Synthesis of calix[4]resorcinarenes with phosphorylaryl substituents at the lower rim of the molecule

Article abstract of DOI:10.1007/s11172-007-0371-y

Reaction of resorcinarenes with 4-phosphorylbenzaldehydes afforded calix[4]resorcinarenes, bearing phosphorylaryl substituents at the lower rim of the molecule.

Full text of DOI:10.1007/s11172-007-0371-y

Russian Chemical Bulletin, International Edition, Vol. 56, No. 11, pp. 2348—2350, November, 2007
2348
Synthesis of calix[4]resorcinarenes with phosphorylaryl substituents
at the lower rim of the molecule
a
b
b
E. L. Gavrilova,a A. A. Naumova, A. R. Burilov, M. A. Pudovik,

E. A. Krasil'nikova,a and A. I. Konovalovb
aKazan State Technological University,
68 ul. Karla Marksa, 420015 Kazan, Russian Federation.
Fax: +7 (843) 231 4103. Eꢀmail: Gavrilova_elena_@mail.ru
bA. E. Arbuzov Institute of Organic and Physical Chemistry,
Kazan Research Center of the Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843) 272 2253. Eꢀmail: pudovik@iopc.knc.ru
Reaction of resorcinarenes with 4ꢀphosphorylbenzaldehydes afforded calix[4]resorcinarenes,
bearing phosphorylaryl substituents at the lower rim of the molecule.
Key words: resorcinarenes, phosphonates, condensation, calix[4]resorcinarenes.
One of the most promising and fast developing trends
into the condensation with resorcinarene or its derivaꢀ
tives. The synthesis of 4ꢀ(diethoxyphosphoryl)benzꢀ
aldehyde (1) and 4ꢀ(diisopropoxyphosphoryl)benzaldeꢀ
hyde (2) was accomplished on the basis of the earlier7—10
developed method of the introduction of phosphorusꢀ
containing structural fragments into aromatic systems,7—10
viz., the catalytic reaction of trialkyl phosphites with
4ꢀbromobenzaldehyde (Scheme 1).
in organic chemistry is exploration of calix[n]arenes, in
particular, calix[4]resorcinarenes.1 This is due to the simꢀ
plicity of their synthesis and the ability to form comꢀ
plexes of the "guest—host" type with various organic
compounds and metal ions, as well as the tendency
to selfꢀassociation, leading to supramolecular ensembles.
All the properties described above make this class of
compounds very prospective from the point of view
of creation of new types of complexꢀforming agents
and the metal ions extragents, as well as new catalytic
systems. In this connection, the functionalized and, esꢀ
pecially, phosphorylated derivatives are of particular inꢀ
terest.
Scheme 1
The data on phosphorusꢀcontaining calixarenes are
recently reviewed,2 indicating that a large number of
Oꢀphosphorylated derivatives of various composition and
structure were obtained by far, whereas calixarenes,
Cꢀphosphorylated at the lower rim of the molecule, were
not studied. This is no wonder, since a direct phosphoryꢀ
lation of calixarene framework can hardly afford the tarꢀ
get products. Recently,3,4 we accomplished for the first
time a oneꢀstep construction of the phosphorusꢀcontainꢀ
ing calixarene matrix by the acidꢀcatalyzed reaction of
resorcinarene and phosphorusꢀcontaining acetal. As a reꢀ
sult, the first representative of calix[4]resorcinarenes, bearꢀ
ing phosphinoylalkyl fragments at the lower rim of the
molecule, was synthesized. Taking into account the litꢀ
erature data,5,6 it was reasonable to suppose that the simiꢀ
lar in structure Cꢀphosphorylarylated calixarenes can be
obtained by involvement of phosphorylated benzaldehyde
Alk = Et (1), Pri (2)
The heating of equimolar amounts of aldehydes 1 or 2
and resorcinarene (3a) (or 2ꢀmethylresorcinarene (3b))
under acidic conditions leads to calix[4]resorcinarenes
4a,b and 5a,b, bearing four phosphorylphenyl fragments
at the lower rim of the molecule (Scheme 2).
The structure of compounds isolated was conꢀ
firmed by IR, 1H and 31P spectroscopy and mass
spectrometry methods, their composition, by elemental
analysis.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2269—2271, November, 2007.
1066ꢀ5285/07/5611ꢀ2348 © 2007 Springer Science+Business Media, Inc.

Phosphorylated calix[4]resorcinarenes
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 11, November, 2007 2349
Scheme 2
4.56 (m, 2 H, CH(CH3)2); 7.95, 8.05 (both d, 2 H each, C6H4,
J = 8.4 Hz); 10.31 (s, 1 H, CHO). 31P NMR, δ: 17.00.
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ2,8,14,20ꢀtetrakis[4ꢀ
diethoxyphosphorylphenyl]pentacyclo[19.3.1.13,7.19,13.115,19]ꢀ
octacosaꢀ1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23ꢀdoꢀ
decaene (4a). Phosphonate 1 (4.39 g, 1.8 mmol) was gradually
and with stirring added to a cooled to 10 °C solution of resorcinꢀ
arene (2 g, 1.8 mmol) in 95% aqueous EtOH (30 mL) and
glacial acetic acid (4.68 mL). The reaction mixture was kept for
40 h at 60 °C. The precipitate formed was washed with ethanol
and kept in vacuo (40 °C, 0.06 Torr) until the weight was conꢀ
stant to obtain compound 4a (1.9 g, 73%), m.p. 275 °C
(decomp.). Found (%): C, 60.71; H, 5.22; P, 9.00. C68H76O20P4.
Calculated (%): C, 61.07; H, 5.68; P, 9.28. IR, ν/cm–1: 1210
1
(P=O); 3300—3400 (OH). H NMR, δ: 1.25 (t, 24 H, Me, J =
7.0 Hz); 3.98 (m, 16 H, CH2); 5.69 (s, 4 H, CH); 6.17 (s, 4 H,
OꢀCHAr, C6H2); 6.84 (s, 4 H, mꢀCHAr, C6H2); 7.30 (d, 8 H,
OꢀCHAr, C6H4, J = 8.0 Hz); 7.33 (d, 8 H, mꢀCHAr, C6H4,
J = 8.0 Hz); 8.54 (s, 8 H, OH). 31P NMR, δ: 20.98. MS:
m/z 1359 [M + Na].
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ5,11,17,23ꢀtetraꢀ
m e t h y l ꢀ 2 , 8 , 1 4 , 2 0 ꢀ t e t r a k i s [ 4 ꢀ d i e t h o x y p h o s p h o r y l ꢀ
phenyl]pentacyclo[19.3.1.13,7.19,13.115,19]octacosaꢀ
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23ꢀdodecaene (4b).
Phosphonate 1 (1.94 g, 0.8 mmol) was gradually and with stirꢀ
ring added to a cooled to 10 °C solution of 2ꢀmethylresorcinarene
3b (1 g, 0.8 mmol) in 95% EtOH (15 mL) and glacial AcOH
(2.34 mL). The reaction mixture was kept for 45 h at 60 °C. The
precipitate formed was washed with ethanol and kept in vacuo
(40 °C, 0.06 Torr) until the weight was constant to obtain comꢀ
pound 4b (1.8 g, 64%), m.p. 250 °C (decomp.). Found (%):
C, 61.81; H, 5.72; P, 8.55. C72H84O20P4. Calculated (%):
R = H (a), Me (b); R´ = C6H4P(O)(OEt)2ꢀ4 (1, 4),
C6H4P(O)(OPri)2ꢀ4 (2, 5)
Experimental
1
Н and 31P NMR spectra were recorded on a Bruker
C, 62.07; H, 6.03; P, 8.91. IR, ν/cm–1
: 1200 (P=O);
MSLꢀ400 spectrometer (400.13 and 166.93 MHz, respectively).
The δ values were calculated relatively to the signals of reꢀ
sidual protons of DMSOꢀd6 (1Н) or of the external standard,
3300—3400 (OH). 1H NMR, δ: 1.24 (t, 24 H, Me, J = 7.0 Hz);
1.82 (s, 12 H, ArMe); 4.00 (m, 16 H, CH2); 5.51 (s, 4 H, CH);
6.84 (s, 4 H, mꢀCHAr, C6H); 7.27 (d, 8 H, OꢀCHAr, C6H4, J =
8.0 Hz); 7.30 (d, 8 H, mꢀCHAr, C6H4, J = 8.0 Hz); 8.00 (s, 8 H,
OH). 31P NMR, δ: 19.56. MS: m/z 1392 [M + Na].
85% aq. H3PO4 (
31P). IR spectra were recorded on a Specord
Mꢀ80 spectrometer in the region 450—4000 cm–1. Crystalline
samples were studied in Nujol mulls. Mass spectra were reꢀ
corded on a MALDI 2 V5.2.0 instrument (1,8,9ꢀtrihydroxyꢀ
anthracene as the matrix).
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ2,8,14,20ꢀtetrakis[4ꢀ
diisopropoxyphosphorylphenyl]pentacyclo[19.3.1.13,7.19,13.115,19]ꢀ
octacosaꢀ1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23ꢀdoꢀ
decaene (5a). Phosphonate 2 (2 g, 7.75 mmol) was gradually and
with stirring added to a cooled to 10 °C solution of resorcinarene
3a (0.853 g, 7.75 mmol) in 95% aq. EtOH (14 mL) and glacial
acetic acid (2.15 mL). The reaction mixture was kept for 40 h at
60 °C. The precipitate formed was washed with ethanol and kept
in vacuo (40 °C, 0.06 Torr) until the weight was constant to
obtain compound 5а (1.5 g, 53%), m.p. > 190 °C (decomp.).
Found (%): C, 62.4; H, 6.0; P, 7.75. C76H92O20P4. Calcuꢀ
lated (%): C, 62.98; H, 6.35; P, 8.56. IR, ν/cm–1: 1200 (P=O);
3300—3400 (OH). 1H NMR, δ: 1.07, 1.10 (both d, 48 H, Me,
J = 7 Hz); 4.56 (m, 8 H, CH); 5.65 (s, 4 H, CH); 6.12 (s, 4 H,
OꢀCHAr, C6H2); 6.20 (s, 4 H, mꢀCHAr, C6H2); 7.00 (d, 8 H,
OꢀCHAr, C6H4, J = 8.1 Hz); 7.50 (d, 8 H, mꢀCHAr, C6H4, J =
8.1 Hz); 8.90 (s, 8 H, OH). 31P NMR, δ: 17.05.
4ꢀDiethoxyphosphorylbenzaldehyde (1). A mixture of triethyl
phosphite (13.5 g, 81 mmol), 4ꢀbromobenzaldehyde (15 g,
81 mmol), and NiBr2 (0.35 g, 1.6 mmol) was kept for 4 h
at 170 °C. Ethyl bromide (5.84 g, 97%) was distilled off during
the reaction. After fractional distillation in vacuo, compound 1
was obtained (10.2 g, 52%), b.p. 134 °C (0.05 Torr). Found (%):
C, 54.00; H, 5.99; P, 12.35. C11H15O4P. Calculated (%):
C, 54.55; H, 6.19; P, 12.81. IR, ν/cm–1: 1210 (P=O); 1715
(CHO). 1H NMR, δ: 1.25 (t, 6 H, Me, J = 7.0 Hz); 4.10 (m,
4 H, CH2); 7.93, 8.03 (both d, 2 H each, C6H4, J = 8.4 Hz);
10.21 (s, 1 H, CHO). 31P NMR, δ: 17.00.
4ꢀDiisopropoxyphosphorylbenzaldehyde (2). A mixture of
triisopropyl phosphite (11 g, 54 mmol), 4ꢀbromobenzaldehyde
(10 g, 54 mmol), and NiBr2 (0.354 g, 1.6 mmol) was kept for 4 h
at 170 °C. Isopropyl bromide (3.6 g, 56%) was distilled off durꢀ
ing the reaction. After fractional distillation in vacuo, comꢀ
pound 2 was obtained (6.3 g, 48%), b.p. 126 °C (0.05 Torr).
Found (%): C, 56.90; H, 6.99; P, 11.18. C13H19O4P. Calcuꢀ
lated (%): C, 57.77; H, 7.03; P, 11.48. IR, ν/cm–1: 1212 (P=O);
1716 (CHO). 1H NMR, δ: 1.02, 1.05 (both d, 12 H, CH(CH3)2);
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ5,11,17,23ꢀtetraꢀ
methylꢀ2,8,14,20ꢀtetrakis[4ꢀdiisopropoxyphosphorylꢀ
phenyl]pentacyclo[19.3.1.13,7.19,13.115,19]octacosaꢀ
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23ꢀdodecaene (5b).
Phosphonate 2 (1.93 g, 7.14 mmol) was gradually and with
stirring added to a cooled to 10 °C solution of 2ꢀmethylresorcinꢀ

2350
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 11, November, 2007
Gavrilova et al.
arene 3b (0.886 g, 7.14 mmol) in 95% aq. EtOH (14 mL) and
glacial acetic acid (2.15 mL). The reaction mixture was kept for
60 h at 60 °C. The precipitate formed was washed with ethanol
and kept in vacuo (40 °C, 0.06 Torr) until the weight was conꢀ
stant to obtain compound 5b (1.69 g, 65%), m.p. > 185 °C
(decomp.). Found (%): C, 63.4; H, 6.41; P, 7.92. C80H100O20P4.
Calculated (%): C, 63.82; H, 6.64; P, 8.24. IR, ν/cm–1: 1200
(P=O); 3300—3400 (OH). 1H NMR, δ: 1.10, 1.20 (both d, 48
H, Me, J = 7 Hz); 2.08 (s, 12 H, ArMe); 4.65 (m, 8 H, CH);
5.60 (s, 4 H, CH); 6.40 (s, 4 H, mꢀCHAr, C6H); 6.90 (d, 8 H,
OꢀCHAr, C6H4, J = 8.1 Hz); 7.49 (d, 8 H, mꢀCHAr, C6H4, J =
8.1 Hz); 8.93 (s, 8 H, OH). 31P NMR, δ: 16.51.
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and A. I. Konovalov, Zh. Obshch. Khim., 2002, 72, 1049
[Russ. J. Gen. Chem., 2002, 72 (Engl. Transl.)].
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Macrocyclic Compounds, Kluwer Academic Publishers,
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7. P. Tavs, Chem. Ber., 1970, 103, 2428.
This work was financially supported by the Russian
Foundation for Basic Research (Projects No. 04ꢀ03ꢀ32512
and No. 07ꢀ03ꢀ00863).
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Received July 11, 2007;
in revised form October 30, 2007