Monoterpenoids dithiophosphates. Synthesis and biological activity

Article abstract of DOI:10.1134/S107036321007008X

O,O-Dialkyldithiophosphoric acids adds at the double bond of the racemic camphene and (+)- limonene in the presence of Lewis acids in accordance with the Markownikoff rule with the formation of Sterpenyl esters of dithiophosphoric acids. The reaction with

Full text of DOI:10.1134/S107036321007008X

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 7, pp. 1267–1271. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.V. Sofronov, I.S. Nizamov, L.A. Almetkina, L.E. Nikitina, D.G. Fatyhova, P.V. Zelenikhin, O.N. Il’inskaya, R.A. Cherkasov, 2010,
published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 7, pp. 1101–1105.
Monoterpenoids Dithiophosphates. Synthesis
and Biological Activity
a
a,b
a
c
A. V. Sofronov , I. S. Nizamov , L. A. Almetkina , L. E. Nikitina ,
a
a
a
a
D. G. Fatyhova , P. V. Zelenikhin , O. N. Il’inskaya , and R. A. Cherkasov
a
Kazan State University, ul. Kremlevskaya 18, Kazan, 420008 Tatarstan, Russia
e-mail: nizamov@iopc.knc.ru
b
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
c
Kazan State Medical University, Kazan, Tatarstan, Russia
Received December 9, 2009
Abstract—O,O-Dialkyldithiophosphoric acids adds at the double bond of the racemic camphene and (+)-
limonene in the presence of Lewis acids in accordance with the Markownikoff rule with the formation of S-
terpenyl esters of dithiophosphoric acids. The reaction with camphene is accompanied by the rearrangement of
camphane structure to that of bornane. Addition of dithiophosphoric acid to (+)-limonene proceeds with the
participation of the exocyclic double bond. Toxic and genotoxic properties of the monoterpenoid
dithiophosphates were studied.
DOI: 10.1134/S107036321007008X
A fundamental problem in the chemistry of natural
compounds is the creation of new types of phosphorus-
modified terpenoid derivatives. These compounds are
promising low-molecular bioregulators playing an
important role in the production by living organisms of
carbohydrate biopolymers of (lipo)-polysaccharide
series, glycoproteins and peptidoglycans. Among the
natural substances terpenoids were found exhibiting
antiulcer, wound healing, hypertensive, antithrombotic,
antitumor, antihypertensive, adrenergic, antiulcero-
genic, hyperprotective and antihypercholesterolemic
activity, as well as participating in the normalization of
immune function, in the restoring liver function, and
are solvents of gallstones [1, 2] . Meanwhile, at the
present time both veterinary and medicine need new
synthetic drugs of bioregulatory type. On the basis of
terpenoids, including their phosphate derivatives,
practically useful materials can be obtained for
forestry, petrochemical, pharmaceutical, and perfume
industries [3–5]. According to the early patent data [4,
lubricants. The structure of the product mixtures was
not established. It is presumable that the primary
products formed in these reactions decompose under
the rigid conditions of the process through isomeriza-
tion and fragmentation characteristic of labile terpene
molecules. In order to obtain stable adducts and elu-
cidate their structure and biological activity we carried
out the reaction of mono- and bicyclic monoterpenoids
with dithiophosphoric acids.
It is known that in the addition reactions of
organophosphorus compounds at the double bond of
unsaturated compounds, the regiochemistry of the
phosphorus fragment addition is determined by the
structure of unsaturated compound, the nature of the
catalyst, and the reaction conditions [6–9]. At the
homolytic addition of dialkylphosphites to olefins in
the presence of free radical initiators or at UV
irradiation, the adducts are formed contrary to the
Markownikoff rule. In the reaction with acidic phos-
phites of unsaturated compounds containing a double
bond activated by electron-donating substituents the
electrophilic mode of the Pudovik reaction is realized.
The electrophilic addition is carried out with hydro-
phosphites with pronounced proton–donor properties
5
], the reaction of O,O-dialkyldithiophosphoric acids
with pinene and dipentene [racemic mixture of (+)-
and (–)-limonene] at 100–200°C led to formation of
the mixtures of phosphorus-containing products that
were suggested for application as additives to
1
267

1
268
SOFRONOV et al.
(
e.g., cyclic hydrophosphites) [8]. It is expectable that
NMR spectra of products IIIa and IIIb of three strong
singlets of methyl protons. In the H NMR spectrum
1
for the implementation of catalyzed electrophilic
addition catalysts with strong electron-acceptor
properties (e.g., Lewis acid) or with a high proton-
donor action (e.g., strong mineral acid) should be used.
the singlets at δ 0.84, 0.93 and 1.00 ppm correspond to
the diisopropyl protons of IIIb homolog. Doublet of
triplets at δ 3.37 ppm with the spin–spin coupling
3
3
constants J 7.3 Hz and J 19.9 Hz belongs to
HH
PH
It is known that thiols and dithiophosphoric acid
containing the SH group depending on their structure
and the catalyst can be added to limonene both along
and contrary to the Markownikoff rule, as well as bis-
adducts can form [10–12]. In our work, the reaction of
O,O-dialkyldithiophosphoric acids Ia and Ib with
monoterpenes was carried out in the presence of Lewis
acids. We found that addition of O,O-dialkyldi-
thiophosphoric acids Ia and Ib to the double bond of
the racemic camphene (II) proceeds in the presence of
catalytic amounts of anhydrous zinc chloride at 50–60°C
over 2–3 h with the formation of S-2-(1-methyl-7-
dimethylbicyclo[2.2.1]heptyl)-O,O-dialkyldithiophos-
phates (IIIa, IIIb). Upon completion of the reaction
the catalyst was removed by washing the reaction mix-
ture with water. According to the data of vibration and
NMR spectroscopy, washing did not lead to hydrolysis.
7
3
2
methine proton at the sulfur atom C H H C HSP.
These data indicate that the two protons at C atom in
A
B
3
the compound IIIb are magnetically equivalent. In
1
contrast, in the H NMR spectrum the methine proton
in the CH H CHSC fragment of the exo-isomer of the
A
B
product obtained by the mercaptans addition to
camphene gives rise to a doublet of doublets, whereas
the endo-adduct gives a multiplet due to the additional
splitting on the protons of the ring [14]. In the case of
1
retention of the camphene structure, in the H NMR
spectrum the signal of methine proton in geminal
position to the dithiophosphoryl fragment would be
absent. Note that a similar reaction of camphene with
methylmercaptoacetate in the presence of zinc chloride
also results in a product of addition along the
Markownikoff rule with the bornane structure, ethyl 1-
methyl(6-dimethylbicyclo[2.2.1]heptyl)-2-mercapto-
2
acetate; the respective methine proton at the C atom
S
1
8
6
2
3
2
1
of C H H C HSC fragment gives in the H NMR
A
B
9
(
RO) PSH +
2
spectrum a signal shifted upfield (δ 2.63 ppm) [15].
This result is consistent with the presence in the
adducts IIIa and IIIb of dithiophosphoryl group which
is more electronegative compared to the alkylthio
3
5
4
1
0
Ia, Ib
II
8
9
1
7
group in alkylthiobornanes. In the H NMR spectrum
4
of adducts IIIa and IIIb were not detected the signals
of vinyl protons at δ 4.5 and 4.7 ppm of the parent
camphene II, which indicates the reaction com-
3
S
5
ZnCl2
1
S
P(OR)2
6
1
0
2
1
3
pleteness. In the C NMR spectra of compound IIIb
IIIa, IIIb
R = Et (а), Pr-i (b).
obtained in the proton decoupling mode there is a
2
singlet signal of carbon fragment PSC H at δ 53.8 ppm,
C
which without the proton decoupling appears as a
1
doublet ( J 151.1 Hz). In contrast, at the retention of
HC
3
1
It follows from the data of P NMR spectroscopy
that the degree of conversion of dithiophosphoric acids
Ia and Ib is 100%. In accordance with H NMR
the camphene structure, the carbon atom to which is
added the thiophosphoryl fragment (the PSC fragment,
which does not contain protons) would appear as a
1
1
3
spectra, addition of acids Ia and Ib to the double bond
of camphene (II) proceeds according to Markownikoff
rule and is accompanied by the Wagner–Meerwein
skeletal rearrangement of camphane structure to that of
bornane, leading to the formation of a mixture of exo-
singlet at recording C NMR spectra in both modes.
The IR spectra of the products IIIa and IIIb do not
–
1
contain the absorption bands at ν = 2500–2400 cm ,
characteristic of stretching vibrations of the SH bond
in the acids Ia and Ib. The C=C absorption band of
3
1
and endo-isomers. In the P NMR spectra of products
III there are the signals at δP 94.0 (IIIa) and
–
1
terpene II in the region of ν = 1600–1650 cm in the
IR spectra of compounds IIIa and IIIb was not
detected also. The absorption bands of the stretching
vibrations of the P=S and P–S bonds in dithio-
9
2.3 (IIIb) ppm characteristic of the esters of
dithiophosphoric acids [13]. Formation of the bornane
structure is indicated also by the presence in the H
1
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 7 2010

MONOTERPENOIDS DITHIOPHOSPHATES
1269
7
7
phosphates IIIa and IIIb are located at ν = 659–655
–
1
1
1
and 547–527 cm , respectively. The electron impact
mass spectra of the products IIIa and IIIb include the
mass peaks m/z = 322.7 and 350.2, respectively, of
S
6
5
2
3
6
5
ZnCl2
2
3
(
RO) PSH +
2
* 4
S
+
* 4
their molecular ions [M] (calculated M 322.2 and
8
8
S
P(OR)2
3
50.2, respectively).
9
9
1
0
1
0
The adducts IIIa and IIIb are of low thermal
Ia, Ib
IV
R = Et (а), Pr-i (b).
Va, Vb
stability and could not be distilled even in a high
vacuum. Their purification was carried out by column
chromatography. Compounds IIIa and IIIb, thus, are
the primary products of reactions, which under the
rigid conditions of vacuum distillation decompose. In
this regard, it is presumable that compounds previously
described as products of addition of O,O-dialkyl-
dithiophosphoric acids to pinene and dipentene at 100–
3
1
in P NMR spectra of adducts Va and Vb are shifted
upfield [δ 90.4 (Va) and 87.1 (Vb) ppm] compared to
products IIIa and IIIb obtained in the reactions with
camphene (δ 92.3 – 94.0 ppm). In the H NMR
spectrum of adduct Vb there are three singlet signals
of protons of three methyl groups at δ 1.53, 1.59 and
1.66 ppm, and the signal of endocyclic vinyl proton
remains at δ 5.37 ppm. The signals of two exocyclic
vinyl protons disappear in H NMR spectra of the
products Va and Vb completely. Note that in the H
NMR spectrum the exocyclic vinyl protons of (+)-
limonene (IV) give a singlet signal at d 4.71 ppm. The
IR spectrum of products Va and Vb shows a weak
absorption band of the C=C bond stretching vibrations
at ν = 1643 cm . The mass peak m/z = 323.2 in the
mass spectrum of chemical ionization (CI) of
P
1
P
2
00°C [4, 5] are actually the products of various
secondary reactions. Inasmuch as this reaction
proceeds in accordance with the Markownikoff rule, as
well as in the case of thiols, mercaptoacetic acid or
methyl mercaptoacetate [12, 14, 15] the dithio-
phosphoric acids possess the ability to the electrophilic
addition to electron-rich alkenes. It is known that
dithiophosphoric acids show a dual reactivity in the
addition reactions: the presence of labile protons and
nucleophilic dithiophosphoryl fragment gives them the
opportunity of entering into both nucleophilic and
electrophilic addition reactions [9].
1
1
–
1
dithiophosphate Va is consistent with its molecular ion
M+H] . The mass spectrum of electron impact of the
+
[
In order to expand the synthetic potential of
unsaturated terpenes by involving them in the
tiophosphorylation reactions and obtaining potential
biologically active products, is interesting to involve
into the reaction with dithiophosphoric acids Ia and Ib
some unsaturated monocyclic terpenes. Among them
of special interest is (+)-limonene, one of the most
stable terpenes, which contains an exocyclic and an
endocyclic double bonds differing in the reactivity.
Therefore we could expect that the electrophilic
addition might occur in various directions. We found
that addition of O,O-dialkyldithiophosphoric acids Ia
and Ib to (+)-limonene (IV) in the presence of zinc
chloride proceeded at room temperature over 1–2 h at
the exocyclic double bond, affording O,O-dialkyl-S-8-
isopropyl homolog Vb contains the mass peak m/z =
+
3
50.2 corresponding to its molecular ion [M] .
It was established that the electrophilic addition of
dithiophosphoric acids Ia and Ib to unsaturated
terpenes II and IV is accelerated in the presence of
other Lewis acids (NiCl , CuCl, CuCl , FeCl ) at room
2
2
3
temperature. The less active catalysts are BF . Et O,
3
2
and AlCl . From a number of Lewis acids we selected
3
zinc chloride as a “soft” Lewis acid, which unlike most
catalysts with higher acceptor strength, for example,
BF ·Et O, commonly does not induce a secondary
3
2
transformation of the terpene molecule. Note also that
the use of protic acids (HCl, H SO , HClO ) as
2
4
4
catalysts in the reactions of thiols with unsaturated
monoterpenes leads to the isomerization of terpene
molecules with the formation of a complex mixture of
products [16]. Presumably the high hygroscopicity of
zinc chloride may contribute to the proceeding of the
reactions of dithiophosphoric acids with monoterpenes
promoting formation in the reaction medium of HCl,
which may also act as catalyst in the reactions of
dithiophosphoric acids with the unsaturated mono-
[
(+)-1-methyl-4-isopropylcyclohex-1-enyl]dithiophos-
phates Va and Vb. At heating the initial reagents at
0°C for 3 h the formation of compounds of the
6
phosphorylation at the endocyclic double bond was not
observed.
The compounds Va and Vb are not stable at high
temperatures in the distillation process and therefore
were isolated by column chromatography. The signals
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 7 2010

1
270
SOFRONOV et al.
terpenes. Thus, we first found the phenomenon of the
catalysis with the Lewis acids in a series of derivatives
of the tetracoordinated phosphorus thioacids by the
example of reactions of electrophilic addition of
dithiophosphoric acids at the double bond of un-
saturated monoterpenoids.
3.9 g of acid Ia and 2.9 g of camphene II at ~20°C in a
stream of dry argon was added at stirring in portions
0.1 g (3.4 wt % ) of ZnCl . The mixture was heated for
2
3 h at 50–60°C. After cooling, the mixture was diluted
with 10 ml of Et O and washed with three 10-ml
2
portions of water. The organic layer was separated and
dried over anhydrous CaCl for ~12 h. After separating
2
The studied reaction showed a route to mono-
terpenoid dithiophosphates with potential biological
activity. This article presents the principal results of
studies of toxic and genotoxic properties of
compounds IIIa, IIIb, Va and Vb. The methods used
in these studies were published in [17–19]. Full
description of the results will be published in a special
biological journal. The study of toxic and genotoxic
properties of dithiophosphates IIIa, IIIb, Va and Vb
was carried out on Salmonella typhimurium TA 100
and Escherichia coli PQ37 as the test bacteria. We
found that dithiophosphates IIIa, IIIb, Va and Vb are
weak toxicants for the test bacteria. Compound IIIa
exhibits the characteristics of a weak inhibitor of
alkaline phosphatase activity in the Escherichia coli
PQ 37 cells, initiates the highest SOS-response and
shows mutagenic activity in Ames test. Dithiophos-
phate IIIa is a direct mutagen and true genotoxicant,
since this compound is practically non-toxic to the test
bacteria, but causes the induction of gene mutations.
Remaining compounds, IIIb, Va and Vb do not show
mutagenic properties.
the drying agent, the filtrate was evaporated in a
vacuum of 0.5 mm Hg at 40°C for 1 h and then in a
vacuum of 0.06 mm Hg at 40°C for 1 h. 5.7 g (84%) of
dithiophosphate IIIa was obtained, which was purified
by column chromatography (silica gel, eluent
о
petroleum ether boiling at 70–100 C), R 0.27
(
f
2
0
–1
petroleum ether ), nD 1.5325. IR spectrum, ν, cm :
983 s, 2956 s, 2880 s [ν (CH ), ν (CH )]; 1465 m
2
as,s
3
as,s
2
[
δ (CH )]; 1390 s [δ (CH )]; 1016 v.s.br, 958 s [ν
as 3 s 3
(
POC]; 826 m, 796 m [ν (PO )], 659 s [ν(P=S)], 527
as,s
2
1
m [ν(PS)]. H NMR spectrum, δ, ppm, (J, Hz): 0.85 s,
.93 s and 1.00 s (9H, CH -ring), 1.37 m [6H,
0
3
3
(
CH CH O) P, J 7.1], 1.24 m, 1.74 m and 2.01 m
3 2 2 HH
(
CH -ring and CH-ring.) 3.31 d.t (1H, CH H CHSP,
2 A B
3
3
3
JHH 7.0, J 19.0) 4.12 m {2H, [(CH CH O) ] P, J
PH
3
2
2 2
HH
7
.1}. Found, %: C 52.27, H 8.46, P 9.43; S 19.48.
C H O PS . Calculated, %: C 52.14, H 8.46, P 9.61;
1
4
27
2
2
S 19.85.
S-2-(1-Methyl-7-dimethylbicyclo[2.2.1]heptyl)-
O,O'-diisopropyldithiophosphate (IIIb) was prepared
similarly from 3.6 g of acid Ib and 2.3 g of camphene
II using 0.23 g ( 3.5 wt %) of ZnCl , yield 4.4 g (75%),
purified by column chromatography (silica gel, eluent
2
EXPERIMENTAL
petroleum ether boiling at 70–100°C/Et O 1:1), R 0.60
2
f
2
0
IR spectra were recorded on a Bruker Vector 22
and a Tensor 27 IR Fourier Spectrometers (400–
(petroleum ether/Et O 1:1), n 1.5025. IR spectrum,
2 D
–
1
ν, cm : 2979 s, 2956 s, 2879 s [ν (CH ), ν (CH )];
as,s
3
as,s
2
–
1
4
000 cm ) from liquid films between KBr plates.
1454 m [δ (CH )]; 1386 m, 1374 m [δ (CH ) C gem]
as 3 s 3 2
3
1
Chemical shifts of
P
nuclei of phosphorus
o.s 993, 970 o.s [ν(POC]; 888 m, 777 s [ν (PO )],
as,s 2
1
compounds were measured on a Bruker CXP-100
spectrometer with an operating frequency of 36.47 MHz
with external 85% H PO . Positive value of the
655 s [ν(P=S)]; 547 m [ν(PS)]. H NMR spectrum, δ,
ppm, (J, Hz): 0.84 s, 0.93 s and 1.00 s [9H, CH -ring),
3
3
3
3
1.34 d and 1.36 d [12H, (CH ) CHOP, J 5.7], 1.41
3 2
HH
chemical shift δ corresponds to the downfield shift.
m, 1.72 m and 2.02 m (CH -ring. and CH-ring), 3.37
P
2
1
3
3
The H NMR spectra were registered on a Bruker
d.t (1H, CH H CHSP, J 7.3, J 19.9), 4.80 m
A B HH PH
3
Avance-400 with operating frequency 400 MHz and a
Bruker Avance-600 (600 MHz) spectrometers in
{2H, [(CH ) CHO] P, J 5.7}. Found, %: C 54.42, H
3 2 2 HH
8.96, P 9.32; S 18.18. C H O PS . Calculated, %: C
1
6
31
2
2
1
3
CDCl solutions. The C NMR spectra were recorded
54.82, H 8.94, P 8.84; S 18.26.
3
on a Bruker Avance-600 spectrometer (100.6 MHz) in
O,O'-Diethyl-S-8-[(+)-1-methyl-4-isopropylcyclo-
hex-1-enyl]dithiophosphate (Va) was obtained
similarly from 8.0 g of acid Ia and 5.6 g of (+)-limo-
CDCl solutions. The electron impact and chemical
3
ionization mass spectra were recorded on a Finnigan
MAT-212 and a`TRACE MS Finnigan MAT mass
spectrometers.
nene (IV) using 0.24 g (3 wt %) of ZnCl , yield 7.0 g
2
(
50%), purified by column chromatography (silica gel,
2
0
S-2-(1-Methyl-7-dimethylbicyclo[2.2.1]heptyl)-
O,O'-diethyldithiophosphate (IIIa). To a mixture of
eluent CCl ), R 0.28 (CCl ), n 1.5320. IR spectrum,
ν, cm : 2962 s, 2926 s, 2667 m [ν (CH ), ν (CH )];
4 f 4 D
–
1
as,s
3
as,s
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 7 2010

MONOTERPENOIDS DITHIOPHOSPHATES
1271
1
642 w [ν(C=C)], 1443 m [δ (CH )]; 1384 m, 1373 m
6. Pudovik, A.N., Gur’janova, I.V., and Ishmaeva, E.A.,
Reaktsii prisoedineniya fosforsoderzhashchikh soedi-
nenii s podvizhnim atomom vodoroda (Combination
Reactions of Phosphorus-Containing Compounds with
Labile Hydrogen Atom), Moscow: Khimiya, 1968.
as
3
[δ (CH ) C gem.] 1017 v.s.br, 957 m [ν(POC]; 798 m
s 3 2
1
[ν (PO )]; 656 m [ν(P=S)]; 533 m [ν(PS)]. H NMR
as,s
2
spectrum, δ, ppm, (J, Hz): δ 1.35 t [3H, (CH CH O) P,
1
3
3
2
2
3
JHH 7.1] and δ 1.36 t [3H, (CH CH O) P, J 6.8],
2
3
2
2
HH
7
. Nifant’ev, E.E., Khimiya gidrophosphoril’nyh soedi-
nenii (Chemistry of Hydrophosphoryl Compounds),
Moscow: Nauka, 1983.
1
.46 s and 1.53 s [6H, (CH ) CS], 1.63 s (3H, CH -
3 2 3
ring.) 1.71–2.15 m (7H, CH -ring and CH-ring); d
4
4
m (H, C=CH-ring). Found, %: C 51.78, H 8.13, P 9.33;
S 19.99. C H O PS . Calculated, %: C 52.14, H 8.46,
P 9.61; S 19.85.
2
1
3
3
.13 d.q [4H, (CH CH O) P, J 7.1, J 9.7] and d2
3 2 2 HH PH
3
3
8. Konovalova, I.V. and Burnaeva, L.A., Reaktsiya
Pudovika, Kazan: Kazan. Gos. Univ., 1991.
.23 d.q [4H, (CH CH O) P, J 6.8, J 7.0]; 5.34
3
2
2
HH
PH
9. Cherkasov, R.A., Stroenie dithiokislot phosphora i ih
1
4
27
2
2
reaktsionnaya sposobnost’ reaktsiyakh prisoe-
v
dineniya. In: Stroenie i reaktsionnaya sposobnost’
organicheskikh soedinenii (Structure and Reactivity of
Organic Compounds), Moscow: Nauka, 1978, p. 107.
O,O-Diisopropyl-S-8-[(+)-1-methyl-4-isopropyl-
cyclohex-1-enyl]dithiophosphate (Vb) was obtained
similarly from 8.0 g of acid Ib and 5.1 g of (+)-
10. Thomas, A.F. and Bessiere, Y., Natur Prod. Rep., 1989,
limonene (IV) using 0.056 g (0.7 wt %) of ZnCl , yield
vol. 6, p. 291.
2
1
.11 g (85%), purified by column chromatography
11. Davletshina, G.R., Kazakova, E.Kh., and Vul’fson, S.G.,
2
0
(
silica gel, eluent CCl ), R 0.24 (CCl ), n 1.5079. IR
Zh. Org. Khim., 1993, vol. 29, p. 1632.
4
f
4
D
–
1
spectrum, ν, cm : 2976 s, 2928 s, 2836 s [ν (CH ),
12. Morgunova, V.A., Nikitina, L.E., Plemenkov, V.V.,
Chugunov, V.V., and Fazlyeva, M.G., Zh. Org. Khim.,
2000, vol. 36, p. 512.
as,s
3
ν (CH )]; 1643 w [ν(C=C)], 1450 m [δ (CH )]; 1384
as,s
2
as
3
m, 1373 m [δ (CH ) C gem] v.s.br 968 [ν(POC]; 887
m, 775 m [ν(PO )]; 650 m [ν(P=S)]; 548 m [ν(PS)]. H
NMR spectrum, δ, ppm, (J, Hz): 1.35 d and 1.37 d
s
3 2
1
2
13. Crutchfield, M.M., Dungan, C.H., Letche,r J.H., Mark, V.,
Van Wazer, J.R., Topics in Phosphorus Chemistry. P31
Nuclear Magnetic Resonance, Grayson, M. and Grif-
fith, E.J., Eds., New York: Wiley, 1967, vol. 5.
3
[12H, (СН ) СНОР, J 6.0]; 1.53 s and 1.59 s [6Н,
3
2
НН
(СН ) СS]; 1.66 s [3Н, СН -ring]; 1.54–2.18 m (7Н,
3
2
3
СН -ring and СН-ring); 4.91 m {2Н, [(СН ) СНО] P,
14. Nikitina, L.E., Shkuro, O.A., and Plemenkov, V.V.,
2
3 2
2
3
Zh.Org. Khim., 1993, vol. 29, p. 1794.
JНН 6.0}; 5.37 m (1Н, С=СН-ring). Found, %: С
4.58; Н 8.38; Р 9.25; S 18.17. С Н О PS .
5
15. Vakulenko, I.A., Candidate Sci. (Chem.) Dissertation,
1
6
31
2
2
Kazan, 2008.
Calculated, % : С 54.82; Н 8.94; Р 8.84; S 18.26.
1
1
6. Nikitina, L.E., Candidate Sci. (Chem.) Dissertation,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 7 2010