Novel synthesis and characterization of N-substituted-calix[4]azacrown derivatives

Article abstract of DOI:10.1080/00397910701845878

Novel calix[4]azacrown derivatives from the reaction between calix[4]amidocrown and the different N-(4-bromoacetamidephthalimido)alkanes derivatives, which may be useful intemediate compounds of pseudorotaxane, have been synthesized and structurally chara

Full text of DOI:10.1080/00397910701845878

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Novel Synthesis and Characterization of
N‐Substituted‐calix[4]azacrown Derivatives
Zhi‐Qiang Shi a , Ya‐Qing Feng a , Na Song a & He‐Wen Wang a
a School of Chemical Engineering and Technology, Tianjin University ,
Tianjin, China
Published online: 22 Feb 2008.
To cite this article: Zhi‐Qiang Shi , Ya‐Qing Feng , Na Song & He‐Wen Wang (2008) Novel Synthesis
and Characterization of N‐Substituted‐calix[4]azacrown Derivatives, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 38:6, 983-990, DOI:
10.1080/00397910701845878
To link to this article: http://dx.doi.org/10.1080/00397910701845878
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Synthetic Communicationsw, 38: 983–990, 2008
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910701845878
Novel Synthesis and Characterization of
N-Substituted-calix[4]azacrown Derivatives
Zhi-Qiang Shi, Ya-Qing Feng, Na Song, and He-Wen Wang
School of Chemical Engineering and Technology, Tianjin University,
Tianjin, China
Abstract: Novel calix[4]azacrown derivatives from the reaction between calix[4]ami-
docrown and the different N-(4-bromoacetamidephthalimido)alkanes derivatives,
which may be useful intemediate compounds of pseudorotaxane, have been syn-
thesized and structurally characterized by IR, 1H NMR, 13C NMR, MS, and
elemental analyses. From their analysis data, it was found that compounds 6a–d
adopted a cone conformation.
Keywords: calix[4]azacrown, characterization, conformation, n-(4-bromoacetami-
dephthalimido)alkanes, synthesis
INTRODUCTION
Interlocked supermolecules such as pseudorotaxanes, catenanes, and
[2]rotaxanes have attracted a great deal of attention in view of the design of
molecular machines, devices, and recognition systems.[1] Calix[4]azacrown
ether is particularly well suited as a pseudorotaxane building block because
of its application as a bulky stopper and its good complexation ability with
metal ions,[2] ammonium ions,[3] and anions.[4] Its incorporation into the pseu-
dorotaxane could give rise to the complexation ability of pseudorotaxane.
N-(4-Aminophthalimido)alkane derivatives (APn), which have the potential
to probe subtle changes in their microenvironment resulting from inter- or
intramolecular interactions,[5] could be bound to b-cyclodextrin (b-CD).[6]
Received December 5, 2007
Address correspondence to Ya-Qing Feng, School of Chemical Engineering and
Technology, Tianjin University, Tianjin 300072, China. E-mail: yqfeng@tju.edu.cn
983

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Z.-Q. Shi et al.
Consequently, calix[4]azacrown derivatives with an APn group may form
pseudorotaxane with b-CD. However, as we know, the pseudorotaxanes con-
taining calix[4]azacrown derivatives and APn unit have not been found
before. In this communication, we report four novel calix[4]azacrown deriva-
tives that may be useful intemediate compounds of pseudorotaxane, and
the further valuation of their self-assembly activities with b-CD is in progress.
RESULTS AND DISCUSSION
The synthetic pathway of the target compounds (6a–d) is depicted as shown
in Scheme 1. Compounds 1, 2, 3a–d, 4a, and 4b were synthesized according
to the literature procedure.[7]
According to the reported literature by Kim,[8] reaction of calix[4]amido-
crown 2 with N-(1-pyrenylmethyl)chloroacetamide using K2CO3 as a base in
acetonitrile with a catalytic amount of sodium iodide provide bis-O-substituted
product in medium yield. However, under similiar conditions, (potassium
iodide instead of sodium iodide), absolutely different products (N-substituted-
calix[4](aza)monocrown 6a–d were obtained. Research into the cause is now
in progress.
The structures of compounds 6a–d were established by infrared radiation
1
(IR), H NMR, 13C NMR, mass spectroscopy (MS), and elemental analyses.
The results showed that compounds 6a–d were in a cone conformation.
1
Take compound 6b as an example. In the H NMR spectra in CDCl3, two
doublets at d 4.16 and 3.54 ppm for the protons of the methylene bridge of
the calix[4]arene skeleton indicated that compound 6b is in a cone confor-
mation in solution. Moreover, in the 13C NMR data, the signal peak of the
methylene carbons of ArCH2Ar appeared at about 31 ppm according to the
Scheme 1.

N-Substituted-calix[4](aza)crown Derivatives
985
Mendoza rule.[9] It is also consistent with the cone conformation. Further-
more, a singlet at d 3.39 corresponding to NCH2CO was found. From
doublets at d 8.21 and d 7.76 both with J ¼ 8 Hz and a singlet at d 8.26,
the structure of the phthalimide unit was confirmed. MS and elemental
analysis data further confirmed their structures.
EXPERIMENTAL
Melting points were measured on a Yanagimoto MP-500 apparatus (uncor-
rected). The fourier transform infrared radiation (FT-IR) spectra (KBr
pellets) were measured on a Bio-Rad FTS3000 infrared spectrometer. The
1H NMR and 13C NMR spectra were recorded in CDCl3 using TMS as an
internal standard on Varian Inova 500-MHz and 75-MHz instruments at
298 K. MS analyses were carried out on an LCQ Advantage MAX spec-
trometer. Elemental analyses were performed on a Vario EL III elemental
analyzer. All reagents are commercially available and purified by standard
methods prior to use.
General Procedure for the Synthesis Compounds 4c–d
A
mixture of N-substituted-4-nitrophthalimide 3c–d (20 mmol) and
.
SnCl2 2H2O (14.89 g, 66 mmol) in 110 mL of 18% aqueous HCl solution
was heated to 408C–908C until no strating material was detected by
thin-layer chromatographys (TLC) (about 0.5–4 h). After cooling to room
temperature, the product, N-substituted-4-aminophthalimide, was collected
by filtration, washed with water, and recrystallized from ethanol. All the
products were characterized by the spectra.
Data
N-Octyl-4-aminophthalimide 4c: yellow solid, yield 46%, mp 52–548C; IR
1
(KBr, cm21): 3470, 3362, 1691; H NMR (CDCl3, d ppm): 7.59 (d, 1H,
J ¼ 8 Hz, ArH), 7.03 (s, 1H, ArH), 6.81 (d, 1H, J ¼ 8 Hz, ArH), 4.36
(w, 2H, NH2), 3.61 (t, 2H, J ¼ 7 Hz, NCH2), 1.64 (m, 2H, CH2), 1.31–1.25
(m, 10H, CH2), 0.86 (t, 3H, J ¼ 7 Hz, CH3). ESI-MS m/z 275.3 (M þ H)þ
(calcd. for C16H22N2O2 274.2). Anal. calcd. for C16H22N2O2: C, 70.04; H,
8.08. Found: C, 70.08; H, 8.06.
N-Benzyl-4-aminophthalimide 4d: yellow solid, yield 81%, mp 126–1278C;
1
IR (KBr, cm21): 3468, 3373, 1693; H NMR (CDCl3, d ppm): 7.58 (d, 1H,
J ¼ 8 Hz, ArH), 7.40 (d, 2H, J ¼ 8 Hz, ArH), 7.31 (t, 2H, J ¼ 8 Hz, ArH),
7.23 (t, 1H, J ¼ 8 Hz, ArH), 7.02 (s, 1H, ArH), 6.79 (d, 1H, J ¼ 8 Hz,

986
Z.-Q. Shi et al.
ArH), 4.79 (s, 2H, NCH2), 4.42 (w, 2H, NH2). ESI-MS m/z 253.2 (M þ H)þ
(calcd. for C15H12N2O2 252.1). Anal. calcd. for C15H12N2O2: C, 71.42; H,
4.79. Found: C, 71.36; H, 4.81.
General Procedure for the Synthesis Compounds 5a–d
To a stirred mixture of N-substituted-4-aminophthalimide 4a–d (3 mmol) and
NEt3 (1 mL, 7 mmol) in 50 mL of CH2Cl2, a solution of bromoacetyl bromide
(0.72 mL, 7 mmol) in 20 mL of CH2Cl2 was added during 3 h. The reaction
mixture was stirred at room temperature for 6 h and poured into 50 mL of
H2O. The CH2Cl2 layer was removed; the aqueous phase was washed with
saturated NaHCO3 and brine, dried over MgSO4, and distilled to afford a
solid, which was purified by column chromatography. After purification, all
the products were characterized by their spectra.
Data
2-Bromo-N-(2-ethyl-phthalimide-4-yl) acetamide 5a: pale yellow solid,
1
yield 83%, mp 156–1588C; IR (KBr, cm21): 3350, 1687; H NMR (CDCl3,
d ppm): 8.61 (s, 1H, NH), 8.06 (s, 1H, ArH), 7.94 (d, 2H, J ¼ 8 Hz, ArH),
7.82 (d, 2H, J ¼ 8 Hz, ArH), 4.07 (s, 2H, BrCH2CO), 3.73 (t, 2H, J ¼ 7 Hz,
NCH2), 1.27 (t, 3H, J ¼ 7 Hz, CH3). ESI-MS m/z 333.3 (M þ Na)þ (calcd.
for C12H11BrN2O3 310.0). Anal. calcd. for C12H11BrN2O3: C, 46.32; H,
3.56. Found: C, 46.34; H, 3.54.
2-Bromo-N-(2-butyl-phthalimide-4-yl) acetamide 5b: pale yellow solid,
1
yield 90%, mp 152–1548C; IR (KBr, cm21): 3346, 1690; H NMR (CDCl3,
d ppm): 8.53 (s, 1H, NH), 8.05 (s, 1H, ArH), 7.93 (d, 2H, J ¼ 8 Hz, ArH),
7.82 (d, 2H, J ¼ 8 Hz, ArH), 4.07 (s, 2H, BrCH2CO), 3.68 (t, 2H, J ¼ 7 Hz,
NCH2), 1.65 (m, 2H, CH2), 1.36 (m, 2H, CH2), 0.95 (t, 3H, J ¼ 7 Hz,
CH3). ESI-MS m/z 339.1 (M þ H)þ (calcd. for C14H15BrN2O3 338.0).
Anal. calcd. for C14H15BrN2O3: C, 49.57; H, 4.46. Found: C, 49.60; H, 4.44.
2-Bromo-N-(2-octyl-phthalimide-4-yl) acetamide 5c: pale yellow solid,
1
yield 94%, mp 136–1388C; IR (KBr, cm21): 3353, 1686; H NMR (CDCl3,
d ppm): 8.54 (s, 1H, NH), 8.06 (s, 1H, ArH), 7.93 (d, 2H, J ¼ 8 Hz, ArH),
7.82 (d, 2H, J ¼ 8 Hz, ArH), 4.08 (s, 2H, BrCH2CO), 3.66 (t, 2H, J ¼ 7 Hz,
NCH2), 1.65 (m, 2H, NCH2CH2), 1.32–1.23 (m, 10H, CH2), 0.87 (t, 3H,
J ¼ 7 Hz, CH3). ESI-MS m/z 417.4 (M þ Na)þ (calcd. for C18H23BrN2O3
394.1). Anal. calcd. for C18H23BrN2O3: C, 54.69; H, 5.86. Found: C, 54.73;
H, 5.83.

N-Substituted-calix[4](aza)crown Derivatives
987
2-Bromo-N-(2-benzyl-phthalimide-4-yl) acetamide 5d: yellow solid, yield
88%, mp 190–1928C; IR (KBr, cm21): 3305, 1697; 1H NMR (CDCl3, d ppm):
8.47 (s, 1H, NH), 8.06 (s, 1H, ArH), 7.90 (d, 2H, J ¼ 8 Hz, ArH), 7.82 (d, 2H,
J ¼ 8 Hz, ArH), 7.42 (d, 2H, J ¼ 7.5 Hz, ArH), 7.31 (t, 2H, J ¼ 7.5 Hz, ArH),
7.26 (t, 1H, J ¼ 7.5 Hz, ArH), 4.84 (s, 2H, NCH2), 4.05 (s, 2H, BrCH2CO).
ESI-MS m/z 373.3 (M þ H)þ (calcd. for C17H13BrN2O3 372.0). Anal. calcd.
for C17H13BrN2O3: C, 54.71; H, 3.51. Found: C, 54.65; H, 3.55.
General Procedure for the Preparation of Compounds 6a–d
Under nitrogen, calix[4]amidocrown (2) (0.24 g, 0.4 mmol), K2CO3(0.14 g,
1 mmol), the appropriate N-(4-bromoacetamidephthalimido)alkanes deriva-
tives 5a–d (0.88 mmol), and a catalytic amount of potassium iodide in
30 mL of acetontrile were heated to reflux temperature. After refluxed for
12 h, acetontrile was removed in vacuo. To the resulting yellow solid, water
(30 mL) and CH2Cl2 (20 mL) were added, and the organic phase was
separated and washed twice with 20 mL of distilled water. The CH2Cl2
layer was dried over MgSO4 and distilled off to afford a yellowish solid.
Column chromatography on silica gel using CH2Cl2/CH3CO2Et ¼ 5/1 as
an eluent gave the products. All the products were characterized by the
spectra.
Data
N-[N-(2-Ethyl-phthalimide-4-yl)aminocarbonylmethoxy]-calix[4](aza)mono-
crown6a: white solid, yield 61%, mp (.2508C decomposed); IR (KBr,
1
cm21): 3410, 3324, 1736, 1708, 1665; H NMR (CDCl3, d ppm): 10.05
(s, 1H, CONH), 9.12 (t, 2H, J ¼ 5.5 Hz), 8.26 (s, 1H, ArH), 8.21 (d, 1H,
J ¼ 8 Hz, ArH), 8.04 (s, 2H, OH), 7.77 (d, 1H, J ¼ 8 Hz, ArH), 7.13
(d, 4H, J ¼ 8 Hz, ArHmeta), 6.99 (d, 4H, J ¼ 8 Hz, ArHmeta), 6.87 (t, 2H,
J ¼ 8 Hz, ArHp), 6.78 (t, 2H, J ¼ 8 Hz, ArHp), 4.66 (s, 4H, OCH2CO),
4.16 (d, 4H, J ¼ 13.5 Hz, ArCH2Ar), 3.72 (q, 2H, J ¼ 7 Hz, NCH2CH3),
3.62 (m, 4H, CONHCH2), 3.54 (d, 4H, J ¼ 13.5 Hz, ArCH2Ar), 3.39
(s, 2H, NCH2CO), 3.02 (m, 4H, NCH2), 1.27 (t, 3H, J¼ 7 Hz, CH3). 13C
NMR (CDCl3): d 14.22 (1CH3), 31.90 (4ArCH2Ar), 33.08 (1 NCH2CH3),
40.63 (2CONHCH2), 54.80 (2 NCH2), 61.96 (1 NCH2CO), 75.27 (2CH2O),
[114.22 (1C), 121.33 (2C), 123.73 (1C), 124.41 (1C), 126.63 (1C), 127.19
(2C), 127.75 (4C), 129.44 (4C), 130.05 (4C), 132.80 (4C), 133.93 (1C),
144.67 (1C), 150.96 (2C), 151.96 (2C)] (aromatic 30C), 168.28 (hetero
2C), 168.35 (1 NCH2CO), 169.37 (2COCH2). ESI-MS m/z 838.3 (M þ H)þ
(calcd. for C48H47N5O9 837.3). Anal. calcd. for C48H47N5O9: C, 68.80; H,
5.65. Found: C, 68.88; H, 5.61.

988
Z.-Q. Shi et al.
N-[N-(2-Butyl-phthalimide-4-yl)aminocarbonylmethoxy]-calix[4](aza)mono-
crown 6b: white solid, yield 55%, mp (.2508C decomposed);
1
IR (KBr, cm21): 3395, 3317, 1735, 1713, 1662; H NMR (CDCl3, d ppm):
10.05 (s, 1H, CONH), 9.12 (t, 2H, J ¼ 5.5 Hz), 8.26 (s, 1H, ArH), 8.21
(d, 1H, J ¼ 8 Hz, ArH), 8.04 (s, 2H, OH), 7.76 (d, 1H, J ¼ 8 Hz, ArH),
7.13 (d, 4H, J ¼ 8 Hz, ArHmeta), 6.99 (d, 4H, J ¼ 8 Hz, ArHmeta), 6.86
(t, 2H, J ¼ 8 Hz, ArHp), 6.78 (t, 2H, J ¼ 8 Hz, ArHp), 4.66 (s, 4H,
OCH2CO), 4.16 (d, 4H, J ¼ 13.5 Hz, ArCH2Ar), 3.64 (m, 2H, NCH2CH2),
3.62 (m, 4H, CONHCH2), 3.54 (d, 4H, J ¼ 13.5 Hz, ArCH2Ar), 3.39
(s, 2H, NCH2CO), 3.02 (m, 4H, NCH2), 1.64 (m, 2H, NCH2CH2), 1.34
(m, 2H, CH2CH3), 0.93 (t, 3H, J ¼ 7 Hz, CH3). 13C NMR (CDCl3): d 13.89
(1CH3), 20.31 (1CH2), 30.91 (1CH2), 31.91 (4ArCH2Ar), 37.99
(1 NCH2CH2CH2CH3), 40.64 (2CONHCH2), 54.80 (2 NCH2), 61.96
(1NCH2CO), 75.27 (2CH2O), [114.22 (1C), 121.33 (2C), 123.72 (1C),
124.41 (1C), 126.55 (1C), 127.19 (2C), 127.75 (4C), 129.44 (4C), 130.05
(4C), 132.79 (4C), 133.85 (1C), 144.67 (1C), 150.96 (2C), 151.96 (2C)]
(aromatic 30C), 168.50 (hetero 2C), 168.56 (1 NCH2CO), 169.37
(2COCH2). ESI-MS m/z 866.4 (M þ H)þ (calcd. for C50H51N5O9 865.4).
Anal. calcd. for C50H51N5O9: C, 69.35; H, 5.94. Found: C, 69.41; H, 5.91.
N-[N-(2-Octyl-phthalimide-4-yl)aminocarbonylmethoxy]-calix[4](aza)mono-
crown 6c: white solid, yield 64%, mp (.2508C decomposed); IR (KBr,
1
cm21): 3361, 3325, 1767, 1708, 1657; H NMR (CDCl3, d ppm): 10.05
(s, 1H, CONH), 9.12 (t, 2H, J ¼ 5.5 Hz), 8.26 (s, 1H, ArH), 8.21 (d, 1H,
J ¼ 8 Hz, ArH), 8.04 (s, 2H, OH), 7.77 (d, 1H, J ¼ 8 Hz, ArH), 7.13
(d, 4H, J¼ 8 Hz, ArHmeta), 6.99 (d, 4H, J ¼ 8 Hz, ArHmeta), 6.85 (t, 2H,
J ¼ 8 Hz, ArHp), 6.78 (t, 2H, J ¼ 8 Hz, ArHp), 4.66 (s, 4H, OCH2CO), 4.13
(d, 4H, J ¼ 13.5 Hz, ArCH2Ar), 3.64 (m, 2H, NCH2CH2), 3.63 (m, 4H,
CONHCH2), 3.54 (d, 4H, J ¼ 13.5 Hz, ArCH2Ar), 3.39 (s, 2H, NCH2CO),
3.02 (m, 4H, NCH2), 1.65 (m, 2H, NCH2CH2), 1.34–1.21 [m, 10H,
(CH2)5CH3], 0.86 (t, 3H, J¼ 7 Hz, CH3). 13C NMR (CDCl3): d 14.31
(1CH3), 22.85 (1CH2), 27.11 (1CH2), 28.92 (1CH2), 29.39 (1CH2), 29.40
(1CH2), 31.90 (4ArCH2Ar), 32.01 (1CH2), 38.28 (1 NCH2CH2CH2), 40.63
(2CONHCH2), 54.81 (2 NCH2), 61.96 (1NCH2CO), 75.27 (2CH2O),
[114.23 (1C), 121.33 (2C), 123.74 (1C), 124.41 (1C), 126.55 (1C), 127.19
(2C), 127.75 (4C), 129.44 (4C), 130.05 (4C), 132.79 (4C), 133.86 (1C),
144.64 (1C), 150.96 (2C), 151.96 (2C)] (aromatic 30C), 168.50 (hetero
2C), 168.54 (1 NCH2CO), 169.38 (2COCH2). ESI-MS m/z 922.4(M þ H)þ
(calcd. for C54H59N5O9 921.4). Anal. calcd. for C54H59N5O9: C, 70.34; H,
6.45. Found: C, 70.38; H, 6.43.
N-[N-(2-Benzyl-phthalimide-4-yl)aminocarbonylmethoxy]-calix[4](aza)mono-
crown 6d: white solid, yield 51%, mp (.2508C decomposed); IR (KBr,
1
cm21): 3352, 3310, 1766, 1712, 1670; H NMR (CDCl3, d ppm): 10.06
(s, 1H, CONH), 9.11 (t, 2H, J ¼ 5.5 Hz), 8.27 (s, 1H, ArH), 8.22 (d, 1H,

N-Substituted-calix[4](aza)crown Derivatives
989
J ¼ 8 Hz, ArH), 8.03 (s, 2H, OH), 7.77 (d, 1H, J ¼ 8 Hz, ArH), 7.12 (d, 4H,
J ¼ 8 Hz, ArHmeta), 7.40 (d, 2H, J ¼ 8 Hz, ArH), 7.29 (t, 2H, J ¼ 8 Hz,
ArHmeta), 7.25 (t, 1H, J ¼ 8 Hz, ArHp), 6.98 (d, 4H, J ¼ 8 Hz, ArHmeta),
6.85 (t, 2H, J ¼ 8 Hz, ArHp), 6.78 (t, 2H, J ¼ 8 Hz, ArHp), 4.82 (s, 2H,
NCH2Ar), 4.65 (s, 4H, OCH2CO), 4.14 (d, 4H, J ¼ 13.5 Hz, ArCH2Ar),
3.61 (m, 4H, CONHCH2), 3.53 (d, 4H, J ¼ 13.5 Hz, ArCH2Ar), 3.38
(s, 2H, NCH2CO), 3.02 (m, 4H, NCH2). 13C NMR (CDCl3): d 31.91
(4ArCH2Ar), 40.63 (2CONHCH2), 41.78 (1 NCH2Ar), 54.78 (2 NCH2),
61.98 (1NCH2CO), 75.27 (2CH2O), [114.39 (1C), 121.32 (2C), 123.84
(1C), 124.64 (1C), 126.44 (1C), 127.19 (2C), 127.75 (4C), 127.93 (1C),
128.72 (2C), 128.85 (2C), 129.44 (4C), 130.05 (4C), 132.79 (4C), 133.81
(1C), 136.81 (1C), 144.84 (1C), 150.96 (2C), 151.96 (2C)] (aromatic 36C),
168.09 (hetero 2C), 168.11 (1 NCH2CO), 169.37 (2COCH2). ESI-MS m/z
900.4 (M þ H)þ (calcd. for C53H49N5O9 899.4). Anal. calcd. for
C53H49N5O9: C, 70.73; H, 5.49. Found: C, 70.80; H, 5.42.
ACKNOWLEDGMENTS
The support of the National Natural Science Foundation of China (No.
20376059) and Natural Science Foundation of Tianjin (No.
07JCZDJC00300) is acknowledged.
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