Diphosphites derived from 1,3:1′,3′-di-O- benzylidenedipentaerythritol-key synthons for new types of phosphorus-containing compounds

Article abstract of DOI:10.1134/s1070428008030111

A number of cyclic diphosphites were synthesized on the basis of an accessible diol, 1,3:1′,3′-di-O-benzylidenedipentaerythritol. The resulting diphosphites were converted into complex covalent and coordination organophosphorus compounds.

Full text of DOI:10.1134/s1070428008030111

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 3, pp. 373–377. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © D.A. Predvoditelev, M.A. Malenkovskaya, E.E. Nifant’ev, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 3,
pp. 379–383.
Diphosphites Derived from 1,3:1′,3′-Di-O-benzylidenedipenta-
erythritol—Key Synthons for New Types of Phosphorus-
Containing Compounds
D. A. Predvoditelev, M. A. Malenkovskaya, and E. E. Nifant’ev
Moscow State Pedagogical University, Nesvizhskii per. 3, Moscow, 119021 Russia
e-mail: chemdept@mtu-net.ru
Received May 23, 2007
Abstract—A number of cyclic diphosphites were synthesized on the basis of an accessible diol, 1,3:1′,3′-di-O-
benzylidenedipentaerythritol. The resulting diphosphites were converted into complex covalent and coordina-
tion organophosphorus compounds.
DOI: 10.1134/S1070428008030111
We recently synthesized first representatives of
complete esters derived from dipentaerythritol and
phosphorous acid and estimated prospects in their ap-
plication as ligands for the preparation of coordination
compounds of platinum subgroup metals [1]. While
developing studies in this line, we made an attempt to
build up structurally related systems containing only
two phosphite moieties located symmetrically with
respect to the central ether oxygen atom. For this
purpose we examined phosphorylation of 1,3:1′,3′-di-
O-benzylidenedipentaerythritol (I) as a mixture of con-
figurational isomers. A procedure for the synthesis of
compound I was developed by us previously [2]. As
phosphorylating agents we used accessible di- and
trimethylene phosphorochloridites II–IV which are
highly reactive at 0°C in the system dioxane–pyridine.
The yield of target phosphites V–VII ranged from 59
to 80% (Scheme 1). The progress of the reactions was
monitored by 31P NMR spectroscopy (δP 122–133 ppm).
Diphosphites V–VII were purified by passing solu-
tions of the crude products through a layer of silica gel.
All tervalent phosphorus compounds V–VII were
stable on storage at room temperature in an inert at-
mosphere. Among these, compounds VI and VII were
the most stable.
1
The H NMR spectra of phosphites V–VII con-
tained signals from all protons present in the assumed
structures. Compounds V–VII displayed in the spectra
signals from methylene protons at δ 3.30–3.39 ppm,
a broadened singlet from the CHC6H5 protons at
δ 5.45 ppm, aromatic proton signals in the region
δ 7.36–7.47 ppm, and doublets from the CH2OP pro-
1
tons at δ 4.11–4.15 ppm with a characteristic H–31P
coupling constant. In addition, the spectrum of bis-
Scheme 1.
OH
O
O
O
O
O
O
O
P
Y
P
O
+
Cl
P
X
O
X
X
O
O
Ph
OH
O
O
Ph
I
II–IV
V–VII
O
II, V, X = CH2CH2; III, VI, X = CH2CH2CH2; IV, VII, X = CH2C(CH3)2CH2; Y =
.
O
O
O
O
Ph
Ph
373

PREDVODITELEV et al.
374
(ethylene phosphite) V contained a multiplet at δ 3.76–
4.09 ppm from methylene protons in the dioxaphos-
pholane rings, and in the spectrum of bis(trimethylene
phosphite) VI axial and equatorial protons in the di-
oxaphosphinane rings resonated as multiplets at δ 1.75,
2.33, and 4.41 ppm. The corresponding proton signals
erythritol were extensively studied with a view to
obtain surface-active dendrimers [3]. Multiionic com-
pounds XI, XIIa, and XIIb were synthesized by
alkylation of trimethylamine with thiophosphates VIII
and IX (Scheme 3). The reaction of VIII with trimeth-
ylamine was carried out at 50°C (reaction time 2–3 h).
As might be expected, the alkylation of trimethylamine
with dithiophosphate IX occurred at 110°C [4]. The
yields of XI and XIIa/XIIb were 60 and 75%, respec-
1
in the H NMR spectrum of diphosphite VII were
located at δ 3.97 and 4.54 ppm, and two singlets at
δ 0.92 and 1.20 ppm were assigned to protons in the
methyl groups.
31
tively. The P NMR spectrum of the reaction mixture
formed in the reaction with bis(O,O-ethylene phos-
phorothioate) VIII contained a singlet at δP 59.32 ppm,
which is typical of acyclic O,O-dialkyl phosphoro-
thioates. In the 31P NMR spectrum of the reaction mix-
ture obtained from thiophosphate IX, apart from the
signal at δP 56.37 ppm belonging to O-(3-trimethyl-
ammoniopropyl) phosphorothioate XIIa, we observed
a signal at δ 18.36 ppm, typical of S-(3-trimethylam-
moniopropyl) derivative XIIb, the signal intensity
ratio being 2:1. The formation of S-alkyl phosphoro-
thioate XIIb indicates that the reaction of trimethyl-
amine with compound IX is accompanied by thione–
thiol isomerization [5]. We failed to isolate compounds
XIIa and XIIb as individual substances.
Bis-phosphites V–VII were readily converted into
the corresponding phosphorothioates VIII–X by treat-
ment with elemental sulfur in dioxane at 30–60°C (re-
action time 1–3 h; Scheme 2). Bis(O,O-ethylene phos-
phorothioate) VIII was isolated as an unstable oily
substance, while six-membered cyclic thiophosphates
IX and X were crystalline products which can be
stored for several months in an inert atmosphere with-
out appreciable decomposition. The observed differ-
ence in the stabilities of five- and six-membered cyclic
thiophosphates is not suprising taking account geo-
metric parameters of these systems.
Scheme 2.
S
The structure of phosphocholines XI, XIIa, and
O
O
1
O
S
O
P
XIIb was proved by 31P and H NMR spectroscopy.
Y
P
V–VII
1
X
X
S
O
The H NMR spectra of these compounds retained
O
signals from protons in the dipentaerythritol skeleton,
and signals from methyl protons in the ammonium
fragments were present at δ 2.97 (XI) and 3.30 ppm
(XIIa/XIIb). The chemical shift of the SCH2 protons
in compound XIIb was characteristic (δ 2.72 ppm).
VIII–X
The structure and purity of thiophosphates VIII–X
were proved by 31P and H NMR spectroscopy and
1
31
TLC data. The P NMR spectra of VIII–X contained
broadened singlets at δP 84.48, 62.10, and 62.11 ppm,
respectively. Their 1H NMR spectra (see Experimental)
were similar to those of phosphites V–VII considered
above and were fully consistent with the assumed
structures.
At the next stage of our study, we made an attempt
to use phosphites V–VII as ligands in the synthesis of
coordination compounds with transition metals (d ele-
ments). The best results were obtained with bis-phos-
phite VII as ligand and platinum and palladium salts.
Bis-phosphite VII reacted with an equimolar amount
of (diacetonitrile)dichloroplatinum(II) in chloroform at
room temperature to give a mixture of two complexes.
According to the MALDI-TOF data, one of these com-
Thiophosphates VIII and IX were used to synthe-
size novel phosphorus-containing choline amphiphiles
XI, XIIa, and XIIb. Previously, structurally related
phosphorus-free ammonium derivatives of dipenta-
Scheme 3.
O
O
O
O
Me3N
NMe3
P
Y
P
Me3N
VIII
S
O
O
S
XI
NMe3
NMe3
O
S
O
O
O
O
O
S
Me3N
Me3N
Me3N
P
P
Y
Y
P
P
IX
+
S
O
O
O
O
O
S
O
XIIa
XIIb
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 3 2008

DIPHOSPHITES DERIVED FROM 1,3:1′,3′-Di-O-BENZYLIDENEDIPENTAERYTHRITOL
phoric acid as external reference. Single-isotope (12C)
375
plexes was monomeric (XIII; it contained two phos-
phorus atoms), while the other (XIV) contained four
phosphorus atoms (Scheme 4); the ratio of complexes
XIII and XIV was 9:1. Mixture XIII/XIV was isolat-
ed by precipitation from chloroform with hexane; it
was a powder stable on storage on exposure to air. The
1H NMR spectrum of XIII/XIV contained signals typ-
ical of initial ligand VII. Like analogous complexes
obtained from complete esters of unsubstituted dipen-
taerythritol [1], the coordination entities in complexes
XIII and XIV have square–planar configuration
characterized by a broadened phosphorus signal at
δP 70.59 ppm (JP, Pt = 5843.37 Hz) in the 31P NMR
spectrum. The value of JP, Pt indicates cis arrangement
of the phosphorus atoms [6, 7].
molecular weights were determined by mass spec-
trometry on a Bruker UltraFlex instrument (Bruker
Daltonics, Germany; positive ion detection in the re-
flector mode; nitrogen laser, λ = 337 nm; accelerating
voltage 25 kV). The elemental compositions were
determined on a Perkin-Elmer 2400 analyzer. Column
chromatography was performed using a 10-mm (i.d.)
column packed with silica gel L (100–250 μm);
Rf values were determined by TLC on Silufol UV-254
plates using benzene–dioxane (3:1, A), hexane–di-
oxane (3 :1, B), chloroform–methanol (3 :1, C), or
chloroform–methanol–water (65:25:4, D) as eluent.
The melting points were measured in sealed capillaries
by heating at a rate of 1 deg/min. All syntheses with
tervalent phosphorus compounds were carried out
under dry argon.
Scheme 4.
VII
+
(MeCN)2PtCl2
VII· PtCl2
+
2VII ·2 PtCl2
5,5′-Oxydimethylenebis(2-phenyl-1,3-dioxan-5-
ylmethanol) (I, a mixture of three conformers) was
synthesized as described in [2]; 2-chloro-1,3,2-dioxa-
phospholane (II) [8], 2-chloro-1,3,2-dioxaphosphinane
(III) [9], and 2-chloro-5,5-dimethyl-1,3,2-dioxaphos-
phinane (IV) [10] were prepared by known methods.
Their physical constants coincided with those reported
in the literature.
XIII
XIV
Likewise, the reaction of VII with palladium(II)
chloride gave (according to the MALDI-TOF data)
a mixture of monomeric and dimeric complexes XV
and XVI involving one or two substituted dipenta-
erythritol molecules and two or four phosphorus
atoms, respectively (Scheme 5). The reaction was
carried out in methylene chloride at room temperature.
Precipitation from methylene chloride with hexane
gave powder-like mixture XV/XVI (ratio 6:1) which
5,5′-Oxydimethylenebis[5-(1,3,2-dioxaphospho-
lan-2-yloxymethyl)-2-phenyl-1,3-dioxane] (V). A so-
lution of 0.5 g (1.16 mmol) of bis-acetal I in 5 ml of
anhydrous pyridine was added dropwise to a solution
of 0.29 g (2.32 mmol) of 2-chloro-1,3,2-dioxaphos-
pholane (II) in 5 ml of anhydrous dioxane under stir-
ring at 0°C. The mixture was kept for 0.5 h at that
temperature and was allowed to warm up to room tem-
perature over a period of 0.5 h. The formation of bis-
1
is stable on storage. The H NMR spectrum of that
mixture contained signals typical of initial ligand VII,
and in the 31P NMR spectrum we observed a broad-
ened singlet at δ 94.38 ppm.
Scheme 5.
31
phosphite V was monitored by P NMR spectroscopy
VII + PdCl2
VII·PtCl2
+
2VII·2PtCl2
(dioxane; δP 132.98 ppm, br.s). Pyridine hydrochloride
was filtered off, the filtrate was passed through 1.5 g of
silica gel, the solvent was removed under reduced
pressure, and the residue was evacuated at a residual
pressure of 1 mm for 1 h at 40°C. Yield 0.4 g (59%),
n2D0 = 1.5930, Rf 0.79 (A). 1H NMR spectrum (C6D6), δ,
ppm: 3.26 s and 3.36 s (4H, CH2OCH2), 3.76 m and
4.09 m (6H, CH2OP, 3JHP = 9.97 Hz), 4.38 m (4H, Hax)
XV
XVI
To conclude, we have proposed an efficient proce-
dure for the synthesis of novel bis(O,O-di- and tri-
methylene phosphites) which are promising as syn-
thons for new covalently bonded organophosphorus
compounds and their complexes with transition metals.
2
and 4.55 m (4H, Heq) (CH2OCH, J = 7.93 Hz),
EXPERIMENTAL
5.44 br.s (2H, CHC6H5), 7.36 br.s (6H, m-H, p-H),
7.48 br.s (4H, o-H). 31P NMR spectrum (benzene):
δP 132.96 ppm, br.s. Found, %: C 55.13; H 6.04;
P 10.23. C28H36O11P2. Calculated, %: C 55.08; H 5.94;
P 10.15. M 610.52.
1
The H NMR spectra were measured on a Bruker
WM-250 spectrometer (250 MHz) relative to tetra-
methylsilane as internal reference; proton signals were
assigned using two-dimensional NMR techniques. The
31P–{1H} NMR spectra were obtained on a Bruker
WP-80SY instrument at 32.4 MHz using 85% phos-
5,5′-Oxydimethylenebis[5-(1,3,2-dioxaphosphi-
nan-2-yloxymethyl)-2-phenyl-1,3-dioxane] (VI) was
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 3 2008

PREDVODITELEV et al.
376
synthesized in a similar way from 0.4 g (2.84 mmol) of
2-chloro-1,3,2-dioxaphosphinane (III) and 0.6 g
(1.42 mmol) of compound I using 8 ml of anhydrous
dioxane and 8 ml of anhydrous pyridine. The forma-
Compound VIII was eluted using 20 ml of benzene–
dioxane (10:1). The eluate was evaporated under
reduced pressure, and the residue was evacuated at
a residual pressure of 1 mm for 2 h at 40°C. Yield
0.12 g (55%); nD20 = 1.5995; Rf 0.70 (A), 0.30 (B). The
1H NMR spectrum of VIII (CDCl3) was similar to the
spectrum of bis-phosphite V. 31P NMR spectrum
(chloroform): δP 84.47 ppm, br.s. Found, %: C 49.92;
H 5.41; P 9.25. C28H36O11P6S2. Calculated, %: C 49.85;
H 5.38; P 9.18. M 674.65.
31
tion of bis-phosphite VI was monitored by P NMR
spectroscopy (dioxane; δP 129.82 ppm, br.s). Yield
1
0.47 g (80%), mp 104–106°C, Rf 0.90 (A). H NMR
spectrum (C6D6), δ, ppm: 1.75 m (2H, Heq) and 2.23 m
(2H, Hax) (OCH2CH2CH2O), 3.31 s and 3.41 s (4H,
CH2OCH2), 3.93 m (8H, Hax) and 4.41 m (8Heq)
2
3
5,5′-Oxydimethylenebis[5-(2-thioxo-1,3,2λ5-di-
oxaphosphinan-2-yloxymethyl)-2-phenyl-1,3-di-
oxane] (IX) was synthesized in a similar way from
0.4 g (0.62 mmol) of compound VI and 0.05 g
(1.4 mmol) of sulfur in 10 ml of anhydrous dioxane
(40°C, 1 h). The product was purified by chromatog-
raphy on a column charged with 15 g of silica gel and
filled with benzene using 35 ml of benzene–dioxane
(5:1) as eluent. The eluate was evaporated under
reduced pressure, and the residue was evacuated at
a residual pressure of 1 mm for 2 h at 40°C. Yield
0.37 g (83%); mp 124–125°C; Rf 0.8 (A), 0.35 (B).
(OCH2CH2CH2O, CH2OCH, J = 9.35, JHP
=
3
11.60 Hz), 4.15 d (4H, CH2OP, JHP = 12.10 Hz),
5.45 br.s (2H, CHC6H5), 7.36 br.s (6H, m-H, p-H),
7.46 br.s (4H, o-H). 31P NMR spectrum (benzene):
δP 129.80 ppm, br.s. Found, %: C 56.37; H 6.29;
P 9.64. C30H40O11P2. Calculated, %: C 56.42; H 6.31;
P 9.70. M 638.57.
5,5′-Oxydimethylenebis[5-(5,5-dimethyl-1,3,2-
dioxaphosphinan-2-yloxymethyl)-2-phenyl-1,3-di-
oxane] (VII) was synthesized in a similar way from
0.23 g (1.39 mmol) of 2-chloro-5,5-dimethyl-1,3,2-di-
oxaphosphinane (IV) and 0.3 g (0.7 mmol) of com-
pound I using 5 ml of anhydrous dioxane and 5 ml of
anhydrous pyridine. The formation of bis-phosphite
VII was monitored by 31P NMR spectroscopy (di-
oxane; δP 121.88 ppm, br.s). Yield 0.38 g (79%),
1
The H NMR spectrum of IX (CDCl3) was similar to
that of bis-phosphite VI. 31P NMR spectrum (chloro-
form): δP 62.10 ppm, br.s. Found, %: C 51.35; H 5.80;
P 8.89. C30H40O11P2S2. Calculated, %: C 51.27; H 5.74;
P 8.82. M 702.70.
1
mp 148–150°C, Rf 0.95 (A). H NMR spectrum
(C6D6), δ, ppm: 0.92 br.s and 1.20 br.s (12H, CH3),
3.30 s and 3.39 s (4H, CH2OCH2), 3.92 m (4H, Hax)
and 4.49 m (4H, Heq) (CH2OCH), 3.97 m (4H, Hax)
5,5′-Oxydimethylenebis[5-(5,5-dimethyl-2-
thioxo-1,3,2λ5-dioxaphosphinan-2-yloxymethyl)-2-
phenyl-1,3-dioxane] (X) was synthesized in a similar
way from 0.3 g (0.43 mmol) of compound VII and
0.03 g (0.91 mmol) of sulfur in 6 ml of anhydrous
dioxane (60°C, 3 h). The product was purified by
chromatography on a column charged with 10 g of
silica gel and filled with benzene using 25 ml of ben-
zene–dioxane (3:1) as eluent. The eluate was evaporat-
ed under reduced pressure, and the residue was evacu-
ated at a residual pressure of 1 mm for 2 h at 40°C.
Yield 0.25 g (80%); mp 232–233°C; Rf 0.85 (A), 0.40
2
and 4.54 m (4H, Heq) [OCH2C(CH3)2CH2O, J =
3
11.33 Hz], 4.11 d (4H, CH2OP, JHP = 6.81 Hz),
5.45 br.s (2H, CHC6H5), 7.37 br.s (6H, m-H, p-H),
7.47 br.s (4H, o-H). 31P NMR spectrum (benzene):
δP 122.88 ppm, br.s. Found, %: C 58.69; H 6.89;
P 8.87. C34H48O11P2. Calculated, %: C 58.78; H 6.96;
P 8.92. M 694.67.
5,5′-Oxydimethylenebis[5-(2-thioxo-1,3,2λ5-di-
oxaphospholan-2-yloxymethyl)-2-phenyl-1,3-di-
oxane] (VIII). Finely powdered sulfur, 0.02 g
(0.69 mmol), was added at room temperature to a solu-
tion of 0.2 g (0.33 mmol) of bis-phosphite V in 3 ml
of anhydrous dioxane, and the mixture was heated to
30°C and kept for 0.5 h at that temperature. Excess
sulfur was filtered off, and the solvent was removed
under reduced pressure. To remove traces of sulfur, the
residue was dissolved in 3 ml of acetone, the solution
was filtered, and the solvent was distilled off. This
procedure was repeated once more. The product was
additionally purified by chromatography on a column
charged with 8 g of silica gel and filled with benzene.
1
(B). The H NMR spectrum of X (CDCl3) was similar
to the spectrum of bis-phosphite VII. 31P NMR spec-
trum (chloroform): δP 62.11 ppm, br.s. Found, %:
C 56.24; H 6.71; P 8.64. C34H48O11P2S2. Calculated, %:
C 56.19; H 6.66; P 8.52. M 726.74.
O,O′-5,5′-Oxydimethylenebis(2-phenyl-1,3-di-
oxan-5-ylmethylene) bis[O-(2-trimethylammonio-
ethyl) phosphorothioate] (XI). An ampule was
charged with a solution of 0.1 g (0.15 mmol) of thio-
phosphate VIII and 0.09 g (1.4 mmol) of trimethyl-
amine in 5 ml of anhydrous benzene. The ampule was
sealed and heated for 2 h at 50°C. The solvent was
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DIPHOSPHITES DERIVED FROM 1,3:1′,3′-Di-O-BENZYLIDENEDIPENTAERYTHRITOL
377
removed under reduced pressure, and the oily residue
was washed with benzene (2×5 ml) and hexane (2×
5 ml) and dried for 2 h at 40°C under reduced pressure
(1 mm). Yield 0.07 g (60%); mp 215–217°C (becomes
wet at 120°C); Rf 0.00 (A), 0.65 (C), 0.45 (D).
1H NMR spectrum (CDCl3), δ, ppm: 2.77 br.s (18H,
NCH3), 2.97 br.m (4H, NCH2), 3.30 br.m (4H,
CH2OCH2), 3.76 m (4H, Hax) and 4.27 m (4H, Heq)
(CH2OCH), 3.87 m (4H, POCH2CH2N), 4.13 m (4H,
CH2OP), 5.42 br.s (2H, CHC6H5), 7.34 br.s (6H, m-H,
(XIV). Calculated, %: C 42.51; H 5.04; P 6.45.
M 960.69 (XIII), 1920.49 (XIV). Mass spectrum, m/z
(12C, 195Pt): 925.25 [M – Cl]+ , 1884.32 [M – Cl]+.
Calculated [M – Cl] (12C, 195Pt): 924.78 (XIII),
1885.03 (XIV).
Palladium complexes XV/XVI. Bis-phosphite
VII, 0.15 g (0.22 mmol), was dissolved in 5 ml of
methylene chloride, 0.05 g (0.26 mmol) of PdCl2 was
added in one portion under stirring, and the mixture
was stirred for 1 h at room temperature. Unreacted
palladium(II) chloride was filtered off, and mixture
XV/XVI was precipitated with hexane. The liquid
phase was separated by decanting, and the precipitate
was washed with hexane and dried for 1 h at 50°C
under reduced pressure (1 mm). Yield 0.19 g, ratio
XV:XVI = 6:1, mp 230–232°C (decomp.), Rf 0.65
(C). 31P NMR spectrum (chloroform): δP 94.38 ppm,
br.s. Found, %: C 46.79; H 5.41; P 7.07. C34H48O11P2·
PdCl2 (XV), C68H96O22P4 ·Pd2Cl4 (XVI). Calculated,
%: C 46.83; H 5.55; P 7.10. M 872.03 (XV), 1744.09
(XVI). Mass spectrum, m/z (12C, 106Pd): 835.62 [M –
Cl]+, 1707.27 [M – Cl]+. Calculated [M – Cl] (12C,
106Pd): 835.78 (XV), 1707.02 (XVI).
31
p-H), 7.45 br.s (4H, o-H). P NMR spectrum (chloro-
form): δP 59.32 ppm, br.s. Found, %: C 51.56; H 6.84;
P 7.78. C34H54N2O11P2S2. Calculated, %: C 51.50;
H 6.86; P 7.81. M 792.87.
O,O′-5,5′-Oxydimethylenebis(2-phenyl-1,3-di-
oxan-5-ylmethylene) bis[O-(3-trimethylammonio-
propyl) phosphorothioate] (XIIa) and O,O′-5,5′-
oxydimethylenebis(2-phenyl-1,3-dioxan-5-ylmeth-
ylene) bis[S-(3-trimethylammoniopropyl) phos-
phorothioate] (XIIb) (mixture of isomers) were syn-
thesized in a similar way from 0.2 g (0.28 mmol) of
thiophosphate IX and 0.17 g (2.79 mmol) of trimethyl-
amine in 5 ml of anhydrous benzene (100–110°C, 3 h).
Yield 0.18 g (75%); mp 270–273°C (becomes wet at
200°C); Rf 0.00 (A), 0.58 (C), 0.20 (D). 1H NMR spec-
trum (CDCl3–CD3OD, 99:1), δ, ppm: 1.94 br.m (4H,
POCH2CH2CH2); 2.72 br.m (4H, PSCH2CH2CH2);
2.85 s, 2.98 s, and 3.08 s (4H, CH2OCH2); 3.08 m
(4H, Hax) and 4.15 m (4H, Heq) (CH2OCH); 3.30 br.s
(18H, NCH3); 3.45 br.m (4H, CH2N); 3.68 br.m (4H,
POCH2CH2); 3.88 br.m (4H, CH2OP); 5.37 br.s (2H,
CHC6H5); 7.29 br.s (6H, m-H, p-H); 7.39 br.s
This study was performed under financial support
by the President of the Russian Federation (program
for support of leading scientific schools, project
no. NSh-5515.2006.3).
REFERENCES
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31
(4H, o-H). P NMR spectrum (chloroform–methanol,
99:1), δP, ppm: 18.36 br.s (XIIb), 56.37 br.s (XIIa);
intensity ratio 2:1. Found, %: C 52.62; H 7.09; P 7.60.
C36H58N2O11P2S2. Calculated, %: C 52.67; H 7.12;
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Platinum complexes XIII/XIV. (Diacetonitrile)di-
chloroplatinum(II), 0.05 g (0.14 mmol), was added in
one portion under stirring to a solution of 0.1 g
(0.14 mmol) of bis-phosphite VII in 2 ml of anhydrous
chloroform. The mixture was stirred for 1.5 h at room
temperature, mixture XIII/XIV was precipitated with
hexane, the liquid phase was separated by decanting,
and the precipitate was repeatedly washed with ben-
zene and hexane and dried for 1 h at 50°C under
reduced pressure (1 mm). Yield 0.15 g, ratio XIII:
XIV = 9:1, mp 287–289°C (decomp.), Rf 0.6 (C).
31P NMR spectrum (chloroform): δP 70.59 ppm, br.s
(1JP, Pt = 5843.37 Hz). Found, %: C 42.48; H 5.36;
P 6.23. C34H48O11P2·PtCl2 (XIII), C68H96O22P4·Pt2Cl4
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 3 2008