Reaction of chloromethyliso(thio)cyanato(thio)phosphonates(-phosphinates) with phenol, ethanol, and thiols

Article abstract of DOI:10.1007/s11176-005-0006-7

(Chloromethyl)isocyanatophosphonates(-phosphinates) take up phenol to form carbamates whose β-cleavage gives rise to phenyl (chloromethyl) phosphonates(-phosphinates). (Chloromethyl)(thio)phosphinic-(phosphonic) isothiocyanates react with phenol at 20°C in the absence of catalyst to afford phenyl phosphinates(-phosphonates). (Alkylsulfanyl)carbamates formed by addition of thiols to (chloromethyl)iso(thio)cyanastophosphonates(-phosphinates) under the action of an equimolar amount of triethylamine undergo cyclization into 1,3,4-oxaza(thiaza)phospholines. 2004 MAIK "Nauka/ Interperiodica".

Full text of DOI:10.1007/s11176-005-0006-7

Russian Journal of General Chemistry, Vol. 74, No. 9, 2004, pp. 1335 1340. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 9, 2004,
pp. 1441 1446.
Original Russian Text Copyright
2004 by Khailova, Bagautdinova, Shaimardanova, Krepysheva, M. Pudovik, Chmutova, Azancheev, Musin,
A. Pudovik.
Reaction of Chloromethyliso(thio)cyanato(thio)phosphonates-
(-phosphinates) with Phenol, Ethanol, and Thiols
N. A. Khailova, R. Kh. Bagautdinova, A. A. Shaimardanova, N. E. Krepysheva,
M. A. Pudovik, G. A. Chmutova, N. M. Azancheev, R. Z. Musin, and A. N. Pudovik
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received October 31, 2002
Abstract (Chloromethyl)isocyanatophosphonates(-phosphinates) take up phenol to form carbamates whose
-cleavage gives rise to phenyl (chloromethyl)phosphonates(-phosphinates). (Chloromethyl)(thio)phosphinic-
(phosphonic) isothiocyanates react with phenol at 20 C in the absence of catalyst to afford phenyl phosphi-
nates(-phosphonates). (Alkylsulfanyl)carbamates formed by addition of thiols to (chloromethyl)iso(thio)cyana-
stophosphonates(-phosphinates) under the action of an equimolar amount of triethylamine undergo cyclization
into 1,3,4-oxaza(thiaza)phospholines.
It is known that isocyanates of P(V) acids take up
phenols and thiols by the C=N bond of the isocyanate
group to give N-phosphorylated carbamates and thio-
carbamates [1]. Previously we showed that phos-
phorylated carbamates in the presence of bases un-
dergo heterocyclization due to intramolecular interac-
tion of the chloromethyl and carbonyl groups to form
unsaturated heterocycles, such as 1,3,2-oxazaphos-
pholines [2]. Aiming at preparing new functionalyzed
(chloromethyl)phosphonates and (chloromethyl)thio-
phosphonates capable of further transformations, we
reacted (chloromethyl)iso(thio)cyanatophosphonates-
(-phosphinates) with phenol, ethanol, and thiols. We
expected that the presence on the phosphorus atom of
several structural fragments capable of interacting
with each other would enable us to synthesize new
phosphorus-containing heteroatomic cyclic and
acyclic compounds.
It was shown that isocyanatophosphonates(-phos-
phinates) Ia and Ib react with phenol (IIa) and ben-
zenethiol (IIb) to form carbamates IIIa IIIc. Their
1
structure was confirmed by IR and 31P and H NMR
spectroscopy. The IR spectra of N-phosphorylated
carbamates IIIa IIIc contain absorption bands
1
1
the P=O (1260 1280 cm ), Ph (1590 cm ), C=O
1
1
1
(1745 cm ), and NH groups (3150 cm ). In the H
NMR spectrum, PCH2 protons give a doublet at 3.77
4.07 ppm and phenyl protons, a multiplet at 7.2
7.3 ppm.
O
R P N
a
C YPh
O
IV
O
O
O
R
R
B
PNCO + PhYH
ClCH2
PNHCYPh
ClCH2
IIIa IIIc
O
b
R
Ia, Ib IIa, IIb
PYPh + (HNCO)n
ClCH2
Va, Vb
I, R = PhO (a), ClCH2 (b); II, Y = O (a), S (b); III, V, R = PhO, Y = O (a); R = ClCH2, Y = O (b); IIIc, R = CH2Cl,
Y = S.
1070-3632/04/7409-1335 2004 MAIK Nauka/Interperiodica

1336
KHAILOVA et al.
However, unlike structurally related alkylurethans
cyanate group by phenoxyl in compound VIIa takes
place to form the same product. According to PM3
calculations for structures VIIb IXb, phenol addition
to isothiocyanate VIIb is unfavorable (the endo effect
whose cyclization under the action of bases gives rise
to 1,3,4-oxazaphospholines IV, phenylurethans IIIa
and IIIb under the same conditions provide -elimina-
tion products, viz. phenyl (chloromethyl)phosphona-
tes(-phosphinates) Va and Vb. Evidence for the pre-
ference of -elimination (pathway b) over cyclization
(pathway a) was also obtained by PM3 semiempirical
quantum-chemical calculations (MOPAC) for the re-
action of isocyanate Ia with phenol [3]. Pathway b is
1
of the addition stage is 101.6 kJ mol ) and, therefore,
direct nucleophilic substitution is more probable.
Phenyl bis(chloromethyl)isothiocyanatophosphinate
(VIIb) reacts with phenol only at 80 C in the pre-
sence of a catalytic amount of triethylamine. The
necessity of prolonged heating of the reaction mixture
for the formation of product Va is explained by the
fact that the whole process has an appreciable endo
1
47.3 kJ mol more favored over pathway a even for
conformer IIIa that is best susceptible to cyclization.
In the presence of a base (triethylamine), which favors
cyclization, the -elimination pathway still remains
1
effect (70.7 kJ mol ). The calculated Hf values
1
(kJ mol ) are as follows: VIIb 286.5; VIIIb 275.2;
1
preferred ( Hf 11.7 kJ mol ). The calculated en-
Va 471.7, and HNCS 165.2.
1
thalpies of formation Hf (kJ mol ) are as follows:
X
X
Ia 516.9; IIa 90.7; IIIa 599.3; IVa 376.0; Va
471.7; HCl 85.7; and HNCO 64.0.
S
R
R
PNCS + PhOH
ClCH2
PNHCOPh
ClCH2
Attempted synthesis of phenylurethan IIIb by
direct phosphorylation of phenylurethan with bis-
(chloromethyl)phosphinic chlorides VI. However,
here, too, the final product of this reaction is phenyl
bis(chloromethyl)phosphinate (Vb).
VIIa, VIIb
VIIIa, VIIIb
X
R
POPh + (HNCS)n,
ClCH2
Va, IXa, IXb
O
O
(ClCH2)2PCl + PhOCNH2
Vb + (HNCO)n.
HCl
VII IX, R = ClCH2, X = S (a); R = PhO, X = O (b).
VI
Thiols Xa and Xb easily add to (chloromethyl)iso-
cyanatophosphonates(-phosphinates) Ia and Ib to
form alkyl thiocarbamates XIa XIc. The reaction
proceeds without catalyst and is complete within
30 min, whereas dialkylphosphinic isocyanates react
slowly (several days) [1].
Bezenethiol adds to isocyanate Ib, affording phos-
phorylated (phenylsulfanyl)urethan IIIc. When treated
with base, the latter, urethans IIIa and IIIb, forms a
series of products. The 31P NMR spectrum of the re-
action mixture contains no signal of S-phenyl bis-
(chloromethyl)thiophosphinate (Vc) ( P 51.6 ppm) ob-
tained in a special experiment by the reaction of phos-
phinic chloride VI with benzenethiol in the presence
of triethylamine. From that it follows that the -eli-
mination pathway does not take place in the case of
phosphorylated urethan IIIc.
O
O
R
Ia, Ib + R SH
PNHCSR
ClCH2
Xa, Xb
XIa XIc
O
O
R P N
B
Et3N
C SR
B HCl
VI + PhSH
(ClCH2)2PSPh.
Et3N HCl
O
Vc
XIIa XIIc
Unlike phosphoric and phosphinic isocyanates that,
according to published data, fail to react with phenol
in the presence of catalyst and at elevated tempera-
tures [4], (chloromethyl)thiophosphinic isocyanate
reacts with phenol reacts with phenol at room tem-
perature without catalyst. However, thiocarbamate
VIIIa could not be detected spectrally. It can be
proposed that adduct VIIIa is unstable and decom-
poses to form O-phenyl bis(chloromethyl)thiophos-
phinate (IXa), or nucleophilic substitution of the iso-
X, R = Bu (a), t-Bu (b); XI, XII, R = PhO, R = t-Bu (a);
R = PhO, R = Bu (b); R = ClCH2, R = Bu (c).
Carbamates XIa XIc are crystalline substances.
1
Their structure was confirmed by IR and H, 13C, and
31P NMR spectroscopy, and their composition, by
elemantal analysis. Under the action of equimolar
amount of triethylamine, compounds XIa XIc under-
go intramolecular cyclization via alkylation of the
carbonyl oxygen with the chloromethyl group to give
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 9 2004

REACTION OF CHLOROMETHYLISO(THIO)CYANATO(THIO)PHOSPHONATES-
1337
oxazaphospholines XIIa XIIc. The IR spectra of
phosphorylated carbamates XIa XIc contain charac-
S
S
S
PhO
PhO
teristic absorption bands of the carbonyl (1670
PNCS + BuSH
ClCH2
PNHCSBu
ClCH2
XIV
1
1
1680 cm ) and NH groups (3060 3070 cm ),
whereas the spectra of compounds XIIa XIIc lack
such bands. Instead, a new absorption band appears at
S
XIII
N
PhO P
1
1545 cm , due to the endocyclic C=N bond. Evi-
C SBu
dence for the formation of phospholines XIIa XIIc is
also provided by the downfield shift of signals in the
31P NMR spectra [ P 48.9 (XIc) and 61.8 ppm (XIIc)].
S
XV
1
In the H NMR spectrum, PCH2 protons appear in as
presence of triethylamine is favorable: The exothermic
effect of this reaction is 101.2 kJ mol .
an octet (ABX system) in the range 4.02 4.22 ppm,
implying an endocyclic position of the methylene
group. The methylene group of carbamates XIa XIc
gives a doublet at 3.7 3.8 ppm (2JHP 11 13 Hz).
Compounds XIIa XIIc were characterized crude,
since they are unstable and disproportionate when
purified to form a series of products.
1
Developing these studies, we turned to reaction of
ethanol with isothiocyanatothiophosphonate XIII. It
was expected that the initially formed carbamate XVI
would undergo an intramolecular transformation in-
volving nucleophilic attack of sulfur on the chloro-
methyl carbon atom and resulting in formation of
intermediate XVII, followed by HCl evolution from
the latter to give thiazaphospholine XVIII (pathway
a). Theoretical consideration showed that this pathway
is really energetically favorable (the exo effect is
116.7 kJ mol ). However, it was found that the most
preferred is pathway b that involves the attack of the
chloride ion on the alkoxyl carbon, yielding saturated
thiazaphospholidine ring XIX ( Hf 134.7 kJ mol ).
O-Phenyl (chloromethyl)isothiocyanatothiophos-
phonate (XIII) reacts with butanethiol to give 2-(bu-
tylsulfanyl)-4-phenoxy-1,3,4 5-thiazaphospholine
4-sulfide (XV). With equimolar amount of triethyl-
amine, the reaction is considerably accelerated. Hence,
in the absence of triethylamine the reaction is com-
plete in two months, while in the presence, it occurs
with heat release and is compete in 30 min. However,
no linear reaction product, thiocarbamate XIV, was
found in both cases. According to 31P NMR, cycle
XV is formed directly.
1
1
1
The calculated enthalpies of formation Hf (kJ mol )
are as follows: XIII 29.4; EtSH 36.4; EtOH 237.5;
thiocarbamate like XIV 18.0; XV 164.4; SEt analog
of compound XV 1.7; XVII 162.3; and EtCl 92.4.
It was found that isothiocyanate XIII readily reacts
with ethanol at 20 C in the absence of base and ac-
tually provides 1,3,4-thiazaphospholidine XIX.
Quantum-chemical calculations reveal unfavoura-
bleness of thiocarbamate formation from compound
XIII and ethanethiol: The heat effect of this stage is
1
30.9 kJ mol . However, formation of cycle XV in the
S
a
NH
PhOP
HCl
S
C OEt
S
S
PhO
Cl
NH
C+ OR
PhOP
XIII
XIII + EtOH
PNHCSOEt
ClCH2
8
7
S
S
S
XVI
b
EtCl
6 O P NH
9
XVII
4
5
C
3
2C=O
1S
HB
HA
XIX
1
The structure of compound XIX was confirmed by
absorption bands, , cm : 1190 (P O Ph), 1590 (Ph),
1
1
IR and H, 13C, and 31P NMR spectroscopy and high-
1680 (C=O), and 3150 (NH). In H NMR spectrum,
resolution mass spectrometry. The IR spectrum of
1,3,4-thiazaphospholidine III contains the following
PCH2 protons appear as eight lines (ABX system) in
the range 4.02 4.22 ppm, implying an endocyclic
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 9 2004

1338
KHAILOVA et al.
2
character of the methylene group. Phenyl protons give
a multiplet (A2B2C system) in the range 7.22
7.44 ppm.
(4H, CH2P, JPH 9 Hz), 7.3 m (5H, Ph), 10.7 br.s (1H,
NH). 31P NMR spectrum:
36.07; H 3.11; Cl 24.29; N 4.87; P 10.47; S 10.46.
C9H10Cl2 NO2PS. Calculated, %: C 36.26; H 3.12; Cl
23.78; N 4.70; P 10.39; S 10.75.
26.5 ppm. Found, %: C
P
EXPERIMENTAL
Diphenyl (chloromethyl)phosphonate (Va). a. To
a solution of 1 g of carbamate IIIa in 20 ml of an-
hydrous benzene, 0.4 g of triethylamine was added
dropwise, and the resulting mixture allowed to stand
for 12 h at 20 C. After removal of the solvent, 0.6 g
(70%) of phosphonate Va was obtained. IR spectrum
The IR spectra of were measured on a UR-20 spec-
1
trometer in the range 400 3600 cm in mineral oil or
thin layer. The 31P NMR spectra were obtained on a
Bruker MSL-400 NMR Fourier spectrometer
(161.97 MHz) and on a KGU-4 custom-made spec-
trometer (10.2 MHz) against internal 85% phosphoric
1
1
1
(KBr), , cm : 1285 (P=O), 1595 (Ph). H NMR
acid. The H NMR spectra were recorded on a Varian
2
spectrum (CCl4), , ppm: 3.63 d (2H, CH2P, JPH
T-60 spectrometer (60 MHz) against internal TMS and
on a Bruker WM-250 spectrometer (250.132 MHz).
The 13C NMR spectra were measured on a Bruker
MSL-400 spectrometer (100.6 MHz). The electron
impact mass spectra were obtained on an MX-1310
spectrometer (R 15000, direct inlet, 120 C).
8Hz), 7.13 m (10H, Ph). 31P NMR spectrum:
P
10.2 ppm.
b. To a solution of 3.05 g of isothiocyanate VIb in
20 ml of anhydrous benzene, a solution of 1.16 g of
phenol in 5 ml of anhydrous benzene was added
dropwise. One drop of triethylamine was then added,
and the resulting mixture was heated for 12 h at 80 C.
The solvent was removed in a vacuum, and the re-
sidue was fractionated to give 0.9 g (26%) of phos-
Phenyl [(chloromethyl)phenoxyphosphinoyl]-
carbamate (IIIa). To a solution of 2.3 g of phos-
phonate Ia in 30 ml of anhydrous ether, 0.33 g of
phenol was added. After 24 h, the precipitate that
formed was filtered off to obtain 2.0 g (65%) of com-
1
phonate Va, bp 130 131 C (0.03 mm Hg). H NMR
2
spectrum (CCl4), , ppm: 3.72 d (2H, CH2P, JPH
pound IIIa, mp 117 119 C. IR spectrum (KBr),
,
1
9 Hz), 7.2 m (10H, Ph). 31P NMR spectrum:
P
cm : 1195 (OPh), 1280 (P=O), 1590 (Ph), 1745
1
10.8 ppm [4].
(C=O), 3100 (NH). H NMR spectrum (CD3CN), ,
ppm: 4.07 d (2H, CH2P, 2JPH 10 Hz), 7.2 m (10H, Ph),
8.17 br.s (H, NH). 31P NMR spectrum: P 15.28 ppm.
Found, %: C 53.97; Cl 11.55; N 4.45; P 9.72.
C14H13ClNO3P. Calculated, %: C 54.29; Cl 11.45; N
4.52; P 10.0.
Phenyl bis(chloromethyl)phosphinate (Vb). a. A
mixture of 4.04 g of phenylurethan and 5.35 g of bis-
(chloromethyl)phosphinic chloride was heated for 8 h
at 125 C, the solvent was removed in a vacuum, and
the residue was fractionated to give 3.4 g (48%) of
phosphinate Vb, bp 118 118 (0.02 mm Hg), nD20
Phenyl [bis(chloromethyl)phosphinoyl]car-
bamate (IIIb). To a solution of 2.1 g of phosphinate
Ib in 30 ml of anhydrous ether, 1.05 g of phenol was
added. After 24 h, the precipitate that formed was
filtered off to obtain 2.4 g (77%) of compound IIIb,
1.5510. 31P NMR spectrum:
38.0 ppm [5].
P
b. To a solution of 1 g of carbamate IIIb in 30 ml
of anhydrous benzene, 1.0 g of triethylamine was
added dropwise with stirring, and the resulting mix-
ture was kept for 12 h at 20 C. After removal of the
solvent, 0.65 g (76%) of phosphinate Vb was obtained.
1
mp 106 C. IR spectrum (KBr), , cm : 1260 (P=O),
1
1600 (Ph), 1745 (C=O), 3100 (NH). H NMR spec-
2
1
trum (CDCl3), , ppm: 4.0 d (4H, CH2P, JHP 8 Hz),
IR spectrum (KBr), , cm : 1270 (P=O), 1590 (Ph).
1H NMR spectrum (CCl4), , ppm: 3.77 d (4H, CH2P,
7.2 m (5H, Ph), 8.0.3 br.s (H, NH). 31P NMR spec-
trum:
27.61 ppm. Found, %: C 38.37; H 3.52; N
2JPH 9 Hz), 7.13 m (5H, Ph). 31P NMR spectrum:
P
P
5.21; P 10.91. C9H10Cl2NO3P. Calculated, %: C
38.32; H 3.58; N 4.97; P 10.98.
36.7 ppm.
S-Phenyl bis(chloromethyl)thiophosphinate
(Vc). To a solution of 5.8 g of bis(chloromethyl)phos-
phinic chloride in 20 ml of anhydrous benzene, a solu-
tion of 3.56 g of benzenethiol and 3.25 g of triethyl-
amine in 10 ml of anhydrous benzene was added
dropwise with stirring. The resulting mixture was
heated for 2 h at 80 C. The triethylamine hydrochlo-
ride was filtered off, the filtrate was evaporated, and
the residue was distilled in a vacuum to obtain 4.5 g
(55%) of phosphinate Vc, bp 130 132 C
N-Bis(chloromethyl)phosphinoyl-S-phenylcar-
bamate (IIIc). To a solution of 2.9 g of phosphinate
Ib in 15 ml of anhydrous benzene, a solution of 1.7 g
of benzenethiol in 7 ml of anhydrous benzene was
added dropwise. After 24 h, the precipitate that
formed was filtered off to give 3.4 g (73%) of com-
pound IIIc, mp 130 132 C. IR spectrum (KBr),
,
1
cm : 1240 (P=O), 1580 (Ph), 1680 (C O), 3060
1
(NH). H NMR spectrum (CDCl3), , ppm: 3.77 d
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 9 2004

REACTION OF CHLOROMETHYLISO(THIO)CYANATO(THIO)PHOSPHONATES-
1339
(0.05 mm Hg), mp 61 65 C. 1H NMR spectrum
(CD3CN), , ppm: 3.93 d (4H, CH2P, JPH 6 Hz),
7.46 m (5H, Ph). 31P NMR spectrum, P, ppm: 51.6.
Found, %: C 38.07; H 3.54; Cl 27.45; P 12.61; S
13.17. C8H9Cl2OPS. Calculated, %: C 37.65; H 3.56;
Cl 27.79; P 12.14; S 12.56.
C, ppm: 13.20 (CH3CH2), 20.82 (CH3CH2), 30.61
2
1
(SCH2CH2), 37.82 (SCH2), 35.82 d (CH2P, JPC
99.8 Hz), 175.2 (O C=O). 31P NMR spectrum:
P
27.0 ppm. Found, %: C 30.42; H 5.02; Cl 25.64; N
5.07; P 11.24; S 11.54. C7H14Cl2NO2PS. Calculated,
%: C 30.22; H 5.08; Cl 25.49; N 5.04; P 11.13;
S 11.53.
Phenyl bis(chloromethyl)thiophosphinate (IXa).
To a solution of 1.85 g of isothiocyanate VIa in 20 ml
of anhydrous ether, a solution of 0.8 g of phenol in
5 ml of anhydrous ether was added dropwise with stir-
ring. After 1 day, the solvent was removed, and the
residue was recrystallized from ether to obtain 1.4 g
5
2-(Butylsulfanyl)-4-phenoxy-1,3,4 -thiazaphos-
pholine 4-sulfide (XV). To a solution of 1.8 g of O-
phenyl (chloromethyl)isothiocyanatothiophosphonate
and 0.7 g of triethylamine in 20 ml of anhydrous
benzene, 0.6 g of butanethiol was added dropwise
with stirring at 5 C. The resulting mixture was kept
for 12 h, the triethylamine hydrochloride was filtered
off, the solvent was removed, and the residue was
subjected to chromatography on neutral aluminum
oxide (Brockmann II), eluent chloroform to obtain
1.4 g (65%) of thiazaphospholine XV as a light
(76%) of phosphinate IXa, mp 55 57 C. 31P NMR
spectrum:
85 ppm [4].
P
S-tert-Butyl [(chloromethyl)phenoxyphosphi-
noyl]thiocarbamate (XIa). tert-Butanethiol, 1.2 g,
was added to 3.1 g of phosphinate Ia. After 1 day, the
reaction mixture crystallized and was washed with
ether to obtain 3.9 g (92%) of compound XIa, mp 94
1
99 C. IR spectrum (KBr), , cm : 1260 (P=O), 1590
1
(Ph), 1680 (C=O), 3060 (NH). H NMR spectrum
(CCl4), , ppm: 1.47 s (9H, CH3), 3.88 d (2H, CH2P,
yellow transparent oil, n2D0 1.5340. IR spectrum (KBr),
2JPH 10 Hz), 7.1 m (5H, Ph), 9.47 br.s (H, NH). 31P
1
1
, cm : 1515 (C=N), 1590 (Ph). H NMR spectrum
[(CD3)2CO], , ppm: 0.98 t (3H, CH3CH2, 2JHH 7 Hz),
1.48 m (2H, CH3CH2), 3.33 m (2H, SCH2), 3.92 m
NMR spectrum:
16.7 ppm. Found, %: C 44.42; H
P
4.88; Cl 11.34; N 4.26; P 9.76; S 9.47. C12H17Cl
NO3PS. Calculated, %: C 44.79; H 5.34; Cl 11.00; N
4.35; P 9.62; S 9.96.
(2H, CH2P), 7.33 m (5H, Ph). 31P NMR spectrum:
P
120.0 ppm. Found, %: P 9.65; S 30.43. C12H16NOPS3.
Calculated, %: P 9.76; S 30.30.
S-Butyl [(chloromethyl)phenoxyphosphinoyl]-
thiocarbamate (XIb). A mixture of 1.3 g of isocya-
nate Ia and 0.5 g of butanethiol was allowed to stand
for 24 h at 20 C. Recrystallization from diethyl ether
gave 0.8 g (44%) of compound XIb, mp 67 69 C.
4-Phenoxy-1,3,4 5-thiazaphospholidin-2-one
4-sulfide (XIX). A mixture of 2.0 of isothiocyanato-
thiophosphonate XIII and 0.35 g of ethanol was
allowed to stand for 1 months at 20 C. The precipitate
that formed was filtered off and washed with benzene
to obtain 0.5 g (27%) of compound XIX, mp 163
1
IR spectrum (KBr), , cm : 1260 (P=O), 1685(C=O),
1
3070 (NH). H NMR spectrum [(CD3)2SO], , ppm:
2
0.89 t (3H, CH3CH2, JHH 7.5 Hz), 1.36 m (2H,
CH3CH2, 1.54 m (2H, SCH2CH2), 2.86 t (2H, SCH2,
2
2JHH 7 Hz), 4.2 d (2H, CH2P, JPH 10.7 Hz, 7.32 m
(5H, Ph), 10.6 br.s (H, NH). 31P NMR spectrum:
1
165 C. H NMR spectrum [(CD3)2SO], , ppm (J,
P
2
2
Hz): 4.22 m [1H, PC1HA, J(PHA) 17.2, J(HAHB)
16.71 ppm. Found, %: C 44.48; H 5.46; Cl 10.49; N
4.28; P 8.56; S 10.01. C7H14Cl2NO2PS. Calculated,
%: C 44.79; H 5.34; Cl 11.01; N 4.35; P 9.63; S 9.96.
14.3], 4.02 m [1H, PCHB, J(PHB) 5.1). 7.22 m (H7,
2
3J(H7H8) 7.7, 4J(H7H9) 1.4], 7.44 m [1H, H8,
3J(H8H9) 7.4], 7.27 m (H, H9 7.4), 10.02 br.s (1H,
NH). 13C NMR spectrum [(CD3)2SO], C, ppm (J,
S-Butyl [bis(chloromethyl)phosphinoyl]thio-
carbamate (XIc). Butanethiol, 1.2 g, was added to
2.5 g of isocyanate Ib. After 30 min, the crystals that
formed were washed with ether to obtain 3.4 g (93%)
Hz): 169.54 d (C=O, JNC 23.4), 32.43 m [C5,
2
of compound XIc, mp 111 114 C. IR spectrum (KBr), 2J(PC5H8) 1.2, JCH 148.0], 149.68 m (C6, 2JPOC 10.5),
1
1
[C7, 3J(POC6C7) 4.8, JCH 166.9,
, cm : 1240 (P=O), 1670 (C=O), 3070 (NH). H
NMR spectrum [(CD3)2SO], , ppm: 0.54 t (3H,
121.36
m
3J(C7C8C9H9) 8.6, J(C7C7C7 H7) 3.3], 128.80 m (C8,
4J(POC6C7C8) 1.4, 3J(C8C7C8 H8 ) 8.0], 125.64 m (C9,
3
2
CH3CH2, JHH 7 Hz), 1.04 m (2H, CH3CH2), 1.20 m
(2H, SCH2CH2, 2.31 t (2H, SCH2, JHH 7 Hz), 3.21,
2
5J(POC6C7C8C9) 1.9, J(C9C8C7H7) 5.2]. 31P NMR
3
2
3.71 2d, (4H, CH2P, JPH 13.4 and 11.9 Hz), 6.9,
10.35 br.s (1H, NH). 13C NMR spectrum [(CD3)2SO],
spectrum: P 81.66 ppm. Mass spectrum, m/z (Irel, %):
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 9 2004

1340
KHAILOVA et al.
(electron impact, 70 eV): 245 [M]+ (67.9), 202 [M
NHCO]+ (2.1), 199 [M CH2S]+ (2.4), 156 [PhOPS]+
(100.0), 152 [M PhO]+ (3.7), 123 [C7H8P]+ (70.4),
110 [C6H6S]+ (13.5), 94 [C6H6O]+ 954.5), 78 [PSNH]+
(11.3), 77 [C6H5]+ (19.6), 63 [PS]+ (21.7), 47 [PO]+
(1.2). Found, %: C 39.84; H 3.17; N 5.80; P 12.66;
S 26.70. C8H8NO2PS2. Calculated, %: C 39.17; H
3.29; N 5.71; P 12.63; S 26.15.
REFERENCES
1. Shokol, V.A. and Kozhushko, B.N., Izotsianaty fosfora
(Phosphorus Isocyanates), Kiev: Naukova Dumka, 1992.
2. Pudovik, M.A., Saakyan, G.M., Khairullin, V.K., Khai-
lova, N.A., and Pudovik, A.N., Izv. Ross. Akad. Nauk,
Ser. Khim., 1999, no. 4, p. 810.
3. Tomaschewski, G. and Zanke, D., Z. Chem., 1970,
vol. 10, no. 3, p. 117.
4. Edmundson, R.S., Dictionary of Organophosphorus
Compounds, London: Chapman and Hall, 1988, pp. 50,
152.
ACKNOWLEDGMENTS
The work was financially supported by the Russian
Foundation for Basic Research (project no. 00-03-
32837).
5. Kosolapoff, G.M. and Maier, L., Organic Phosphorus
Compounds, New York: Wiley, 1975.
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