Synthesis of calix[4]resorcinarenes, containing phosphoryl fragments at the lower rim of the molecule

Article abstract of DOI:10.1007/s11172-007-0173-2

Reaction of resorcinol with phosphorylated acetals or ethoxyvinylphosphonic acid esters in acidic media leads to calix[4]resorcinarenes, containing dialkoxyphosphoryl fragments at the lower rim of the molecule. When the alkyl substituent in alkoxy groups at phosphorus atom is not very long, a partial hydrolysis of the initially formed products takes place to give calixarenes with alkoxyhydroxyphosphoryl fragments.

Full text of DOI:10.1007/s11172-007-0173-2

Russian Chemical Bulletin, International Edition, Vol. 56, No. 6, pp. 1144—1148, June, 2007
1144
Synthesis of calix[4]resorcinarenes, containing
phosphoryl fragments at the lower rim of the molecule
b
b
a
A. R. Burilov,a I. R. Knyazeva,a Yu. M. Sadykova,a M. A. Pudovik,a W. D. Habicher, I. Baier, and A. I. Konovalov
ꢀ
аA. 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) 275 2253. Eꢀmail: pudovik@iopc.knc.ru
bInstitute of Organic Chemistry, Dresden University of Technology,
13 Mommsenstrasse, Dꢀ01062 Dresden, Germany.*
Fax: +49 (351) 463 4093
Reaction of resorcinol with phosphorylated acetals or ethoxyvinylphosphonic acid esters in
acidic media leads to calix[4]resorcinarenes, containing dialkoxyphosphoryl fragments at the
lower rim of the molecule. When the alkyl substituent in alkoxy groups at phosphorus atom is
not very long, a partial hydrolysis of the initially formed products takes place to give calixarenes
with alkoxyhydroxyphosphoryl fragments.
Key words: acetals, vinylphosphonic acids, resorcinols, calix[4]resorcinarenes, organoꢀ
phosphorus compounds.
Exploration of chemistry of calix[n]arenes, in particuꢀ
lar calix[4]resorcinarenes, is one of the most promising
and intensively developing trends in organic chemistry.1—3
The simplicity of their synthesis and the ability to form
complexes of the "guest—host" type with various in strucꢀ
ture organic compounds and metal ions, as well as the
tendency to selfꢀassociation, leading to supramolecular
ensembles, are the conditions of it. All the properties
described above make this class of compounds very proꢀ
spective from the point of view of creation of new types of
complexꢀforming agents and the metal ions extragents, as
well as new catalytic systems. The most widely used apꢀ
proach to the formation of calixarene matrix includes the
reaction of polyphenols with aldehydes and their derivaꢀ
tives. However, it has certain limitations, since the quesꢀ
tion about influence of the starting aldehyde and polypheꢀ
nol structures on the composition of the forming final
products is not entirely clear. It is known4—6 that unꢀ
substituted aliphatic and aromatic aldehydes, as well as
aliphatic aldehydes with functional substituents, separated
from the reaction center by four—eight carbon atoms,
afford calix[4]resorcinarenes by condensation with resorꢀ
cinol in acidic media. At the same time, such structures
are not formed in the reaction of αꢀhalogenꢀsubstituted
aliphatic aldehydes with resorcinol.5 Within the frameꢀ
work of approach under discussion, there is no informaꢀ
tion about a possibility of the synthesis of calixarenes by
the reaction of resorcinol with aldehydes, containing funcꢀ
tional substituents, separated from the carbonyl group by
two—three carbon atoms.
Calix[4]resorcinarenes, bearing phosphorylꢀsubstiꢀ
tuted alkyl groups at the lower rim of the molecule, are of
particular interest as complexꢀforming agents and
extragents. Methods for the preparation of compounds of
this type are not described in the literature, which, apparꢀ
ently, is mainly connected with the difficulties in the
synthesis of phosphorylated aliphatic aldehydes. It should
be also noted that so far the attempts to obtain calixarenes,
bearing phosphorusꢀcontaining alkyl fragments at the
lower rim of the molecule, by phosphorylation of the
already made calixarene matrix failed and it is doubtful
whether such an approach will be implemented in the
nearest future. We came to a conclusion that the synthesis
of calix[4]resorcinarenes, phosphorylated at the lower rim
of the molecule, most likely can be fulfilled during formaꢀ
tion of calixarene matrix. Since, as it was already menꢀ
tioned above, phosphorylated aldehydes are not easily
available, we tried to perform the "acetal" method, i.e., we
decided to involve into condensation with resorcinol phosꢀ
phorylated acetals. The latter can be easily obtained by
the Arbuzov reaction, viz., by interaction of trialkylꢀ
phosphites with bromoacetaldehyde acetal 1. Some of the
phosphono acetals were described earlier7 and we exꢀ
tended this series by preparation of compounds 2a—e
(Scheme 1).
* Institut für organische Chemie, Technische Universität
Dresden, 13 Mommsenstraβe, Dꢀ01062 Dresden, Germany.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1102—1106, June, 2007.
1066ꢀ5285/07/5606ꢀ1144 © 2007 Springer Science+Business Media, Inc.

Phosphorylated calix[4]resorcinarenes
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 6, June, 2007
1145
Scheme 1
It is safe to suggest that phosphorylated сarboсations A,
resulting from protonation of acetals 2a—e, serve as the
intermediates in electrophilic substitution reactions beꢀ
tween phosphono acetals and resorcinol in acidic media
(Scheme 3).
R = Et (a), Pr (b), Pri (c), Bu (d), Bui (e)
Scheme 3
Phosphono acetals react with resorcinol under heating
in acidic media, giving rise to calix[4]resorcinarenes with
phosphorylmethyl groups at the lower rim of the molecule
in high yields. The synthetic outcome of the reaction is
considerably affected by the experimental conditions.
Thus, heating of equimolar amounts of resorcinol and
acetals 2a—e for 3 h at 50—60 °C leads to a mixture of full
esters of phosphonic acid 3a—e (δP 29.90 (3a)) as the
main products and a small amount of partially hydrolyzed
products 4a—e (δP 32.21 (4a)) (Scheme 2). Eventually,
hydrolytically labile calixarenes 3a—e completely turned
into compounds 4a—e, which were isolated and characꢀ
terized.
As it follows from the stated above, the use of the
phosphorylated acetals allowed one to obtain a series of
calixarenes, phosphorylated at the lower rim of the molꢀ
ecule. However, the insufficient versatility should be menꢀ
tioned as a disadvantage of the "acetal" method, since for
the synthesis of the key phosphorylated acetals, a set of
phosphites of various structure is required. Taking into
account the hypothesis of the participation of intermediꢀ
ates A in the key step of the formation of calixarene frameꢀ
work, we suggested that carbocations of the similar type
can be generated by the use of ethoxyvinylphosphonates
in the reaction with calixarenes in acidic media. The comꢀ
mon representative of this series, (βꢀethoxyvinyl)dichloroꢀ
phosphonate (5), can be easily obtained from available
and inexpensive reagents: diethyl ether, phosphorus
pentachloride, and acetone8 (Scheme 4).
Scheme 2
Scheme 4
R = Et (a), Pr (b), Pri (c), Bu (d), Bui (e)
Calixarenes 4a—e were obtained as powders white in
color, soluble in ethanol and DMF, as well as in a mixture
of these solvents with water. Their 31Р NMR spectra have
one signal each in the region δ 30—33. Position of the
signal slightly changes depending on the size of the
R substituent. In the 1Н NMR spectrum, there are signals
for the protons of methyl groups (δ 1.10—1.40), methylꢀ
ene groups adjacent to phosphorus atom (δ 1.63—3.20),
methylene groups next to oxygen atom (δ 2.70—4.20),
and methyne groups (δ 5.07—5.90), as well as of the
protons in orthoꢀ (δ 6.26—6.77) and metaꢀpositions
(δ 7.25—7.32) of the aromatic ring. In the IR spectra, the
absorption bands of Р=О (1170—1220 cm–1) and ОН
groups (3100—3580 cm–1) are observed.
The challenge for the use of dichlorophosphonate 5 is
due to the possibility of easy variations of substituents at
phosphorus atom. This can be accomplished by the reacꢀ
tion of dichlorophosphonate 5 with alcohols in the presꢀ
ence of a base (Scheme 5).
The suggested possibility of the utilization of ethoxyꢀ
vinylphosphonates in the synthesis of calix[4]resorcinꢀ
arenes was confirmed by reaction of dichlorophosphonate
5 with resorcinol in acidic media, which led to waterꢀ
soluble calix[4]resorcinarene 7, containing four fragments
of phosphonic acid at the lower rim of calixarene matrix
(Scheme 6).

1146
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 6, June, 2007
Burilov et al.
Scheme 5
the starting phosphonate the more stable the obtained
compounds are toward hydrolysis, resulting in isolation
of calixarenes 8e,f with dialkoxyphosphoryl fragments at
the lower rim of the molecule.
Experimental
R = Et (a), Pr (b), Pri (c), Bu (d), C7H15 (e), C12H25 (f)
1
Н, 13С, and 31Р NMR spectra were recorded on a Bruker
MSLꢀ400 spectrometer (400.13, 100.62, and 166.93 MHz, reꢀ
spectively) in D2O, CD3OD, and CDСl3 solutions. The δ values
are given relatively to the signals of residual protons of the
deuterated solvent (1Н, 13С) or to the external standard,
85% aq. Н3РО4 (31Р). IR spectra were recorded on a URꢀ20
spectrometer in the region 500—3700 cm–1 in Nujol mulls. Mass
spectra were recorded on a MALDI 2 V5.2.0 instrument
(1,8,9ꢀtrihydroxyanthracene as the matrix).
Scheme 6
Diethyl 2,2ꢀdiethoxyethylphosphonate (2a). A mixture of
triethylphosphite (16.6 g, 100 mmol) and bromoacetaldehyde
diethyl acetal (1) (29.55 g, 150 mmol) was heated with stirring
(4 h, 170—180 °C), distilling the forming during the reaction
ethylbromide and excess of the acetal off. After fractional distilꢀ
lation in vacuo, compound 2a was obtained (18.8 g, 74%), b.p.
92 °C (0.03 Torr), nD20 1.4280. Found (%): Р, 12.14. C10H23O5P.
1
Calculated (%): Р, 12.20. Н NMR (CDCl3), δ: 0.73 (t, 6 H,
Me, 3JH,H = 7.05 Hz); 0.86 (t, 6 H, Me, 3JH,H = 7.31 Hz); 1.69
3
2
(dd, 2 H, РСН2, JH,H = 5.48 Hz, JP,H = 18.69 Hz); 3.08 (m,
3
3
2 H, ОСН2, JH,H = 7.05 Hz); 3.18 (m, 2 H, ОСН2, JH,H
=
The stability of compound 7 in acidic media makes it a
prospective extragent of the rare earth metals from strong
acidic solutions. At the same time we anticipate that the
presence of acid functions will make it possible to syntheꢀ
size new waterꢀsoluble saltꢀlike structures, including the
tubular ones, by its reaction with organic amines and
diamines.
The acidꢀcatalyzed reaction of vinylphosphonates
6a—f with resorcinol in aqueous alcohols also gave
calix[4]resorcinarenes (Scheme 7). It should be also noted
that, similarly to the case of phosphorylated acetals, if
alkyl substituent is not too long, condensation products
4a—d with alkoxy and hydroxy groups at phosphorus atom
are eventually formed. The longer the alkyl substituent in
7.05 Hz); 3.63 (m, 4 H, ОСН2, 3JH,H = 7.31 Hz); 4.41 (dt, 1 H,
СН, JH,H = 5.48 Hz, JP,H = 15.48 Hz). 31Р NMR (CDCl3),
3
3
δ: 22.21.
Dipropyl 2,2ꢀdiethoxyethylphosphonate (2b) was obtained
similarly from tripropylphosphite (8.32 g, 40 mmol) and
bromoacetal 1 (11.82 g, 60 mmol). The yield was 8.8 g (55%),
b.p. 102—105 °C (0.03 Torr), nD20 1.4330. Found (%): Р, 10.79.
C12H27O5P. Calculated (%): Р, 10.99. 31Р NMR (CDCl3),
δ: 26.93.
Diisopropyl 2,2ꢀdiethoxyethylphosphonate (2c) was obtained
similarly from triisopropylphosphite (8.32 g, 40 mmol) and
bromoacetal 1 (11.82 g, 60 mmol). The yield was 7.36 g (46%),
20
b.p. 70—72 °C (0.03 Torr), nD 1.4360. Found (%): Р, 10.82.
C12H27O5P. Calculated (%): Р, 10.99. 1Н NMR (CDCl3), δ:
3
1.03, 1.04 (both t, 3 H each, Me, JH,H = 7.05 Hz); 1.15 (d,
12 H, Me, JH,H = 6.27 Hz); 1.98 (dd, 2 H, СН2Р, JH,H
3
3
=
=
2
3
5.48 Hz, JP,H = 18.65 Hz); 3.38 (q, 2 H, ОСН2, JH,H
Scheme 7
7.05 Hz); 3.48 (q, 2 H, ОСН2, 3JH,H = 7.05 Hz); 4.54 (m, 2 H,
3
3
ОСН, JH,H = 6.27 Hz, JH,H = 12.28 Hz); 4.71 (dt, 1 H, СН,
3JH,H = 5.48 Hz, 3JP,H = 7.12 Hz). 31Р NMR (CDCl3), δ: 20.64.
Dibutyl 2,2ꢀdiethoxyethylphosphonate (2d) was obtained simiꢀ
larly from tributylphosphite (10.0 g, 40 mmol) and bromoacetal 1
(11.82 g, 60 mmol). The yield was 6.0 g (55%), b.p. 102—105 °C
20
(0.03 Torr), nD 1.4330. Found (%): Р, 9.82. C14H31O5P. Calꢀ
culated (%): Р, 10.00. 31Р NMR (CDCl3), δ: 26.93.
Diisobutyl 2,2ꢀdiethoxyethylphosphonate (2e) was obtained
similarly from triisobutylphosphite (5.0 g, 20 mmol) and
bromoacetal 1 (5.91 g, 30 mmol). The yield was 4.0 g (65%),
20
b.p. 118—120 °C (0.03 Torr), nD 1.4340. Found (%): P, 9.79.
C14H31O5P. Calculated (%): Р, 10.00. 1Н NMR (CDCl3), δ:
3
1.07 (t, 6 H, Me, JH,H = 7.10 Hz); 1.14—1.50 (m, 14 H,
3
2
(CH3)2СН); 1.93 (dd, 2 H, РСН2, JH,H = 5.43 Hz, JP,H
=
8: R = C7H15 (e), C12H25 (f)
17.60 Hz); 3.42, 3.54 (both q, 2 H each, ОСН2, 3JH,H = 7.10 Hz);

Phosphorylated calix[4]resorcinarenes
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 6, June, 2007
1147
3
4.63 (m, 4 H, ОСН2); 4.84 (dt, 1 H, СН, JH,H = 5.43 Hz,
3JP,H = 7.15 Hz). 31Р NMR (CDCl3), δ: 26.09.
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23ꢀdodecaene (4c).
А. Product 4c (4.43 g, 86%), m.p. 233—235 °C (decomp.), was
obtained similarly from resorcinol (2.2 g, 20 mmol), water
(10 mL), ethanol (10 mL), conc. hydrochloric acid (1.0 mL),
and acetal 2c (5.64 g, 20 mmol). Found (%): С, 50.97; Н, 5.56;
Р, 11.57. C44H60O20P4. Calculated (%): С, 51.16; Н, 5.81;
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ2,8,14,20ꢀ
t e t r a [ ( e t h o x y h y d r o x y p h o s p h o r y l ) m e t h y l ] p e n t a ꢀ
c y c l o [ 1 9 . 3 . 1 . 1 3 , 7 . 1 9 , 1 3 . 1 1 5 , 1 9 ] o c t a c o s a ꢀ
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23ꢀdodecaene (4a).
A. Acetal 2a (3.69 g, 14.5 mmol) was added dropwise with coolꢀ
ing to a mixture of resorcinol (1.6 g, 14.5 mmol), water (10 mL),
ethanol (5 mL), and conc. hydrochloric acid (3.6 mL). The
reaction mixture was heated with stirring (1 h, 50—60 °C) and
kept for 10 h at 20 °C. The oil layer was decanted, triturated
with acetonitrile, and filtered. The solvent was evaporated and
the residue was dried in vacuo (40 °C, 0.04 Torr) until the
weight was constant. Compound 4a was obtained (2.0 g, 56%),
m.p. 193—195 °C. Found (%): С, 48.81; Н, 5.72; P, 12.88.
C40H52O20P4. Calculated (%): С, 49.18; Н, 5.33; P, 12.70.
1Н NMR (CD3OD), δ: 1.40 (t, 12 Н, Me, 3JН,Н = 7.0 Hz); 1.63
(m, 8 Н, СН2Р); 3.95 (m, 8 Н, ОСН2); 5.07 (br.m, 4 Н, СН);
6.50 (s, 4 Н, oꢀН arom.); 7.25 (s, 4 Н, mꢀН arom.).
13С NMR ((CD3)2CO), δ: 17.35 (q, Me, JC,H = 124.4 Hz);
63.45 (t, СН2О, JС,Н = 142.6 Hz); 79.64 (dd, СН, JС,Н
149.0 Hz, JС,Р = 7.0 Hz); 102.55 (d, mꢀС arom., JС,Н
155.9 Hz); 123.4 (s, C arom.—СН); 139.25 (d, oꢀС arom.,
1JС,Н = 153.55 Hz); 154.37 (s, C arom.—ОН). 31P NMR
(CD3OD), δ: 32.21. MS, m/z: 976.
B. A mixture of resorcinol (0.61 g, 5.5 mmol), water (3 mL),
ethanol (3 mL), conc. hydrochloric acid (0.6 mL), and phosꢀ
phonate 6а (1.15 g, 5.5 mmol) was heated with stirring (1 h,
50 °C) and kept 3 days at 20 °C. The solvent was evaporated
in vacuo, the residue was reꢀprecipitated from ethanol with waꢀ
ter, the product was filtered off and kept in vacuo (40 °C,
0.04 Torr) until the weight was constant. The yield was 1.2 g
(85%), m.p. 192—194 °C. Found (%): С, 49.87; Н, 5.47;
P, 12.42. C40H52O20P4. Calculated (%): С, 49.18; Н, 5.33;
Р, 12.70. IR, ν/cm–1: 1190 (P=O); 1615 (C=C arom.);
3100—3580 (ОН). 31Р NMR (CD3OD), δ: 32.23.
1
3
Р, 12.02. Н NMR (CD3OD), δ: 1.46 (d, 24 Н, Me, JН,Н
=
6.8 Hz); 1.83 (m, 8 Н, СН2Р); 3.85 (m, 4 Н, ОСН); 5.17 (br.m,
4 Н, СН); 6.26 (s, 4 Н, oꢀН arom.); 7.28 (s, 4 Н, mꢀН arom.).
IR, ν/cm–1: 1162 (Р=О); 3100—3580 (ОН). 31Р NMR
(CD3OD), δ: 30.82.
B. Product 4c (0.45 g, 89%), m.p. 233—235 °C (decomp.),
was obtained similarly from resorcinol (0.22 g, 2 mmol), water
(3 mL), ethanol (2 mL), conc. hydrochloric acid (0.4 mL), and
phosphonate 6с (0.47 g, 2 mmol). Found (%): С, 50.94; Н, 5.40;
P, 11.54. C44H60O20P4. Calculated (%): С, 51.16; Н, 5.81;
Р, 12.02. IR, ν/cm–1: 1160 (P=O); 1610 (C=C arom.);
3100—3580 (ОН). 31Р NMR (CD3OD), δ: 30.90.
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ2,8,14,20ꢀ
t e t r a [ ( b u t o x y h y d r o x y p h o s p h o r y l ) m e t h y l ] p e n t a ꢀ
c y c l o [ 1 9 . 3 . 1 . 1 3 , 7 . 1 9 , 1 3 . 1 1 5 , 1 9 ] o c t a c o s a ꢀ
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23ꢀdodecaene (4d).
А. Product 4d (4.0 g, 74%), m.p. 166—168 °C, was obtained
similarly from resorcinol (2.2 g, 20 mmol), water (8 mL), ethaꢀ
nol (30 mL), conc. hydrochloric acid (2.4 mL), and acetal 2d
(6.2 g, 20 mmol). Found (%): С, 52.55; Н, 6.43; P, 11.85.
C48H68O20P4. Calculated (%): С, 52.94; Н, 6.25; P, 11.40.
1Н NMR (CD3OD), δ: 1.10 (t, 12 Н, Me, 3JН,Н = 7.0 Hz); 1.55
(br.m, 16 Н, СН2); 1.89 (m, 8 Н, СН2Р); 4.20 (m, 8 Н, ОСН2);
1
1
1
=
=
2
1
5.17 (br.m, 4 Н, СН); 6.48 (s, 4 Н, oꢀН arom.); 7.32 (s, 4 Н,
1
mꢀН arom.). 13С NMR (CD3OD), δ: 13.99 (q, Me, JC,H
=
124.4 Hz); 19.64 (t, (СH2)2, 1JС,Н = 122.06 Hz); 33.48 (t, СН2Р,
1JС,Н = 125.60 Hz); 66.71 (t, СН2О, JС,Н = 142.60 Hz); 69.65
(dd, СН, JС,Н = 150.90 Hz, JС,Р = 7.04 Hz); 104.05 (d,
mꢀС arom., JС,Н = 155.90 Hz); 122.53 (s, C arom.—СН);
1
1
2
1
1
129.96 (d, oꢀС arom., JС,Н = 154.60 Hz); 154.26 (s,
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ2,8,14,20ꢀ
t e t r a [ ( p r o p o x y h y d r o x y p h o s p h o r y l ) m e t h y l ] p e n t a ꢀ
c y c l o [ 1 9 . 3 . 1 . 1 3 , 7 . 1 9 , 1 3 . 1 1 5 , 1 9 ] o c t a c o s a ꢀ
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23ꢀdodecaene (4b).
А. Product 4b (8.1 g, 79%), m.p. 201—203 °C, was obtained
similarly to compound 4a (method А) from resorcinol (4.4 g,
40 mmol), water (50 mL), ethanol (50 mL), conc. hydrochloric
acid (7.75 mL), and acetal 2b (11.28 g, 40 mmol). Found (%):
С, 50.45; Н, 5.53; Р, 12.07. C44H60O20P4. Calculated (%):
C arom.—ОН). 31Р NMR (CD3OD), δ: 31.14. MS, m/z: 1088.
B. Product 4d (4.5 g, 84%), m.p. 166—168 °C, was obtained
similarly from resorcinol (2.20 g, 20 mmol), water (10 mL),
ethanol (7 mL), conc. hydrochloric acid (2 mL), and vinylꢀ
phosphonate 6d (5.28 g, 20 mmol). Found (%): С, 52.48; Н, 6.39;
Р, 11.09. C48H68O20P4. Calculated (%): С, 52.94; Н, 6.25;
P, 11.40. IR, ν/cm–1: 1190 (P=O); 1615 (C=C arom.);
3100—3580 (ОН). 31Р NMR (CD3OD), δ: 31.76.
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ2,8,14,20ꢀ
t e t r a [ ( i s o b u t o x y h y d r o x y p h o s p h o r y l ) m e t h y l ] p e n t a ꢀ
c y c l o [ 1 9 . 3 . 1 . 1 3 , 7 . 1 9 , 1 3 . 1 1 5 , 1 9 ] o c t a c o s a ꢀ
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23ꢀdodecaene (4e)
was obtained similarly (method А) from resorcinol (1.1 g,
10 mmol), water (20 mL), ethanol (20 mL), conc. hydrochloric
acid (4.75 mL), and phosphono acetal 2e (3.1 g, 10 mmol). The
yield was 6.8 g (67%), m.p. 247—250 °C (decomp.). Found (%):
С, 52.60; Н, 6.15; Р, 11.04. C48H68O20P4. Calculated (%):
С, 52.94; Н, 6.25; Р, 11.40. IR, ν/cm–1: 1165 (Р=О); 3100—3580
(ОН). 31Р NMR (CD3OD), δ: 32.90.
1
С, 51.16; Н, 5.81; Р, 12.02. Н NMR (CD3OD), δ: 1.49 (br.m,
20 H, СН3СН2); 1.81 (m, 8 Н, СН2Р); 4.01 (m, 8 Н, ОСН2);
5.10 (br.m, 4 Н, СН); 6.23 (s, 4 Н, oꢀН arom.); 7.30 (s, 4 Н,
mꢀН arom.). IR, ν/cm–1: 1160 (Р=О); 3100—3580 (ОН).
31Р NMR (CD3OD), δ: 33.30.
B. Product 4b (1.41 g, 89%), m.p. 201—203 °C, was obꢀ
tained similarly to compound 4a (method B) from resorcinol
(0.68 g, 6.18 mmol), water (8 mL), ethanol (6 mL), conc. hydroꢀ
chloric acid (1.1 mL), and vinylphosphonate 6b (1.45 g,
6.18 mmol). Found (%): С, 51.22; Н, 5.62; P, 11.79.
C44H60O20P4. Calculated (%): С, 51.16; Н, 5.81; Р, 12.02. IR,
ν/cm–1: 1160 (P=O); 3100—3580 (ОН). 31Р NMR (CD3OD),
δ: 33.15.
Diethyl 2ꢀethoxyvinylphosphonate (6а). A solution of phosꢀ
8
phonic dichloroanhydride 5 (6 g, 32 mmol) in benzene
(12.0 mL) was added dropwise with stirring and cooling to a
mixture of ethanol (2.94 g, 64 mmol) and pyridine (5.2 mL,
64 mmol) in benzene (20 mL). The reaction mixture was stirred
for 3 h at 20 °C, the formed precipitate of pyridine hydrochloꢀ
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ2,8,14,20ꢀ
tetra[(isopropoxyhydroxyphosphoryl)methyl]pentaꢀ
c y c l o [ 1 9 . 3 . 1 . 1 3 , 7 . 1 9 , 1 3 . 1 1 5 , 1 9 ] o c t a c o s a ꢀ

1148
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 6, June, 2007
Burilov et al.
ride was filtered off, the filtrate was concentrated, and the resiꢀ
was dried in vacuo (40 °C, 0.04 Torr) until the weight was conꢀ
stant. Product 7 was obtained (1.1 g, 92%), m.p. >350 °C.
Found (%): С, 44.35; Н, 4.71; Р, 13.48. C32H36O20P4. Calcuꢀ
lated (%): С, 44.44; Н, 4.16; Р, 13.05. 1Н NMR (D2O), δ: 1.07
(m, 8 H, РСН2); 3.79 (m, 4 H, СН); 6.28 (s, 4 H, oꢀH arom.);
7.04 (s, 4 H, mꢀH arom.). IR, ν/cm–1: 995—1024 (P(O)OН);
1195 (P=O); 1620 (C=C arom.); 3100—3580 (ОН). 31Р NMR
(CD3OD), δ: 28.28.
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ2,8,14,20ꢀ
t e t r a [ ( d i h e p t y l o x y p h o s p h o r y l ) m e t h y l ] p e n t a ꢀ
c y c l o [ 1 9 . 3 . 1 . 1 3 , 7 . 1 9 , 1 3 . 1 1 5 , 1 9 ] o c t a c o s a ꢀ
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23ꢀdodecaene (8e)
was obtained similarly to compound 4a from resorcinol (1.20 g,
11 mmol), water (12 mL), ethanol (8 mL), conc. hydrochloric
acid (1.8 mL), and phosphonate 6e (3.80 g, 11 mmol). The yield
was 3.8 g (85%), m.p. 138 °C. Found (%): С, 63.67; Н, 9.35;
P, 8.02. C88H148O20P4. Calculated (%): С, 64.07; Н, 8.98;
Р, 7.62. IR, ν/cm–1: 1240 (P=O); 1610 (C=C arom.);
3100—3580 (ОН). 31Р NMR (CD3OD), δ: 32.77.
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ2,8,14,20ꢀ
t e t r a [ ( d i d o d e c y l o x y p h o s p h o r y l ) m e t h y l ] p e n t a ꢀ
c y c l o [ 1 9 . 3 . 1 . 1 3 , 7 . 1 9 , 1 3 . 1 1 5 , 1 9 ] o c t a c o s a ꢀ
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23ꢀdodecaene (8f)
was obtained similarly from resorcinol (1.51 g, 13.7 mmol),
water (15 mL), ethanol (10 mL), conc. hydrochloric acid
(2.3 mL), and vinylphosphonate 6f (6.69 g, 13.7 mmol). The
yield was 6.5 g (89%), m.p. 128 °C. Found (%): С, 69.18;
Н, 10.98; P, 5.36. C128H228O20P4. Calculated (%): С, 69.56;
Н, 10.32; Р, 5.61. IR, ν/cm–1: 1210 (P=O); 1620 (C=C);
3100—3580 (ОН). 31Р NMR (CDCl3), δ: 33.25.
due was fractionally distilled. Compound 6a (4.7 g, 72%) was
20
obtained, b.p. 83 °C (0.04 Torr), nD 1.4500. Found (%):
Р, 14.81. C8H17O4P. Calculated (%): Р, 14.90. 1Н NMR
3
(СDCl3), δ: 0.81 (t, 3 H, СН3CH2OC, JH,H = 6.86 Hz); 0.84
3
(t, 6 H, СН3CH2OP, JH,H = 7.20 Hz); 3.42 (q, 2 H, СОСН2,
3
3JH,H = 6.86 Hz); 3.54 (dq, 4 Н, СН2OР, JH,H = 7.20 Hz,
3JP,H = 7.20 Hz); 4.21 (dd, 1 Н, СНР, 3JH,H = 13.28 Hz, 2JP,H
=
=
3
3
9.95 Hz); 6.87 (dd, 1 Н, ОСН, JH,H = 13.28 Hz, JP,H
11.66 Hz). IR, ν/cm–1: 950—1050 (POCH2); 1250 (P=O); 1615
(C=C); 3030 (=НС). 31Р NMR (CD3OD), δ: 22.23.
Dipropyl 2ꢀethoxyvinylphosphonate (6b) was obtained simiꢀ
larly from propanol (3.12 g, 52 mmol), pyridine (4.2 mL,
52 mmol), benzene (25 mL), and compound 5 (4.9 g, 26 mmol).
The yield was 4.2 g (69%), b.p. 90—92 °C (0.04 Torr),
nD20 1.4510. Found (%): Р, 13.06. C10H21O4P. Calculated (%):
3
Р, 13.14. 1Н NMR (СDCl3), δ: 0.56 (t, 6 H, Me, JH,H
=
3
7.36 Hz); 0.94 (t, 3 H, Me, JH,H = 6.99 Hz); 1.29 (m, 4 H,
СН2); 3.53 (m, 6 H, ОСН2Р, ОСН2); 4.32 (dd, 1 Н, =СНР,
2
3JH,H = 13.60 Hz, JP,H = 9.56 Hz); 6.79 (dd, 1 Н, ОСН=,
3JH,H = 13.60 Hz, 3JP,H = 11.77 Hz). IR, ν/cm–1: 1240 (P=O);
1620 (C=C); 3040 (=НC). 31Р NMR (CDCl3), δ: 21.69.
Diisopropyl 2ꢀethoxyvinylphosphonate (6c) was obtained simiꢀ
larly from propanꢀ2ꢀol (3.12 g, 52 mmol), pyridine (4.2 mL,
52 mmol), and compound 5 (4.94 g, 26 mmol). The yield was
3.6 g (59%), b.p. 92—93 °C (0.04 Torr), nD20 1.4475. Found (%):
Р, 12.87. C10H21O4P. Calculated (%): Р, 13.14. 1Н NMR
(СDCl3), δ: 0.88 (br.m, 15 Н, Me, (СН3)СН); 3.46 (q, 2 H,
ОСН2,3JH,H = 6.62 Hz); 4.18 (m, 2 H, СНOР); 4.29 (dd, 1 Н,
3
2
=СНР, JH,H = 13.24 Hz, JP,H = 10.29 Hz); 6.75 (dd, 1 Н,
ОСН=, 3JH,H = 13.24 Hz, 3JP,H = 12.71 Hz). IR, ν/cm–1: 1260
(P=O); 1635 (C=C); 3030 (=НC). 31Р NMR (CDCl3), δ: 19.46.
Dibutyl 2ꢀethoxyvinylphosphonate (6d) was obtained simiꢀ
larly from nꢀbutanol (8.35 g, 44 mmol), pyridine (7.1 mL,
88 mmol), and compound 5 (8.35 g, 44 mmol). The yield was
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 05ꢀ03ꢀ
32136).
20
8.2 g (70%), b.p. 142 °C (0.02 Torr), nD 1.4720. Found (%):
References
Р, 11.47. C12H25O4P. Calculated (%): Р, 11.74. 31Р NMR
(CDCl3), δ: 21.64.
1. C. D. Gutsche, Calixarenes, The Royal Society of Chemistry,
Cambridge, 1989, 132.
2. J. Vicens and V. Böhmer, Calixarenes: a Versatile Class of
Macrocyclic Compounds, Kluwer Acad. Publ., Dordrecht,
1991, 15.
3. Z. Asfari, V. Böhmer, J. Harrowfield, and J. Vicens, Calixꢀ
arenes 2001, Kluwer Acad. Publ., Dordrecht—Boston—Lonꢀ
don, 2001.
4. R. J. Egbering, P. L. Cobben, W. Verboom, S. Harkema, and
D. N. Reinhoudt, J. Inclusion Phenom., 1992, 151.
5. L. M. Tunstad, J. A. Tucker, E. Dalcanale, J. Weiser, J. A.
Bryant, J. C. Sherman, R. C. Helgeson, C. B. Knobler, and
D. J. Cram, J. Org. Chem., 1989, 1305.
Diheptyl 2ꢀethoxyvinylphosphonate (6e) was obtained simiꢀ
larly from heptanol (11.14 g, 96 mmol), pyridine (7.7 mL,
96 mmol), and compound 5 (9.0 g, 48 mmol). The yield was
10.9 g (66%), b.p. 170 °C (0.02 Torr). Found (%): Р, 9.33.
C16H33O4P. Calculated (%): Р, 9.68. IR, ν/cm–1: 1240 (P=O);
1620 (C=C); 3030 (=НC). 31Р NMR (CDCl3), δ: 21.62.
Didodecyl 2ꢀethoxyvinylphosphonate (6f) was obtained simiꢀ
larly from dodecanol (6.51 g, 35 mmol), pyridine (2.8 mL,
35 mmol), and compound 5 (3.30 g, 17.5 mmol). The yield was
7.2 g (84%). Compound 6f was further used without additional
purification. Found (%): Р, 5.94. C28H57O4P. Calculated (%):
Р, 6.35. IR, ν/cm–1: 1250 (P=O); 1620 (C=C); 3030 (=HC).
31Р NMR (CDCl3), δ: 21.52.
6. E. U. Thoden van Velzen, J. F. Engbersen, and D. N.
Reinhoudt, J. Am. Chem. Soc., 1994, 3597.
7. V. V. Kormachev and M. S. Fedoseev, Preparativnaya khimiya
fosforа [The Preparative Chemistry of Phosphorus], UrО RAS
Publ., Perm, 1992, 189 (in Russian).
4,6,10,12,16,18,22,24ꢀOctahydroxyꢀ2,8,14,20ꢀ
t e t r a [ ( d i h y d r o x y p h o s p h o r y l ) m e t h y l ] p e n t a ꢀ
c y c l o [ 1 9 . 3 . 1 . 1 3 , 7 . 1 9 , 1 3 . 1 1 5 , 1 9 ] o c t a c o s a ꢀ
1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23ꢀdodecaene (7).
A mixture of resorcinol (0.76 g, 6.9 mmol), water (7 mL), ethaꢀ
nol (5 mL), conc. hydrochloric acid (1 mL), and compound 5
(1.30 g, 6.9 mmol) was heated with stirring (0.5 h, 60 °C) and
kept for 5 days at 20 °C. The solvent was evaporated, the residue
was reꢀprecipitated from ethanol with diethyl ether, the product
8. А.s. 883047; Byul. Izobret., 1981, No. 43.
Received December 2, 2005;
in revised form February 19, 2006