Dithiophosphorylation of racemic and enantiomerically pure trimethyl-N-(1-phenylethyl)silanamine

Article abstract of DOI:10.1134/S1070428013040052

Trimethylsilyl P-aryl-N-[(RS)-, (S)-(-)-, and (R)-(+)-(1-phenylethyl)] phosphonamidodithioates were synthesized by reactions of 2,4-diaryl-1,3, 2λ⁵,4λ⁵-dithiadiphosphetane 2,4-disulfides with racemic and and enantiomerically pure tri

Full text of DOI:10.1134/S1070428013040052

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 4, pp. 526–529. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © I.S. Nizamov, E.M. Mart’yanov, I.D. Nizamov, A.R. Nurmukhametov, R.A. Cherkasov, 2013, published in Zhurnal Organicheskoi
Khimii, 2013, Vol. 49, No. 4, pp. 543–546.
Dedicated to the 100th Anniversary of Corresponding Member
of the Russian Academy of Sciences A.A. Petrov
Dithiophosphorylation of Racemic and Enantiomerically Pure
Trimethyl-N-(1-phenylethyl)silanamine
I. S. Nizamova, b, E. M. Mart’yanova, I. D. Nizamova,
A. R. Nurmukhametova, and R. A. Cherkasova
a Kazan Federal University, ul. Kremlevskaya 18, Kazan, 420008 Tatarstan, Russia
e-mail: isnizamov@mail.ru
b Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
Received February 25, 2013
Abstract—Trimethylsilyl P-aryl-N-[(RS)-, (S)-(–)-, and (R)-(+)-(1-phenylethyl)]phosphonamidodithioates
were synthesized by reactions of 2,4-diaryl-1,3,2λ5,4λ5-dithiadiphosphetane 2,4-disulfides with racemic and
and enantiomerically pure trimethyl-N-(1-phenylethyl)silanamine.
DOI: 10.1134/S1070428013040052
In recent years, structural, chemical, physicochem-
ical, and applied properties of various enantiomeric
organophosphorus compounds have attracted increased
attention [1–3]. The chiral center in their molecules
may be located both on the phosphorus atom and in
substituents. Four-coordinate phosphorus dithio acids,
their ammonium and metal salts, and S-esters occupy
a particular place among organophosphorus com-
pounds due to their potential applications as pesticides,
corrosion inhibitors, antioxidants, lubricant additives,
extractants, and complexing agents. A promising line
in the synthesis of phosphorus dithio acids and their
derivatives implies introduction of a dithiophosphoryl
fragment into molecules of natural compounds, e.g.,
terpenes possessing chiral centers. By reactions of
tetraphosphorus decasulfide and 2,4-diaryl-1,3,2λ5,4λ5-
dithiadiphosphetane 2,4-disulfides with unsaturated
monoterpene hydrocarbons and alcohols [camphene,
(R)-(+)-limonene, L-(–)-menthol, D-(+)-menthol,
(1S)-endo-(–)-borneol], as well as with (2S,3S)-(+)-di-
methyl tartrate, we previously synthesized a number of
new dithiophosphoric and mono- and bis-dithiophos-
phonic acid derivatives having a chiral center in the
O-substituents [4–12]. The reaction of racemic 1-phe-
nylethanol with tetraphosphorus decasulfide gave
a mixture of isomeric (R,S)-O,O-di(1-phenylethyl) di-
thiophosphates [13].
Reactions of tetraphosphorus decasulfide and
1,3,2λ5,4λ5-dithiadiphosphetane 2,4-disulfides with
silyl ethers derived from chiral synthetic alcohols and
with aminosilanes were not studied. These reactions
could provide a synthetic route to new phosphorus
dithio acid derivatives with asymmetric centers in the
substituents on the oxygen and nitrogen atoms.
Reagents containing readily departing groups can be
brought into substitution and exchange reactions with
organic compounds possessing pharmacophoric groups
with a view to obtain new phosphorus dithio acid
S-esters as potentially physiologically active com-
pounds. Reactions of achiral trimethylalkoxysilanes
Scheme 1.
Me
S
P
Me
Me3Si
Ar
S
S
S
+
2
2
*
*
P
P
Me3Si
S
Ar
N
H
Ph
N
H
Ph
S
Ar
Ia, Ib
(RS)-IIa/IIb
(RS)-IIIa/IIIb, (RS)-IIIc/IIId
R = 3,5-di-tert-butyl-4-hydroxyphenyl (a), 4-phenoxyphenyl (b).
526

DITHIOPHOSPHORYLATION OF RACEMIC AND ENANTIOMERICALLY PURE
527
Scheme 2.
Me
S
P
Me
Me3Si
Ar
S
S
S
+
2
2
*
*
P
P
Me3Si
H
S
Ar
H
N
H
N
H
S
Ar
Ph
Ph
Ia, Ib
(S)-(–)-IIa
(S)-IIIa, (S)-IIIc
R = 3,5-di-tert-butyl-4-hydroxyphenyl (a), 4-phenoxyphenyl (b).
and N,N-dialkyl(trimethyl)silanamines with tetraphos-
phorus decasulfide and 1,3,2λ5,4λ5-dithiadiphosphe-
tane 2,4-disulfides were reported previously to produce
S-trimethylsilyl dithiophosphates, phosphonodi-
thioates, diamidophosphorodithioates amidophos-
phonodithioates [14–20].
Trimethylsilyl P-aryl-N-[(R)-(1-phenylethyl)]phos-
phonamidodithioates IIIb and IIId were formed as
mixtures of diastereoisomers in the reaction of tri-
methyl-N-[(R)-(+)-(1-phenylethyl)]silanamine (IIb)
with diphosphetane disulfides Ia and Ib (30–45°C,
2 h). Compounds IIIb and IIId were isolated as solid
substances. Two signals were present in their 31P NMR
spectra at δP 70.57 and 70.71 ppm (1:1) for IIIb and at
δP 76.85 and 77.02 ppm (1 : 0.3) for IIId. In the
1H NMR spectrum of IIId, protons in the methyl
groups on the silicon atom resonated as two strong
singlets at δ 0.453 and 0.457 ppm, and two doublets at
δ 7.91 (3JPH = 8.8 Hz) and 7.95 ppm (3JPH = 9.1 Hz)
were assigned to aromatic protons in the ortho-posi-
tions of the substituted phenyl ring on the phosphorus.
In the present article we report on the results of
studying the reactions of 2,4-diaryl-1,3,2λ5,4λ5-dithia-
diphosphetane 2,4-disulfides Ia and Ib with racemic
and enantiomerically pure trimethyl-N-(1-phenylethyl)-
silanamine. Compounds Ia and Ib readily reacted with
racemic trimethyl-N-[(RS)-(1-phenylethyl)]silanamine
(IIa/IIb) in benzene at 20–30°C (1–1.5 h) to afford
crystalline trimethylsilyl P-aryl-N-(1-phenylethyl)-
phosphonamidodithioates IIIa/IIIb and IIIc/IIId
31
(Scheme 1). The P NMR spectrum of IIIa/IIIb con-
Compounds IIIa–IIId (both racemic and nonrace-
mic) are sensitive to atmospheric moisture, and they
undergo fast hydrolysis on exposure to air. When the
above reactions were carried out under more severe
conditions or without protection from atmospheric
moisture and oxygen, complex mixtures of phos-
phorus-and-sulfur containing compounds were formed
tained two signals at δP 70.65 and 70.53 ppm at a ratio
of 1:1; the corresponding signals (1:1) of stereoiso-
mers IIIc/IIId were observed in a weaker field
1
(δP 76.82, 77.00 ppm). In the H NMR spectrum of
IIIa/IIIb protons in the (CH3)3Si group resonated as
two strong signals at δ 0.453 and 0.457 ppm. Two
doublets at δ 7.800 and 7.805 ppm belong to the ortho-
protons in the 3,5-di-tert-butyl-4-hydroxyphenyl sub-
stituent in IIIa and IIIb (3JPH = 16.0 and 16.4 Hz,
respectively). Phosphonamidodithioates IIIc/IIId
showed in the IR spectrum absorption bands at 3631
and 3409 cm–1 due to stretching vibrations of the O–H
and N–H bonds, respectively.
31
(according to the P NMR data), which were difficult
to identify. Nevertheless, trimethylsilyl phosphon-
amidodithioates synthesized in the present work may
be used as synthons to introduce an S=P–N–C* frag-
ment into organic molecules with a view to obtain
biologically active compounds.
EXPERIMENTAL
Enantiomerically pure trimethyl-N-[(S)-(–)-(1-phe-
nylethyl)]silanamine (S-IIa) reacted with disulfides Ia
and Ib at 30–50°C (1.5–2 h) to give crystalline tri-
methylsilyl P-aryl-N-[(S)-(1-phenylethyl)]phosphon-
amidodithioates (S)-IIIa and (S)-IIIc, respectively. The
31P NMR spectrum of IIIa contained two signals at
δP 70.65 and 70.52 ppm (1:1) due to the presence of
two diastereoisomers. Likewise, trimethylsilyl ester
IIIc displayed in the 31P NMR spectrum two signals at
δP 76.86 and 76.96 ppm. In the electron impact mass
spectrum of IIIa we observed the molecular ion peak,
m/z 494.0 [M]+·. Symmetric bending and rocking vibra-
tions of methyl groups in the Me3Si fragment of ester
IIIc gave rise to IR absorption bands at 1242 and
887 cm–1, respectively.
The IR spectra were recorded in the range from 400
to 4000 cm–1 on a Bruker Vector 22 spectrometer with
1
Fourier transform. The H NMR spectra were meas-
ured on Bruker Avance-400 (400 MHz) and Bruker
31
Avance-600 (600 MHz) spectrometers; the P NMR
spectra were recorded on a Bruker Avance-400 instru-
ment (161.98 MHz) from solutions in benzene relative
to 85% H3PO4 (external reference). The electron im-
pact (70 eV) and chemical ionization mass spectra
were obtained on a DFS Thermo Electron Corporation
GC–MS system. All operations, including spectral
measurements, were carried out in a stream of dry
argon with thorough protection from air.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 4 2013

NIZAMOV et al.
528
Trimethylsilyl P-(3,5-di-tert-butyl-4-hydroxy-
58%, mp 85–87°C. IR spectrum (mineral oil), ν, cm–1:
3619 m (N–H), 1583 m (C–Harom), 1431 m (δasCH3),
1323 m (δsCH3), 1242 m [δsCH3(Si)], 1023 m
[(P)O–C], 965 s.br (O–C, OC–C), 887 s [ρCH3(Si)],
phenyl)-N-[(RS)-(1-phenylethyl)]phosphonamido-
dithioate (IIIa/IIIb, mixture of stereoisomers). Com-
pound Ia, 2.3 g (3.8 mmol), was added in portions
under stirring in a stream of dry argon to a solution of
1.5 g (7.8 mmol) of racemic aminosilane IIa/IIb in
20 ml of anhydrous benzene, heated to 50°C. The mix-
ture was stirred for 1 h at 50°C, kept for ~12 h at 20°C,
and evacuated for 1 h at 0.5 mm (40°C) and for 1 h at
0.02 mm. Yield 3.5 g (92%), mp 77–78°C. IR spec-
trum (KBr), ν, cm–1: 3631 s (O–H), 3409 m.br (N–H),
3060 sh, 3030 sh (C–Harom), 2957 s, 2910 v.s, 2875 v.s
(C–Haliph), 1584 m, 1494 s (C=Carom), 1428 v.s
(δasCH3), 1365 m (δsCH3), 1060 s [(P)O–C], 977 s.br,
890 s (O–C, OC–C), 847 v.s [ρCH3(Si)], 654 m (P=S),
1
675 s (P=S), 531 m (P–S), 436 m (δSPC). H NMR
spectrum, δ, ppm: 0.44 s [9H, (CH3)3Si], 1.67 d (3H,
3
CH3CHN, JHH = 6.8 Hz), 4.43 m (1H, CH3CHN),
7.33–7.85 m (12H, C6H5, m-H), 7.93 d (2H, o-H,
3JPH = 9.2 Hz), 7.97 d (2H, o-H, 3JPH = 8.7 Hz), 8.68 m
(1H, NH). Found, %: C 60.02; H 6.19; N 3.27; P 6.57;
S 14.01; Si 5.88. C23H28NOPS2Si. Calculated, %:
C 60.36; H 6.17; N 3.06; P 6.77; S 14.01; Si 6.14.
Trimethylsilyl P-(3,5-di-tert-butyl-4-hydroxyphe-
nyl)-N-[(R)-(1-phenylethyl)]phosphonamidodi-
thioate (IIIb). Yield 80%. Found, %: C 61.19; H 8.00;
N 2.70; P 6.22; S 13.34; Si 5.50. C25H40NOPS2Si.
Calculated, %: C 60.81; H 8.17; N 2.84; P 6.27;
S 12.99; Si 5.59.
Trimethylsilyl N-[(R)-(1-phenylethyl)]-P-(4-phe-
noxyphenyl)phosphonamidodithioate (IIId). Yield
93%, mp 88–89°C. Mass spectrum (EI), m/z (Irel, %):
442.96 (1) [M – Me]+·, 428.96 (1) [M – 2Me]+·, 413.01
(1) [M – 3 Me]+·, 381.00 [M – Ph]+·. Found, %:
C 60.35; H 6.39; N 3.21; P 6.47; S 14.35; Si 5.93.
C23H28NOPS2Si. Calculated, %: C 60.36; H 6.17;
N 3.06; P 6.77; S 14.01; Si 6.14. M 457.68.
1
532 m (P–S), 460 m (SPC). H NMR spectrum, δ,
ppm: 0.453 s and 0.457 s [9H each, (CH3)3Si], 1.47 s
and 1.48 s (18H each, t-Bu), 1.64 d (3H, CH3CHN,
3
3JHH = 6.9 Hz), 4.49 d.q (1H, CH3CHN, JHH
=
6.8 Hz), 7.11–7.36 m (5H, C6H5), 7.800 d (2H, o-H,
3JPH = 16.0 Hz), 7.805 d (2H, o-H, JPH = 16.4 Hz),
3
8.20 m (1H, NH). Found, %: C 61.06; H 8.36; N 2.91;
P 5.92; S 13.29; Si 5.34. C25H40NOPS2Si. Calculated,
%: C 60.81; H 8.17; N 2.84; P 6.27; S 12.99; Si 5.59.
Compounds IIIc/IIId (mixture of isomers), IIIa,
IIIb, IIIc, and IIId were synthesized in a similar way.
Trimethylsilyl N-[(RS)-(1-phenylethyl)]-P-(4-
phenoxyphenyl)phosphonamidodithioate (IIIc/IIId,
mixture of stereoisomers). Yield 52%, mp 80–82°C.
1H NMR spectrum, δ, ppm: 0.453 s and 0.457 s [9H
each, (CH3)3Si], 1.69 d (3H, CH3CHN, 3JHH = 5.0 Hz),
4.40 m (1H, CH3CHN), 7.00–7.44 m (12H, C6H5,
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 11-03-00264-a).
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3
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phenylethyl)]phosphonamidodithioate (IIIc). Yield
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DITHIOPHOSPHORYLATION OF RACEMIC AND ENANTIOMERICALLY PURE
529
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