1,3,4-thiazaphosphol-2-ines containing acetal groups in the molecule

Full text of DOI:10.1134/S1070363209100296

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 10, pp. 2274–2275. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © M.A. Pudovik, R.Kh. Bagautdinova, D.A. Pudovik, A.R. Burilov, A.S. Gazizov, 2009, published in Zhurnal Obshchei Khimii, 2009,
Vol. 79, No. 10, pp. 1751–1752.
LETTERS
TO THE EDITOR
1,3,4-Thiazaphosphol-2-ines Containing Acetal Groups
in the Molecule
M. A. Pudovik, R. Kh. Bagautdinova, D. A. Pudovik, A. R. Burilov, and A. S. Gazizov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
fax: (8432) 752253
e-mail: pudovik@iopc.knc.ru
Received March 2, 2009
DOI: 10.1134/S1070363209100296
Primary and secondary amines were shown to react
readily with chloromethyliso(thio)cyanato(thio)phos-
phonates to form the corresponding ureas or thioureas.
The latter undergo ring closure to 1,3,4-oxaza(thiaza)
phosphols in the presence of base [1–3]. We assumed
that the use of C-substituted amines in this reaction can
produce ring structures with P–C endocyclic bond
containing additional functional groups. These
compounds are of interest as the base compounds in
organic and organoelemental synthesis. To realize this
assumption we involved aminoacetals IIa–IIc into the
reaction with phosphorylated isothiocyanate I. These
reactions proceed readily in the presence of base under
mild conditions to give 1,3,4-thiazaphosphols contain-
ing acetal fragments in the molecule. The course of the
reaction includes intermediate formation of phos-
phorylated thioureas IIIа–IIIc. They were not isolated
nor registered spectrally due to the fast transformation
into the end-products. Cyclization occurs as a result of
a nucleophilic attck by thione sulfur atom on the
chloromethyl carbon atom to release hydrogen chloride
as triethylamine hydrochloride.
S
S
R
PhO
PhO
Et3N
1
PNHC(S)N(CH2)nCH(OR1)2
PNCS
+ RNH(CH2)nCH(OR )2
−Et3N·HCl
ClCH2
ClCH2
I
IIIа−IIIc
IIа−IIc
S
R
N
Et3N
PhO
P
N(CH2)nCH(OR1)2
C
−Et3N·HCl
S
IVа−IVc
II, III, IV, R = R1 = Me, n = 1 (а); R = H, R1 = Me, n = 1 (b); R = H, R1 = Et, n = 3 (c).
2-[N-Methyl-N-(O,O-dimethyl)ethyl]amino-4-phe-
sodium sulfate and concentrated in a water-jet pump
vacuum. Yield 0.55 g (28%), colorless viscous liquid.
noxy-4-thioxo-1,3,4-thiazaphosphol-2-ine (IVа). To
a mixture of 0.66 g of aminoacetal IIа, 0.60 g of
triethylamine in 20 ml of anhydrous benzene was
dropwise added 1.48 g of isocyanate I. The reaction
mixture was kept for 24 h. Triethylamine hydro-
chloride was separated. Benzene solution was treated
with distilled water (3×10 ml), dried with anhydrous
1
Mass spectrum, m/z: 346 [M+]. H NMR spectrum
[(CD3)2CO : C6H6=1:1], δ, ppm: 3.10 s (3H, NCH3),
3.36 s (3H, OCH3), 3.38 s (3H, OCH3), 3.40 d (2H,
3
2
NCH2, JHH 3.15 Hz), 3.58 d. d (1H, PCH2, JPH 3.6,
2JHH 13.50 Hz), 3.89 d. d (1H, PCH2, JPH = JHH
=
2
2
13.50 Hz), 4.63 t (1H, OCH, 3JHH 5.40 Hz), 7.21–7.41 m
2274

1,3,4-THIAZAPHOSPHOL-2-INES CONTAINING ACETAL GROUPS
2275
(5H, Ph). 31P NMR spectrum (acetone-d6 : C6H6 = 1:1],
δP, ppm: 115.70. Found, %: C 44.45; H 5.56; N 7.43; P
8.41; S 17.97. C13H19N2O3PS2. Calculated, %: C 45.06;
H 5.54; N 8.09; P 8.94; S 18.51.
(1H, NH). 31P NMR spectrum (acetone-d6), δP, ppm:
116.67. Found, %: C 49.00; H 6.18; N 7.07; P 8.33; S
16.49. C16H25N2O3PS2. Calculated, %: C 49.46; H
6.50; N 7.21; P 7.97; S 16.51.
The IR spectra were registered on a UR-20 spec-
2-[N-(O,O-Dimethyl)ethyl]amino-4-phenoxy-4-thi-
oxo-1,3,4-thiazaphosphol-2-yne (IVb) was prepared
similarly from 0.59 g of aminoacetal IIb, 0.6 g of tri-
ethylamine and 1.48 g of isothiocyanate I. Yield 0.90 g
trometer in the range of 400–3600 сm–1 (mineral oil).
1
The H NMR spectra were measured on a Bruker
31
AVANCE-600 spectrometer (600 MHz). The P NMR
1
spectra were recorded on a Bruker MSL-400 spec-
trometer (162 MHz). The mass spectra were taken on a
TRACE-MS Finnigan-MAT device.
(49%), colorless viscous liquid. H NMR spectrum
[(CD3)2CO], δ, ppm: 3.34 s (3H, OCH3), 3.35 s (3H,
3
OCH3), 3.40 d (2H, NCH2, JHH 3.15 Hz), 3.53 d. d
2
2
(1H, PCH2, JPH 3.60, JHH 13.05 Hz), 3.60 m (2H,
2
2
ACKNOWLEDGMENTS
NCH2), 3.90 d. d (1H, PCH2, JPH = JHH 13.05 Hz),
4.53 t (1H, OCH, 3JHH 4.95 Hz), 7.18-7.23 m (5H, Ph),
7.82 s (1H, NH). 31P NMR spectrum (acetone-d6), δP,
ppm: 117.96. Found, %: C 43.45; H 5.18; N 7.93; P
9.21. C12H17N2O3PS2. Calculated, %: C 43.35; H 5.16;
N 8.43; P 9.32.
This work was financially supported by the Russian
Foundation for Basic Research (grant no. 09-03-
00029).
REFERENCES
2-[N-(O,O-Diethyl)butyl]amino-4-phenoxy-4-thi-
oxo-1,3,4-thiazaphosphol-2-yne (IVc) was prepared
similarly from 0.94 g of aminoacetal IIc, 0.6 g of
triethylamine, and 1.54 g of isothiocyanate I. Yield
1.47 g (65%), colorless viscous liquid. 1H NMR
spectrum, [(CD3)2CO], δ, ppm: 1.07–1.20 m (6H,
CH3), 1.86–1.95 m (2H, CH2), 2.03–2.08 m (2H, CH2),
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2
3.45–3.62 m (2H, NCH2), 3.60 d. d (1H, PCH2, JPH
3.76, 2JHH 13.51 Hz), 3.73–3.92 m (4H, OCH2), 3.94 d.
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2
2
d (1H, PCH2, JPH 5.41, JHH 13.51 Hz), 5.10 t (1H,
2
OCH, JHH 4.95 Hz), 7.19–7.28 m (5H, Ph), 7.43 s
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 10 2009