(10)
7075(12)
6718(12)
7118(12)
7895(9)
12717(8)
13595(8)
14734(9)
14986(9)
14110(10)
Collect. Czech. Chem. Commun. (Vol. 60) (1995)

600
Tabba, Yousef, Al-Arab:
TABLE IV
Characteristic data of the compounds IV and V
Calculated/Found
M.p., °C
Yield, %
Formula
(M.w.)
IR
Compound
IVa
ν, cm−1
% C
% H % N % X
145 – 146
65
C25H28N2O2
(388.2)
2 240 (C≡N)
77.28 7.27
77.42 7.25
7.21
7.25
–
–
–
–
–
1 680 (C=O)
1 640 (C=O)
IVb
155 – 157
67
C28H28N2O2
(424.2)
2 245 (C≡N)
79.21 6.65
79.85 6.70
6.60
6.50
1 670 (C=O)
1 640 (C=O)
IVc
154 – 156
72
C24H28N2O2
(376.2)
2 240 (C≡N)
76.55 7.50
76.45 7.54
7.44
7.49
1 680 (C=O)
1 640 (C=O)
IVd
148 – 149
75
C23H24N2O2
(360.2)
2 240 (C≡N)
76.63 6.72
76.85 6.60
7.78
7.81
1 670 (C=O)
1 645 (C=O)
IVe
168 – 170
68
C25H28N2O2
(388.2)
2 245 (C≡N)
77.28 6.72
77.78 7.07
7.21
6.93
1 680 (C=O)
1 640 (C=O)
Va
234 – 235
65
C43H33Br2NO4
(787.6)
3 480 (OH)
65.73 4.24
65.40 4.08
1.78 20.10
2.08 19.97
2 250 (C≡N)
1 740 (C=O)
1 660 (C=O)
Vb
Vc
Vd
Ve
216 – 218
71
C35H27Br2Cl2NO4 3 490 (OH)
55.78 3.61
55.62 3.59
1.68
1.66
–
–
–
–
(753.0)
2 245 (C≡N)
1 740 (C=O)
1 665 (C=O)
160 – 161
69
C45H39NO6
(689.3)
3 480 (OH)
78.34 5.70
78.17 5.77
2.03
1.68
2 250 (C≡N)
1 740 (C=O)
1 660 (C=O)
193 – 195
70
C35H31NO4
(529.2)
3 485 (OH)
79.36 5.90
79.66 6.01
2.65
2.65
2 245 (C≡N)
1 745 (C=O)
1 660 (C=O)
207 – 208
68
C44H37NO4
(643.3)
3 485 (OH)
82.08 5.80
82.53 5.96
2.18
2.07
2 240 (C≡N)
1 740 (C=O)
1 655 (C=O)
Collect. Czech. Chem. Commun. (Vol. 60) (1995)

Michael–Michael Aldol Reaction of Chalcones
601
TABLE IV
(Continued)
Calculated/Found
% H % N % X
M.p., °C
Yield, %
Formula
(M.w.)
IR
Compound
ν, cm−1
% C
Vf
243 – 245
C42H29Cl4NO4 3 485 (OH)
67.10 3.89
67.23 4.09
1.86 18.62
1.76 18.68
72
(751.1)
2 245 (C≡N)
1 745 (C=O)
1 660 (C=O)
Vg
Vh
Vi
221 – 223
C42H31Br2NO4 3 480 (OH)
65.36 4.05
65.84 4.16
1.82 20.47
1.80 20.75
69
(771.1)
2 240 (C≡N)
1 740 (C=O)
1 665 (C=O)
208 – 209
C36H33NO4
(543.2)
3 485 (OH)
79.52 6.12
79.43 6.29
2.58
2.60
–
–
70
2 240 (C≡N)
1 740 (C=O)
1 665 (C=O)
223 – 224
C46H41NO8
(735.3)
3 480 (OH)
75.09 5.62
75.64 5.73
1.90
1.91
68
2 245 (C≡N)
1 745 (C=O)
1 660 (C=O)
The 13C NMR spectra exhibit a signal at δ 203 – 205 ppm due to the aroyl carbonyl
group. The cyano carbon appeared at around δ 117.0 ppm. Another signal at δ 166.0
ppm appeared due to the carbethoxy carbonyl group carbon in addition to the remaining
aliphatic carbons at δ (ppm) 74.9, 62.1, 52.7, 49.5, 45.4, and 42.0.
EXPERIMENTAL
Cyanoacetylurea and cyanoacetylpiperidine were purchased from Aldrich Chemical Co. Reagent
quality solvents were used without further purification. IR spectra were recorded as a KBr disc using
a Pye–Unicam SP3-100 instrument. 1H and 13C NMR spectra (δ, ppm; J, Hz) were run in CDCl3
using a Bruker WP 80-SY instrument with TMS as internal standard. Compounds were analyzed at
M-H-W Laboratories, Phoenix, Arizona, U.S.A. Melting points were determined on an Electrother-
mal melting point apparatus and were uncorrected.
The single crystal X-ray crystallographic analysis of the compound Vd was carried out on a Ni-
colet R3 m/V 4-circle X-ray diffractometer. The crystal system was triclinic with space group P1,
a = 10.4835 Å, b = 11.0533 Å, c = 24.1180 Å; α = 94.767°, β = 95.853°, γ = 98.144°. The selected
Collect. Czech. Chem. Commun. (Vol. 60) (1995)

602
Tabba, Yousef, Al-Arab:
TABLE V
1H NMR spectra (δ, ppm; J, Hz) of the compound IV and V
Compound
1H NMR spectrum
IVa
1.59 m, 6 H (H′-3,H-4′,H-5′); 2.28 s, 3 H (ArCH3); 2.38 s, 3 H (ArCH3); 3.45 m, 4 H
(H-2′,H-6′); 3.76 m, 2 H (H-2,H-3); 4.06 dd, 2 H, J = 3.6 (H-4); 7.25 – 8.05 m,
8 H (ArH)
IVb
IVc
IVd
IVe
1.58 m, 6 H (H-3′,H-4′,H-5′); 2.27 s, 3 H (ArCH3); 3.46 m, 4 H (H-2′,H-6′); 3.90 m,
2 H (H-2,H-3); 4.10 dd, 2 H, J = 4.0 (H-4); 7.15 – 8.50 m, 11 H (ArH)
1.65 m, 6 H (H-3′,H-4′,H-5′); 2.31 s, 3 H (ArCH3); 3.36 m, 4 H (H-2′,H-6′); 3.80 m,
2 H (H-2,H-3); 4.44 dd, 2 H, J = 3.6 (H-4); 7.10 – 8.00 m, 9 H (ArH)
1.58 m, 6 H (H-3′,H-4′,H-5′); 3.50 m, 4 H (H-2′,H-6′); 3.78 m, 2 H (H-2,H-3);
4.09 m, 2 H (H-4); 7.05 – 8.10 m, 10 H (ArH)
1.59 m, 6 H (H-3′,H-4′,H-5′); 2.28 s, 3 H (ArCH3); 3.46 m, 4 H (H-2′,H-6′); 3.73 m,
2 H (H-2,H-3); 3.85 s, 3 H (ArCH3); 4.06 dd, 2 H, J = 3.8 (H-4); 6.80 – 8.00 m,
8 H (ArH)
Va
Vb
Vc
Vd
Ve
0.85 t, 3 H, J = 7.2 (CH3); 2.25 dd, 1 H, J = 13.3, J = 3.2 (H-5); 3.02 dt, 1 H,
J = 14.4, J = 2.5, J = 13.0 (H-5); 3.86 q, 2 H, J = 7.2 (CH2); 4.38 dd, 2 H, J = 14.2,
J = 13.2, J = 2.6 (H-2,H-6); 5.13 d, 1 H, J = 12.3 (H-3); 5.51 d, 1 H (OH);
6.69 – 8.06 m, 22 H (ArH)
0.95 t, 3 H, J = 7.2 (CH3); 2.02 dd, 1 H, J = 13.6, J = 3.3 (H-5); 3.09 dt, 1 H,
J = 14.3, J = 2.6, J = 13.1 (H-5); 3.95 q, 2 H, J = 7.1 (CH2); 4.22 dd, 2 H, J = 14.2,
J = 13.1, J = 2.6 (H-2,H-6); 5.60 d, 1 H, J = 12.2 (H-3); 5.85 d, 1 H (OH);
7.08 – 7.70 m, 16 H (ArH)
0.80 t, 3 H, J = 7.2 (CH3); 2.21 dd, 1 H, J = 13.2, J = 3.2 (H-5); 3.06 dt, 1 H,
J = 14.3, J = 2.5, J = 13.1 (H-5); 3.40 s, 3 H (OCH3); 3.75 s, 3 H (OCH3); 3.80 q,
2 H, J = 7.2 (CH2); 4.37 dd, 2 H, J = 13.2, J = 2.5 (H-2,H-6); 5.14 d, 1 H, J = 12.2
(H-3); 5.55 d, 1 H (OH); 6.39 – 8.06 m, 22 H (ArH)
0.75 t, 3 H, J = 7.1 (CH3); 2.17 dd, 1 H, J = 13.2, J = 3.1 (H-5); 2.97 dt, 2 H,
J = 14.3, J = 2.5, J = 13.1 (H-5); 3.73 q, 2 H, J = 7.1 (CH2); 4.29 dd, 2 H, J = 14.2,
J = 13.2, J = 2.6 (H-2,H-6); 4.92 d, 1 H, J = 12.3 (H-3); 5.32 d, 1 H (OH);
7.34 – 8.20 m, 20 H (ArH)
1.97 s, 3 H (ArCH3); 2.24 dd, 1 H, J = 13.1, J = 3.2 (H-5); 2.30 s, 3 H (ArCH3); 3.10
dt, 1 H, J = 14.3, J = 2.6, J = 13.1 (H-5); 3.32 s, 3 H (OCH3); 4.42 dd, 2 H, J = 14.1,
J = 13.1, J = 2.5 (H-2,H-6); 5.16 d, 1 H, J = 12.2 (H-3); 5.48 d, 1 H, J = 2.5 (OH);
6.69 – 8.06 m, 22 H (ArH)
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Michael–Michael Aldol Reaction of Chalcones
603
TABLE V
(Continued)
Compound
1H NMR spectrum
Vf
2.24 dd, 1 H, J = 13.1, J = 3.2 (H-5); 3.10 dt, 1 H, J = 14.3, J = 2.5, J = 13.1 (H-5);
3.30 s, 3 H (OCH3); 4.42 dd, 2 H, J = 14.1, J = 13.2, J = 2.6 (H-2,H-6); 5.18 d, 1 H,
J = 12.1 (H-3); 5.46 d, 1 H, J = 2.5 (OH); 6.70 – 8.10 m, 20 H (ArH)
Vg
2.22 dd, 1 H, J = 13.2, J = 3.2 (H-5); 3.11 dt, 1 H, J = 14.3, J = 2.6, J = 13.1 (H-5);
3.33 s, 3 H (OCH3); 4.45 dd, 2 H, J = 14.1, J = 13.2, J = 2.6 (H-2,H-6); 5.19 d, 1 H,
J = 12.1 (H-3); 5.52 d, 1 H, J = 2.5 (OH); 6.90 – 8.20 m, 22 H (ArH)
Vh
Vi
2.24 dd, 1 H, J = 13.1, J = 3.2 (H-5); 2.09 s, 3 H (ArCH3); 2.35 s, 3 H (ArCH3);
3.12 dt, 1 H, J = 14.2, J = 2.5, J = 13.2 (H-5); 3.32 s, 3 H (OCH3); 4.40 dd, 2 H,
J = 14.3, J = 13.2, J = 2.5 (H-2,H-6); 5.16 d, 1 H, J = 12.1 (H-3); 5.48 d, 1 H,
J = 2.5 (OH); 6.65 – 8.25 m, 18 H (ArH)
2.25 dd, 1 H, J = 3.3, J = 3.1 (H-5); 3.10 dt, 1 H, J = 14.1, J = 2.6, J = 13.2 (H-5);
3.34 s, 3 H (OCH3); 3.57 s, 6 H (OCH3); 3.85 s, 3 H (OCH3); 3.91 s, 3 H (OCH3);
4.45 dd, 2 H, J = 14.1, J = 13.2, J = 2.5 (H-2,H-6); 5.10 d, 1 H, J = 12.2 (H-3);
5.40 d, 1 H, J = 2.6 (OH); 6.75 – 8.20 m, 20 H (ArH)
bond angles are listed in Table I. Figure 1 shows X-ray plot of the compound Vd. The bond lengths,
the atomic coordinates and equivalent isotropic displacement parameters are listed in Tables II and
III. The relative configuration of each of the five chiral carbons in the cyclohexane ring was also
determined from the X-ray molecular picture.
(1S*, 2S*, 3R*, 4S*, 5R*)-(±)-3-Aroyl-2,4,6-triaryl-1-cyano-4-hydroxycyclohexane Carboxylates V
and N-(3,5-Diaryl-2-cyano-5-oxopentanoyl)piperidine IV. General Procedure
To a solution of the appropriate sodium alkoxide (0.01 mol) in anhydrous alcohol (150 ml) contain-
ing cyanoacetylurea or cyanoacetylpiperidine (0.01 mol) was added chalcone (0.02 mol for the urea
derivative or 0.01 mol for the piperidine derivative). The mixture was stirred at room temperature for
12 – 18 h, the solid formed was filtered and crystallized from glacial acetic acid. The filtrate was
poured into water (150 ml), the organic layer separated, dried by anhydrous sodium sulfate and evap-
orated to give the crude unreacted starting materials.
1
The characteristic data of the compounds IV and V are given in Table IV. For the H NMR spectra
see Table V.
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