Synthesis of 1,3,4-thiazaphosphols by reaction of O- phenylchloromethylisothiocyanatothiophosphonate with 1,2-diaminocyclohexane

Full text of DOI:10.1134/S1070363208050320

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 5, pp. 1014–1015. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © M.A. Pudovik, R.Kh. Bagautdinova, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 5, pp. 871–872.
LETTERS
TO THE EDITOR
Synthesis of 1,3,4-Thiazaphosphols by Reaction
of O-Phenylchloromethylisothiocyanatothiophosphonate
with 1,2-Diaminocyclohexane
M. A. Pudovik and R. Kh. Bagautdinova
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 January 25, 2008
DOI: 10.1134/S1070363208050320
Primary and secondary amines were found earlier
to add readily to chloromethylisothiocyanatothiophos-
phonates (-phosphinates) yielding initially phos-
phorylated thioureas, that underwent fast cyclization to
form 1,3,4-thiazaphosphols [1, 2]. We found that the
involvement of 1,2-diaminocyclohexanes IIа and IIb
into the reaction with О-phenylchloromethylisothio-
cyanatothiophosphones I gives rise to compounds IVа
and IVb with two phosphorus-containing five-
membered heterocycles. The intermediately forming
phosphorylated thioureas IIIa and IIIb we failed to
register spectrally due to their rapid cyclization.
Chemical shifts of the endocyclic phosphorus nuclei of
compounds IVа and IVb resonate in the region of
116–118 ppm characteristic of compounds of this type
[1, 2].
S
S
S
PhO
PhO
OPh
NH
HN(S)CHN
PNCS
P
NHC(S)NHP
2
+
ClCH2
ClCH2
CH2Cl
NH2
IIIа, IIIb
I
IIа, IIb
S
S
2 Et3N
N
N
S
PhO P
P OPh
−2 Et3N HCl
C
HN
IVа, IVb
II, III, IV 1,2-diaminocyclohexane (isomers mixture) (а); (1R,2R)-(–)-1,2-diaminocyclohexane (b).
NH
C
S
It should be noted that compounds IVа and IVb
have four chiral centers and therefore form complex
mixture of diastereomers. The 31Р NMR spectrum of
IVа contains two broad signals at 118.77 and 118.34 ppm
(in the ratio 81 : 19), and spectrum of IVb has three
signals at 116.09, 116.64, and 117.21 ppm (in the ratio
21 : 34 : 45). These results demonstrate that stereo-
selectivity of the studied processes is low. In the Н
NMR spectra there are complex multiple signals
assigned to methyl and methine protons of
1
1014

1015
SYNTHESIS OF 1,3,4-THIAZAPHOSPHOLS
cyclohexane ring (1.15–2.16 ppm), methyl protons at
the phosphorus atom (3.77–3.98 ppm), and protons of
phenyl fragments (7.22–7.49 ppm).
H 4.19; N 9.77; P 10.66; S 22.31. C22H24N4O2P2S4.
Calculated, %: С 46.65; H 4.27; N 9.89; P 10.94; S
22.60.
IR spectra were recorded on a UR-20 spectrometer
in the range of 400–3600 сm–1 (mineral oil). 31Р NMR
spectra were measured on a Bruker MSL-400 Fourier-
spectrometer (100.62 МHz). The mass spectrum was
taken on a TRACE–MS Finnigan–MAT device.
N,N'-Bis(4-phenoxy-4-thioxo-1,3,4-thiazaphos-
phol)-1,2-diaminocyclohexane (IVа). To a mixture of
0.22 g of 1,2-diaminocyclohexane IIа and 0.49 g of
triethylamine in 50 ml of anhydrous benzene at
stirring and cooling to 5°С was added 1.3 g of
isothiocyanate I. After 24 h triethylamine hydrochlo-
ride was separated, and benzene was removed. To the
residue was added 10 ml of anhydrous hexane.
Precipitate formed was filtered off and washed with
hexane. Yield 0.61 g (44%), mp 271–273°С. IR spec-
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Foundation for Basic Research (grant No. 06-03-
32085).
31
trum (KBr), ν, сm–1: 1568 (C=N). Р NMR spectrum,
δР, ppm (DMSO-d6): 118.77, 118.34. Mass spectrum,
m/z 566 [M]+. Found, %: С 46.46; H 4.32; N 9.74;
P 10.87; S 22.14. C22H24N4O2P2S4. Calculated, %: С
46.65; H 4.27; N 9.89; P 10.94; S 22.60.
REFERENCES
1. Kamalov, R.М., Khaylova, N.А., Gazikasheva, А.А.,
Chertanova, L.F., Pudovik, М.А., and Pudovik, А.N.,
Dokl. Akad. Nauk SSSR, 1991, vol. 316, no. 6, p. 1406.
N,N'-Bis(4-phenoxy-4-thioxo-1,3,4-thiazaphos-
phol)-1,2-diaminocyclohexane (IVb) was prepared
similarly from 0.32 g of diamine IIb, 0.60 g of tri-
ethylamine and 1.50 g of isothiocyanate I. Yield 0.51 g
(32%), 97–100°С. IR spectrum (KBr), ν, сm–1: 1571
(C=N). 31Р NMR spectrum, δР, ppm (C6D6): 116.09,
116.64, 117.21 (ratio 21 : 34 : 45). Found, %: С 46.39;
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baydullin, А.Т., Zverev, V.V., Pudovik, М.А., and
Pudovik, А.N., Zh. Obshch. Khim., 2002, vol. 72, no. 7,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 5 2008