A facile and efficient synthetic approach to novel lariat macrocyclic diamides and bis macrocyclic diamides

Article abstract of DOI:10.1002/jhet.5570420113

The hydroxy macrocycles 8, 19a-c were prepared in 40-55% yields by reacting the dipotassium salts 2a-c with each of epichlorohydrin (7) and bis(chloromethyl) derivative 18. Acylation of the hydroxyl group of each of 8, 19a-c with 2-chloroacetylchloride (9

Full text of DOI:10.1002/jhet.5570420113

Jan-Feb 2005
93
A Facile and Efficient Synthetic Approach to Novel Lariat
Macrocyclic Diamides and Bis Macrocyclic Diamides
Ashraf A. Abbas*, Ahmed H. M. Elwahy and Ahmed A. M. Ahmed
Department of Chemistry, Faculty of Science, Cairo University, Giza, A. R. Egypt
E-mail: ashraf@chem-sci.cairo.eun.eg; ashrafaa50@yahoo.com
Received August 10, 2004
The hydroxy macrocycles 8, 19a-c were prepared in 40-55% yields by reacting the dipotassium salts 2a-c
with each of epichlorohydrin (7) and bis(chloromethyl) derivative 18. Acylation of the hydroxyl group of
each of 8, 19a-c with 2-chloroacetylchloride (9) in DMF gave the corresponding esters 10, 20a,b. Reaction
of the latter with different amines as well as phenoxides furnished exclusively the target lariat macrocycles
13a-c, 22a-c and 23a-c in 60-63% and 50-55% yields, respectively. Amination of two equivalents of the
chloroacetyloxy derivative 10 and 2a,b with 1 equiv. of piperazine (12c) afforded the corresponding bis-
macrocycles 14 and 26a,b respectively, in 60-65% yields. Moreover, the novel bis(macrocycles) 27-29 were
prepared in 45-50% yields, respectively, by reacting each of 20a,b with the dipotassium salts 2b, 24 and 25
respectively, in DMF.
J. Heterocyclic Chem., 42, 93 (2005).
which exhibiting low cytotoxicity [24]. Many other linked
mixed-donor macrocycles are also known and open possi-
bilities in cooperative receptors and switching materials
[25-31]. In connection with these findings and in continua-
tion of our interest in synthesizing macrocyclic di- and
tetralactams [32-38], and bis macrocycles [39-41] we
report here on the synthesis of novel lariat macrocyclic
diamides as well as bis(macrocyclic diamides) with
enhanced cation binding properties compared with their
corresponding precursors.
Introduction.
Since Pedersen [1,2] reported the synthesis and com-
plexing properties of crown ethers, the influence of struc-
ture variation within such ligands have received much
attention [3,4]. One of such structural variation is the
replacement of oxygen with nitrogen and/or sulfur [5,6].
Another is the development of functional groups in the
macrocyclic receptors, for example, incorporation of an
amide linkage in a polyether macrocycle has been reported
to modify the binding properties of crown ether com-
pounds to favor alkali and alkaline earth cations [6-8].
Moreover macrocyclic amides are precursors in the prepa-
ration of azacrown compounds, which are used for the syn-
thesis of cryptands [9,10]. Furthermore, insertion of aro-
matic rings into the macrocyclic ring was reported to facil-
itate the modification of macrocyclic hosts with various
UV and/or fluorescent active groups [11], proton ionizable
fragments [12] and functional groups, which can be
attached to proteins to provide radionuclide carriers for
medicals diagnosis and therapy [13]. In addition, attach-
ment of a functional side arm to the ligand framework
which provides the potential for three dimentional com-
plexation of metal ions have attracted much interest in the
last decades [14-19]. If the side arm attached site is a car-
bon atom of the macrocycle, the ligand is called a C-pivot
lariat ether. If it is a nitrogen atom of an azacrown ether,
the ligand is identified as N-pivot lariat ether. Moreover,
recent attention has also been given to bis(macrocycles)
which are capable of binding simultaneously to two or
more metal ions [20-22]. One interest in such systems have
reflected their potential for exhibiting cooperative behav-
ior of the type found in particular metaloenzymes incorpo-
rating two metal centres [23]. A number of such com-
pounds have been observed to act as anti-HIV agents,
Results and Discussion.
Recently [32-36] we reported the synthesis of a series of
benzo-substituted macrocyclic diamides of type 4 by react-
ing the appropriate dipotassium salt 2 (obtained upon treat-
ment of the bis phenols 1 with the corresponding dihalo or
ditosylate compounds 3 as outlined in Scheme 1. Other
research groups [42-44] reported the synthesis of 4 by
reacting the appropriate α,β-dicarboxylic acid derivatives
(diester 5a, or diacid dichloride 5b) with various diamines
6. Some macrocyclic diamide derivatives have also
recently been used as new catalysts in the highly regiose-
lective cleavage of epoxides with elemental halogens [44].
To improve the cation binding abilities of the macrocycles
4 our attention focused on functionalizing them with ligat-
ing side arms. We have also planned to study the connect-
ing of two units of these macrocycles by a flexible bridge
aiming at the synthesis of the first bis (macrocyclic
diamides) which should show promising analytical uses on
account of their capability of binding two or more metal
ions. For this purpose macrocyclic diamide with pendant
hydroxyl group 8 was prepared by reacting the potassium
salt 2 (obtained upon treatment of 1 with methanolic potas-
sium hydroxide solution) with epichlorohydrin (7) in aque-
ous media as depicted in Scheme 2.

94
A. A. Abbas, A. H. M. Elwahy and A. A. M. Ahmed
Vol. 42
the corresponding lariat macrocycles 13a-c. The novel bis
macrocycles 14 were obtained in 60% yields by reacting 2
equiv. of 10 with 1 equiv. of piperazine (12c) in refluxing
acetone (Scheme 2).
In an attempt to extend the spacing between the terminal
bis functional group in compounds 3 and to increase the
intervening ether functions we reported also the synthesis
of the novel macrocyclic diamides 19 as outlined in
Scheme 3. Thus, reduction of the bis aldehyde 15 [39] with
NaBH in refluxing methanol gave the corresponding
4
bis(hydroxymethyl) ether 16 in 75% yield. Treatment of
the latter compound with SOCl in chloroform gave the
2
corresponding bis(chloromethyl) ethers 18 in 65% yield. It
1
is noteworthy to mention that the H-NMR spectrum of
the crude product indicate the absence of the trichloro
derivative 17. The macrocycles 19 could be obtained in
40-55% yields by heating 18 with the dipotassium salts 2
in refluxing DMF. Acylation of the hydroxy group of com-
pounds 19a,c with 2-chloroacetylchloride (9) in DMF
afforded the corresponding chloroacetyloxy macrocycles
20a,b in 60-62% yields.
The reactivities of 20a,b towards different nucle-
ophiles were investigated aiming at the preparation of
their lariat analogues as well as their bis-macrocyclic
derivatives. Thus, compounds 20 react exclusively with
piperidine (12a) and morpholine (12b) to give the corre-
sponding amino derivatives 22a-c in 60-63% yields,
Acylation of the hydroxy group of compounds 8 with
2-chloroacetylchloride (9) in DMF afforded the corre-
sponding chloroacetoxy macrocycles 10 in 70% yields.
The latter compound could be used as a key intermediate
for the synthesis of lariat macrocycles 13a-c. Thus, reac-
tion of compounds 10 with a series of secondary amines
namely, diethyamine (11), piperidine (12a) and morpho-
line (12b) in acetone for 2 h furnished 60-65% yields of

Jan-Feb 2005
A Facile and Efficient Synthetic Approach to Novel Lariat Macrocyclic Diamides
95
respectively. Moreover, compound 20a,b reacted suc-
cessfully with the potassium salts 21a-c (obtained upon
treatment of the corresponding phenol with methanolic
KOH) in DMF to give the corresponding lariat deriva-
tives 23a-c in 50-55% yields, respectively. The now
available chloroacetoxy macrocycles 20a,b and its suc-
cessful reaction with amines as well as phenols, to give
the corresponding lariat macrocycles prompted us to
study its reaction with diamines, dihydroxy arenas and
bis phenols aiming at preparing a new series of novel
bis-macrocyclic diamines. Thus, reaction of 20a,b with
piperarazine in boiling acetone gave the corresponding
bis(macrocycles) 26a,b in 62% and 60% yields, respec-
tively, as outline in Scheme 4.
Moreover, the novel bis(macrocycles) 27-29 could be
prepared in 45-52% yields by reacting 20a,b with the
dipotassium salts 2a, 24 and 25, respectively, in DMF as
shown in Scheme 4. The salts 24 and 25 were obtained
directly from the corresponding bis-phenols upon treat-
ment with methanolic KOH. The successful synthesis of
the new bis-macrocycles 27 and 28 from the reaction of
20a,b with the appropriate bis-phenols should open new
access to novel heteronuclear metal ion receptors.
The structures of all the new compounds were con-
1
13
firmed by IR, H NMR, C NMR and elemental analyses
1
13
data. A comparison of the H NMR and C NMR spectra
of the macrocycles 4 ( A = (CH ) , n = 2-5, o-CH -C H -
2 n
2
6 4
CH , m-CH -C H -CH , etc; Y = (CH ) , n = 2-4) [32-34]
2
2
6
4
2
2 n

96
A. A. Abbas, A. H. M. Elwahy and A. A. M. Ahmed
Vol. 42
with the new macrocycles 8, 13, 14, 19, 22, 23, 26-29
reveals some interesting conclusions:- 1) The magentic
macrocyles entirely as one stable non-convertible con-
former comes from C NMR data (c.f. Experimental).
13
equivalence of the OCH and NCH protons in compounds
In conclusion we prepared a new series of macrocyclic
diamides having pendant hydroxyl group and utilized them
successfully as a key intermediate for the synthesis of
novel lariat macrocyclic dilactams containing strong donor
atoms as a supporting ligand at the end of the side-arm. We
expect this should improve the binding abilities of the new
macrocycles compared to their corresponding precursors
where the side arm can effectively participate in the coor-
dination and lead to higher cation-binding. We also pre-
pared a series of novel bis macrocycles in which two
2
2
4 indicate rapid conformational change in these macro-
cyles; 2) Contorary to compounds 4, the hydroxyl substi-
tuted macrocyles 8, 19, the chloroacetoxy macrocycles 10,
20, the lariat macrocycles 13, 22, 23 and the bis-macrocy-
cles 14, 26-29 are evidently present in one stable con-
former or in slowly (on the time scale of NMR) intercon-
vertible conformers. This is indicated by the presence of
geminal coupling and non-equivalence of all OCH and
2
NCH protons. 3) Evidence for the existence of the new
2

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A Facile and Efficient Synthetic Approach to Novel Lariat Macrocyclic Diamides
97
A solution of 1 [Y = (CH2)2] (10 mmol), NaOH (20 mmol)
and water 200 ml are stirred at 90 °C until solution is achieved.
After the solution is cooled to 50 °C, epichlorohydrin (7) (10
mmol) was added over a period of 3 h. Upon completion of the
addition, the reaction mixture is stirred at 50 °C for an addi-
tional 3-5 h and then cooling to room temperature. The solid
obtained was collected by filtration and crystallized from
macrocyclic dilactam units are connected by a flexible
bridge. We believe that these new series of compounds
should exhibit useful analytical uses on account of their
abilities to bind two or more metal ions. The new synthe-
sized macrocycles offer an advantage due to their easy
synthesis on a large scale in a simple procedure from inex-
pensive starting materials. Study of the cation binding
properties of the new macrocycles is still underway.
1
ethanol as colorless crystals, mp. 216-218 °C; H NMR
(CDCl3): δ 3.38−3.66 (m, 4H, NHCH2), 4.20- 4.42 (m, 4H,
OCH2), 4.36 (m, 1H, CH-O), 5.78 (d, 1H, J = 3.9 Hz, OH),
7.05-7.84 (m, 8H, ArH's), 8.5 (brs, 2H, NH).
Anal. Calcd for C19H20N2O5 (356.37): C, 64.04; H, 5.66; N,
7.86. Found: C, 64.30; H, 5.70; N, 8.00.
EXPERIMENTAL
All melting points are uncorrected. IR spectra (KBr) were
Synthesis of macrocycles 19a-c.
recorded on a Perkin-Elmer 1430 spectrophotometer. NMR spec-
1
tra were measured with a Varian Mercury 300 (300 MHz
H
General Procedure.
13
NMR, 75 MHz C NMR) spectrometer and chemical shifts are
given in ppm from TMS. C NMR spectra were recorded using
A solution of the appropriate potassium salts of 2a-c (10
mmol) and the dichloro compound 18 (10 mmol) in DMF (20 ml)
was heated under reflux for 10 min. during which time KCl was
precipitated. The solvent was then removed in vacuo and the
remaining material was washed with water (50 ml) and purified
to give compounds 19a-c.
13
APT pulse sequence. Mass spectra were recorded on HP 5988A
(EI, 15 eV). 1,2-Diaminoethane, 1,3-diaminopropane, 1,4-
diaminobutane and epichlorohydrin were used as purchased from
Aldrich. The starting compound 15 were prepared as reported
[39].
13-Hydroxy-6,12,13,20,28,29-hexahydro-14H-tetrabenzo-
[b,f,n,r][1,5,16,20,9,12]tetraoxadiazatricosin-26,31-
(27H,30H)dione (19a).
1,3-Bis(2-hydroxymethylphenoxy)propan-2-ol (16).
To a hot stirred solution (50 °C) of the bis(carbonyl) ethers 15
(10 mmol) in methanol (15 mmol) was added solid sodium boro-
hydride (20 mmol) over a period of 10 minutes. The reaction
mixture was heated under reflux for 1 h. The solvent was then
removed in vacuo and the remaining material was washed with
water. The solid obtained was collected and crystallized from
With the use of the general procedure 2a and 18 gave crude
19a which was crystallized from dioxane as colorless crystals
-1
(55%), mp. 284-286 °C; IR (cm ) 3363 (broad, OH, NH), 1640
(C=O); MS: m/z 568 (M+, 12%), 447 (13%), 404 (10%), 300
1
(100%), 250 (13%), 162 (50%), 150 (70%); H NMR (DMSO): δ
-1
toluene to give colorless crystals (75%), mp.125 °C; IR (cm )
3.15 ( brs, 4H, NCH2), 3.92-4.1 (m, 5H, OCH2, CHOH), 5.01-
5.21 (m, 4H, OCH2Ar), 5.42 (d, 1H, J = 4.4 Hz, OH), 6.66-7.90
(m, 18H, ArH's, NH).
Anal. Calcd for C33H32N2O7 (568.625): C, 69.71; H, 5.67; N,
4.93. Found: C, 69.80; H, 5.90; N, 5.10.
1
3425, 3279 (OH); HNMR (CDCl3) δ 3.43 (brs, 2H, CH2OH),
4.10-4.21 (m, 4H, CH2O), 4.33 (brs, 1H, CHOH), 4.62 (s, 4H,
CH2Ar), 4.97 (brs, 1H, OH), 6.85-7.28 (m, 8H, ArH's).
Anal. Calcd for C17H20O5 (304.34): C, 67.09; H, 6.62. Found:
C, 66.90; H, 6.80.
13-Hydroxy-6,12,13,20,28,29-hexahydro-14H,30H-tetra-
benzo[b,f,o,s][1,5,17,21,9,13]tetraoxadiazatetracosin-26,32-
(27H,31H)dione (19b).
1,3-Bis(2-chloromethylphenoxy)propan-2-ol (18).
To a cold stirred solution (-2 °C) of 16 (10 mmol) in chloro-
form (100 ml) was added dropwise thionyl chloride (5 ml).
Stirring was continued for 2 h at 0 °C. The solvent was then
removed in vacuo and the remaining residue was collected and
crystallized from benzene/petroleum ether (40-60) mixture as
With the use of the general procedure 2b and 18 gave crude
19b which was crystallized from ethanol as colorless crystals
-1
(35%), mp. 238-240 °C; IR (cm ) 3381 (broad, OH, NH),
1641 (C=O); MS: m/z 582 (M+, 9%), 461 (23%), 404 (38%),
-1
1
colorless crystals (65%), mp. 70-72 °C; IR (cm ) 3287 (OH); H
NMR (CDCl3) δ 2.93 (d, 1H, J = 5.7 Hz, OH), 4.30 (d, 4H, J =
5.6 Hz, OCH2), 4.48 (m, 1H, CHOH), 4.66 (s, 4H, CH2Cl), 6.94-
7.35 (m, 8H, ArH's).
1
314 (64%), 269 (100%), 194 (12%), 132 (23%); H NMR
(CDCl3): δ 1.15 (quintet, 2H, J = 6.3 Hz, NCH2CH2), 2.46 (d,
1H, J = 6.2 Hz, OH), 2.61-2.71 (m, 4H, NCH2CH2), 4.03 (d,
4H, J = 4.8 Hz, OCH2), 4.18 (brs, 1H, CHOH), 5.07 (d, 2H,
J = 9.1 Hz, upfield of OCH2Ar), 5.12 (d, 2H, J = 9.2 Hz,
downfield of OCH2Ar), 6.62-8.26 (m, 16H, ArH's), 7.65 (t,
2H, J = 5.4 Hz, NH).
Anal. Calcd for C17H18O3Cl2 (341.233): C, 59.84; H, 5.32.
Found: C, 59.70; H, 5.60.
Preparation of the Potassium Salts 2a-c, 21a-c, 24 and 25.
Anal. Calcd for C34H34N2O7 (582.652): C, 70.09; H, 5.88; N,
4.81. Found: C, 70.20; H, 6.10; N, 4.60.
To a solution of KOH (1.14 g, 10 mmol) in methanol (10 ml)
was added each of salicylaldehyde, o-nitrophenol and p-hydroxy-
benzaldehyde (10 mmol) or bis-phenols 1a-c, 24 and 25 (5
mmol). The mixture was stirred at room temperature for 10 min.
The solvent was then removed in vacuo. The remaining solid was
triturated with dry ether, collected, dried, and used in the next
step without further purification.
13-Hydroxy-6,12,13,20,28,29,30,31-octahydro-14H-tetra-
benzo[b,f,p,t][1,5,18,22,9,14]tetraoxadiazapentacosin-26,33-
(27H,32H)dione (19c).
With the use of the general procedure 2c and 18 gave crude 19c
which was crystallized from dioxane as colorless crystals (40%),
-1
17-Hydroxy-5,6,7,8,9,10,17,18-octahydro-16H-dibenzo[b,j]-
[1,12,5,8]dioxadiazacyclopentadecine-5,10-dione (8).
mp. 254-256 °C; IR (cm ) 3380 (broad, OH, NH), 1641(C=O);
MS: m/z 596 (M+, 7%), 404 (23%), 328 (100%), 251 (4%), 208

98
A. A. Abbas, A. H. M. Elwahy and A. A. M. Ahmed
Vol. 42
1
General Procedure.
(10%), 120 (37%); H NMR (DMSO): δ 0.79 (brs, 4H,
NCH2CH2), 2.87 (brs, 4H, NCH2), 3.82-3.99 (m, 5H, OCH2,
CHOH), 5.13 (d, 2H, J = 9.5 Hz, upfield of OCH2Ar), 5.19-5.28
(m, 3H, downfield of OCH2Ar, OH), 6.59-8.06 (m, 16H, ArH's),
7.69 (brs, 2H, NH).
A mixture of each of 10, and 20a,b (5 mmol) and excess of the
appropriate secondary amines (N,N-diethylamine (11), piperidine
(12a), morpholine (12b) or [(6 mmol) of compounds 10, 20a,b
and (3 mmol) of piperazine (12c) and few drops of triethylamine
for synthesis of compounds 14, 26a,b] in acetone (50 ml) was
heated under reflux for 10 min, then stirring at rt over night. [In
case of synthesis of compound 14 and 26a,b, the reaction mixture
was heated under reflux for 24 h]. The solvent was then removed
in vacuo. The solid obtained was washed with cold water and
purified using the proper method to give compounds 13a-c, 14,
22a-c and 26a,b.
Anal. Calcd for C35H36N2O7 (596.678): C, 70.45; H, 6.08; N,
4.69. Found: C, 70.60; H, 6.10; N, 4.90.
Reaction of Chloroacetyl Chloride with 8 and 19a,c. (Synthesis
of Compounds 10 and 20a,b).
General Procedure.
To a solution of each of 8 and 19a,c (5 mmol) in DMF (10 ml)
was added chloroacetyl chloride (9) (12 mmol). The reaction
mixture was stirred at room temperature for 2 h then poured on
crushed ice. The solid obtained was collected by filtration and
crystallized from the proper solvent for each derivative to afford
compounds 10 and 20a,b.
17-(N,N-diethylaminoacetoxy-5,6,7,8,9,10,17,18-octahydro-
16H-dibenzo[b,j][1,12,5,8]-dioxadiazacyclopentadecine-5,10-
dione (13a).
With the use of the general procedure 10 and 11 gave crude
material which was purified by column chromatography using
ethyl acetate/petroleum ether (40-60) to give 13a as oily product
17-Chloroacetoxy-5,6,7,8,9,10,17,18–octahydro-16H-dibenzo-
[b,j][1,12,5,8]dioxadiazacyclopentadecine-5,10-dione (10).
1
(60%); H NMR (CDCl3): δ 0.95 (t, 6H, J = 7.2 Hz, NCH2CH3),
2.56 (q, 4H, J = 7.2 Hz, NCH2CH3), 3.34 (s, 2H, NCH2CO),
3.51-3.72 (m , 4H, NCH2CH2N), 4.28-4.44 (m, 4H, OCH2), 5.45
(brs, 1H, CH-O) , 6.93-7.97 (m, 10H, ArH's, NH).
Anal. Calcd for C25H31N3O6 (469.536): C, 63.95; H, 6.65; N,
8.95. Found: C, 64.10; H, 6.30; N, 8.70.
With the use of the general procedure, 8 gave crude 10
which was crystallized from ethanol as colorless crystals
1
(70%), mp. 152 °C; H NMR (CDCl3): δ 3.64-3.83 (m, 4H,
NHCH2CH2NH), 4.42- 4.56 (m, 4H, OCH2), 4.17 (s, 2H,
OCOCH2Cl), 5.56 (quintet, 1H, J = 6.0 Hz, CH-O), 7.02-8.09
(m, 10H, ArH's, NH).
Anal. Calcd for C21H21N2O6Cl (432.86): C, 58.27; H, 4.89; N,
6.47. Found: C, 58.40; H, 4.70; N, 6.70.
17-(N-Piperidinoacetoxy-5,6,7,8,9,10,17,18–octahydro-16H-
dibenzo[b,j][1,12,5,8]-dioxadiazacyclopentadecine-5,10-dione
(13b).
With the use of the general procedure, 10 and 12a gave crude
material which was purified by column chromatography using
ethyl acetate/petroleum ether (40-60) to give 13b as oily product
13-Chloroacetoxy-6,12,13,20,28,29-hexahydro-14H-tetrabenzo-
[b,f,n,r][1,5,16,20,9,12]tetraoxadiazatricosin-26,31-(27H,30H)-
dione (20a).
1
(61%); H NMR (CDCl3): δ 1.2 ( brs, 2H, NCH2CH2CH2), 1.33
With the use of the general procedure 19a gave crude 20a
(brs, 4H, NCH2CH2CH2), 3.07 (s, 4H, NCH2), 3.34-3.63 (m, 4H,
NHCH2), 4.14-4.34 (m, 4H, OCH2), 5.35 (brs, 1H, CH-O), 6.8-
which was crystallized from benzene as colorless crystals
-1
13
(60%), mp. 90-92 °C; IR (cm ) 3374 (NH), 1760 (OCO),
7.80 (m, 8H, ArH's), 8.00 (brs, 2H, NH); C NMR (CDCl3) δ
1650 (CO, amide); MS: m/z 645 (M+, 2.5%), 523 (6%), 374
23.78, 25.72, 39.35, 54.47, 60.40, 69.09 (Alipahtic CH2's), 69.09
(Alipahtic CH), 114.55, 122.56, 131.62, 132.78 (Aromatic CH's),
123.44, 156.29 (Aromatic C's), 165.68, 16968 (C=O).
Anal. Calcd for C26H31N3O6 (481.547): C, 64.85; H, 6.49; N,
8.73. Found: C, 64.70; H, 6.60; N, 8.90.
1
(8%), 300 (33%), 251 (9.5%), 147 (100%), 121 (64%); H
NMR (CDCl3): δ 3.13 (s, 4H, NCH2), 3.92-3.98 (m, 4H,
OCH2), 4.02 (s, 2H, CH2Cl), 5.0-5.07 (m, 4H, OCH2Ar), 5.27
(quintet, 1H, J = 4.2 Hz, CHOCO), 6.25-8.23 (m,16H, ArH's),
7.59 (brs, 2H, NH).
Anal. Calcd for C35H33N2O8Cl (645.107): C, 65.17; H, 5.16; N,
4.34. Found: C, 65.20; H, 5.30; N, 4.50.
17-(N-Morpholinoacetoxy-5,6,7,8,9,10,17,18–octahydro-16H-
dibenzo[b,j][1,12,5,8]dioxadiazacyclopentadecine-5,10-dione
(13c).
13-Chloroacetoxy-6,12,13,20,28,29,30,31-octahydro-14H-tetra-
benzo[b,f,p,t][1,5,18,22,9,14]tetraoxadiazapentacosin-26,33-
(27H,32H)dione (20b).
With the use of the general procedure 10 and 12b gave crude
material which was purified by column chromatography using
ethyl acetate/petroleum ether (40-60) to give 13c as oily product
1
(65%); H NMR (CDCl3): δ 2.55 (t, 4H, J = 6.4 Hz,
With the use of the general procedure 19c gave crude 20b
which was crystallized from benzene as colorless crystals (65%),
mp. 212-214 °C; MS: m/z 673 (M+, 2.3%), 551 (6%), 480 (8%),
NCH2CH2O), 3.29 (s, 2H, NCH2CO), 3.67 (t, 4H, J = 6.4Hz,
OCH2CH2N), 3.59-3.84 (m, 4H, CH2N), 4.34-4.51 (m, 4H,
OCH2), 5.52 (m, 1H, CH-O), 6.92-8.07 (m, 10H, ArH's , NH).
Anal. Calcd for C25H29N3O7 (483.52): C, 62.10; H, 6.05; N,
8.69. Found: C, 62.40; H, 6.20; N, 8.90.
1
404 (8%), 328 (37%), 251 (49%), 147 (100%); H NMR
(CDCl3): δ 0.74 (s, 4H, NCH2CH2), 2.98 (m, 4H, NCH2), 3.88 (s,
2H, CH2Cl), 3.98-4.11 (m, 4H, OCH2), 5.11 (s, 4H, OCH2Ar),
5.19 (quintet, 1H, J = 3 Hz, CHOCO), 6.59-8.38 (m, 16H,
ArH's), 7.74 (brs, 2H, NH).
Anal. Calcd for C37H37N2O8Cl (673.161): C, 66.02; H, 5.54; N,
4.16. Found: C, 65.90; H, 5.60; N, 4.30.
13-(N-Piperidinoacetoxy)-6,12,13,20,28,29-hexahydro-14H-
tetrabenzo[b,f,n,r][1,5,16,20,9,12]tetraoxadiazatricosin-26,31-
(27H,30H)dione (22a).
With the use of the general procedure 20a and 12a gave crude
22a which was crystallized from benzene as colorless crystals
(60%), mp. 180-182 °C; MS: m/z 693 (M+, 0.16%), 568 (2%),
Reaction of Compounds 10 and 20a,b with Secondary Amines
(Synthesis of Compounds 13a-c, 14, 22a-c and 26a,b).

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A Facile and Efficient Synthetic Approach to Novel Lariat Macrocyclic Diamides
99
404 (17.5%), 300 (34%), 269 (100%), 203 (60%), 147 (99%),
121 (35%); H NMR (CDCl3): δ 1.42 (quintet, 2H, J = 5.1 Hz,
With the use of the general procedure 20a and 12c gave crude
26a which was crystallized from dioxane as colorless crystals
1
-1
NCH2CH2CH2), 1.59 (quintet, 4H, J = 5.1 Hz, NCH2CH2CH2),
2.46 (t, 4H, J = 5.1 Hz, NCH2CH2CH2), 3.14 (s, 4H, NCH2), 3.17
(s, 2H, COCH2N), 3.90-3.99 (m, 4H, OCH2), 4.99-5.06 (m, 4H,
OCH2Ar), 5.25 (m, 1H, CHOCO), 6.25-8.23 (m,16H, ArH's),
7.56 (brs, 2H, NH).
(62%), mp.144-146 °C; IR (cm ) 3385 (NH), 1750 (OCO), 1653
1
(CO amide); H NMR (CDCl3): δ 2.60 (s, 8H, NCH2), 3.14 (brs,
8H, NHCH2), 3.20 (s, 4H, COCH2N), 3.91-3.99 (m, 8H, OCH2),
4.99-5.05 (m, 8H, OCH2Ar), 5.25 (m, 2H, CHOCO) 6.24-8.23
(m, 32H, ArH's), 7.55 (brs, 4H, NH).
Anal. Calcd for C40H43N3O8 (693.795): C, 69.25; H, 6.25; N,
6.06. Found: C, 69.40; H, 6.30; N, 5.90.
nal Calcd for C74H74N6O16 (1303.429): C, 68.19; H, 5.72; N,
A
.
6.45. Found: C, 68.40; H, 5.90; N, 6.70.
13-(N-Piperidinoacetoxy)-6,12,13,20,28,29,30,31-octahydro-
14H-tetrabenzo[b,f,p,t][1,5,18,22,9,14]tetraoxadiazapentacosin-
26,33-(27H,32H)dione(22b).
1,4-Bis{6,12,13,20,28,29,30,31-octahydro-14H-tetrabenzo-
[b,f,p,t][1,5,18,22,9,14]tetraoxadiazapentacosin-26,33-
(27H,32H)dion-13-yloxycarbonylmethyl}piperazine(26b).
With the use of the general procedure 20b and 12a gave crude
22b which was crystallized from ethanol as colorless crystals
(63%), mp 181-183 °C; H NMR (CDCl3): δ 0.73 (brs, 4H,
HNCH2CH2), 1.41 (quintet, 2H, J = 5.1 Hz, NCH2CH2CH2), 1.58
(quintet, 4H, J = 5.1 Hz, NCH2CH2CH2), 2.43 (t, 4H, J = 5.1 Hz,
NCH2CH2CH2), 2.97 (m, 4H, HNCH2), 3.04 (s, 2H, COCH2N),
3.95-4.05 (m, 4H, OCH2), 5.10 (m, 4H, OCH2Ar), 5.17 (m, 1H,
CHOCO), 6.59- 8.38 (m, 16H, ArH's), 7.72 (brs, 2H, NH).
Anal. Calcd for C42H47N3O8 (721.85): C, 69.88; H, 6.56; N,
5.82. Found: C, 70.10; H, 6.70; N, 5.60.
With the use of the general procedure 20b and 12c gave crude
26b which was crystallized from ethanol as colorless crystals
1
-1
(60%), mp.122-124 °C; IR (cm ) 3387 (NH), 1750 (OCO), 1652
1
(CO, amide); H NMR (CDCl3): δ 0.72 (brs, 8H, HNCH2CH2),
2.53 (s, 8H, NCH2), 2.97 (m, 8H, HNCH2), 3.04 (s, 4H,
COCH2N), 3.94-4.05 (m, 8H, OCH2), 5.05-5.15 (m, 8H,
OCH2Ar), 5.17 (quintet, 2H, J = 2.7 Hz, CHOCO), 6.57-8.36 (m,
13
32H, ArH's), 7.71 (t, 4H, J = 3.9 Hz, NH); C NMR(CDCl3): δ
25.78, 39.79, 52.42, 58.53, 63.83, 67.2 (Aliphatic CH2's), 69.92
(Aliphatic CH), 111.84, 111.92, 121.29, 131.37, 131.71, 132.19,
132.64 (Aromatic CH's), 121.21, 122.94, 156.57, 157.21
(Aromatic C's), 164.49, 169.02 (CO).
Anal. Calcd for C78H82N6O16 (1359.536): C, 68.91; H, 6.08; N,
6.18. Found: C, 69.10; H, 6.10; N, 6.30.
13-(N-Morpholinoacetoxy)-6,12,13,20,28,29,30,31-octahydro-
14H-tetrabenzo[b,f,p,t][1,5,18,22, 9,14]tetraoxadiazapentacosin-
26,33-(27H,32H)dione (22c).
With the use of the general procedure 20b and 12b gave crude
22c which was crystallized from ethanol as colorless crystals
Reaction of Compounds 20a,b with 21a-c, 2b, 24 and 25.
(Synthesis of Compounds 23a-c, and 27-29).
-1
(60%), mp. 188-190 °C; IR (cm ) 3380 (NH), 1753 (OCO), 1650
(CO, amide); MS: m/z 723 (M+, 1.4%), 680 (5.5%), 475 (5%),
General Procedure.
1
359 (20%), 328 (18%), 246 (37%), 205 (59%), 100 (100%); H
A solution of the appropriate potassium 21a-c, 2a, 24 and 25
(10 mmol) and the chloroacetoxy compounds 20a,b (10 mmol for
synthesis of compounds 2a-c or 20 mmol for synthesis of com-
pounds 27-29) in DMF (20 ml) was heated at 80-90 °C for 5 h.
during which time KCl was precipitated. The solvent was then
removed in vacuo and the remaining material was washed with
water (50 ml) and purified to give compounds 23a-c, and 27-29.
NMR (CDCl3): δ 0.73 (s, 4H, NCH2CH2), 2.51 (t, 4H, J = 4.5
Hz, NCH2CH2O), 2.98 (m, 4H, NCH2), 3.06 (s, 2H, COCH2N),
3.71 (t, 4H, J = 4.5 Hz, NCH2CH2O), 3.90-4.08 (m, 4H, OCH2),
5.13 (m, 4H, OCH2Ar), 5.18 (quintet, 1H, J = 3 Hz,CHOCO),
13
6.59-8.38 (m, 16H, ArH's), 7.72 (brs, 2H, NH);
C
NMR(CDCl3) δ 25.85, 39.89, 53.00, 59.00, 63.92, 66.70, 67.29
(Aliphatic CH2's), 70.31 (Aliphatic CH), 111.91, 111.97, 121.37,
131.37, 131.45, 131.81, 132.31, 132.71 (Aromatic CH's), 121.32,
123.00, 156.65, 157.30 (Aromatic C's), 164.58, 169.04 (CO).
Anal. Calcd for C41H45N3O9 (723.82): C, 68.03; H, 6.27; N,
5.81. Found: C, 68.20; H, 6.40; N, 5.90.
13-(4-Formylphenoxy)acetoxy-6,12,13,20,28,29-hexahydro-
14H-tetrabenzo[b,f,n,r][1,5,16,20,9,12]tetraoxadiazatricosin-
26,31-(27H,30H)dione (23a).
With the use of the general procedure 20a and 21a gave crude
product which was purified by preparative thin layer chromatog-
raphy using CH2Cl2:MeOH (25:1) as an eluent to give 23a as col-
1,4-Bis{5,6,7,8,9,10,17,18–octahydro-16H-dibenzo[b,j]-
[1,12,5,8]dioxadiazacyclopentadecine-5,10-dion-17-yloxycar-
bonylmethyl}piperazine (14).
-1
orless crystals (50%), mp. 98-100 °C; IR (cm ) 3384 (NH), 2878
(CHO), 1763 (OCO), 1691 (CO, aldehyde), 1652 (CO, amide);
With the use of the general procedure 10 and 12c gave crude
14 which was crystallized from ethanol as colorless crystals
(60%), mp. 110-112 °C; H NMR (CDCl3): δ 2.5 (s, 8H,
MS: m/z 730 (M+, 39%), 592 (27%), 489 (33%), 414 (33%), 310
1
(72%), 166 (100%), 81 (52%); H NMR (CDCl3): δ 3.13 (brs,
1
4H, NCH2), 3.19-4.03 (m, 4H, OCH2), 4.71 (s, 2H, COCH2), 4.9-
5.0 (m, 4H, OCH2Ar), 5.32 (m, 1H, CHOCO), 6.32-8.24 (m,
22H, ArH's, NH), 9.81 (s, 1H, CHO).
Anal. Calcd for C42H38N2O10 (730.769): C, 69.03; H, 5.24; N,
3.83. Found: C, 68.90; H, 5.40; N, 4.10.
NCH2CH2N), 3.25 (s, 4H, CH2COO), 3.45-3.77 (m, 8H,
NHCH2), 4.31-4.48 (m, 8H, OCH2), 5.49 (q, 2H, J = 4.0 Hz,
13
CHOCO), 6.95-8.01 (m, 20H, ArH's, NH); C NMR (CDCl3) δ
39.29, 52.44, 59.06, 68.73 (Aliphatic CH2's), 69.47 (Aliphatic
CH), 114.29, 122.63, 131.71, 132.58 (Aromatic CH's), 132.21,
155.85 (Aromatic C's), 165.22, 68.89 (C=O).
Anal. Calcd for C46H50N6O12 (878.934): C, 62.86; H, 5.73; N,
9.56. Found: C, 62.90; H, 5.40; N, 9.40.
13-(2-Formylphenoxy)acetoxy-6,12,13,20,28,29,30,31-octahy-
dro-14H-tetrabenzo[b,f,p,t][1,5,18,22,9,14]tetraoxadiazapenta-
cosin-26,33-(27H,32H)dione (23b).
1,4-Bis{6,12,13,20,28,29-hexahydro-14H-tetrabenzo[b,f,n,r]-
[1,5,16,20,9,12]tetraoxadiazatricosin-26,31-(27H,30H)dion-13-
yloxycarbonylmethyl}piperazine (26a).
With the use of the general procedure 20b and 21b gave crude
23b which was crystallized from ethanol as colorless crystals
(55%), mp.188-190 °C; IR (cm ) 3392 (NH), 2873 (CHO), 1749
-1

100
A. A. Abbas, A. H. M. Elwahy and A. A. M. Ahmed
Vol. 42
1
With the use of the general procedure 20b and 25 gave oily
product which was purified by column chromatography using
ethyl acetate/petroleum ether (40-60) to give 29 as colorless crys-
(OCO), 1686 (CO, aldehyde), 1652(CO, amide); H NMR
(CDCl3): δ 0.72 (brs, 4H, NHCH2CH2), 2.97 (brs, 4H, NHCH2),
3.95-4.11 (m, 4H, OCH2), 4.62 (s, 2H, COCH2), 4.99 (d, 2H, J =
9 Hz, upfield of OCH2Ar), 5.02 (d, 2H, J = 9 Hz, downfield of
OCH2Ar), 5.26 (m, 1H, CHOCO), 6.56-8.37 (m, 20H, ArH's),
7.68 (brs, 2H, NH), 10.52 (s, 1H, CHO).
-1
tal (52%), mp.188-190 °C; IR (cm ) 3390 (NH), 2874 (CHO),
1
1759 (OCO), 1685 (CO, aldehyde), 1652 (CO, amide); H NMR
(CDCl3): δ 0.72 (m, 8H, NHCH2CH2), 2.98 (brs, 8H, NCH2),
3.95-4.1(m, 8H, OCH2), 4.34 (s, 2H, COCH2O), 4.54 (s, 2H,
COCH2O), 4.95-5.08 (m, 8H, OCH2Ar), 5.19-5.3 (m, 2H,
CHOCO), 6.28-8.38 (m, 39H, ArH's, NH), 10.35 (s, 1H, CHO).
Anal. Calcd for C81H78N4O19 (1411.522): C, 68.92; H, 5.57; N,
3.97. Found: C, 69.20; H, 5.60; N, 4.20.
Anal. Calcd for C44H42N2O10 (758.82): C, 69.65; H, 5.58; N,
3.69. Found: C, 69.80; H, 5.70; N, 3.90.
13-(2-Nitrophenoxy)acetoxy-6,12,13,20,28,29-hexahydro-14H-
tetrabenzo[b,f,n,r][1,5,16,20,9,12]tetraoxadiazatricosin-26,31-
(27H,30H)dione (23c).
Acknowledgements.
With the use of the general procedure 20a and 21c gave crude
product which was purified by preparative thin layer chromatogra-
phy using CH2Cl2:MeOH (20:1) as an eluent to give 23c as pale
The authors thank the Microanalytical Center, Cairo
University, Faculty of Science for valuable assistance.
+
yellow crystals (50%), mp.118-120 °C; MS: m/z 747 (M , 6%),
732 (9%), 611 (7.5%), 551 (10%), 431 (13%), 388 (17.5%), 149
(100%), 121 (45%); H NMR (CDCl3): δ 3.12 (m, 4H, NCH2), 3.8-
REFERENCES AND NOTES
1
4.02 (m, 4H, OCH2), 4.76 (s, 2H, COCH2), 4.97 (s, 4H, OCH2Ar),
5.32 (m, 1H, CHOCO), 6.18-8.23 (m, 22H, ArH's, NH).
Anal. Calcd for C41H37N3O11 (747.756): C, 65.86; H, 4.99; N,
5.62. Found: C, 65.90; H, 5.20; N, 5.90.
[1] C. J. Pedersen, J. Am. Chem. Soc., 89, 7017 (1967).
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1,2-Bis{2-[6,12,13,20,28,29-hexahydro-14H-tetrabenzo[b,f,n,r]-
[1,5,16,20,9,12]tetraoxadiazatricosin-26,31-(27H,30H)dion-13-
yloxycarbonylmethyloxyphenyl]carbonylamino}ethane (27).
With the use of the general procedure 20a and 2a gave crude prod-
uct which was purified by preparative thin layer chromatography
using ethyl acetate/petroleum ether (40-60) (10:1) to give 27 as color-
1
less crystals (45%), mp.158-160 °C; H NMR (CDCl3): δ 3.12 (brs,
8H, NHCH2), 3.67-3.68 (m, 4H, NHCH2), 3.87-3.94 (m, 8H, OCH2),
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4.72 (s, 4H, OCH2CO), 4.85-5.0 (m, 8H, OCH2Ar), 5.28 (m, 2H,
13
CHOCO), 6.18-8.56 (m, 46H, ArH's, NH); C NMR(CDCl3): δ
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39.69, 39.98, 64.14, 65.39, 66.59 (Aliphatic CH2's), 71.16 (Aliphatic
CH), 111.27, 112.12, 121.26, 121.55, 122.2, 130.49, 131.196, 132.37,
132.55, 132.74 (Aromatic CH's), 122.19, 123.01, 123.01, 155.54,
156.05, 157.07 (Aromatic C's), 165.08, 165.22, 167.65 (CO).
Anal. Calcd for C86H80N6O20 (1517.606): C, 68.06; H, 5.31; N,
5.54. Found: C, 68.30; H, 5.40; N, 5.70.
1,3-Bis{2-[6,12,13,20,28,29-hexahydro-14H-tetrabenzo[b,f,n,r]-
[1,5,16,20,9,12]tetraoxadiazatricosin-26,31-(27H,30H)dion-13-
yloxycarbonylmethyloxy]phenyl}propane (28).
With the use of the general procedure 20a and 24 gave crude
product which was purified by preparative thin layer chromatogra-
phy using ethyl acetate/petroleum ether (40-60) (20:1) as an eluent
1
to give 28 as colorless crystals (45%), mp. 108-110 °C; H NMR
(CDCl3): δ 2.28 (quintet, 2H, J = 6 Hz, OCH2CH2CH2O), 3.12
(brs, 8H, NCH2), 3.87-3.97 (m, 8H, OCH2), 4.21 (t, 4H, J = 6 Hz,
OCH2CH2CH2O), 4.62 (s, 4H, OCH2CO), 4.94 (s, 8H, OCH2Ar),
5.27 (quintet, 2H, J = 3.6 Hz, CHOCO), 6.20-8.22 (m, 40H,
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13
ArH's), 7.54 (brs, 4H, NH); C NMR(CDCl3): δ 29.36, 29.99,
39.66, 64.16, 65.83, 66.59 (Aliphatic CH2's), 70.58 (Aliphatic CH),
111.32, 112.04, 114.4, 115.27, 121.19, 121.47, 122.91, 130.42,
131.20, 132.34, 132.69 (Aromatic CH's), 121.52, 123.03, 147.59,
148.97, 156.16, 157.06 (Aromatic C's), 165.09, 168.36 (CO).
Anal. Calcd for C85H80N8O20 (1533.61): C, 66.57; H, 5.26; N,
7.31. Found: C, 66.70; H, 5.30; N, 7.10.
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[1,5,18,22,9,14]tetraoxadiazapentacosin-26,33-(27H,32H)dion-13-
yloxycarbonylmethyloxy}benzaldehyde (29).

Jan-Feb 2005
A Facile and Efficient Synthetic Approach to Novel Lariat Macrocyclic Diamides
101
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