Chiral molecular cavities based on 1,4;3,6-dianhydro-D-mannite bis(tetraethylphosphorodiamidite)

Article abstract of DOI:10.1023/A:1023313901660

The possibility of forming chiral molecular cavities from an accessible bisphosphorylated derivative of 1,4;3,6-dianhydro-D-mannite and various bisphenols was examined.

Full text of DOI:10.1023/A:1023313901660

Russian Journal of General Chemistry, Vol. 72, No. 11, 2002, pp. 1813 1819. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 11, 2002,
pp. 1918 1924.
Original Russian Text Copyright
2002 by Grachev, Kurochkina, Soboleva, Vasyanina, Nifant’ev.
Chiral Molecular Cavities Based
on 1,4;3,6-Dianhydro-D-mannite
Bis(tetraethylphosphorodiamidite)
M. K. Grachev, G. I. Kurochkina, N. O. Soboleva,
L. K. Vasyanina, E. E. Nifant’ev
Moscow Pedagogical State University, Moscow, Russia
Received March 7, 2001
Abstract The possibility of forming chiral molecular cavities from an accessible bisphosphorylated
derivative of 1,4;3,6-dianhydro-D-mannite and various bisphenols was examined.
We have studied previously phosphorylation of
1,4;3,6-dianhydro-D-mannite I, a chiral diol in which
the hydroxy groups are closely located in space, with
amides of trivalent phosphorus acids [1]. An impor-
tant structural feature of I is that its molecule consists
of two fused furanose rings, with the hydroxyls occu-
pying the endo positions relative to the internal chiral
cavity. Thanks to this feature, bis-P(III)-phosphory-
lated derivatives of I are of interest as bidentate lig-
ands with two chelating P(III) atoms located on a
bulky chiral matrix [1, 2]. Furthermore, bisphosphoro-
amidite derivatives of I show promise as synthetic
precursors of phosphorus-containing chiral macrohet-
erocycles [3]. Such structures are of particular interest
for molecular encapsulation, enantioselective catalysis,
synthesis of host guest complexes, and other lines of
supramolecular chemistry [4].
The second problem concerns the selectivity of the
process which can, generally speaking, occur by sev-
eral pathways: (a) diphosphocyclization (each phos-
phamide group in II singly phosphorylates different
hydroxyls of the bisphenol to form a diphosphite
macroheterocycle); (b) monophosphocyclization (one
or both phosphamide groups of II doubly phosphory-
late the dihydric phenol); and (c) incomplete phos-
phorylation without formation of phosphocycles (one
or both phosphamide groups singly phosphorylate the
bisphenol).
OH
H6B
H6A
H1B
H1A
OH
O
H3
H4
H2
H5
O
I
In this context, our goal was to design chiral mo-
lecular cavities based on D-mannite bis(tetraalkyl-
phosphorodiamidite) II, using modern methods of
trivalent phosphorus chemistry [5]. The molecules of
II have a shape of a deep basket with a fixable grip
(i.e., a bisphenol or diol residue). Therefore, in de-
signing such structures, two problems should be
solved. The first is the choice of a grip, namely,
of a bisphenol geometrically suited for formation of a
bridge with II. Among available bisphenols, we chose
six compounds: 2,2 -dihydroxydiphenyl III, 2,2 -dihy-
droxy-5,5 -dimethyl-3,3 -di-tert-butyldiphenylmethane
IV, 2,2-di(p-hydroxyphenyl)propane V, di(p-hydroxy-
phenyl)diphenylmethane VI, 4,4 -dihydroxydiphenyl
ether VII, and 4,4 -dihydroxydiphenyl sulfide VIII.
The progress of phosphorylation was monitored by
31P NMR spectroscopy. Experiments were started
from the simplest of the selected dihydric phenols, di-
phenyl derivative III. We showed that the reaction of
II (138 ppm) with an equimolar amount of III follows
pathway b: After phosphorylation completion, only
two signals of equal intensity at 138 and 136 ppm are
detected, belonging, respectively, to the phosphorus
atoms of the phosphorodiamidite and phosphite moie-
ties of IX. Addition of sulfur yields product X whose
31P NMR spectrum consists of two signals of equal
intensity at 79 and 73 ppm, belonging, respectively,
to the phosphorodiamidothioate and phosphorothioate
moieties. The reaction of the second equivalent of III
with IX, or the reaction of II with III in a 1 : 2 ratio
1070-3632/02/7211-1813$27.00 2002 MAIK Nauka/Interperiodica

1814
GRACHEV et al.
OP(NEt2)2
O
HO
HO
+
O
OP(NEt2)2
II
III VI
a
b
c
NEt2
NEt2
NEt2
OPO
O
O
O
OP
OP
O
OP
OP
OP
OPO
O
O
O
O
O
O
O
HO
HO
HO
OPO
NEt2
NEt2
NEt2
NEt2
O
O
O
O
O
O
OP
OPO
NEt2
NEt2
yields bisphosphocyclic structures: phosphites XI and
(after uptake of S) phosphorothioates XIII. These
compounds give singlets at 136 and 73 ppm, respec-
tively.
bridge and the hydroxyls are sterically shielded by
bulky substituents reacts exclusively by pathway c,
without formation of phosphocycles.
X
O
HO
OP
O
O
1) 1:1;
2) S
X
O
II + III
OP
O
1) 1:1;
2) S
NEt2
NEt2
O
OP
X
NEt2
NEt2
NEt2
IX, X
O
OP
X
1) 1:2;
2) S
XIII, XIV
X
O
O
OP
II + IV
HO
O
1) 1:1;
2) S
X
O
OP
III + IX
O
1) 1:2;
2) S
O
NEt2
O
O
OP
X
NEt2
O
O
OP
X
XI, XII
HO
X = lone electron pair (IX, XI); X = S (X, XII).
XV, XVI
X = lone electron pair (XIII, XV); X = S (XIV, XVI).
Bisphenol IV in which the distance between the
hydroxyls is larger owing to the additional methylene
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CHIRAL MOLECULAR CAVITIES BASED ON 1,4;3,6-DIANHYDRO-D-MANNITE
1815
In the spectrum of the reaction mixture in synthesis
of XIII, after the reaction completion, two signals
X
NEt2
O
of equal intensity are observed at 138 and 152 ppm,
belonging, respectively, to phosphorus atoms of the
phosphorodiamidite and phosphoramidite moieties.
After addition of sulfur, we isolated pure unsymmet-
rical adduct XIV in which the phosphorus atoms of
the phosphorodiamidothioate and phosphoramidothio-
ate moieties gave, respectively, the signals at 80 and
74 ppm. The suggested structure of XIV was also
OP
O
1) 1:1;
2) S
II + V (VI VIII)
Y
O
O
OP
X
NEt2
XVII XXIV
1
confirmed by the H NMR spectra, e.g., by the rela-
X = lone electron pair (XVII, XIX, XXI, XXIII); X = S
(XVIII, XX, XXII, XXIV); Y = CMe2 (V, XVII, XVIII),
CPh2 (VI, XIX, XX), O (VII, XXI, XXII), S (VIII, XXIII,
XXIV).
tive integral intensities of the proton signals of the
ethyl and tert-butyl groups.
On treatment of bisphosphite II with two equiva-
lents opf bisphenol IV, we could expect firther substi-
tution of the second amido group at the same P atom
and substitution of the amido group at the second
P atom. However, disappearance of the signal at
137 ppm and appearance of only one signal at 152 ppm
suggest the symmetrical structure of XV and location
of the second residue of bisphenol IV at the second
P atom. Bis(phosphoramidothioate) XVI also gives a
single signal at 74 ppm. On the whole, it should be
noted that the P(III)-phosphorylation products IX,
XI,1 XIII, and XV, detected in the reaction mixture,
were the major products; other possible products,
according to the 31P NMR spectra, were present in
trace amounts. The corresponding phosphorothioate
derivatives X, XII, XIV, and XVI were isolated pure
by reprecipitation (X), recrystallization (XII, XIV),
and column chromatography (XVI) in 76 85% yields.
To conclude, bisphenols III and IV appeared to be
unsuitable for formation of macroheterocycles because
of unfavorable steric arrangement of the hydroxy
groups.
(XXIII); 71.8, 72.2 (XVIII); 72.0, 72.2 (XX); 71.6,
72.0 (XXII); and 72.1, 72.4 (XXIV). The splitting
may be due to the magnetic nonequivalence resulting
from different steric orientation of the two phosphorus
atoms in these molecules relative to the chiral cavity.
1
A similar splitting is observed in the H NMR spectra
of pure phosphorothioates XVIII, XX, XXII, and
XXIV. Furthermore, in compound XXII containing
an oxygen bridge between the phenyl groups, which
provides the largest angle (120 124 [6]) between the
central axes of the two phenylene residues, the ethyl
groups at the same nitrogen atom are also magnetical-
ly nonequivalent: Two separate groups of multiplets
of the methylene protons of the ethyl groups are ob-
served at 3.10 and 3.22 ppm, and the geminal cou-
pling of the methylene protons in one of the two ethyl
groups is clearly detected after decoupling with the
methyl protons. This feature of XXII may be due to
braked rotation of the N-diethyl groups, in contrast to
XVIII, XX, and XXIV.
The desired diphosphocyclic structures (pathway a)
were obtained with bisphenols V VIII containing two
sterically accessible hydroxyls fairly distant from each
other, with dimethylmethylene (V), diphenylmethyl-
ene (VI), oxygen (VII), and sulfide (VIII) bridges
providing a favorable angle (109 124 [6]) between
the central axes of the two phenylene residues.
We also attempted to prepare the product of com-
plete substitution of the amido groups by two molar
equivalents of bisphenols V VIII, including the reac-
tion at elevated temperatures (100 C); however, we
failed to isolate and identify the reaction products
because of tarring.
Bisphenol V also appeared to be a convenient start-
ing compound for preparing more complex macrocy-
clic systems based on dianhydro-D-mannite I and
containing three phosphoryl functional groups. In this
case, we chose a principally different synthesis strat-
egy, so as to exclude formation of XVII (pathway a).
The first step of the synthesis was the reaction of two
equivalents of the phenol with an equivalent amount
of hexaethylphosphorous triamide. The resulting phos-
phoramidite XXV without isolation was treated with
sulfur to obtain phosphoramidothioate XXVI, which
was isolated in 95% yield. Compound XXVI was
The phosphorylation products XVII, XIX, XXI,
and XXIII containing trivalent phosphorus atoms and
their sulfide derivatives XVIII, XX, XXII, and XXIV
give a pair of closely located signals of equal intensity
in the 31P NMR spectra (ppm): 144.8, 145.2 (XVII);
145.7, 146.1 (XIX); 144.6, 145.5 (XXI); 145.2, 146.1
1
Compound XI was also mentioned in [2], but, in contrast to
our procedure [1], it was prepared using 2,2 -binaphthyl
phosphorochloridite and was taken in further reactions without
isolation.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

1816
GRACHEV et al.
phosphorylated with a double molar excess of phenyl-
dichlorophosphine in the presence of triethylamine to
obtain an original phosphorylated agent XXVII cap-
able of cyclophosphorylating dianhydro-D-mannite I.
This reaction was performed in the presence of tri-
ethylamine.
EXPERIMENTAL
1
The H NMR spectra were recorded on a Bruker
WP-250 spectrometer, and the 31P {1H} NMR spec-
tra, on a Bruker WP-80 spectrometer (working fre-
1
quencies 250 and 32.4 MHz, respectively; H, internal
reference TMS; 31P, external reference 85% H3PO4).
All the synthesis were performed in a dry nitrogen
atmosphere using dehydrated solvents. Thin-layer
chromatography was performed on Silufol UV-366
plates in the systems benzene dioxane, 6 : 1 (A);
benzene dioxane, 10 : 1 (B); chloroform ethanol,
3 : 1 (C); chloroform ethanol, 10 : 1 (D); ethanol
dioxane, 10 : 1 (E); acetone methanol, 1 : 3 (F); and
acetone dioxane, 1 : 1 (G).
1) P(NEt2)3;
X
HO R O
HO R O
2) S
P
2HO R OH
NEt2
V
XXV, XXVI
Ph
S
P
ClPO R O
2PhPCl2
ClPO R O
Ph
NEt2
1,4;3,6-Dianhydro-D-mannite 2,5-O,O-bis(tetra-
ethylphosphorodiamidite) II was prepared as
described in [1].
XXVII
Me
2-O-(4,5;6,7-Dibenzo-2-thioxo-1,3,2 5-dioxa-
phosphepan-2-yl)-5-O-[bis(diethylamino)thiophos-
phoryl]-1,4;3,6-dianhydro-D-mannite X. A solution
of 0.23 g of bisphenol III in 3 ml of benzene was
added with stirring at 20 C to a solution of 0.61 g of
II in 7 ml of benzene; the mixture was kept at 75
80 C for 2.5 h in a weak nitrogen flow, with removal
of diethylamine. 31P NMR spectrum of the reaction
mixture (compound IX), P, ppm: 137.5 and 138,
ratio of integral intensities 1 : 1. To the reaction mix-
ture, we added 0.0795 g of finely divided sulfur and
stirred for 1 h at 80 C; excess sulfur was filtered off,
and the solvent was distilled off in a vacuum. The
residue was dissolved in 5 ml of benzene, 10 ml of
hexane was added, the mixture was stirred, and the
light yellow viscous oily precipitate was separated.
Y
Ph
OP O
O
O
O
Me
Me
1) I, NEt3;
2) S
S
P
NEt2
O
OP O
Me
Y
Ph
XXVIII, XXIX
R = 2,2-diphenylpropane-p,p -diyl; X = lone electron pair
(XXV), S (XXVI); Y = lone electron pair (XXVIII), S
(XXIX).
By addition of sulfur to bisphosphonite XXVIII,
we obtained heterocyclic derivative XXIX containing
three phosphorus functionalities. Compound XXIX
was isolated in 76% yield as a colorless powder. Its
1
Yield 0.68 g (92%), Rf 0.8 (A). H NMR spectrum
1
(CDCl3), , ppm: 1.05 1.17 m (12H, CH3); 3.06
3.18 m (8H, NCH2); 3.64 3.71 m, 3.82 3.94 m,
purity and structure were proved by TLC, H and 31P
NMR spectroscopy, and elemental analysis. Similar to
the above-mentioned phosphorothioates XVIII, XX,
XXII, and XXIV, compound XXIX gives in the 31P
NMR spectrum the singlets at 88 and 86 ppm of two
magnetically nonequivalent phosphorus atoms of the
phosphonothioate moieties directly linked to the dian-
hydro-D-mannite residue; additionally, it contains the
singlet at 67 ppm belonging to the phosphoramido-
thioate phosphorus atom. The ratio of the integral
4.09 4.21 m (4H, H1A, H1B, H6A, H6B); 4.54 4.66 m,
4.87 5.03 m (2H, H3, H4); 4.73 4.83 m, 5.23 5.37 m
(2H, H2, H5), 7.34 7.56 m (8H, Harom). 31P NMR
spectrum (C6H6), P, ppm: 73 and 79; ratio of integral
intensities 1 : 1. Found, %: C 51.75; H 6.15; P 10.39.
C26H36N2O6P2S2. Calculated, %: C 52.16; H 6.06;
P 10.34.
5
2,5-O,O-Bis(4,5;6,7-dibenzo-2-thioxo-1,3,2 -di-
1
intensities of these signals is 1 : 1 : 1. The H NMR
oxaphosphepan-2-yl)-1,4;3,6-dianhydro-D-mannite
XII. A solution of 0.23 g of bisphenol III in 3 ml of
benzene was added with stirring at 20 C to the reac-
tion mixture containing IX. The mixture was heated
at 75 80 C for 2.5 h in a weak nitrogen flow, with the
removal of diethylamine. 31P NMR spectrum of the
spectrum of XXIX is also complicated by additional
splitting (see Experimental).
Thus, starting from accessible dianhydro-D-man-
nite bis(phosphorodiamidites) and bisphenols, it is
possible to design original chiral phosphorus-contain-
ing cavity systems showing promise for supramolec-
ular chemistry.
reaction mixture (compound XI):
136 ppm. To the
P
reaction mixture, we added 0.08 g of finely divided
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CHIRAL MOLECULAR CAVITIES BASED ON 1,4;3,6-DIANHYDRO-D-MANNITE
1817
sulfur; the mixture was stirred for 1 h at 80 C, excess
sulfur was filtered off, the solvent was distilled off in
a vacuum, and the residue was recrystallized from
3 ml of benzene. Yield 0.65 g (85%), mp 111 112 C,
dioxane, 6 : 1). Yield 1.55 g (76%), mp 95 96 C,
1
Rf 0.9 (B). H NMR spectrum (CDCl3), , ppm (J,
3
Hz): 1.20 t (12H, CH3, JHH 7.3); 1.41 s, 1.45 s [36H,
C(CH3)3]; 2.17 s, 2.30 s (12H, Carom CH3); 3.15
1
3
3.29 m (8H, NCH2, JHP 7.5); 3.59 3.77 m (4H, H1A,
Rf 0.8 (A), 0.6 (B). H NMR spectrum (CDCl3), ,
2
ppm (J, Hz): 3.87 d.d (2H, H1A, H6A, J1A,1B 6.4);
H1B, H6A, H6B); 3.80 4.00 m (2H, H3, H4); 4.15
4.25 m (4H, Carom CH2 Carom); 4.57 4.61 m, 4.74
2
4.12 d.d (2H, H1B, H6B, J6A,6B 6.4); 4.81 d (2H, H3,
4.90 m (2H, H2, H5); 6.47 7.12 m (4H, Harom). 31P
NMR spectrum (C6H6), P, ppm: 74. Found, %: C
65.19; H 8.51; P 5.59. C60H90N2O8P2S2. Calculated,
%: C 65.90; H 8.29; P 5.66.
3
3
H4, J3,4 3.8); 5.25 5.37 m (2H, H2, H5, JHP 10.3),
7.21 7.58 m (16H, Harom). 31P NMR spectrum
(C6H6), P, ppm: 73. Found, %: C 56.49; H 3.89;
P 9.61. C30H24O8P2S2. Calculated, %: C 56.42; H
3.79; P 9.70.
2,5-O,O-[O,O -(2,2-Diphenylpropane-p,p -diyl)-
bis(diethylaminothiophosphoryl)]-1,4;3,6-dianhyd-
ro-D-mannite XVIII. A solution of 1.18 g of II in
10 ml of benzene was added with stirring to a solution
of 0.55 g of bisphenol V in 20 ml of benzene; the mix-
ture was heated at 75 C for 2 h in a weak nitrogen
flow, with the removal of diethylamine. 31P NMR
spectrum of the reaction mixture (compound XVII),
P, ppm: 145 and 146, respectively; intensity ratio
1 : 1. To the reaction mixture, we added 0.15 g of
finely divided sulfur; the mixture was stirred for 2 h
at 20 C, excess sulfur was filtered off, and the solvent
was distilled off in a vacuum. The residue was dis-
solved in 15 ml of acetone, 20 ml of water was added,
the mixture was stirred, and the precipitate was sep-
arated. Yield 0.93 g (60%), mp 75 77 C. Rf 0.1 (C).
2-O-{O-[2-(2-Hydroxy-5-methyl-3-tert-butyl-
phenylmethyl)-4-methyl-6-tert-butylphenyl]diethyl-
aminothiophosphoryl}-5-O-[bis(diethylamino)thio-
phosphoryl]-1,4;3,6-dianhydro-D-mannite XIV. A
solution of 0.63 g of bisphenol IV in 3 ml of benzene
was added with stirring at 20 C to a solution of 0.92 g
of II in 7 ml of benzene. The mixture was heated at
75 80 C for 2.5 h in a weak nitrogen flow, with the
removal of diethylamine. 31P NMR spectrum of the
reaction mixture (compound XIII), P, ppm: 137 and
152, ratio of integral intensities 1 : 1. To the reaction
mixture, we added 0.12 g of finely divided sulfur; the
mixture was stirred for 1 h at 80 C, the solvent was
distilled off in a vacuum, and the residue was recrys-
tallized from 3 ml of benzene. Yield 1.95 g (85%),
1H NMR spectrum (acetone-d6), , ppm (J, Hz): 1.05
1
mp 55 56 C, Rf 0.9 (A), 0.7 (B). H NMR spectrum
m (12H, CH2CH3); 1.22 s (3H, CH3); 3.28 m (8H,
(CDCl3), , ppm: 1.00 1.16 m (18H, CH3); 1.37
1.41 m [18H, C(CH3)3]; 2.15 s, 2.27 s (6H, Carom
CH3); 2.90 3.26 m (12H, NCH2); 3.59 3.94 m (4H,
H1A, H1B, H6A, H6B); 4.06 4.12 m (2H, H3, H4);
4.53 4.59 m (2H, Carom CH2 Carom); 4.72 4.78 m,
4.89 5.01 m (2H, H2, H5); 6.45 7.07 m (4H, CHarom).
31P NMR spectrum (C6H6), P, ppm: 74 and 80, ratio
of integral intensities 1 : 1. Found, %: C 59.23; H
8.36; P 7.39. C41H69N3O6P2S2. Calculated, %: C
59.61; H 8.42; P 7.5.
3
2
NCH23, JHP 14.5); 3.68 m (2H, H1A, H6A, J1A,1B
17.9, J1A,2;6A,5 8.9); 3.93 m (2H, H1B, H6B, J6A,6B
2
17.1, J1B,2;6B,5 8.5); 4.58 m (2H, H3, H4); 4.85 m
3
(2H, H2, H5); 7.07 m, 7.12 m (8H, Harom). 31P NMR
spectrum (C6H6), P, ppm: 71.8 and 72.2; ratio of the
integral intensities 1 : 1. Found, %: C 54.41; H 6.66;
P 9.64. C29H42N2O6P2S2. Calculated, %: C 54.36;
H 6.60; P 9.66.
2,5-O,O-[O,O -(Tetraphenylmethane-p,p -diyl)-
bis(diethylaminothiophosphoryl)]-1,4;3,6-dian-
hydro-D-mannite XX. A solution of 0.57 g of bis-
phenol VI in 3 ml of dioxane was added with stirring
at 20 C to a solution of 0.8 g of II in 7 ml of dioxane.
The mixture was heated at 75 80 C for 2.5 h in a
weak nitrogen flow, with the removal of diethylamine.
31P NMR spectrum of the reaction mixture (compound
XIX), P, ppm: 144 and 146; ratio of the integral
intensities 1 : 1. To the reaction mixture, we added
0.1 g of finely divided sulfur; the mixture was stirred
for 1 h at 80 C, excess sulfur was filtered off, the sol-
vent was distilled off in a vacuum, and the residue
was recrystallized from 3 ml of benzene. Yield 1.08 g
2,5-O,O-Bis{O-[2-(2-Hydroxy-5-methyl-3-tert-
butylphenylmethyl)-4-methyl-6-tert-butylphenyl]di-
ethylaminothiophosphoryl}-1,4;3,6-dianhydro-D-
mannite XVI. A solution of 0.63 g of bisphenol IV in
3 ml of benzene was added with stirring at 20 C to
the reaction mixture containing XIII and prepared as
described above for synthesis of XIV. The mixture
was heated at 75 80 C for 2.5 h in a weak nitrogen
flow, with the removal of diethylamine. 31P NMR
spectrum of the reaction mixture (compound XV):
P 152 ppm. To the reaction mixture, we added 0.12 g
of finely divided sulfur; the mixture was stirred for
1 h at 80 C, the solvent was distilled off in a vacuum,
and compound XVI was purified by column chroma-
tography on (alumina, Brockmann grade II; benzene
1
(88%), mp 141 142 C, Rf 0.1 (C). H NMR spectrum
(CDCl3), , ppm (J, Hz): 1.00 1.12 m (12H, CH3);
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

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GRACHEV et al.
3
3.20 3.40 m (8H, NCH2, JHP 13.7); 3.66 3.78 m,
4.59 m (2H, H3, H4); 4.89 4.95 m (2H, H2, H5);
7.10 7.14 m (4H, Harom); 7.24 7.30 m (4H, Harom).
31P NMR spectrum (dioxane), P, ppm: 72.1 and 72.4;
ratio of the integral intensities 1 : 1. Found, %: C
49.61; H 5.86; P 9.94. C26H36N2O6P2S3. Calculated,
%: C 49.51; H 5.75; P 9.82.
4.00 4.12 m (4H, H1A, H1B, H6A, H6B); 4.51 4.61 m
(2H, H3, H4); 4.83 4.99 m (2H, H2, H5); 7.05 7.20 m
(18H, Harom). 31P NMR spectrum (C6H6), P, ppm:
72.0 and 72.2; ratio of the integral intensities 1 : 1.
Found, %: C 60.29; H 6.21; P 8.25. C39H46N2O6P2S2.
Calculated, %: C 61.24; H 6.06; P 8.09.
2,5-O,O-{Diethylaminothiophosphorylidenebis-
[p-(2-p-oxyphenylprop-2-ylphenoxy)(phenyl)thio-
phosphoryl]}-1,4;3,6-dianhydro-D-mannite XXIX.
A solution of 2.09 g of bisphenol V was added to
a solution of 2.27 g of hexaethylphosphorous triamide
in 40 ml of benzene. The mixture was stirred for 6 h
at 75 C, after which an additional 2.09 g of V was
added, and the mixture was stirred for 6 h at 75 C.
31P NMR spectrum of the reaction mixture (com-
2,5-O,O-{O,O -[(Diphenyl oxide)-p,p -diyl]bis(di-
ethylaminothiophosphoryl)}-1,4;3,6-dianhydro-D-
mannite XXII. A solution of 2.22 g of II in 10 ml
of dioxane was added with stirring to a solution of
0.91 g of bisphenol VII in 20 ml of dioxane. The mix-
ture was heated at 75 C for 2 h in a weak nitrogen
flow, with the removal of diethylamine. 31P NMR
spectrum of the reaction mixture (compound XXI),
P, ppm: 145 and 146; ratio of the integral intensities
1 : 1. To the reaction mixture, we added 0.29 g of
finely divided sulfur; the mixture was stirred for 2 h
at 75 C, excess sulfur was filtered off, and the solvent
was distilled off in a vacuum. The residue was dis-
solved in 15 ml of acetone, 30 ml of water was added,
the mixture was stirred, and the viscous oily precipi-
tate was separated. Yield 2.4 g (90%), mp 74 75 C,
pound XXV):
140 ppm. To the solution, we added
0.29 g of finelyPdivided sulfur; the mixture was stirred
for 2 h at 75 C and cooled, excess sulfur was filtered
off, the filtrate was evaporated in a vacuum, the re-
sidue was dissolved in 15 ml of acetone, the precipi-
tate of sulfur was filtered off, and the filtrate was
vacuum-evaporated. Yield of O,O-diaryl phosphor-
amidothioate XXVI 2.97 g (95%); light brown vis-
cous oily substance. 31P NMR spectrum (CDCl3):
67 ppm. A solution of 2.7 g of XXVI and 1.04 g oPf
triethylamine in 15 ml of benzene was added with
stirring to a solution of 1.7 g of dichlorophenylphos-
phine in 10 ml of benzene, cooled to 5 C. The mix-
ture was stirred for 2 h at 20 C; the precipitate of tri-
ethylamine hydrochloride was filtered off and washed
with benzene (2 2.5 ml). 31P NMR spectrum of the
reaction mixture (compound XXVII), P, ppm: 67 and
172; ratio of integral intensities 1 : 2. To the combined
filtrates, we added with stirring 0.638 g of 1,4;3,6-di-
anhydro-D-mannite I and 1.04 g of triethylamine; the
mixture was stirred for 1 h at 20 C, and the precipitate
of triethylamine hydrochloride was filtered off and
washed with benzene (2 5 ml). 31P NMR spectrum
of the reaction mixture (compound XXVIII), P, ppm:
67 and 157; ratio of integral intensities 1 : 2. To the
combined filtrates, we added 0.288 g of finely divided
sulfur; the mixture was stirred for 1 h at 20 C, excess
sulfur was filtered off, the filtrate was vacuum evap-
orated, the residue was dissolved in 15 ml of acetone,
undissolved sulfur was filtered off, and the filtrate was
vacuum-evaporated. The resulting viscous oily prod-
uct was triturated in a mortar with a small amount of
water until a colorless powder formed, which was fil-
tered off, washed with water, and dried in a vacuum.
Yield of XXIX 3.5 g (76%); mp 96 97 C, Rf 0.2 (C).
1H NMR spectrum (CDCl3), , ppm: 1.10 (6H,
NCH2CH3); 1.61 (12H, CH3); 3.40 (4H, NCH2CH3);
1
Rf 0.6 (F), 0.9 (G). H NMR spectrum (CDCl3), ,
ppm (J, Hz): 1.09 m (12H, NCH2CH3); 3.08 3.12 m
(4H, NCH2CH3, JHP 11.5); 3.30 3.34 m (4H,
3
3
2
NCH2CH3, JHP 20.66, JHH 12.0); 3.7 3.75 m (2H,
H1A, H6A, J1A,1B 8.11); 4.05 4.09 m (2H, H1B, H6B,
2
2J6A,6B 6.97); 4.54 4.56 m (2H, H3, H4); 4.91 4.95
m (2H, H2, H5); 7.15 7.20 m (8H, Harom). 31P NMR
spectrum (dioxane), P, ppm: 71.6 and 72.0; ratio of
the integral intensities 1 : 1. Found, %: C 50.71; H
5.86; P 10.04. C26H36N2O7P2S2. Calculated, %: C
50.81; H 5.90; P 10.08.
2,5-O,O-{O,O -[(Diphenyl sulfide)-p,p -diyl]bis-
(diethylaminothiophosphoryl)}-1,4;3,6-dianhydro-
D-mannite XXIV. A solution of 1.67 g of II in 5 ml
of dioxane was added with stirring to a solution of
0.74 g of bisphenol VIII in 15 ml of dioxane. The
mixture was heated at 75 C for 2 h in a weak nitrogen
flow, with the removal of diethylamine. 31P NMR
spectrum of the reaction mixture (compound XXIII),
P, ppm: 145 and 146; ratio of the integral intensities
1 : 1. To the reaction mixture, we added 0.11 g of
finely divided sulfur; the mixture was stirred for 2 h at
75 C, excess sulfur was filtered off, the solvent was
distilled off in a vacuum, and the product was purified
by column chromatography (alumina, Brockmann
grade II; dioxane ethanol, 1 : 10). Yield 1.32 g (44%),
1
mp 84 85 C, Rf 0.8 (D), 0.1 (E). H NMR spectrum
(CDCl3), , ppm: 1.12 m (12H, NCH2CH3); 3.21
3
3.42 m (8H, NCH2CH3, JHP 11.5); 3.7 3.8 m (2H,
3.7 4.0 (4H, H1A, H1B, H6A, H6B); 4.39 4.61 (2H,
H3, H4); 4.92 5.14 (2H, H2, H5); 7.08 7.14 (16H,
H1A, H6A); 4.05 4.12 m (2H, H1B, H6B); 4.54
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

CHIRAL MOLECULAR CAVITIES BASED ON 1,4;3,6-DIANHYDRO-D-MANNITE
Ed. Engl., 1999, vol. 38, no. 1/2, p. 179.
1819
Harom); 7.42 7.58 (6H, Harom); 7.76 8.03 (4H, Harom
)
(3JPN 13.8 Hz). 31P NMR spectrum (CHCl3), P, ppm:
67, 86, and 88; ratio of the integral intensities 1 : 1 : 1.
Found, %: C 61.79; H 5.64; P 9.21. C52H56NO8P3S3.
Calculated, %: C 61.71; H 5.58; P 9.18.
3. Kurochkina, G.I., Grachev, M.K., Vasyanina, L.K., Pis-
kaev, A.E., and Nifant’ev, E.E., Dokl. Ross. Akad.
Nauk, 2000, vol. 371, no. 2, p. 189.
4. Lehn, J.M., Supramolecular Chemistry, New York:
VCH, 1995.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002