Di(adamant-1-yl)- and di(adamant-2-yl)thiophosphoric acids and their triethylammonium salts in alkylation reactions

Article abstract of DOI:10.1134/S1070363209080076

By reaction of di(adamant-1-yl) and di(adamant-2-yl) phosphites with sulfur in the presence of triethylamine diadamantylthiophosphoric acid triethylammonium salts were obtained. The latter by the action of hydrochloric acid were converted into free thiophosphoric acids and by the reaction of alkylation into the respective triesters which have thionic structure. Applicability in such reactions also of triethylammonium salts of diadamantyldithiophosphoric acids was demonstrated.

Full text of DOI:10.1134/S1070363209080076

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 8, pp. 1632–1634. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © R.I. Yurchenko, Yu.M. Klimko, A.A. Esipenko, E.D. Butova, A.G. Yurchenko, 2009, published in Zhurnal Obshchei Khimii, 2009,
Vol. 79, No. 8, pp. 1274–1276.
Di(adamant-1-yl)- and Di(adamant-2-yl)thiophosphoric Acids
and Their Triethylammonium Salts
in Alkylation Reactions
R. I. Yurchenko, Yu. M. Klimko, A. A. Esipenko, E. D. Butova, and A. G. Yurchenko
National Technical University of Ukraine, Kiev Polytechnic Institute,
pr. Pobedy, 37, Kiev, 03056 Ukraine
e-mail: ag@xtf.ntu-kpi.kiev.ua
Received October 28, 2008
Abstract—By reaction of di(adamant-1-yl) and di(adamant-2-yl) phosphites with sulfur in the presence of
triethylamine diadamantylthiophosphoric acid triethylammonium salts were obtained. The latter by the action
of hydrochloric acid were converted into free thiophosphoric acids and by the reaction of alkylation into the
respective triesters which have thionic structure. Applicability in such reactions also of triethylammonium salts
of diadamantyldithiophosphoric acids was demonstrated.
DOI: 10.1134/S1070363209080076
Dialkylthio- and dialkyldithiophosphoric acids are
well studied types of organophosphorus compounds.
However, only di(adamant-1-yl)- and di(adamant-2-yl)-
dithiophosphoric acids and some their derivatives are
known among these acids of adamantane series [1, 2].
As known [5], in the alkylation reaction not thio- or
dithiophosphoric acids are usually used but their
sodium, potassium or ammonium salts. We established
that triethylammonium salts I and II are suitable for
these reactions. In this case alkylation products III and
IV form with comparatively high yields (72–98%) at
heating of the reagents in alcohol for a short time.
Dialkylthiophosphoric acids can be obtained by
addition of sulfur to the corresponding phosphorous
diesters [3]. The reaction is carried out at high
temperature and under pressure. We failed to obtain
diadamantylthiophosphoric acids by this method under
the milder conditions. The corresponding diadamantyl-
phosphites were isolated in the initial state after the
reagents reflux in dioxane for a few hours [4]. If the
reaction with sulfur is carried out in triethylamine
medium, the corresponding thiophosphoric acid tri-
ethylammonium salts I and II form in high yields. By
treatment with hydrochloric acid of the latter the acids
III and IV were quantitatively obtained.
Note that by IR spectral data the diada-
mantylthioacids and their derivatives have thione
structure (compare with [6]).
By similar procedure the alkylation products V and
VI of dithiophosphoric acids of adamantane series can
be prepared from triethylammonium salts described
earlier [1].
S
RO
RO
HlgCH2R'
S
RO
RO
P
P
SNH(Et)3
SCH2R'
O
RO
S, N(Et)3
S
RO
P
P
V, R = 1-Ad, R' = CH2Ad-1 (а), CH=CH2 (b), C6H5 (c), 2-
C6H4Cl (d), 4-C6H4NO2 (e); VI, R = 2-Ad, R' = CH2Ad-1
(а), 4-C6H4NO2 (b).
RO
RO
H
ONH(Et)3
I, II
HlgCH2R'
S
RO
RO
P
OCH2R'
III, IV
Composition and structure of the compounds
obtained were proved by elemental analysis, IR and 1H
NMR spectroscopy (Tables 1, 2).
I, R = 1-Ad; II, R = 2-Ad; III, R = 1-Ad, R' = CH2Ad-1 (а),
CH=CH2 (b), 4-C6H4NO2 (c); IV, R = 2-Ad, 4-C6H4NO2 (а).
1632

DI(ADAMANT-1-YL)- AND DI(ADAMANT-2-YL)THIOPHOSPHORIC ACIDS
Table 1. Yields, melting points and data of elemental analyses of compounds I–VI
1633
mp, °С
(ethyl acetate + hexane)
161–163 (methanol)
Found, %
Calculated, %
Comp.
no.
Yield, %
Formula
P
S
P
S
90
87
98
72
98
84
95
79
98
76
77
91
81
83
6.35
6.33
8.00
5.61
7.28
5.93
8.15
5.90
6.96
6.25
6.05
5.83
5.47
5.87
6.64
С26Н46NO3PS
С26Н46NO3PS
C20H31O3PS
6.40
6.40
8.10
5.69
7.33
5.98
8.10
5.98
7.06
6.34
5.92
5.80
5.52
5.80
6.63
6.63
I
181–183 (methanol)
6.60
II
92–93
8.44
8.38
III
149–150
5.85
C32H49O3PS
5.89
IIIа
IIIb
IIIc
IV
86–87 (ethanol)
7.64
C23H35O3PS
7.59
147–148
6.15
C27H36NO5PS
C20H31O3PS
6.19
83–85
8.30
8.38
92–93
6.25
C27H36NO5PS
C23H35O2PS2
C27H37O2PS2
C27H36ClO2PS2
C27H36NO4PS2
C32H49O2PS2
C27H36NO4PS2
6.19
IVа
Vа
Vb
Vc
94–95 (ethanol)
14.58
13.17
12.04
12.12
11.47
12.17
14.62
13.12
12.26
12.02
11.43
12.02
118–119
97–99
163–165 (ethyl acetate + methanol)
132–134
Vd
VIа
VIb
102–103 (ethyl acetate + methanol)
Table 2. IR and 1H NMR spectra of compounds I–VI
Comp.
IR spectrum, ν, cm–1
1H NMR spectrum, δ, ppm (СDCl3)
no.
675 (P=S), 1085 (POC), 2700 1.30 t (9H, СH3, JHH 6 Hz), 1.60 s (12H, β-СH2), 2.10 s (6H, γ-СH), 2.19 s (12H, δ-СH2),
(POH), 3450 HNEt3+
3.11 q (6H, СH2N, JHH 6 Hz)
695 (P=S), 1030 (POC), 2660 1.33 t (9H, СH3, JHH 6 Hz), 1.53–2.10 m (30H), 3.10 q (6H, СH2N, JHH 6 Hz), 4.50 d
(POH), 3450 HNEt3+
(2H, СHO, JHP 12 Hz)
660 (P=S), 1010 (POC), 2690 (POH) 1.62 s (12H, β-СH2), 2.18 s (12H, δ-СH2, 6H, γ-СH), 4.82 s (1H, OH)
I
II
III
685 (P=S), 990 (POC)
640 (P=S), 990 (POC)
630 (P=S), 1020 (POC)
1.45 t (2H, СH2 JHH 6 Hz), 1.51 s (6H, β-СH2), 1.64 s (12H, β-СH2), 1.95 s (3H, γ-СH),
2.25 s (12H, δ-СH2, 6H, γ-СH), 2.83 m (2H, СH2)
IIIa
1.62 s (12H, β-СH2), 2.14 s (12H, δ-СH2, 6H, γ-СH), 3.47 d.d (2H, SCH2, JHP 15 Hz, JHH
7 Hz), 5.06 d (1H, =СH, JHH 7 Hz), 5.22 d (1H, =СH, JHH 12 Hz), 5.88 m (1H, СH)
IIIb
IIIc
1.60 s (12H, β-СH2), 2.17 s (12H, δ-СH2, 6H, γ-СH), 4.19 d (2H, SCH2, JHP 15 Hz, JHH
Hz), 7.51 d (2H, С6H4, JHH 6 Hz), 9.14 d (2H, С6H4, JHH 6 Hz)
7
710 (P=S), 1000 (POC), 2690 (POH) 1.46–2.10 m (30H), 4.62 d (2H, СHO, JHP 12 Hz), 5.38 s (1H, OH)
IV
615 (P=S), 1030 (POC)
1.43–1.95 m (30H), 4.13 d (2H, OСH2, JHP 13 Hz), 4.58 d (2H, СHO, JHP 12 Hz), 7.55 d
(2H, С6H4, JHH 7 Hz), 8.19 d (2H, С6H4, JHH 7 Hz)
IVa
590 (P–S), 700 (P=S), 990 (POC)
580 (P–S), 690 (P=S), 1020 (POC)
600 (P–S), 685 (P=S), 1000 (POC)
580 (P–S), 675 (P=S), 1010 (POC)
1.64 s (12H, β-СH2), 2.25 s (12H, δ-СH2, 6H, γ-СH), 3.55 d.d (2H, SCH2, JHP 15 Hz, JHH
7 Hz), 5.06 d (1H, =СH, JHH 7 Hz), 5.22 d (1H, =СH, JHH 12 Hz), 5.90 m (1H, СH)
1.62 s (12H, β-СH2), 2.22 s (12H, δ-СH2, 6H, γ-СH), 4.10 d (2H, SCH2, JHP 12 Hz),
7.31 d (5H, С6H5)
Va
Vb
Vc
Vd
1.62 s (12H, β-СH2), 2.21 s (12H, δ-СH2, 6H, γ-СH), 4.20 d (2H, SCH2, JHP 13 Hz), 7.25 m
(4H, С6H4)
1.61 s (12H, β-СH2), 2.18 s (12H, δ-СH2, 6H, γ-СH), 4.17 d (2H, SCH2, JHP 15 Hz), 7.53 d
(2H, С6H4, JHH 6 Hz), 9.16 d (2H, С6H4, JHH 6 Hz)
1.50–2.14 m (47H), 2.87 m (2H, SCH2), 4.72 d (2H СHO, JHP 12 Hz)
1.43–1.92 m (30H), 4.20 d (2H, SCH2, JHP 15 Hz), 4.66 d (2H, СHO, JHP 12 Hz), 7.53 d
(2H, С6H4, JHH 6 Hz), 8.14 d (2H, С6H4, JHH 6 Hz)
VIa
VIb
570 (P–S), 700 (P=S), 980 (POC)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

1634
YURCHENKO et al.
EXPERIMENTAL
dithiophosphate (Vd), O,O'-di(adamant-2-yl)-S-[(2-
adamant-1-yl)ethyl-1]dithiophosphate (VIa), O,O'-
di(adamant-2-yl)-S-(4-nitrobenzyl)dithiophosphate
(VIb). A mixture of equimolar amounts (0.001 mol) of
corresponding triethylammonium salts and alkylating
agents, 1-bromoethyladamantane (IIIa, VIa), benzyl
chloride (Vb), o-chlorobenzyl chloride (Vc), p-
nitrobromobenzyl bromide (IIIc, IVa, Vd, VIb) or
0.002 mol of allyl chloride (IIIb, Va), was refluxed for
2–3 min or 5 h for compounds IIIa and VIa. At the
next day the products were separated. The reaction
mixture was treated with water, when the occasion
requires, and the precipitate was separated.
The IR spectra were recorded on a Specord 75-IR
instrument from KBr pellets. The H NMR spectra
1
were taken on a JNM FX90 spectrometer (90 MHz) in
1
CDCl3; H signals assignment for adamantane nucleus
is given in accordance with notation agreed in [4].
O,O'-Di(adamant-1-yl)triethylammoniothiophos-
phate (I), O,O'-di(adamant-2-yl)triethylammonio-
thiophosphate (II). A mixture of equimolar quan-
tities (0.01 mol) of corresponding diadamantyl-
phosphite, disperse sulfur, and 30 ml of triethylamine
was heated for 30 min at 75ºC, and then refluxed to
full sulfur dissolution. At the next day the precipitate
was separated and washed with pentane some times.
ACKNOWLEDGMENTS
Authors are grateful to Ukrainian Scientific-
Technological Centre for financial support.
O,O'-Di(adamant-1-yl)thiophosphoric acid (III).
To a suspension of 0.001 mol of salt I in 2.5 ml of
water was added 5 ml of conc. hydrochloric acid. The
reaction mixture was stirred for 1 h. The precipitate
was separated and washed with water.
REFERENCES
1. Yurchenko, R.I., Esipenko, A.N., and Yurchenko, V.G.,
O,O'-Di(adamant-2-yl)thiophosphoric acid (IV).
A solution of 0.001 mol of salt II in 25 ml of methanol
was acidified with 3 % HCl methanol solution under
stirring and stirred for 1.5 h. Then the solvent was
removed under a water-jet-pump vacuum. The residue
was treated with water and the precipitate was separated.
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i
primeneniyu fosforor-
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009