(+)-Dimethyl tartrate in the synthesis of optically active bis-arylphosphonodithioic acids

Full text of DOI:10.1134/S1070428010100258

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 10, pp. 1581–1582. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © L.A. Al’metkina, I.S. Nizamov, A.V. Sofronov, D.A. Terenzhev, R.A. Cherkasov, 2010, published in Zhurnal Organicheskoi Khimii,
2
010, Vol. 46, No. 10, pp. 1574–1575.
SHORT
COMMUNICATIONS
(+)-Dimethyl Tartrate in the Synthesis of Optically Active
Bis-arylphosphonodithioic Acids
a
a–c
a
c
a
L. A. Al’metkina , I. S. Nizamov , A. V. Sofronov , D. A. Terenzhev , and R. A. Cherkasov
a
Kazan State University, ul. Kremlevskaya 18, Kazan, 420008 Tatarstan, Russia
e-mail: nizamov@iopc.knc.ru; Ilyas.Nizamov@ksu.ru
b
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
c
Tatar State Humanitarian Pedagogical University, Kazan, Tatarstan, Russia
Received October 19, 2009
DOI: 10.1134/S1070428010100258
5
5
Among four-coordinate phosphorus thio acids,
(I). We have found that 2,4-diaryl-1,3,2λ ,4λ -dithiadi-
phosphetane 2,4-disulfides IIa and IIb react with diol
I to give optically active dimethyl 2,3-bis{[aryl(sulfa-
nyl)phosphorothioyl]oxy}butanedioates IIIa and IIIb;
promising thiophosphorylating agents are bis-dithio-
phosphonic acids having two terminal P(=S)SH frag-
ments. Bis-dithiophosphonic acids with methyl groups
on the phosphorus atoms were synthesized by reaction
of methyl analog of Lawesson’s reagent with glycols in
diethyl ether [1]. After several unsuccessful attempts to
synthesize stable bis-dithiophosphonic acids with aryl
groups on the phosphorus atoms in acetonitrile [2, 3],
we have developed a procedure for the preparation of
bis-arylphosphonodithioic acids via reaction of homo-
logs of Lawesson’s reagent with triethylene glycol in
benzene [4]. Despite the presence of different substit-
uents at the four-coordinate phosphorus atoms in bis-
dithiophosphonic acid molecules, the proposed proce-
dure did not ensure synthesis of optically active prod-
ucts owing to 1,3-prototropic migration in the S=P–SH
heteroatom triad where the sulfur atoms become equiv-
alent. Therefore, we presumed that optically active bis-
arylphosphonodithioic acids could be obtained using
chiral glycols. Among the latter, of particular interest
from the viewpoint of selective biological activity are
naturally occurring diols, e.g., (+)-dimethyl L-tartrate
2
2
[α] = –13.6° and –20.3°, respectively (c = 1.0, C H ).
D
6
6
Dimethyl 2,3-bis{[(3,5-di-tert-butyl-4-hydroxy-
phenyl)(sulfanyl)phosphorothioyl]oxy}butanedioate
IIIa). Diol I, 2.1 g (11.8 mmol), was dissolved in
a mixture of 20 ml of anhydrous benzene and 20 ml of
chloroform, 7.0 g of compound IIa was added in small
portions under stirring at 20°C in a stream of dry
argon, and the mixture was heated for 1 h at 50°C and
kept for ~12 h at 20°C. The mixture was filtered, the
filtrate was evaporated at 40°C under reduced pressure
0.5 mm, 1 h), and the residue was evacuated for 1 h at
.02 mm. Yield 9.0 g (99%). IR spectrum, ν, cm :
446 (O–H), 2950, 2925, 2800 (C–Haliph), 2550 (S–H),
1742 (C=O), 1560, 1518 (C=C), 1430 (δ CH ), 1144
(O–C), 684 (P=S), 618 (P–S). H NMR spectrum, δ,
ppm (J, Hz): 1.47 s and 1.48 s (18H each, t-Bu), 3.68 s
(
(
0
3
–
1
as
3
1
and 3.71 s (3H each, CH O), 5.70 m (2H, SH), 5.84 d
3
3
3
and 5.85 d (1H each, CH, J = 12.0, J = 16.5),
HH
PH
3
3
7.90 d.d (2H, 2′-H, 6′-H, J = 1.8, J = 16.5).
HH
PH
SH
Ar
P
OMe
HO
O
Ar
O
O
S
S
MeO
O
S
+
P
P
S
S
OMe
S
Ar
P
O
O
OH
Ar
MeO
SH
I
IIa, IIb
IIIa, IIIb
2 6 2 6 4
Ar = 3,5-(t-Bu) -4-HOC H (a), 4-PhOC H (b).
1
581

1
582
AL’METKINA et al.
3
1
1
P NMR spectrum (C H ): δ 94.3 ppm. Mass spec-
examined as thin films. The H NMR spectra were
6
6
P
+
trum (EI): m/z 778.5 (Irel = 5%) [M] . Found, %:
C 52.13; H 6.88; P 7.76; S 16.23. C H O P S . Cal-
measured on a Bruker Avance-600 spectrometer
(600 MHz) from solutions in CDCl , and the P NMR
31
3
4
52
8
2
4
3
culated, %: C 52.42; H 6.73; P 7.95; S 16.47. M 778.9.
spectra were obtained on a Bruker CXP-100 instru-
ment (36.5 MHz) using 85% H PO as external refer-
3
4
Dimethyl 2,3-bis{[(4-phenoxyphenyl)(sulfanyl)-
phosphorothioyl]oxy}butanedioate (IIIb) was syn-
thesized in a similar way from 1.0 g (5.6 mmol) of diol
I and 3.0 g (5.7 mmol) of compound IIb. Yield 3.8 g
ence. The mass spectra (electron impact, 70 eV) were
recorded on a Trace MS Finnigan MAT instrument
with direct sample admission into the ion source. The
2
2
–
1
optical rotations [α] were determined on a Perkin–
D
(
(
95%). IR spectrum, ν, cm : 3065, 3063, 3024
Elmer 341 polarimeter (λ 589 nm, sodium halide lamp).
C–Harom), 2953, 2843 (C–Haliph), 2528 (S–H, free),
2
1
430 (S–H, assoc.), 1765 (C=O), 1528, 1487 (C=Carom),
REFERENCES
436 (δ CH ), 1357 (δ CH ), 1109, 1061 (O–C), 694
as
3
s
3
1
(
P=S), 534 (P–S). H NMR spectrum, δ, ppm (J, Hz):
.78 br.s (6H, CH O), 5.87 d and 5.88 d (1H each, CH,
JHH = 12.5, J = 16.5), 7.04 d.d (4H, m-H, J
1
. Kutyrev, G.A., Korolev, O.S., Safiullina, N.R., Yarko-
va, E.G., Lebedeva, O.E., Cherkasov, R.A., and Pudo-
vik, A.N., Zh. Obshch. Khim., 1986, vol. 56, p. 1227.
3
3
3
3
3
=
PH
HH
4
3
7
.0, J = 3.2); 7.09 d.d (4H, o′-H, J = 7.0);
PH HH
3
2. Shabana, R.Sh., Osman, F.H., and Atrees, S.S., Tetra-
hedron, 1993, vol. 49, p. 1271.
7
.23 d.d (2H, p′-H, J = 7.3), 7.42 m (4H, m′-H,
HH
3
3
3
J
= 7.7), 8.01 d.d (4H, o-H, J = 8.8, J = 14.7).
HH
HH PH
3
1
3. He, L.-N., Li, K., Luo, Y.-P., Liu, X.-P., Ding, M.-W.,
Zhuo, Q.-C., Wu, T.-J., and Cai, F., Phosphorus, Sulfur,
Silicon Relat. Elem., 2000, vol. 156, p. 173.
P NMR spectrum (CHCl ): δ 91.2 ppm. Found, %:
3
P
C 50.96; H 3.67; P 8.47; S 18.26. C H O P S . Cal-
culated, %: C 50.98; H 3.99; P 8.77; S 18.15.
3
0
28
8 2 4
4
. Nizamov, I.S., Popovich, Ya.E., Nizamov, I.D., Gabdul-
lina, G.T., and Cherkasov, R.A., Russ. J. Org. Chem.,
2007, vol. 43, p. 1874.
The IR spectra were recorded on a Bruker Vector
2 spectrometer with Fourier transform; samples were
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 10 2010