Enhanced etherification of calix[4]arenes by microwave irradiation

Article abstract of DOI:10.1007/s10847-017-0709-5

Microwave irradiation has been found to be a highly efficient method for etherification of p-tert-butylcalix[4]arene with alkyl bromides or ditosylate. The corresponding products were obtained as a pure form in modest yield within short reaction time when

Full text of DOI:10.1007/s10847-017-0709-5

J Incl Phenom Macrocycl Chem (2017) 88:77–83
DOI 10.1007/s10847-017-0709-5
SHORT COMMUNICATION
Enhanced etherification of calix[4]arenes by microwave
irradiation
1
1
1
Zhen Xu · Zao Sheng Lü · Lei Chen
Received: 23 October 2016 / Accepted: 6 March 2017 / Published online: 19 March 2017
Springer Science+Business Media Dordrecht 2017
©
Abstract Microwave irradiation has been found to be a
highly efficient method for etherification of p-tert-butyl-
calix[4]arene with alkyl bromides or ditosylate. The corre-
sponding products were obtained as a pure form in modest
yield within short reaction time when the reactions were
performed under microwave irradiation.
Microwave-assisted organic synthesis has been widely
used in synthetic organic reactions. Many organic reac-
tions proceed much faster with higher yields under micro-
wave irradiation compared to conventional heating.
Recently preparation of calixarenes by using microwave
irradiation has been reported [7–16]. Masafumi reported
a rapid and convenient laboratory method for the prepa-
ration of p-tert-butylcalix[4]arene using microwave irra-
diation [13]. Yan et al. initiated microwave irradiation
assisted synthesis of aryl pyrogallol[4]arenes and their
O-alkylation reactions [14]. Sardjono concluded that the
synthesis of cyclic tetramers calix[4]resorcinarenes from
vanillin, cynnamaldehyde and anisaldehyde could be per-
formed under microwave irradiation within very short
reaction time compared to the conventional heating [15].
Keywords Microwave irradiation · p-tert-Butylcalix[4]
arene · Crown ethers · Phosphonium
Introduction
Calix[4]arenes are a kind of macrocyclic compounds
obtained by phenolic units linked via methylene bridges
which have received the greatest attention due to their wide
application in the selective separation of specific metal and
molecular recognition [1–4]. They can easily be functional-
ized in various ways at the phenolic hydroxyl groups (lower
rim) or at the para positions of the phenolic rings (upper
rim). The etherification reactions of calix[4]arenes with
haloalkanes or ditosylate are generally carried out by reflux
using acetonitrile as a solvent in the presence of K CO [5,
’
In the Vladimir s work, Oalkylation of p-tertbutylcalix[4]
arene with haloalkanes under microwave irradiation was
studied, and excellent yields were attained within short
reaction time when the reaction was performed under
microwave irradiation [16].It is feasible that microwave
irradiation can be reasonable to be extended into calix-
arene chemistry. In this work, we would like to report a
very facile and convenient method to synthesize calix[4]
arene derivatives(1,3-p-tert-butylcalix[4]arene crown-
5(2), 1,3-2,4-p-tert-butylcalix[4]arene biscrown-5(3),
2
3
6
]. One of the main problems in calixarene functionaliza-
tion is long reaction time required several hours to days for
completion, so this method is not considered as an environ-
mentally friendly reaction.
25,27-bis[4-(3-methylimidazolium)
droxy-5,11,17,23-tetra-(tert-butyl)calix[4]arene
mide(6), 25,27-bis[4-(3-methylimidazolium)butoxy]-
ethoxy]-26,28-dihy-
dibro-
2
6,28-dihydroxy-5,11,17,23-tetra-(tert-butyl)calix[4]arene
dibromide(7), 25,27-bis(4-triphenylphosphoniumbutoxy)-
26,28-dihydroxy-5,11,17,23-tetra-(tert-butyl)calix[4]arene
dibromide(8),25,27-bis(4-triphenylphosphoniumbutoxy)-
*
Zhen Xu
xuzhen@wust.edu.cn
5
,11,17,23-tetra-(tert-butyl)calix[4]arene-crown-5 dibro-
1
College of Chemical Engineering and Technology, Wuhan
University of Science and Technology, Wuhan 430081,
Hubei Province, China
mide(10)) under microwave irradiation (Scheme 1). This
Vol.:(0
1
123456789)
3

7
8
J Incl Phenom Macrocycl Chem (2017) 88:77–83
RX, K CO , MeCN
2
3
Microwave irradiation
OR1 OR2
4
3
OH OH OH HO
R O
OR
1
1
1
1
2
3
3
4
2
2
4
4
Scheme 1 Synthetic route for calix[4]arene derivatives. 2 R and
R =R =(CH CH )
C H N Br,
R =R =H,
n=1,2,
1
8
2
8
2 n
3
4
6
2
3
3
2
4
2
4
R
bridged by X, X=CH CH (OCH CH ) , R =R =H, 3 R and
R =R =C H PPh Br, R =R =H, 10 R =R =C H PPh Br, R and
2
2
2
2 3
4
4
8
3
2
4
R bridged by X, R and R bridged by X, X=CH CH (OCH CH ) ,
R bridged by X, X=CH CH (OCH CH )
2
2
2
2 3
7
2
2
2
2 3
1
3
2
4
4
,
5
R =R =(CH CH ) Br,
R =R =H,n=1,2,
6,
2
2 n
O
O
O
TGD, K CO3
TGD, Cs
MeCN
2
CO
3
2
O
O
MeCN
OH O
O
HO
O
O
OH OH OH HO
O O
O
O
O
O
1
2
3
Scheme 2 Synthetic route for p-tert-butylcalix[4]arene crown-5 and biscrown-5
Table 1 The yields of the monocrown 2 and biscrown 3 via
Reaction of compound 1 with tetraethylene glycol dito-
sylate (TGD) in the presence of K CO under microwave
Scheme 2
2
3
irradiation for 2 h could provide 48.7% yield of 2 (entry
Entry Substrate Base
Time (h) Product Yield (%)
1
). With the increasing of the reaction time, the mono-
1
2
3
4
5
6
7
8
9
1
K CO
2
3
4
3
2
2
4
3
4
2
3
48.7
71.6
70.4
20.5
64.4
85.8
18.4
47.8
54.6
2
3
3
3
crown 2 was obtained in 71.6% yield (entry 2). The yield of
the monocrown 2 did not significantly increase for longer
microwave irradiation over 4 h (entry 3); while the yield
of 2 by the same reaction carried out under conventional
oil heating for 24 h was 40% [17]. Because the preparation
and purification of the monocyclic calixcrown is a precur-
sor of the calix-bis-crown compound, the biscrown 3 was
prepared from monocrown 2 with ditosylates. After reac-
tion under microwave irradiation for 2 h, the spots of the
monocrown disappeared and provided 85.8% yield of bis-
crown 3 in the presence of Cs CO (entry 6). But the same
K CO
2
K CO
2
Cs CO
2
3
2
1
K CO
2
3
Cs CO
2
3
K CO
2
3
a
a
K CO +Cs CO
2
3
2
3
K CO +Cs CO
2
3
2
3
aThe base was added in two portions
2
3
reaction provided 64.4% yield of biscrown 3 in the pres-
microwave irradiation for preparing the calix[4]arene
derivatives may be a useful laboratory method.
ence of K CO (entry 5); while under oil heating the reac-
2
3
tion need refluxed for 48 h. It shows that K CO as a base
2
3
can provide the best yield of the monocrown and Cs CO
2
3
may give optimum yield of calix-bis-crown in the next step.
The biscrown 3 was also prepared from calix[4]arene 1
with ditosylates by one-step procedure. The base was added
in two portions [18], and the progress of the reaction was
monitored by TLC. After the previous portion K CO was
Results and discussion
The
1,3-p-tert-butylcalix[4]arene
crown-5(2)
and
2
3
1
,3-2,4-p-tert-butylcalix[4]arene biscrown-5(3) were pre-
added for 2 h, the spots of monocrown 2 appeared. When
pared via the synthetic routes displayed in Scheme 2. The
reaction conditions and corresponding yields were listed in
Table 1.
the last portion Cs CO was added, the spots of the mono-
2
3
crown disappeared after 2 h and biscrown 3 was obtained
in 54.6% yields under microwave irradiation (entry 9).
1
3

J Incl Phenom Macrocycl Chem (2017) 88:77–83
79
Accordingly, the addition of K CO in one portions for 4 h
the conventional heating method, these compounds 6, 7
could be prepared within 2–3 days reaction time, and the
yields were comparable [23].
2
3
gave a poor yield (entry 7).
Bis(imidazolium) quaternary salts have received con-
siderable attention in N-heterocyclic carbine chemistry, the
introduction of imidazolim moieties at the lower or upper
rim of calixarenes is a cation or anion receptors and sensors
Compound 8 consisting of a calix[4]arene bearing
two alkytriphenyl phosphonium is a novel anionic recep-
tor, which has been prepared by two different procedures
(Scheme 4). The reaction conditions and corresponding
yields were listed in Table 2.
[
19–21]. The synthetic route for p-tert-butylcalix[4]arene
1
,3-diimidazolium salts (6,7) was outlined in Scheme 3.
First, alkylation of p-tert-butylcalix[4]arene (1) with an
excess of the respective dibromides was carried out in
MeCN in the presence of K CO as a base. Dibromides 4,
For the preparation of the 25, 27-bis(4-bromobutoxy)-
26,28-dihydroxy-5,11,17,23-tetra-(tert-butyl)calix[4]arene
5 under the conditions of entries 1 and 2, the product yield
was 72.8% under microwave irradiation for 2 h and 50.2%
under oil bath for 32 h.
2
3
5
were obtained in yields 89 and 72.8% under microwave
irradiation for 2 h, while the same reaction carried out
under conventional oil heating for 4 days provided 87 and
The reaction of calix[4]arene 1 and 4-bromobutyl-
phenyltriphosphonium bromide 9 using K CO under
6
2% yield of 4, 5, respectively [22]. Subsequent reactions
2
3
of 4, 5 with an excess of N-methylimidazole were also car-
ried out in MeCN. The corresponding bis(imidazolium)
quaternary salts 6, 7 were obtained in 83.6 and 76.2%
yields under microwave irradiation for 2 h. Compared to
irradiation for 2 h and gave 54.3% yields of 8 (entry 4).
In different method, 8 was prepared by reaction of 25,
27-bis(4-bromobutoxy)-26,28-dihydroxy-5,11,17,23-tetra-
(tert-butyl)calix[4]arene 5 with triphenyl phosphine and
Scheme 3 Synthesis of p-tert-
butylcalix[4]arene 1,3-diimida-
zolium salts with N-methylim-
idazole
Br(CH CH ) Br
MeCN
2
2 n
O
OH OH
O
K CO ,MeCN
O
OH OH
O
N-methylimidazole
2
3
OH OH OH HO
n
n
n
n
N
N
N
N
Br
Br
Br
Br
6
7
,n=1
,n=2
4
5
,n=1
,n=2
1
Scheme 4 Synthetic route
for ditriphenylphosphonium
calix[4]arene dibromide
PPh ,MeCN
1
,4 dibromobutane
K CO ,MeCN
3
O
OH OH
O
O
OH OH
O
2
3
OH OH OH HO
Ph P+ Br-
Br- +PPh3
Br
Br
3
1
5
8
+
PPh ,toluene
Br
3
PPh
3
-
Br
Br
Br
reflux
9
9
,K CO ,MeCN
2
3
O
OH OH
O
OH OH OH HO
Ph P Br-
+
Br- +PPh3
3
1
8
1
3

8
0
J Incl Phenom Macrocycl Chem (2017) 88:77–83
Table 2 The yields of the
Entry
Substrate
Heating resource
Base
Time (h)
Product
Yield (%)
compound 5 and 8 via Scheme 4
1
2
3
4
5
6
1
1
1
1
5
5
Oil bath
MW
Oil bath
MW
Oil bath
MW
K CO
32
2
24
2
96
2
5
5
8
8
8
8
50.2
72.8
32.6
54.3
31.2
58.4
2
3
3
3
3
K CO
2
K CO
2
K CO
2
–
–
obtained 58.4% yield (entry 6). The two different ways
under oil bath gave a poor yield for longer reaction time
standard. IR spectra were recorded on BRUKER VER-
TEX70 spectrometer with KBr pellets for solids. The
mass spectra were tested using a FT-ICR MS SolariX 7.0
(Bruker Daltonics) spectrometer. Reactions were carried
in PJ23C-SC1 chemistry-oriented microwave oven which
made in GuangZhou Midea microwave oven Manufactur-
ing Co. Ltd. All solvents were dried over 4A molecular
sieve for at least 1 week. K CO was further dried in Muffle
(
entry 3, 5).
Calix[4]arene-crown-5 derivatives have been testified to
have high extraction abilities and selectivities for different
metal cations [24]. Finally, 25,27-bis(4-triphenyl-phospho-
nium-butoxy)-5,11,17,23-tetra-(tert-butyl)calix[4]arene-
crown-5 dibromide 10 was directly prepared (Scheme 5) by
reaction of monocrown 2 with 9 in the presence of K CO
2
3
furnace at 400°C for 2 h before used. All reactions were
carried out in a nitrogen atmosphere. Compounds 1 and 9
were prepared as described in the literature.
2
3
in acetonitrile under oil bath heating and microwave irra-
diation, obtaining 27.4 and 45.2% yields, respectively.
1
,3‑p‑tert‑butylcalix[4]arene crown‑5(2)
Conclusions
2
.19 g(3.38 mmol) of p-tert-butylcalix[4]arene,
The monocrown/biscrown of p-tert-butylcalix[4]arene and
quaternary salts containing di(alkyl-N-methylimidazole
and triphenyl phosphine)-substituted p-tert-butylcalix[4]
arene were prepared under microwave irradiation. Compar-
ing with conventional heating, microwave irradiation can
be finished in very short time and obtained nearly same
yields, which demonstrates that calix[4]arene derivatives
can be prepared simply and efficiently under microwave
irradiation condition.
1.92 g(3.82 mmol) of tetraethylene glycol ditosylate,
0.53 g(3.82 mmol) of K CO and 150 mL of acetonitrile
2
3
were added into a 250 mL of flask equipped with a con-
densed-water trap. The mixture was heated by microwave
irradiation for 2 h with a power of 400 W. After cooling
to room temperature, the mixture was filtrated and sol-
vent was evaporated under reduced pressure. The obtained
crude product was dissolved in 50 mL CH Cl , and the
2
2
mixture was washed with 50 mL 0.1 M HCl and 50 mL
water, then the organic layer were dried with anhydrous
MgSO . After evaporation of the solvent, the residue was
4
Experimental
subjected to flash column chromatography (silica gel,
hexane: ethyl acetate=3:1) to give a white, pure solid 2,
1
Melting points were determined with an electrothermal
mp246-248℃(mp246–248°C [25]), H NMR(600 MHz,
I
melting point apparatus and were uncorrected. H NMR and
CDCl ) δ:7.17(s, 2 H, –OH), 7.07(s, 4H, ArH), 6.75(s, 4H,
3
1
3
C NMR spectra were recorded on Agilent 600 MHz DD2
ArH), 4.38(d, J=13.0 Hz, 4H, ArCH Ar), 4.20–3.70(m,
2
spectrometer with Me Si as an internal standard. Chemi-
16H, –OCH CH O–), 3.30(d, J=13.0 Hz, 4H, ArCH Ar),
4
2
2
2
1
3
cal shifts were reported in ppm relative to the appropriate
1.31(s, 18H, –C(CH ) ), 0.91(s, 18H, –C(CH ) );
C
3
3
3 3
Scheme 5 Synthetic route
for ditriphenylphosphonium
calix[4]arene-crown-5 dibro-
mide
9
,K CO ,MeCN
2
3
O
O
O
O
O
OH O
O
HO
O
O O
O
O
Ph3+P Br-
-
+
Br P Ph
3
2
10
1
3

J Incl Phenom Macrocycl Chem (2017) 88:77–83
81
NMR(600 MHz, CDCl )δ:150.78, 149.76, 146.80, 141.16,
was subjected to flash column chromatography (silica gel,
3
1
32.47, 127.80, 125.40, 124.92, 76.61, 71.04, 70.86, 70.34,
3.81, 31.73, 31.31, 30.96; IR(KBr): 3436, 2958, 2866,
598, 1485, 1455, 1395, 1300, 1200, 1120, 1065, 967,
CH OH:CH Cl =1:10) to give white, pure compound 6 and
3
2
2
3
7.
1
−1
8
69 cm . Anal. Calcd for C H O :C, 77.28; H, 8.90.
25,27‑Bis[4‑(3‑methylimidazolium)ethoxy]‑26,28‑dihy‑
droxy‑5,11,17,23‑tetra‑(tert‑butyl)calix[4]arene dibro‑
mide(6)
5
2
70
7
Found:C, 77.38; H, 8.74.
1
,3‑2,4‑ p‑tert‑butylcalix[4]arene biscrown‑5 (3)
Yield 83.6%; white solid, mp227~228°C(mp229–231°C
1
Pathway A
[23]), HNMR(600 MHz, CDCl ) δ:10.22(s, 2H, –NCHN–),
3
8
.31(s, 2H, –NCHCHN–), 7.50(s, 2H, –NCHCHN–), 7.05(s,
1
,3-2,4-p-tert-butylcalix-[4]arene bis-crown-5(3) was pre-
4H, ArH), 6.64(s, 4H, ArH), 6.19(s, 2H, –OH), 5.17(t,
pared according to the same procedure as for (2), except
that 1,3-p-tert-butylcalix[4]arene crown-5 (2)and Cs CO
J=7.4 Hz, 4H, –OCH ), 4.35(t, J=6.1 Hz, 4H, –CH N),
2
2
3.96(s, 6H, –NCH ), 3.86(d, J=13.0 Hz, 4H, ArCH Ar),
2
3
3
2
was used as a base.
3.27(d, J=13.2 Hz, 4H, ArCH Ar), 1.30(s, 18H, –C(CH ) ),
2 3 3
13
0
.84(s, 18H, –C(CH ) ). C NMR(600 MHz, CDCl )
3 3 3
Pathway B
δ:149.6, 148.6, 147.8, 142.9, 138.5, 131.4, 127.9, 125.8,
25.4, 123.7, 122.8, 74.3, 50.3, 36.8, 33.9, 33.8, 31.6, 31.0,
1
p-tert-butylcalix[4]arene(1.09 g, 1.69 mmol), tetraethyl-
30.78. IR(KBr):3431, 3151, 3088, 2958, 2868, 1628, 1570,
−1
ene glycol ditosylate (1.81 g, 3.53 mmol), K CO (0.48 g,
1483, 1362, 1300, 1200, 1121, 1051, 874 cm . Anal. Calcd
for C H O N Br :C, 65.5; H, 7.26; N, 5.45. Found:C,
2
3
3
2
.4 mmol) and acetonitrile (100 mL) were added to a
56
74
4
4
2
50 mL of flask and was heated by microwave irradiation.
65.39; H, 7.14; N, 5.41.
The spots of the monocrown appeared after 2 h by TLC.
Then Cs CO (1.1 g, 3.4 mmol) was added slowly and the
25,27‑Bis[4‑(3‑methylimidazolium)butoxy]‑26,28‑dihy‑
droxy‑5,11,17,23‑tetra‑(tert‑butyl)calix[4]arene dibro‑
mide(7)
2
3
mixture was heated by microwave irradiation for 2 h with
a power of 400 W. After cooling to room temperature, the
mixture was filtrated and acetonitrile was removed under
reduced pressure. The residue was dissolved in 50 mL
CH Cl , and washed with 50 mL 0.1 M HCl and 50 mL
Yield 76.2%,white solid, mp228–229°C(mp230–232°C
1
[23]), H NMR(600 MHz, CDCl ) δ:10.04(s, 2H, –NCHN–),
2
2
3
water, and then the organic layer were dried with anhydrous
7.93(s, 2H, –NCHCHN–), 7.50(s, 2H, –NCHCHN–), 7.09(s,
4H, ArH), 6.87(s, 2H, –OH), 6.70(s, 4H, ArH), 4.76(t,
J=7.4 Hz, 4H, –OCH ), 4.14(d, J=13.2 Hz, 4H, ArCH Ar),
MgSO , followed by removal of the solvent in vacuum to
4
obtain a brownish solid. Column chromatography with hex
2
2
ane:CH Cl :CH COOC H =20:5:1 as eluent provided the
4.07(s, 6H, –NCH ), 3.97(t, J=6.1 Hz, 4H, –CH N), 3.35(d,
2
2
3
2
5
3
2
pure 3 as a white solid, mp>280°C (mp>280°C [25]),
J=13.0 Hz, 4H, ArCH Ar), 2.18~2.23(m, 4H,–CH CH –),
2 2 2
1
H NMR(600 MHz, CDCl ) δ:7.02(s, 8H, ArH), 3.88(s,
1.81~1.87(m, 4H, –CH CH –), 1.30(s, 18H,–C(CH ) ),
2 2 3 3
3
13
8
–
–
1
3
1
H, ArCH Ar), 3.61(m, 8H, –OCH CH O–), 3.40(m, 16H,
0.87(s, 18H, –C(CH ) ). C NMR(600 MHz, CDCl )
3 3 3
2
2
2
OCH CH O–), 2.90(m, 8H, –OCH CH O–), 1.38(s, 36H,
δ:149.88, 149.37, 147.21, 142.34, 136.96, 131.91, 127.89,
125.59, 125.23, 123.69, 122.85, 76.24, 49.49, 36.87, 33.86,
33.84, 31.65, 31.46, 30.87, 27.78, 26.12. IR(KBr):3417,
3153, 3101, 2957, 2866, 1630, 1574, 1479, 1364, 1300,
2
2
2
2
1
3
C(CH ) ). C NMR(600 MHz, CDCl )δ:154.02, 144.62,
3
3
3
32.84, 142.95, 73.55, 70.98, 70.15, 66.96, 39.19, 33.99,
1.89. IR(KBr):2962, 2894, 1623, 1479, 1367, 1303, 1212,
−
1
−1
155, 1116, 1039, 997, 867, 779 cm . Anal. Calcd for
1202, 1115, 1040, 874 cm . Anal. Anal. Calcd for
C H O :C, 74.29; H, 8.87. Found:C, 74.50; H, 8.96.
C H O N Br :C, 66.54; H, 7.63; N, 5.17. Found:C, 66.47;
6
0
86 10
60 82
4
4
2
H, 7.54; N, 5.09.
General procedure for the preparation of compounds 6
and 7
25,27‑Bis(4‑triphenylphosphoniumbutoxy)‑26,28‑dihy‑
droxy‑5,11,17,23‑tetra‑(tert‑butyl)calix[4]arene dibro‑
mide (8)
The corresponding p-tert-butylcalix[4]arene bromide deriva-
tives (4,5)(1 mmol), N-methylimidazole(4 mmol) and ace-
tonitrile (100 mL) were mixed into a 250 mL of flask. The
mixture was heated by microwave irradiation for 2 h with
a power of 400 W. After cooling to room temperature, the
mixture was filtrated and acetonitrile was removed under
reduced pressure to obtain the crude product. The residue
Pathway A
This compound was prepared according to the same pro-
cedure of (2), except that 4-bromobutyl-phenyltriphospho-
nium bromide (9) was used.
1
3

8
2
J Incl Phenom Macrocycl Chem (2017) 88:77–83
Pathway B
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,3-butyldibromo p-tert-butylcalix[4]arene(5) (0.92 g,
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1
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calixarene ligand frame work by Nickel. J. Am. Chem. Soc. 130,
3
.
(
silica gel, CH CN:CH OH:CH Cl =3:1:1) to obtain
3 3 2 2
the pure 8 as a white solid, mp>280°C (mp>280°C
8
617–8619 (2008)
1
[
26]), H NMR(600 MHz, DMSO-d ) δ:8.24(s, 2H,
6
4. Silvia B., Alejandro G.C., Susan E.M., Françoise A., Volker B.,
Jean-François D., Hélène R., Marie-José S.: Calix[4]arenes with
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+
–
7
3
4
1
1
OH), 7.79–7.63(m, 30H, –P Ph ), 7.10(s, 4H, ArH),
3
.07(s, 4H, ArH), 3.98(d, J=12.5 Hz, 4H, ArCH Ar),
2
.93(t, J=6.4 Hz, 4H, –OCH –), 3.64(t, J=15.1 Hz,
2
5
6
7
.
.
.
Alekseeva, E.A., Basok, S.S., Mazepa, A.V., Gren, A.I.: Facile
synthesis of cone p-tert-butylcalix[4]arene-crown conformers.
Mendeleev Commun. 17, 330–331 (2007)
+
H, –CH –P Ph ), 3.35(d, J=12.5 Hz, 4H, ArCH Ar),
2
3
2
.85–2.02(m, 8H, –CH CH –), 1.17(s, 18H, –C(CH ) ),
2
2
3 3
1
3
Verboom, W., Datta, S., Asfari, Z., Harkema, S., Reinhoudt, D.
N.: Tetra-O-alkylated calix[4]arenes in the 1,3-alternate confor-
mation. J. Org. Chem. 57, 5394–5398 (1992)
.07(s, 18H, –C(CH ) ). C NMR(600 MHz, DMSO-d )
3
3
6
δ:150.42, 149.86, 147.50, 141.86, 135.31, 134.00, 133.52,
1
3
30.65, 127.86, 126.00, 125.67, 119.11, 118.54, 74.95,
4.42, 34.05, 31.85, 31.31, 31.125, 20.78, 20.45, 18.84.
Hedidi, M., Hamdi, S.M., Mazari, T., Boutemeur, B., Rabia, C.,
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IR(KBr):3412, 3053, 2955, 2866, 1629, 1480, 1438, 1362,
−1
8. Funck, M., Guest, D.P., Cave, G.W.V.: Microwave-assisted syn-
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1
301, 1200, 1111, 1031, 934, 874, 738, 690 cm . Anal.
Calcd for C H Br O P :C, 73.35; H, 6.87. Found:C,
8
8
100
2
4 2
7
3.22; H, 6.98.
9. Nayak, S.K., Choudhary, M.K.: Microwave-assisted synthesis of
1
,3-dialkyl ethers of calix[4]arenes: application to the synthesis
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2
5,27‑Bis(4‑triphenyl‑phosphoniumbutoxy)‑5,11,17,23‑t
etra‑(tert‑butyl)calix[4]arene‑crown‑5 dibromide (10)
1
1
0. Soares, A. M., Barros, B. S., Kulesza, J., lves-Júnior, S. A., Cam-
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de Resende-Stoianoff, M.A., Martins, F.T., de Fátima, Â.: Imi-
necalix[4]arenes: microwave-assisted synthesis, X-ray crystal
structures, and anticandidal activity. Arab J. Chem. In Press,
Corrected Proof, Available online 27 June 2016
This compound was prepared according to the same pro-
cedure of 2, except that 1,3-p-tert-butylcalix[4]arene
crown-5 (2) and 4-bromobutylphenyltriphosphonium bro-
mide (9) was used. Purification by flash column chroma-
tography (CH Cl :CH OH=10:1) a white, pure solid prod-
2
2
3
1
12. Rego, Y.F., da Silva, C.M., da Silva, D.L., da Silva, J.G., Ruiz,
A.L.T.G., de Carvalho, J.E., Fernandes, S.A., de Fa´tima, A.:
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solvents and their anticancer activities against human cancer
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16 April 2016
uct 10 were obtained, mp>280°C, H NMR(600 MHz,
+
DMSO-d )δ:7.65–7.85(m, 30H, –P Ph ), 7.04(s, 4H, ArH),
6
3
6
3
2
8
.40(s, 4H, ArH), 4.05(d, J=12.5 Hz, 4H, ArCH Ar),
2
.94(t, J=8.4 Hz, 4H, –OCH –), 3.77(m, 8H, –OCH-
2
+
CH O–), 3.62(t, J=14.5 Hz, 4H, –CH –P Ph ), 3.51(m,
2
2
3
1
3. Masafumi T., Asao H., Hajime M., Yasuhito M., Keiichi K.,
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H, –OCH CH O–), 3.02(d, J=12.5 Hz, 4H, ArCH Ar),
2
2
2
1
0
.68–1.94(m, 8H, –CH CH –), 1.22(s, 18H, –C(CH ) ),
2 2 3 3
1
3
.76(s, 18H, –C(CH ) ). C NMR(600 MHz, DMSO-d )
3
3
6
1
4. Yan, C., Chen, W., Chen, J., Jiang, T., Yao, Y.: Microwave irra-
diation assisted synthesis, alkylation reaction, and configuration
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δ:154.51, 152.16, 144.83, 143.60, 135.31, 134.96, 134.05,
1
1
3
2
1
32.06, 130.71, 128.41, 125.92, 125.64, 124.53, 119.16,
18.59, 74.23, 72.51, 71.37, 70.76, 69.68, 34.18, 33.66,
1.86, 31.26, 30.85, 20.99, 20.66, 19.70. IR(KBr):3056,
955, 2867, 1627, 1479, 1438, 1395, 1359, 1298, 1243,
1
1
5. Sardjono, R.E., Kadarohman, A., Mardhiyah, A.: Green synthe-
sis of some calix[4] resorcinarene under microwave irradiation.
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−
1
195, 1114, 996, 947, 870, 800, 725, 690 cm . Anal.
6. Vladimir A.B., Ramil I.N., Regina R.I., Svetlana E.S., Igor S.A.,
Alexander I.K.: Microwave-assisted alkylation of p-tert-butyl-
calix[4]arene lower rim: the effect of alkyl halides. Mendeleev
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Calcd for C H Br O P :C, 72.18; H, 7.28. Found:C,
9
6
114
2
7 2
7
1.99; H, 7.17.
1
3

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1
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1
2
9. Dinares, I., de Miguel, C.G., Mesquida, N., Alcalde, E.:
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2
2
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1
3