Dithiophosphorylation of nerol and geraniol trimethylsilyl derivatives

Article abstract of DOI:10.1134/S1070428017020026

Reaction of tetraphosphorus decasulfide with О-(cis- and trans-3,7-dimethylocta-2,6-dien-1-yl)-trimethylsilanes affords О,О-bis(cis- and trans-3,7-dimethylocta-2,6-dien-1-yl) S-(trimethylsilyl)dithiophosphates.

Full text of DOI:10.1134/S1070428017020026

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2017, Vol. 53, No. 2, pp. 157–159. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © I.S. Nizamov, D.A. Terenzhev, I.D. Nizamov, G.G. Shumatbaev, E.S. Batyeva, R.A. Cherkasov, 2017, published in Zhurnal
Organicheskoi Khimii, 2017, Vol. 53, No. 2, pp. 171–173.
Dithiophosphorylation of Nerol and Geraniol
Trimethylsilyl Derivatives
I. S. Nizamova,b,* D. A. Terenzheva, I. D. Nizamova, G. G. Shumatbaeva,
E. S. Batyevab, and R. A. Cherkasova
a Kazan (Volga Region) Federal University, Kremlevskaya ul. 18, Kazan, 420008 Russia
*e-mail: isnizamov@mail.ru
b Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, Kazan, Russia
Received June 5, 2015
Abstract—Reaction of tetraphosphorus decasulfide with О-(cis- and trans-3,7-dimethylocta-2,6-dien-1-yl)-
trimethylsilanes affords О,О-bis(cis- and trans-3,7-dimethylocta-2,6-dien-1-yl) S-(trimethylsilyl)dithiophos-
phates.
DOI: 10.1134/S1070428017020026
One of fundamental problems of the chemistry of
natural compounds is the designing of new types of
isoprenoids derivatives modified with phosphorus.
These compounds are promising bioregulators playing
an important part in the generation by living bodies of
carbohydrate biopolymers [(lipo)polysaccharides,
glycoproteins, and peptidoglycans] [1–3]. Nowadays
the veterinary and the medicine require new
pharmaceuticals of bioregulator type. The introduction
of phosphorus-containing fragments in an isoprenoid
molecule may result in obtaining biologically active
substances of diverse action. Formerly some
specimens of open-chain isoprenoid alcohols [nerol,
geraniol, and (R,S)-linalool] were converted by
treatment with diethyl chlorophosphite, diphenyl-
chlorophosphine, and N,N-diethylamido-О,О-propy-
lenephosphite to isoprenoid phosphites with various
geometric configurations of dienyl fragments [4–6].
The replacement of phosphite and phosphate fragments
by dithiophosphate in the isoprenoids modified by
phosphorus may expectably decrease their toxicity
since pesticides of the dithiophosphate structure are
less toxic for warm-blooded animals [7].
alcohols into analogous reactions. However the
difficultly accessible О,О-dialkenyldithiophosphoric
acids are unstable compounds [9, 10], therefore the
synthesis of the corresponding isoprenoid dithio-
phosphoric acids can be impeded by possible
secondary transformations, including the addition of
the obtained unsaturated dithiophosphoric acids to the
multiple bonds of the initial isoprenoid alcohols and/or
of the proper phosphorus dithioacids. At the same time
S-trimethylsilyl esters of О,О-diallyl-dithiophosphoric,
О,О-dipropargyldithiophosphoric, and О,О-dicyclo-
alkenyldithiophosphoric acids formed cleanly in
reactions of (allyloxy)trimethylsilane, trimethyl(prop-2
-ynoxy)silane, and trimethylsilyl ethers of cyclic enols
with tetraphosphorus decasulfide [11, 12].
After the introduction of a silyl protection of the
hydroxyl group of alcohols we explored the chemical
behavior of trimethylsilyl derivatives of isoprenoid alco-
hols (nerol and geraniol) with respect to tetraphos-
phorus decasulfide. These reactions may also take several
pathways due to the presence of several reaction sites
in the molecules of the trimethylsilyl derivatives of iso-
prenoid alcohols (hydroxyl group and two multiple
bonds). Therefore to avoid unwanted secondary proces-
ses we used relatively mild conditions for the synthesis
of unsaturated S-(trimethylsilyl)dithiophosphates.
Considering that the alcohols reaction with tetra-
phosphorus decasulfide is a traditional procedure for
the preparation of diverse dithiophosphoryl com-
pounds [8] we have decided aiming at the synthesis of
isoprenoid derivatives of dithiophosphoric acids
possessing potential bioactivity to bring isoprenoid
Tetraphosphorus decasulfide 1 reacts with О-(cis-
3,7-dimethylocta-2,6-dien-1-yl)trimethylsilane 2а at a
molar ratio 1 : 8 at 55°С within 2 h in benzene giving
157

NIZAMOV et al.
158
Scheme 1.
28
20
26
5
11
4
S
2
SSi
1
21
22
10
12
13
6
19
4
7
P4S10 + 8
+ 2 (Me3Si)2S
18
9
P3
8
23
24
4
1
17
O
14
O
OSiMe3
15
29
25
16
27
2a
3a
Scheme 2.
S4
P3
28
20
26
18
11
10
9
17
19
8
21
O
12
O
OSiMe3
1
5
6
2S Si
4
+ 2 (Me3Si)2S
P4S10 + 8
22
13
23
24
4
1
14
7
15
29
27
16
25
2b
3b
О,О-bis(cis-3,7-dimethylocta-2,6-dien-1-yl) S-(trime-
thylsilyl)dithiophosphate 3а and bis(trimethylsilyl)-
sulfide 4 (Scheme 1).
the same conditions forms О,О-bis(trans-3,7-dimethyl-
octa-2,6-dien-1-yl) S-(trimethylsilyl)dithiophosphate 3b
and sulfide 4 (Scheme 2).
In the 31Р-{1H} NMR spectrum of compound 3а
registered in benzene a singlet is observed at 80.0 ppm.
The 29Si–{1Н} NMR spectrum contains a narrow singlet
at 27.0 ppm corresponding to chemical shifts range of
Parameters of NMR spectra of isomers 3а and 3b
are alike. The signal of compound 3b in the 31Р-{1H}
NMR spectrum taken in benzene (δ 79.8 ppm)
practically coincides with the chemical shift of cis-
isomer 3а. The IR spectrum of compound 3b contains
at 1669 cm–1 a characteristic absorption band of medium
intensity belonging to stretching vibrations of the С=С
bonds. The absorption band at 1253 cm–1 is due to
symmetric bending vibrations of the CH3 groups at the
silicon atom. A wide absorption band at 998 cm–1
corresponds to the stretching vibrations of the bonds
(P)O–C and О–С.
1
compounds of four-coordinate silicon [13]. In the Н
NMR spectrum taken in acetone-d6 the protons of
trimethylsilyl group resonate as a singlet at 0.37 ppm.
Carbon atoms of the same group in the 13С–{1H} NMR
spectrum recorded in СDCl3 appear as a singlet at
0.18 ppm whereas in the 13С NMR spectrum this signal
is a quartet (1JCH 119.6 Hz). The singlet at 16.9 ppm in
the 13С–{1H} NMR spectrum corresponds to atoms C26
and C28 of two methyl groups (fragments C26H3С=С
and C28H3С=С); this signal in the 13С NMR spectrum
appears as a quartet (1JCH 126.2 Hz). The singlet (and
the respective quartet in the 13С NMR spectrum) at δ
24.9 ppm belongs to the methyl atoms C27 and C29 from
fragments C27H3С=С and C29H3С=С (1JCH 125.5 Hz).
A similar pattern is observed as well for atoms C16 and
C25 in the fragments C16H3С=С and C25H3С=С (a
singlet and respectively a quartet in the 13С NMR
spectrum at 25.5 ppm, 1JCH 125.5 Hz). Atoms С24, С15,
С11, С20 at the unsaturated bonds in both modes of
carbon spectra registration appear as singlets at 131.2
(С24=С), 131.4 (С15=С), 139.7 (С11=С), and 141.2 ppm
(С20=С).
Thus, S-trimethylsilyl esters of isoprenoid phos-
phorus dithioacids are formed under mild conditions at
treating with tetraphosphorus decasulfide of trimethyl-
silyl derivatives of nerol and geraniol. They contain a
labile S–Si bond and may be utilized in addition and
substitution reactions with removal of the silyl protective
group. The obtained unsaturated S-(trimethylsilyl)-
dithiophosphates are promising for the introduction of
isoprenoid synthons of the necessary geometric
configuration into molecules of organic compounds in
designing new biologically active substances.
EXPERIMENTAL
IR spectra of compounds were recorded on a
Fourier spectrophotometer Bruker Vector 22 (400–
Geraniol trimethylsilyl derivative 2b, trans-isomer
of nerol, in the reaction with phosphorus sulfide 1 in
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 2 2017

DITHIOPHOSPHORYLATION OF NEROL AND GERANIOL TRIMETHYLSILYL DERIVATIVES
159
4000 cm–1). NMR spectra were registered on a
spectrometer Bruker Avance (III) 400: Н NMR spec-
6.77; S 13.76; Si 6.18. С23H43O2PS2Si. Calculated, %:
С 58.18; Н 9.13; P 6.52; S 13.51; Si 5.92.
1
tra (operating frequency 400.13 МHz) in acetone-d6,
31Р–{1Н} NMR spectra (161.97 МHz) in benzene with
respect to external reference (85% Н3РО4), 13С and 13С–
{1H} NMR spectra (100.61 МHz) in СDCl3. In 1Н and
13С NMR spectra the signals of residual protons of the
deuterated solvent and the carbon signal of the latter
served respectively as internal reference.
ACKNOWLEDGMENTS
The study was carried out under the financial
support of the Russian Foundation for Basic Research
(grant no. 14-03-00897-а).
REFERENCES
О,О-Bis(cis-3,7-dimethylocta-2,6-dien-1-yl) S-
(trimethylsilyl)dithiophosphate (3а). To a solution of
4.0 g (17.6 mmol) of silane 2а in 20 mL of anhydrous
benzene at 20°С was added at stirring in a dry argon
flow by portions 0.98 g (2.2 mmol) of phosphorus
sulfide 1. The mixture was heated with stirring for 2 h
at 55°С, and then kept for 12 h at 20°С. The reaction
mixture was filtered, evaporated for 1 h in a vacuum
(0.5 mmHg) at 40°С and for 1 h at 0.02 mmHg at 40°С.
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1
Yield 3.2 g (76%). Н NMR spectrum (acetone-d6), δ,
ppm: 0.37 s [9Н, (CH3)3Si], 1.59 s (6Н, С27Н3С=С,
С28Н3С=С), 1.68 s [12Н, (CH3)2C=С], 2.07 m (8Н,
3
СН2СН2), 3.53 d.d [4Н, POC9(18)H2CH=С, JHH 7.1,
3
3JPH 14.2 Hz], 3.64 d.d [4Н, POC9(18)H2CH=С, JHH
3
7.4, JPH 14.2 Hz], 5.08 m [2H, HC14(23)=CMe2], 5.33
m [2H, С=С10(19)HOP]. 13С NMR spectrum (СDCl3), δ,
ppm (the form of the signal in 13С-{1H} NMR
spectrum is given in parentheses): 0.18 q (s) [(CH3)3Si,
1JCH 119.6 Hz], 16.9 q (s) (C26H3С=С, C28H3С=С, 1JCH
1
126.2 Hz), 24.9 q (s) (C27H3С=С, C29H3С=С, JCH
1
125.5 Hz), 25.5 q (s) (C16H3С=С, C25H3С=С, JCH
125.5 Hz), 25.6 t (s) (CH2C22H2СН=С, 1JCH 129.1 Hz),
1
31.2 t (s) (С=СC21H2CH2, JCH 123.3 Hz), 31.3 t (s)
1
(С13H2C14H=С, JCH 123.3 Hz), 38.8 t (s) (С=СC12H2,
1
1JCH 129.1 Hz), 75.7 t (s) (POC9,18H2, JCH 125.5 Hz),
122.9 d (s) (HC23=С, HC14=С, 1JCH 153.3 Hz), 123.4 m
(s) (HC19=С), 130.9 m (s) (HС10=С), 131.2 s (s)
(С24=С), 131.4 s (s) (С15=С), 139.7 s (s) (С11=С),
141.2 s (s) (С20=С). 31Р-{1H} NMR spectrum (C6H6),
δ, ppm: 80.0. 29Si-{1Н} NMR spectrum (С6Н6), δ,
ppm: 27.0. Found, %: С 58.34; Н 9.44; P 6.23; S
13.86; Si 5.76. С23H43O2PS2Si. Calculated, %: С
58.18; Н 9.13; P 6.52; S 13.51; Si 5.92.
О,О-Bis(trans-3,7-dimethyl-octa-2,6-dien-1-yl) S-
(trimethylsilyl)dithiophosphate (3b) was obtained
similarly. Yield 78%. IR spectrum (liquid film), ν, cm–1:
2968 s, 2921 v.s, 2857 s [νas,s(СН3)], [νas,s(СН2)], 1669
m [ν(С=С)], 1447 s [δas(СН3)], 1379 m [δs(СН3)],
1253
m
[νs(CH3‒Si)], 998 v.s.br [ν(P)O–C],
[ν(О–СС)], 662 m [ν(P=S)], 585 m [ν(Р–S)]. 31Р-{1H}
(С6Н6), δ, ppm: 79.8. Found, %: С 57.84; Н 8.90; P
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 2 2017