Unexpected configuration in stereoselectively synthesis of some novel (1Z)-1-(morpholin-1-yl)-N2-arylamidrazones

Article abstract of DOI:10.2174/157017812802139636

The nucleophilic substitution reaction of hydrazono-N-(aryl)- propanehydrazonyl chlorides 7 with piperidine or morpholine, under the same reaction conditions, resulted in the formation of 1-(piperdin-1-yl/morpholine-1- yl)-N²-arylamidrazones 8a

Full text of DOI:10.2174/157017812802139636

Letters in Organic Chemistry, 2012, 9, 487-492
487
Unexpected Configuration in Stereoselectively Synthesis of Some Novel
(1Z)-1-(morpholin-1-yl)-N2-Arylamidrazones
Mashooq A. Bhat, Khalid A. Al-Rashood and Hatem A. Abdel-Aziz*
Department of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, P.O. Box. 2457, Riyadh 11451,
Kingdom of Saudi Arabia
Received December 12, 2011: Revised April 08, 2012: Accepted May 12, 2012
Abstract: The nucleophilic substitution reaction of hydrazono-N-(aryl)-propanehydrazonyl chlorides 7 with piperidine or
morpholine, under the same reaction conditions, resulted in the formation of 1-(piperdin-1-yl / morpholine-1-yl)-N2-
arylamidrazones 8a-k, respectively. The X-ray diffraction of piperidin-1-yl-N2-arylamidrazone (8b) confirmed its 1E-
configuration in agreement with the previously reported, whereas X-ray showed the unexpected 1Z-configuration of their
analogs, morpholin-1-yl-N2-arylamidrazone (8j). This study established the role of hydrogen bond interaction in the
stereochemistry of this class of amidrazones.
Keywords: Amidrazones, hydrogen bond interaction, stereoselectively, x-ray diffraction analyses.
INTRODUCTION
syntheses of some morpholine-based amidrazones as
structural analogs for
(1E)-1-(piperdin-1-yl)-N2-
Open-chain or cyclic amidrazones have received much
attention as shown by the numerous published studies due to
their biological interests. Amidrazones are known to exhibit
inhibitory activity against enzymes of arachidonic acid
cascade which is responsible for the formation of important
metabolites [1]. These substances are considered as potent
mediators of inflammatory and allergic reaction in humans
[2]. Amidrazones have been found to be effective towards
cholinesterase, nucleoside hydrolase and glycosidase [3-5].
Consequently, the efficient construction of these molecules
has received significant attention [6, 7]. In the light of
pharmacological activity of amidrazones, several reports in
the literature have focused on their configuration using X-
ray diffraction analyses which revealed the role of hydrogen
bond interaction in their stereochemistry [8-10].
arylamidrazones 2-4. Our latter studies prompted us to
combine our present study with X-ray diffraction analysis to
determine the configuration of the new 1-(morpholin-1-yl)-
N2-arylamidrazones.
Reaction of acid hydrazides
5
with 2-oxo-N-
arylpropanehydrazonyl chlorides 6 yielded hydrazono]-N-
(aryl)-propanehydrazonyl chlorides 7 [9, 10] (Fig. 1). Next,
heating each of the compounds 7, in absolute ethanol, with
piperidine or morpholine resulted in the formation of a
precipitate, in each case during reflux. Single product was
evidenced by TLC analysis of the product [19]. However, 1H
NMR and mass spectra were comparable with desired
structures 8a-k [20]. The IR spectra of the latter amidrazones
exhibited, in each case, a band in the region of 1700-1680
cm-1 due to the carbonyl absorption, 1620-1590 cm-1 due to
C=N stretching, whereas the absorption bands of 2 NH
Recently, we have been reported the synthesis of a new
class of benzofuran-based (1Z)-N-arylpropanehydrazonoyl
chlorides 1 with highly synthetic potency for stereoselective
synthesis of (1E)-1-(piperdin-1-yl)-N2-arylamidrazones 2
and 3 [9]. X-ray analyses of the latter amidrazones showed a
conversion of configuration with respect to 1. Moreover,
Abdel-Aziz et al. have reported the (1E)-1-(piperidin-1-yl)-
2-(benzathiazol-2-oyl)-N2-arylamidrazones 4 with the same
configuration of amidrazones 2 and 3 [10]. However, X-ray
diffraction analyses of the latter piperidine-based
amidrazones identified a different intra- and intermolecular
hydrogen bond interaction.
1
functions appeared in the region 3350-2980 cm-1. Their H
NMR spectra were characterized by the two D2O
exchangeable signals of 2 NH groups in the region of ꢀ 8.26-
1
9.86 and ꢀ 9.38-11.19. H NMR spectra of piperidine-based
amidrazones showed two signals of piperidine moiety in the
regions ꢀ 1.54-1.63 and ꢀ 2.98-3.33, whereas, morpholine
signals appeared in the region of ꢀ 2.95-3.13 and ꢀ 3.71-3.82
for morpholine-based amidrazones. The 13C NMR spectra
showed signals of sp3 signals of piperidine carbons in the
region ꢀ 25.5-39.9 and morpholine carbons in the region ꢀ
30-39.
In continuation of our interest in the synthesis of
bioactive heterocycles [11-18], here, we deal with the
The single crystal of 8b was cultured from EtOH by slow
evaporation at room temperature. The X-ray analysis of
amidrazone 8b showed its structure geometry as (1E,2E)-
configuration (Fig. 2) which confirms a conversion of
configuration with respect to the geometry of their reactants
hydrazonyl halides (1E,2Z) [10]. X-ray of the latter
amidrazone confirmed both of the stereoselectivity of the
reaction and the E configuration of amidrazone skeleton (1E
*
Address correspondence to this author at the Department of
Pharmaceutical Chemistry, College of Pharmacy, King Saud University,
P.O. Box. 2457, Riyadh 11451, Kingdom of Saudi Arabia; Tel: +966-1-
4677343; Fax: +966-1-4676220; E-mail addresses: hatem_741@yahoo.com
1875-6255/12 $58.00+.00
© 2012 Bentham Science Publishers

488 Letters in Organic Chemistry, 2012, Vol. 9, No. 7
Bhat et al.
(E)
Ar
Cl
O
N
N
N
O
Me
N
Me
N
H
(Z)
H
N
(E)
N
O
N
N
H
Ar
N
N
N
N
H
H
Ar1
Me
O
O
Me
HN
Ar
O
Me
(1Z)-1
(1E)-2
(1E)-3
O
Ar
(E)
O
N
N
N
N
O
N
Me
(E)
N
(Z)
N
H
H
N
N
S
N
H
N
N
N
N
Ar
N
H
Ar1
H
N
S
Me
HN
Me
O
Ar
O
(1Z)-8j
(1E)-8b
(1E)-4
Fig. (1). Structure of hydrazonyl chloride 1 and amidrazones 2-4, 8b, and 8j.
O
O
Cl
N
O
H
N
Ar1
N
N
NH2
+
Me
N
Ar
N
Ar1
Ar
N
H
H
H
Cl
Me
5
6
7
X
X
O
N
HN
H
N
N
Ar
N
N
Ar1
H
Me
8
Comp.
Ar
Ar1
X
8a
8b
8c
8d
8e
8f
4-Me-C6H4-
4-Br-C6H4-
4-Me-C6H4-
4-Br-C6H4-
4-F-C6H4-
CH2
CH2
O
N
S
O
O
4-NH2SO2-C6H4-
2-Cl-C6H4-
O
8g
8h
8i
CH2
CH2
CH2
O
Me
3-Cl-C6H4-
4-NH2SO2-C6H4-
2-Cl-C6H4-
8j
O
8k
4-NH2SO2-C6H4-
O
Scheme 1. Synthesis of compounds 8a-k.

Unexpected Configuration in Stereoselectively Synthesis
Letters in Organic Chemistry, 2012, Vol. 9, No. 7 489
Fig. (2). X-ray structure of (1E,2E)-8b ethanol solvated.
Table 1. Characteristic Bond Lengths [Å], Torsion Angles [°] and Intramolecular H-bond of (1E,2E)-8b.
Br1
Br
C15
C14
C16
C17
C13
C12
N5
N
O1
O
NH
N4
S1
S
N3
N2
C7
N
C10
C11
N6
N
C19
C18
C1
C8
N
C2
C3
C4
H
C20
C21
N
N1
Me
C9
C22
C6
C5
Bond Length [Å]
N6ꢀC22
Br1ꢀC15
S1ꢀC1
1.902 (1)
1.732 (1)
1.736 (1)
1.220 (2)
1.387
1.478 (1)
1.399
1.410
1.376
1.400
1.384
1.400
1.483
1.505 (1)
1.479
1.398
1.391
1.380
1.391
C15ꢀC16
C16ꢀC17
C18ꢀC19
C19ꢀC20
C20ꢀC21
C21ꢀC22
O2ꢀC23
O2 ꢀC24
C23ꢀC24
C24ꢀO2
C24ꢀC24
O2ꢀC23
C23ꢀC24
1.381
C1ꢀ C2
C1ꢀC6
C2ꢀC3
C3ꢀC4
C4ꢀC5
C5ꢀC6
C7ꢀC8
C9ꢀC10
1.384
S1ꢀC7
1.525 (1)
1.510 (1)
1.525 (1)
1.524 (1)
1.513 (1)
1.478 (1)
1.497 (1)
1.478 (1)
1.176 (1)
1.513 (1)
1.497 (1)
O1ꢀC8
N1ꢀC6
N1ꢀC7
N2ꢀN3
N2ꢀC8
N3ꢀC10
N4ꢀN5
N4ꢀC11
N5ꢀC12
N6ꢀC11
N6ꢀC18
1.298
1.366
1.361
1.294
1.354 (1)
1.301
C10ꢀC11
C12ꢀC13
C12ꢀC17
C13ꢀC14
C14ꢀC15
1.392 (1)
1.412 (1)
1.469 (1)
Torsion Angles [°]
(1E) N6–C11–N4–N5
(2E) C11–C10–N3–N2
177.20
178.99
Intramolecular H-bond
DꢀH----A
N5ꢀH5-----N6
DꢀH
H----A
1.870
D----A
2.578
<(DHA)
128.27
0.961
The bond lengths [Å], torsion angles [°] and intramolecular H-bond of (1E,2E)-8b are well within the range
that typically occurred in similar amidrazone derivatives [9,10].
= 177.20º and 2E = 178.99º) [21, 22]. The intramolecular
hydrogen bond interaction N5ꢀH5-----N3 played a crucial
role in stabilizing the configuration of compound 8b in solid
state [8]. Selected bond distances, torsion angles [°] and
intramolecular H-bond of bis-hydrazone 8b are illustrated in
Table 1.

490 Letters in Organic Chemistry, 2012, Vol. 9, No. 7
Bhat et al.
Table 2. Characteristic Bond Lengths [Å] and Torsion Angles [°] of (1Z,2E)-8j.
O O8
C24
C25
C23
C19
Me
C18
C26
C6
O7
Cl1
O
N4
N
Cl
N9
N
H
N
N28
N5
C29
C20
C10
C16
C21
C22
C15
C14
C13
N
H
C30
C31
N
N3
O
Me
C11
C27
O2
C17
C12
C32
Bond length [Å]
Cl1—C29
O2—C17
O2—C20
N3—N28
N3—C22
N4—C22
N4—C26
N4—C23
N5—N9
1.725 (5)
1.358 (5)
1.404 (4)
1.354 (4)
1.296 (4)
1.425 (4)
1.458 (4)
1.453 (5)
1.379 (4)
1.359 (5)
1.271 (4)
1.502 (5)
C6—C22
O8—C25
O8—C24
O7—C21
N28—C10
C16—C17
C16—C18
C16—C15
C17—C12
C20—C18
C20—C21
C18—C19
1.441 (5)
1.402 (5)
1.425 (5)
1.207 (4)
1.403 (5)
1.364 (5)
1.417 (6)
1.398 (6)
1.396 (6)
1.345 (5)
1.469 (5)
1.510 (5)
C27—C32
C27—C10
C25—C26
C32—C31
C29—C30
C29—C10
C14—C15
C14—C13
C31—C30
C12—C13
C23—C24
1.397 (7)
1.377 (6)
1.496 (5)
1.385 (11)
1.390 (9)
1.377 (6)
1.368 (6)
1.388 (7)
1.336 (11)
1.394 (6)
1.503 (5)
N5—C21
C6—N9
C6—C11
Torsion angles [°]
(1Z) N4–C22–N3–N28
(2E) C22–C6–N9–N5
-0.7(9)
-178.0(15)
The bond lengths [Å] and the torsion angles [°] of (1Z,2E)-8j are well within the range that typically
occurred in similar amidrazone derivatives [9,10].
Fig. (3). X-ray structure of (1Z,2E)-8j.
Interestingly, the X-ray analysis of amidrazone 8j, in
contrast to that of compound 8b, showed its structure
geometry as (1Z,2E)-configuration (Fig. 3) which confirms a
retention of configuration with respect to the geometry of
their reactants hydrazonyl chlorides (1E,2Z). Although, the
single crystal of 8j was cultured from the same solvent of
crystal 8b, EtOH, no intramolecular hydrogen bond
interactions were detected in 8j. Selected bond distances of 2
and torsion angles 1Z and 2E are illustrated in Table 2.
In conclusion, we have uncovered an unexpected 1Z-
configuration of morpholin-1-yl-N2-arylamidrazone with
respect to that of their analogs, piperidin-1-yl-N2-
arylamidrazone with 1E-configuration.

Unexpected Configuration in Stereoselectively Synthesis
Letters in Organic Chemistry, 2012, Vol. 9, No. 7 491
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ACKNOWLEDGEMENT
Declared none.
CONFLICT OF INTEREST
[18]
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Dawood, K.M.; Farag, A.M.; Abdel-Aziz, H.A. A convenient
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The author(s) confirm that this article content has no
conflicts of interest.
Synthesis
of
1-(piperdin-1-yl
/
morpholine-1-yl)-N2-
arylamidrazones 8a-k. To
a
solution of hydrazono-N-(aryl)-
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washed with ethanol and dried, recrystallized from ethanol to
afford the amidrazones 8a-k in 65-78% yield.
(1E,2E)-1-(Piperidin-1-yl)-1-[(4-methylphenyl)hydrazono]-2-
[benzothiazol-2-oyl)hydrazono]propane (8a). Mp 178-180 °C; IR
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NMR (DMSO-d6) ꢀ 1.62 (s, 3CH2, piperidino), 2.1 (s, 3H, CH3),
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ꢀ 1.59 (s, 3CH2, piperidino), 2.26 (s, 3H, CH3), 3.05 (s, 2CH2,
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1
IR (KBr) v 3000, 2900 (2NH), 1740 (C=O), 1640 (C=N) cm-1; H
NMR (DMSO-d6) ꢀ 1.0 (s, 3H, CH3), 2.23 (s, 3H, CH3), 3.09 (s,
2CH2, morpholino), 3.79 (s, 2CH2, morpholino), 7.00-7.20 (m, 8H,
Ar-H), 9.57 (s, 1H, =NNH, D2O exch.), 10.28 (s, 1H, CONH, D2O
exch.); ESI MS m/z (%) 436.9 [M+]. (1Z,2E)-1-(Morpholin-1-yl)-1-
[(4-bromophenyl)hydrazono]-2-[benzothiazol-2-
oyl)hydrazono]propane (8d). Mp 188-190 °C; IR (KBr) v 3000,
2960 (2NH), 1700 (C=O), 1600 (C=N) cm-1; 1H NMR (DMSO-d6)
ꢀ 2.3 (s, 3H, CH3), 3.06 (s, 2CH2, morpholino), 3.78 (s, 2CH2,
morpholino), 7.29-8.2 (m, 8H, Ar-H), 9.68 (s, 1H, =NNH, , D2O
exch.), 10.12 (s, 1H, CONH, D2O exch.); ESI MS m/z 501.0 [M+].
(1Z,2E)-1-(Morpholin-1-yl)-1-[(4-flourophenyl)hydrazono]-2-
[benzothiazol-2-oyl)hydrazono]propane (8e). Mp 210-212 °C; IR
(KBr) v 3100, 3060 (2NH), 1710 (C=O), 1620 (C=N) cm-1; 1H
NMR (DMSO-d6) ꢀ 2.3 (s, 3H, CH3), 2.95 (s, 2CH2, morpholino),
3.71 (s, 2CH2, morpholino), 7.02-8.27 (m, 8H, Ar-H), 9.60 (s, 1H,
=NNH, D2O exch.), 10.80 (s, 1H, CONH, D2O exch.); 13C NMR
(DMSO-d6) ꢀ 30.64, 38.9, 39.9, 121.5, 147.3, 150.2, 167.6, 2.6.5;
ESI MS m/z 440.9 [M+]. (1Z,2E)-1-(Mopholin-1-yl)-1-[(4-
sulphonamidophenyl)hydrazono]-2-[benzothiazol-2-
[9]
[10]
[11]
[12]
[13]
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3000 (2NH), 1680 (C=O), 1590 (C=N) cm-1; 1H NMR (DMSO-d6)
ꢀ 1.63 (s, 3CH2, piperidino), 2.29 (s, 3H, CH3), 2.58 (s, 3H, CH3),
2.98 (s, 2CH2, piperidino), 7.31-7.80 (m, 8H, Ar-H), 9.37 (s, 1H,
=NNH, D2O exch.), 10.61 (s, 1H, CONH, D2O exch.); ESI MS m/z
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451.7
[M+].
(1E,2E)-1-(Piperidin-1-yl)-1-[(3-
chlorophenyl)hydrazono]-2-[3-methylbenzofuran-2-
oyl)hydrazono]propane (8h). Mp 233-235°C; IR (KBr) v 3020,
2980 (2NH), 1690 (C=O), 1600 (C=N) cm-1; 1H NMR (DMSO-d6)
ꢀ 1.54 (s, 3CH2, piperidino), 2.24 (s, 3H, CH3), 2.62 (s, 3H, CH3),
3.33 (s, 2CH2, piperidino), 6.66-7.83 (m, 8H, Ar-H), 8.91 (s, 1H,
=NNH, D2O exch.), 10.80 (s, 1H, CONH, D2O exch.); ESI MS m/z
[15]
[16]
Abdel-Wahab, B.F.; Abdel-Aziz, H.A.; Ahmed, E.M. Synthesis
and antimicrobial evaluation of some new 1,3-thiazole, 1,3,4-
thiadiazole,
1,2,4-triazole
and
[1,2,4]triazolo[3,4-
b][1,3,4]thiadiazine derivatives including 5-(benzofuran-2-yl)-1-
phenyl-pyrazole moiety. Monatsh. Chem. 2009, 140, 601-605.
Abdel-Wahab, B.F.; Abdel-Aziz, H.A.; Ahmed, E.M. Convenient
synthesis and antimicrobial activity of some new 3-substituted-5-
(benzofuran-2-yl)-pyrazole derivatives. Arch. Pharm., 2008, 341,
734-739.
449.7
[M+].
(1E,2E)-1-(Piperidin-1-yl)-1-[(4-
sulphonamidophenyl)hydrazono]-2-[3-methylbenzofuran-2-
oyl)hydrazono]propane (8i). Mp 220-222 °C; IR (KBr) v 3040,
3000 (2NH), 1700 (C=O), 1590 (C=N) cm-1; MS m/z 497.3 [M++1].
Mp 228-230; °C; IR (KBr) v 3300, 3100 (2NH), 1690 (C=O), 1600

492 Letters in Organic Chemistry, 2012, Vol. 9, No. 7
Bhat et al.
(C=N) cm-1; 1H NMR (DMSO-d6) ꢀ 2.36 (s, 3H, CH3), 3.13 (s,
2CH2, morpholino), 3.82 (s, 2CH2, morpholino), 7.13 (s, 2H,
SO2NH2), 7.42-8.30 (m, 8H, Ar-H), 9.86 (s, 1H, =NNH, , D2O
exch.), 11.19 (s, 1H, CONH, D2O exch.); ESI MS m/z 501.7 [M+].
(1Z,2E)-1-(Morpholin-1-yl)-1-[2-chlorophenyl)hydrazono]-2-[3-
methylbenzofuran-2-oyl)hydrazono]propane (8j). Mp 222-225°C;
IR (KBr) v 3360, 3280 (2NH), 1680 (C=O), 1590 (C=N) cm-1; ESI
[21]
[22]
The X-ray diffraction measurements of compound 8b was made
using Bruker (2009). APEX2 and SAINT (Bruker AXS Inc.,
Madison, Wisconsin, USA), at wavelength ꢀ = 1.54184 Å. The X-
ray diffraction measurements of compound 8j was made using
maXus (Bruker Nonius, Delft, The Netherlands and MacScience,
Yokohama, Japan), at wavelength ꢀ = 0.71073 Å.
Crystallographic data for the structures 8b and 8j have been
deposited with the Cambridge Crystallographic Data Center
(CCDC) under the numbers 833322 and 835060, respectively.
Copies of the data can be obtained, free of charge, on application to
CCDC 12 Union Road, Cambridge CB2 1EZ, UK [Fax: +44-1223-
MS
m/z
453.9
[M+].
(1Z,2E)-1-(Morpholin-1-yl)-1-[4-
sulphonamidophenyl)hydrazono]-2-[3-methylbenzofuran-2-
oyl)hydrazono]propane (8k). Mp 230-232 °C; IR (KBr) v 3400,
3280 (2NH), 1680 (C=O), 1600 (C=N) cm-1; 1H NMR (DMSO-d6)
ꢀ 2.0 (s, 3H, CH3), 3.0 (s, 2CH2, morpholino), 3.7 (s, 2CH2,
morpholino), 6.52 (s, 2H, SO2NH2), 7.01-7.62 (m, 8H, Ar-H), 8.26
(s,1H, =NNH, D2O exch.), 9.38 (s, 1H, CONH, D2O exch.) ; ESI
MS m/z 497.1 [M+].
336033;
e-mail:
deposit@ccdc.cam.ac.uk
or
http://www.ccdc.cam.ac.uk].