Synthesis and structure of 1,3,4-oxaza(thiaza)phospholines

Article abstract of DOI:10.1023/A:1020746615033

Bis(chloromethyl)phosphinic (-phosphinothioic) iso(thio)cyanates add secondary amines to form N-phosphorylated (thio)ureas, which cyclize in the presence of a base to 1,3,4λ⁵-oxaza(thiaza)phospholines. Phosphorylated ureas obtained by addition of ammonia and primary amines to chloromethylphosphonic (-phosphinic) isocyanates cyclize to give 1,4,2-diazaphospholidines or 1,3,4-oxazaphospholines. Prototropic transformations in the series of 1,3,4λ⁵-oxazaphospholines were revealed; the electronic and steric structures of the tautomers were studied. Chloromethylphosphonothioic (-phosphinothioic) isothiocyanates add primary amines to give 1,3,4λ⁵-thiazaphospholines.

Full text of DOI:10.1023/A:1020746615033

Russian Journal of General Chemistry, Vol. 72, No. 7, 2002, pp. 1071 1081. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 7, 2002,
pp. 1145 1156.
Original Russian Text Copyright
2002 by Khailova, Krepysheva, Saakyan, Bagautdinova, Shaimardanova, Zyablikova, Azancheev, Litvinov,
Gubaidullin, Zverev, M. Pudovik, A. Pudovik.
Synthesis and Structure of 1,3,4-Oxaza(thiaza)phospholines
N. A. Khailova, N. E. Krepysheva, G. M. Saakyan, R. Kh. Bagautdinova,
A. A. Shaimardanova, T. A. Zyablikova, N. M. Azancheev, I. A. Litvinov,
A. T. Gubaidullin, V. V. Zverev, M. A. Pudovik, and A. N. Pudovik
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy
of Sciences, Kazan, Tatarstan, Russia
Received October 19, 2000
Abstract Bis(chloromethyl)phosphinic (-phosphinothioic) iso(thio)cyanates add secondary amines to form
N-phosphorylated (thio)ureas, which cyclize in the presence of a base to 1,3,4 5-oxaza(thiaza)phospholines.
Phosphorylated ureas obtained by addition of ammonia and primary amines to chloromethylphosphonic
(-phosphinic) isocyanates cyclize to give 1,4,2-diazaphospholidines or 1,3,4-oxazaphospholines. Prototropic
transformations in the series of 1,3,4 5-oxazaphospholines were revealed; the electronic and steric
structures of the tautomers were studied. Chloromethylphosphonothioic (-phosphinothioic) isothiocyanates
add primary amines to give 1,3,4 5-thiazaphospholines.
Our present efforts are aimed at developing syn-
thetic routes to heterocyclic phosphorus compounds
containing endocyclic P C bonds. These routes are
based on intramolecular transformations of polyfunc-
tional derivatives of four-coordinate phosphorus, in-
cluding chloromethyl groups in combination with
other structural fragments. By such procedures, we
were able to prepare various saturated and unsaturated,
mono- and bicyclic polyheterophosphacyclanes [1 5].
One of the simplest and most convenient routes to
functionally substituted chloromethylphosphonates
(-phosphonothioates, -phosphinates, phosphinothio-
ates) is addition of protic nucleophiles to the corre-
sponding phosphorylated iso(thio)cyanates. The reac-
tion of ethyl 1-alkoxy-1-chloroalkylhosphonoisocya-
natidates with primary amines was reported in [6].
Previously we showed that phosphorylated (thio)ureas
cyclize under the action of bases to give 1,3,4-aza-
phospholines [1, 7]. To extend the synthetic potential
of this approach, examine the conditions of cycliza-
tion of phosphorylated ureas (or thioureas), and pre-
with the chloromethyl group, with elimination of HCl
and cyclization into 1,3,4 -oxaza(thiaza)phos-
pholines IIIa IIId.
5
X
X
Y
(ClCH2)2PNCY + R1R2NH
(ClCH2)2PNHCNR1R2
Ia, Ib
IIa IIe
X
N
ClCH2
C NR1R2
B
P
B HCl
Y
IIIa IIId
I, X = Y = O (a), X = Y = S (b); II, X = Y = O, R1 =
R2 = Et (a); X = Y = O, R1 = R2 = Pr (b); X = Y = O,
R1 = R2 = Bu (c); X = Y = O, R1, R2 = N(CH2CH2)2O (d);
X = Y = O, R1, R2 = N(CH2)5 (e); III, X = Y = O, R1 =
R2 = Et (a); X = Y = O, R1, R2 = N(CH2CH2)2O
(b); X = Y = O; R1, R2 = N(CH2)5 (c); X = Y = S, R1,
R2 = N(CH2CH2)2O (d).
5
Compounds IIa IIe and IIIa IIId were prepared
in good yields; their structure was determined by
NMR and IR spectroscopy. The characteristic absorp-
pare new types of 1,3,4 -oxaza(thiaza)phospholines,
we studied the reactions of some primary and second-
ary amines with phosphorylated iso(thio)cyanates.
1
tion bands of the carbonyl (1670 1690 cm ) and NH
1
We found that bis(chloromethyl)phosphinic (-phos-
phinothioic) iso(thio)cyanates Ia, Ib readily add sec-
ondary amines to give N-phosphorylated (thio)ureas
IIa IIe. In the presence of a base, the oxygen atom
of the carbonyl group or the sulfur atom of the thio-
carbonyl group undergoes intramolecular alkylation
(3100 cm ) groups present in the IR spectra of phos-
phorylated ureas are absent in the spectra of IIIa IIId,
1
but a band appears at 1610 1625 cm , belonging to
the endocyclic C=N bond. Formation of phospholines
IIIa IIId is also confirmed by a downfield shift of
the 31P NMR signals. It should be noted that the reac-
1070-3632/02/7207-1071$27.00 2002 MAIK Nauka/Interperiodica

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KHAILOVA et al.
5
tion of isothiocyanate Ib with morpholine is very fast
and strongly exothermic; it directly yields IIId. This
is due to easier alkylation of the thiocarbonyl sulfur,
compared to carbonyl oxygen.
energies of isomeric 1,3,4 -oxazaphospholine VIIb
5
and 1,4,2 -diazaphospholidine VIb, and also of
phospholidine VIII and oxazaphospholine IX (ab ini-
tio, HF/3-21G , GAMESS program [8], and MNDO
*
and PM3 [9, 10]).
Reactions of phenyl chloromethylphosphonoiso-
cyanatidate IV with primary amines yield N-phospho-
rylated ureas Va Ve containing two labile protons: at
the bridging and terminal nitrogen atoms. In this case,
two pathways of intramolecular alkylation are possi-
ble: that of the terminal nitrogen atom, yielding the
O7
O7
O
3
3
8
8
2 N
2 N
N
MeOP
9
9
H
C4 O5
H
MeOP
MeOP
6
C4 NH2
O5
IXa
C N
O
H
N6
1
1
H
5
VIII
IXb
saturated 1,4,2 -diazaphospholidine system (com-
pounds VIa and VIb, pathway a), and that of the car-
bonyl oxygen atom, yielding 1,3,4 -oxazaphos-
pholines VIIa VIId (pathway b). We found that both
pathways are actually realized, depending on the pres-
ence and structure of the substituent R2 at the terminal
nitrogen atom.
All the three methods show that the phospholidine
5
structure VIII is preferable relative to the oxazaphos-
1
pholine structure IX (by 87, 55, and 78 kJ mol ,
respectively). The MNDO and PM3 calculations also
indicate that the saturated diazaphospholidine hetero-
cycle VIb is more stable than the unsaturated oxaza-
1
phospholine derivative VIIb (by 31 and 70 kJ mol ,
O
O
O
R1
R1
R2NH2
respectively). Thus, the diazaphospholidine form is
more stable for both derivatives. Thus, the cycliza-
tions under consideration are not thermodynamically
controlled. Preferable formation of 1,3,4-oxazaphos-
pholine structure VIIb rather than more stable diaza-
phospholidine structure VIb may be due to kinetic
control of this reaction or to steric hindrance produced
by the bulky tert-butyl group at the terminal nitrogen
atom.
PNHCNHR2
PNCO
ClCH2
ClCH2
Va Ve
Ia, IV
O
NH
a
b
R1
P
C O
N R2
B
VIa, VIb
B HCl
O
N
R1
It should be noted that compounds VIIa VIId pre-
pared from N-phosphorylated N -substituted ureas
contain an amidine group, which suggests the possi-
C NHR2
P
O
VIIa VIId
5
bility of a tautomeric equilibrium between the 1,3,4 -
IV, R1 = PhO; V, R1 = PhO, R2 = H (a); R1 = PhO, R2 =
t-Bu (b); R1 = ClCH2, R2 = H (c); R1 = ClCH2, R2 = t-Bu
(d); R1 = ClCH2, R2 = Ph (e); VI, R1 = PhO, R2 = H (a);
R1 = ClCH2, R2 = H (b); VII, R1 = PhO, R2 = H (a);
R1 = PhO, R2 = t-Bu (b); R1 = ClCH2, R2 = t-Bu (c);
R1 = ClCH2, R2 = Ph (d).
5
oxazaphospholine form A and 1,3,4 -oxazaphospho-
lidine form B. Indeed, both forms were detected by
5
31P NMR spectroscopy. Each of 1,3,4 -oxazaphos-
pholines VIIa VIId gives two downfield singlets
(see Experimental). For VIIb, the chemical shifts
P
(ppm) are 53.41 (A, 88.7%) and 48.36 (B, 11.3%).
The tautomeric equilibrium is also manifested in the
Pathway a is realized with N-(bischloromethyl-
phosphinyl)urea Vc containing a primary amino group.
After its treatment with triethylamine, we isolated
1
13C and H NMR spectra (Table 1, Experimental).
O
P
O
P
5
2-chloromethyl-2,5-dioxo-1,4,2 -diazaphospholidine
R1
R1
N
NH
C NR2
VIb. Introduction of alkyl or aryl substituents at
the terminal nitrogen atom of phosphorylated urea V
C NHR2
5
O
O
yields 1,3,4 -oxazaphospholines VIIa VIId as the
A
B
only products. N-(O-Phenylchloromethylphosphonyl)-
urea Va cyclizes by two pathways to give a mixture
The electronic structures and geometries of the
5
5
of 1,3,4 -diazaphospholine VIIa and 1,4,2 -diaza-
phospholidine VIa. Compound VIa was isolated
analytically pure.
tautomers were studies by semiempirical and ab initio
*
(HF/3-21G , GAMESS program) calculations. As ex-
amples, we also took oxazaphospholines VIIb and IX
with endocyclic and exocyclic C=N bonds. The total
energy of isomers IXa and IXb is 778.858767 and
778.848057 au, respectively, i.e., the structure with
To examine the possibillity of predicting the cycli-
zation pathway of phosphorylated ureas, we have per-
formed quantum-chemical calculations of the relative
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 7 2002

SYNTHESIS AND STRUCTURE OF 1,3,4-OXAZA(THIAZA)PHOSPHOLINES
1073
the endocyclic C=N bond appeared to be more stable
Table 1. 31P and 13C NMR spectra of tautomers A and B
of VIIb
1
1
by 28.1 kJ mol . Similar difference ( 25 kJ mol )
was obtained by MNDO and PM3 calculations [9, 10].
For VIIb, according to MNDO calculations, form B
5
5
O
O
8
8
O
O
7
4
7
6
6
P
P
1
1
1
H
H
H
H
H CH
4CH3
is more stable (by 10 kJ mol ), whereas PM3 calcu-
N
NH
3
C
C
2
2
O C N3 C CH3
O C N3 C CH3
lations give an opposite result: form A is more stable
1
by 18 kJ mol . Apparently, the total energies of these
CH3
CH3
A
B
tautomers are close, but form A is somewhat more
stable, as also indicated by NMR data. Figure 1 shows
the steric structures of tautomers A and B of VIIb.
Atom
A, , ppm (J, Hz)
B, , ppm (J, Hz)
31P
C1
53.41
59.37 (JPC 98.5,
48.36
59.37 (JPC 98.5,
The atomic charges, atomic populations of HOMO,
and bond lengths and orders in VIII and tautomers A
1
1
*
and B of IX, calculated ab initio (HF/3-21G ), are
1
1
JC H 153.5, 155.6)
JC H 153.5, 155.6)
compared in Tables 2 and 3. All the structures are
characterized by the presence of very polar bonds with
the largest negative charges on the nitrogen atoms;
in both heterocycles, the negative charge on the three-
coordinate N atom is larger than that on the imine N
atom. Passing from tautomer A to B should also be
accompanied by a shift of the electron density from
the phosphorus atom. The highest occupied molecular
orbitals in these structures appreciably differ both in
energy and in composition. The HOMO ( CO) energy
in VIII is 10.88 eV. The HOMO energy in IXa
( 8.73 eV) is considerably lower (in absolute value)
compared to IXb ( 10.33 eV), but the LUMO ener-
gies in these tautomers are close (5.41 and 5.96 eV,
respectively). The HOMO of IX is mainly localized
C2
C3
C4
C5
C6
C7
161.95 (2JPC 8.5)
162.16 (2JPC 8.5)
2
2
52.21
28.34 (JC H 127.1)
150.65 (2JPOC 8.5)
53.35
29.09 (JC H 126.6)
150.65 (2JPOC 8.5)
4
4
5
5
6
6
6 6
120.72 (JC H 164.3)
120.49 (JC H 164.3)
7
7
7 7
129.53 (JC H 162.4,
128.16 (JC H 162.4,
3
3
7
7
7 7
JC H 8.5)
JC H 8.5)
C8
127.76 (JC H 163.0,
123.63 (JC H 163.0,
8
8
8 8
3
3
8
8
8 8
JC H 7.4)
JC H 7.4)
Table 2. Effective atomic charges and atomic populations
of HOMO of VIII and tautomers IXa and IXb (HF/3-21G*
calculations)
Chargea
HOMO population
VIII IXa IXb
on the endo- and exocyclic nitrogen atoms. It is a
*
Atom
combination of antibonding orbitals
,
CN, and
nN. The interference of the orbital interaCcNtions [11] of
VIII
IXa
IXb
*
nN with
and
results in that the contribution
C1
P2
0.549 0.499 0.482 0.063 0.001 0.009
1.630 1.521 1.604 0.001 0.029 0.018
1.035 0.825 1.022 0.005 0.896 0.477
1.142 1.091 1.052 0.697 0.075 0.178
0.642 0.675 0.682 1.058 0.070 0.172
0.907 0.961 0.775 0.007 0.447 0.997
0.613 0.613 0.611 0.011 0.399 0.064
0.724 0.723 0.723 0.001 0.121 0.041
CN
of the central atomCoNf the N=C N triad to HOMO of
N3
C4
O5
N6
O7
O8
both tautomeric forms is insignificant.
The electronic structure of this triad was discussed
previously [11, 12]. Note that tautomer B with the
exocyclic multiple bond also has two isomeric struc-
tures, of which the structure with the cisoid arrange-
ment of the OCNH atoms is more stable. The structure
with the transoid arrangement of the OCNH atoms
a
In electron charge units.
1
Table 3. Bond lengths (d) and orders ( p) in molecules
of VIII and of tautomers IXa and IXb (HF/3-21G*
calculations)
(E 787.838219 au) is less stable (by 25.8 kJ mol )
and will not be considered further. The bond lengths
and orders in the molecules in question are compared
in Table 3. First, it should be noted that the orders of
all the bonds in structure B are low and do not exceed
0.85. Proton migration to the N3 atom is accompanied
not only by apparent elongation of the N3 C4 bond,
but also by slight elongation of the P3 N3 and C4 O5
bonds. These changes are manifested more clearly in
the bond orders. According to calculations, the ar-
rangement of all the five atoms in both tautomers is
approximately coplanar. The exocyclic C O bond is
in the gauche position relative to the P=O bond; the
d,
IXa
p
Bond
VIII
IXb
VIII
IXa
IXb
C1 P2 1.812 1.835 1.810 0.786 0.740 0.774
P2 N3 1.657 1.645 1.643 0.843 1.001 0.863
N3 C4 1.401 1.279 1.395 0.868 1.577 0.875
C4 O5 1.209 1.371 1.380 1.789 0.927 0.844
C1 O5 1.466 1.475 1.460 0.847 0.764 0.793
C4 N6 1.364 1.325 1.239 0.909 0.981 1.796
P2=O7 1.462 1.462 1.461 1.940 1.940 1.936
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 7 2002

1074
KHAILOVA et al.
Fig. 1. Steric structure of tautomers A and B of VIIb (PM3 calculations).
torsion angle C9O8P2O7 in forms A and B is 22.2
and 24.6 , respectively.
jected to hydrolysis. The hydrolysis products are
crystalline compounds sparingly soluble in organic
solvents. Based on elemental analysis and spectra,
these products were identified as isouroniomethyl-
(chloromethyl)phosphinates Xa and Xb. The 31P NMR
spectrum of each of these inner salts contains
Phosphinate Ia reacts with primary amines (tert-
butylamine, aniline) similarly to phosphonate IV.
However, we failed to isolate cyclic products VIIc
and VIId analytically pure. The 31P NMR spectrum
one singlet,
(ppm) 23 (Xa) and 24 (Xb); their IR
P
of each of the products contains two signals with
P
1
spectra contain absorption bands (cm ) at 1230 1240
in the ranges 64 66 and 58 60 ppm in a 3.5 : 1
ratio, which suggests that these compounds also exist
in solutions as tautomeric mixtures. According to the
1H NMR and IR spectra, the cyclic products contain
small amounts of the amine hydrochlorides. To con-
firm the structures of the products, they were sub-
(PO2), 1565 1580, and 2600 2780 (NH+2).
NH
O
VIIc, VIId + H2O
ClCH2PCH2OCNHR
OH
ClCH2
O
O
NH2
+
PCH2OC
NHR
Xa, Xb
X, R = t-Bu (a), Ph (b).
Phosphinothioate Ib and O-phenyl chloromethyl-
phosphonoisothiocyanatidothioate XI react with pri-
5
mary amines to form 1,3,4 -thiazaphospholines XIIa
and XIIb. The compositions of XIIa and XIIb were
confirmed by elemental analysis, and their structures
were determined by 1H, 31P, and 13C NMR and
IR spectroscopy. The IR spectra of thiazaphospholines
XIIa and XIIb contain absorption bands at 1565
1
1575 cm , characterizing vibrations of the endocyclic
C=N bond. According to the spectral data, phospho-
lines XIIa and XIIb in solutions occur in a single
tautomeric form.
Fig. 2. Geometry of an independent molecule of XIIb
in the crystal.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 7 2002

SYNTHESIS AND STRUCTURE OF 1,3,4-OXAZA(THIAZA)PHOSPHOLINES
1075
S
S
S
R
R
P NCS + t-BuNH2
P NHCNHBu-t
ClCH2
ClCH2
Ib, XI
S
P
N
R
C NHBu-t
B
S
B HCl
XIIa, XIIb
XI, R = PhO; XII, R = ClCH2 (a), R = PhO (b).
The crystal and molecular structure of 2-tert-butyl-
5
amino-4-phenoxy-4-thioxo-1,3,4 -thiazaphospholine
XIIb was studied by single crystal X-ray diffrac-
tion. Two independent molecules of XIIb in the crys-
tal have approximately the same geometries; one of
them is shown in Fig. 2. The ring conformation in this
molecule is P-envelope, although, taking into account
the presence of the C=N bond, the C5-envelope con-
formation could be expected. The torsion angle about
the C2=N3 bond is 12.7(2) , and that about the S1 C2
bond is 0.5(2) . In the other molecule, the ring con-
formation is twist, with the above-mentioned torsion
angles being 7.4(3) and 7.1(2) , respectively. The
phenoxy group at P occupies the axial position, which
is typical of phosphacyclanes with endocyclic P O
and P N bonds. The bond lengths and bond angles in
the independent molecules coincide within experimen-
tal error. The exocyclic P O bond is somewhat elon-
gated [average 1.605(2) ] as compared to the values
typical of four-coordinate phosphorus, whereas the
endocyclic P N bond is somewhat shortened [average
1.638(8) ], which may be due to the anomeric effect.
Fig. 3. System of hydrogen bonds in the crystal of XIIb.
The other geometric parameters have usual values.
The crystal packing of the molecules is determined
by intermolecular hydrogen bonds N H S with the
sulfur atom of the thiophosphoryl group (Fig. 3).
The parameters of the N6A H S4B (x, y 1, z) bond
are as follows: N6A H 1.08(2), N6A S4B 3.382(2),
H S4B 2.37(2) ; angle N6A H S4B 155(2) . The
parameters of the N6B H S4A" (x 1, y + 1, z) bond
are as follows: N6B H 0.89(2), N6B S4A" 3.538(2),
H S4A" 2.75(2)
; angle N6B H S4A" 149(2) .
The molecules form infinite zigzag chains running
along the x-axis. The atomic coordinates, bond
lengths, bond angles, and torsion angles for XIIb are
listed in Tables 4 6.
Table 4. Atomic coordinates in the structure of XIIb and the equivalent isotropic temperature factors of nonhydrogen
atoms B = 4/3 (aij)B(i, j) ( 2) and isotropic temperature factors of hydrogen atoms Biso
First molecule
Second molecule
Atom
x
y
z
B, Biso
x
y
z
B, Biso
S1
1.42930(7)
1.02812(7)
1.19420(6)
1.2573(2)
1.1839(2)
1.3259(2)
1.2968(2)
1.3361(3)
1.2465(3)
1.3358(3)
1.1065(3)
1.2304(3)
1.2619(3)
1.3838(3)
1.3838(3)
1.2720(4)
0.00858(6)
0.22932(7)
0.13009(6)
0.1664(2)
0.0339(2)
0.2255(2)
0.0966(2)
0.1497(2)
0.3188(2)
0.4460(2)
0.3491(3)
0.2576(3)
0.2965(2)
0.3674(3)
0.4947(3)
0.5431(3)
0.63455(4)
0.78426(5)
0.77049(4)
0.8544(1)
0.7576(1)
0.6942(1)
0.7036(1)
0.6741(2)
0.7509(1)
0.7227(2)
0.7330(2)
0.8491(2)
0.9049(1)
0.8861(2)
0.9420(2)
1.0112(2)
4.58(2)
5.76(2)
3.85(1)
4.76(4)
3.98(5)
3.64(4)
3.38(5)
4.63(6)
3.81(5)
5.85(8)
6.28(7)
5.36(7)
4.16(5)
5.43(7)
7.75(8)
8.19(9)
0.97194(7)
0.60690(7)
0.76291(6)
0.8530(2)
0.7256(2)
0.8277(2)
0.8239(2)
0.9021(3)
0.7194(3)
0.7877(4)
0.5935(4)
0.6837(4)
0.7973(2)
0.8034(3)
0.7592(3)
0.7093(3)
0.10110(7)
0.33112(7)
0.29298(6)
0.4242(2)
0.2125(2)
0.0683(2)
0.1320(2)
0.1916(3)
0.0698(3)
0.0018(4)
0.0056(4)
0.2122(3)
0.5367(2)
0.5427(3)
0.6601(3)
0.7669(3)
0.59906(4)
0.51690(4)
0.56572(4)
0.5556(1)
0.6708(1)
0.7692(1)
0.6878(1)
0.5121(2)
0.8556(2)
0.9279(2)
0.8580(2)
0.8667(2)
0.5905(1)
0.6748(2)
0.7056(2)
0.6550(2)
4.91(2)
4.58(2)
3.41(1)
4.39(4)
3.52(4)
4.65(5)
3.64(5)
4.39(6)
4.71(6)
7.9(1)
S4
P4
O11
N3
N6
C2
C5
C7
C98
C10
C12
C13
C
7.7(1)
6.52(8)
3.70(5)
4.90(6)
5.82(7)
5.47(7)
C14
C15
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1076
KHAILOVA et al.
Table 4. (Contd.)
First molecule
Second molecule
Atom
x
y
z
B, Biso
x
y
z
B, Biso
C16
C167
H13
H14
H15
H16
H
1.1548(4)
1.1483(3)
1.430(2)
1.465(2)
1.447(2)
1.288(4)
1.068(3)
1.088(2)
1.313(3)
1.378(2)
1.349(3)
1.422(3)
1.285(3)
1.135(3)
1.061(3)
1.060(3)
1.196(3)
1.332(3)
1.170(3)
0.4707(3)
0.3454(3)
0.257(2)
0.325(2)
0.518(2)
0.624(3)
0.506(3)
0.297(2)
0.168(2)
0.224(2)
0.493(3)
0.418(3)
0.511(2)
0.390(3)
0.266(3)
0.405(2)
0.319(2)
0.227(3)
0.181(3)
1.0288(2)
0.9754(2)
0.653(1)
0.834(1)
0.921(1)
1.056(2)
1.074(2)
0.982(1)
0.631(1)
0.693(1)
0.656(2)
0.731(2)
0.757(1)
0.663(2)
0.748(2)
0.768(1)
0.884(1)
0.856(2)
0.866(2)
7.67(9)
5.65(7)
5.7(6)
5.6(6)
4.5(5)
13(1)
10.3(9)
5.6(6)
6.7(7)
5.9(6)
8.3(8)
7.5(7)
6.4(6)
9.4(9)
8.9(8)
6.4(7)
6.5(7)
9.4(9)
7.6(7)
0.7030(3)
0.7459(3)
0.905(2)
0.844(2)
0.761(3)
0.693(3)
0.671(2)
0.744(2)
0.962(2)
0.871(2)
0.826(3)
0.730(3)
0.889(4)
0.537(3)
0.619(3)
0.565(3)
0.637(3)
0.618(3)
0.762(3)
0.7562(3)
0.6421(3)
0.020(2)
0.457(2)
0.658(2)
0.853(2)
0.819(2)
0.632(2)
0.237(2)
0.136(2)
0.077(2)
0.005(3)
0.074(3)
0.001(3)
0.098(3)
0.040(3)
0.249(3)
0.207(2)
0.269(3)
0.5718(2)
0.5392(2)
0.767(1)
0.711(1)
0.764(1)
0.681(1)
0.540(1)
0.483(1)
0.471(1)
0.481(1)
0.918(2)
0.983(2)
0.917(2)
0.918(2)
0.848(2)
0.815(2)
0.820(2)
0.924(2)
0.857(2)
5.30(7)
4.50(6)
6.1(6)
5.0(5)
6.5(7)
6.5(7)
4.9(5)
4.9(5)
4.3(5)
4.7(5)
7.4(7)
7.0(7)
13(1)
8.9(8)
12(1)
8.9(8)
7.9(8)
7.1(7)
8.7(8)
H17
H51
H52
H81
H82
H83
H91
H92
H93
H101
H102
H103
Table 5. Bond lengths (d) and angles ( ) in independent molecules of XIIb
d,
d,
Bond
Bond
first molecule
second molecule
first molecule
second molecule
S1 C2
S1 C5
S4 P4
P4 O11
P44 N3
O11 C12
N3 C2
N6 C2
N6 C7
1.793(2)
1.798(2)
1.924(1)
1.607(2)
1.634(2)
1.803(2)
1.396(3)
1.303(3)
1.322(3)
1.488(3)
1.793(2)
1.790(3)
1.927(1)
1.602(2)
1.642(2)
1.806(2)
1.397(3)
1.297(3)
1.331(3)
1.486(3)
N6 H6
1.07(2)
0.89(2)
C7 C8
1.520(4)
1.513(4)
1.520(3)
1.372(4)
1.371(3)
1.403(4)
1.348(4)
1.340(5)
1.380(4)
1.530(4)
1.496(5)
1.506(4)
1.378(4)
1.374(3)
1.387(4)
1.369(4)
1.375(4)
1.368(4)
C77 C9
C12C10
C12 C13
C13 C17
C14 C14
C15 C15
P
C5
C
C16
C16 C17
Angle
, deg
Angle
, deg
C2S1C5
S4P4O11
S4P4N3
S4P4C5
94.2(1)
114.94(7)
118.05(8)
113.8(1)
100.5(1)
105.8(1)
102.0(1)
124.4(2)
113.2(2)
126.3(2)
115(1)
94.1(1)
113.51(7)
115.88(7)
117.7(1)
107.5(1)
98.5(1)
101.7(1)
123.6(1)
113.1(1)
127.1(2)
111.1(1)
121.1(1)
120.8(2)
114.2(2)
125.0(2)
S1C5P4
106.2(1)
105.3(2)
109.7(2)
109.9(2)
110.7(2)
109.3(2)
111.8(2)
118.7(2)
119.1(2)
122.1(2)
115.9(2)
122.1(3)
120.8(3)
119.7(3)
119.5(3)
105.7(1)
105.0(2)
108.5(2)
110.9(2)
112.7(2)
108.2(3)
111.4(3)
118.4(2)
120.2(2)
121.3(2)
117.9(2)
121.7(3)
118.6(3)
121.3(2)
119.1(2)
N6C7C8
N6C7C9
N6C7C10
C8C7C9
O11P4N3
O11P4C5
N3P4C5
P4O11C12
P4N3C2
C2N6C7
C2N6H6
C7N6H6
S1C2N3
S1C2N6
N3C2N6
C8C7C10
C9C7C10
O11C12C13
O11C12C17
C13C12C17
C12C13C14
C13C14C15
C14C15C16
C15C16C17
C12C17C16
117(1)
120.6(2)
114.2(1)
125.3(2)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 7 2002

SYNTHESIS AND STRUCTURE OF 1,3,4-OXAZA(THIAZA)PHOSPHOLINES
Table 6. Torsion angles ( ) in independent molecules of XIIb
, deg
1077
, deg
second molecule
Angle
Angle
first molecule
second molecule
first molecule
C5S1C2N3
S1C2N3P4
C2N3P4C5
N3P4C5S1
C2S1C5P4
S4P4N3C2
O11P4N3C2
0.5(2)
12.7(2)
19.1(2)
18.3(2)
11.6(1)
144.6(2)
89.6(2)
7.1(2)
7.4(3)
S4P4O11C12
N3P4O11C12
C5P4O11C12
S4P4C5S1
39.0(2)
166.8(2)
87.4(2)
146.54(9)
86.4(1)
57.9(2)
71.6(2)
176.8(2)
149.16(9)
88.6(1)
18.1(2)
21.4(2)
16.5(1)
147.9(2)
84.8(2)
O11P4C5S1
P4O11C12C13
98.2(3)
92.8(2)
1
Table 7. H ( , ppm), 31P [ P, ppm (J, Hz)], and 13C [ C, ppm (J, Hz)] NMR spectra of IIId, XIIa, and XIIba
Atom
IIId
XIIa
XIIb
31P
C1
106.0
107.00
31.94 (JPC 30.5, JC H 145.5,
119.38
1
1
1
1
1
1
33.09 (JPC 31.1, JC H 145.2,
34.64 (JPC 55.5, JC H 145.2,
148.8)
164.90
3
1
3
148.8)
149.3, JC PC H 3.2)
C2
C3
169.83 (2JPC 5.5, JC SC H 3.6,
165.55 (2JPC 1.2, JC SC H 4.2,
JC SC H 2.3)
3
3
2
2
1
e
2
2
1 e
3
3
2
1
a
2
1 a
JC SC H 2.0)
3
3
3
3
43.98 (JPC 68.5, JC H 152.7,
43.34 (JPC 68.2, JC H 152.5,
3
3
3
1
3
1
JC PC H 1.7)
JC PC H 1.5)
C4
C5
48.78 (JC H 139.5)
55.04 (2JC NH 3.5, JC C H 3.6)
55.43
2
4
4
4 5
66.27 (5JPNC NC C 7.8, JC H
29.27 (JC H 127.9, JC C NH 4.4,
28.53 (JC H 127.0, JC C NH
3
3
2
4
5
5
5
5
4
5
5 4
3
3
5
4
5
5 4 5
144.1)
JC C C H 3.7)
2.8, JC C C H 4.6)
HA
HB
HA
HB
3.77 (2JPH 0.5, JH H
14.4)
3.62 (2JPH 1.1, JH H
13.8)
12.5)
3.50 (2JPH 3.9, JH H 13.0)
2
2
2
A
A
B
A
A
B
A
A B
3.84 (2JPH
3.63 (2JPH
3.26 (2JPH
8.5)
3.96 (2JPH
3.44 (2JPH
3.23 (2JPH
14.9)
3.70 (2JPH
13.0)
B
B
B
2
2
A
B
A
B
A HB
A HB
6.3, JPH
13.1)
1.6, JPH
2.1)
5.1)
a
2
3
3
6
6 7 8
C2
C7
PC
C3
PC
C H
C6
P C
C C C H
For XI, , ppm (J, Hz):
56.76,
1.5),
149.30 (J
1.9),
42.24 (J
119.5, J
152.4),
148.74 (J
10.7, J
8.7,
1.6,
9.1,
1.4,
0.8,
P
6
7
6
7
8
9
6
7
7
7
8
9
7
6
7
6 7 8
C C H
C C C C H
POC C
C H
C C C H
C C C H
C8
POC C C
J
J
J
J
J
2.4, J
120.99 (J
4.8, J
163.9, J
8.0, J
4.9),
129.55 (J
6
8
8
9
8
9
9
9
8
7
6
6 7 8
C H
C C C H
C9
PC
C H
C C C H
i
POC
C C C H
162.9, J
2.4, J
8.9),
125.94 (J
2.2, J
162.8, J
7.7). For XII C 150.76 (J
10.3, J
7
8
6
7
6
7
8
9
6
7
7
7
6
7
7
8
9
6 7 8
1.6), C 121.33 (J
4.5, J
3.6, J
163.5, J
162.6, J
4.6, J
9.2), C 129.24 (J
C C H
C C C C H
o
POC C
C H
C C C H
C C C H m POC C C
9
7
8
8
9
8
6
7
9
9
9
8
7
7
7
8
7
8
161.9, J
8.7), C 124.74 (J
8.1), H 7.19 (J
1.4, J
7.4, J
C H
C C C H
p
POC C C
7.4); H 7.16 (J
C H
C C C H
o
PH
H H H H
8
9
7
9
8
8
9
9
2.5), H 7.32 (J
2.2, J
1.2).
H H
m
PH
H H
p
PH
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 7 2002

1078
KHAILOVA et al.
The structures of IIId, XIIa, XIIb, and also XI
tropic and then in the anisotropic approximation. All
the hydrogen atoms were revealed from the differen-
tial electron density series and were refined isotropi-
cally in the final stage. The structure was refined to
R 0.33, RW 0.047 for 4005 unique reflections with
F2 3 . All the calculations were performed with a
DEC Alpha Station 200 computer using MolEN pro-
gram package [19]. The intermolecular contacts in the
crystal were analyzed, and the molecular and crystal
structures plotted, using the PLATON program [20].
(taken for comparison) in solution were studied by
1H, 13C, and 31P NMR spectroscopy [13]. The param-
eters of the spectra are listed in Table 7. It is seen that
the molecules of XIIa and XIIb in solution exist
as single isomers. It should be noted that the direct
coupling constants in the compounds under considera-
tion take two values (Tables 1, 7). This may be as-
sociated with the axial and equatorial positions of the
C H bonds in the ring, by analogy with cyclohexane
[14, 15] and 2,2-dimethyl-1,3,2,6-dioxasilaphosphocins
[16, 17]. According to the X-ray structural data, the
C H bond lengths with the axial and equatorial hydro-
N,N-Diethyl-N -[bis(chloromethyl)phosphinyl]-
urea IIa. Diethylamine (0.73 g) was added dropwise
with stirring to a solution of 1.88 g of Ia in 10 ml
of dry diethyl ether, cooled to 0 C. After 1 day, the
solvent was vacuum-evaporated, and the residue was
recrystallized from diethyl ether. Compound IIa was
obtained; yield 1.8 g (69%), mp 110 111 C. IR
gen atoms in XIIb are also different: 0.84 and 0.88
,
respectively. The chemical shifts of these methylene
protons are different, and their assignment was based
1
on analysis of the ABX pattern in the H NMR spec-
tra (A, axial proton; B, equatorial proton; X, phos-
1
spectrum (KBr), , cm : 1255 (P=O), 1660 (C=O),
3140 (NH). 31P NMR spectrum (acetone):
32 ppm.
phorus) assuming that the more negative coupling
2
Found, %: N 10.25; P 11.65. C7H15Cl2N2O2PP. Calcu-
lated, %: N 10.73; P 11.86.
B
constants, JPH
8.5 to 14.9 Hz, correspond to
the equatorial protons of the ring with the dihedral
angles HBC1PS 85 90 . This is consistent with data
for the geminal coupling constants PIV H [15, 17].
According to X-ray diffraction data, this angle in
XIIb is about 85 .
Substituted ureas IIb IIe were prepared similarly.
N,N-Dipropyl-N -[bis(chloromethyl)phosphinyl]-
urea IIb. Yield 73%, mp 80 81 C. IR spectrum
1
(KBr), , cm : 1215 (P=O), 1640 (C=O), 3100 (NH).
EXPERIMENTAL
31P NMR spectrum (acetone):
30 ppm. Found, %:
C 37.35; H 6.56; N 9.63; P 10P.61. C9H19Cl2N2O2P.
Calculated, %: C 37.38; H 6.64; N 9.69; P 10.71.
The IR spectra were taken on a UR-20 spectrom-
eter (mulls in mineral oil or thin films) in the range
1
400 3600 cm . The 31P NMR spectra were recorded
N,N-Dibutyl-N -[bis(chloromethyl)phosphinyl]-
urea IIc. Yield 54%, mp 83 84 C. IR spectrum
on Bruker MSL-400 (161.97 MHz) and KGU-4
(10.2 MHz) spectrometers; external reference 85%
H3PO4. The 13C NMR spectra were recorded on a
1
(KBr), , cm : 1210 (P=O), 1630 (C=O), 3140 (NH).
31P NMR spectrum (acetone):
29 ppm. Found, %:
P
1
Bruker MSL-400 spectrometer (100.6 MHz). The H
C 41.12; H 7.20; N 8.80; P 9.80. C11H23Cl2N2O2P.
Calculated, %: C 41.64; H 7.32; N 8.83; P 9.76.
NMR spectra were measured on Bruker MSL-400
(400.132 MHz), WM-250 (250.132 MHz), and Varian
T-60 (60 MHz) spectrometers; internal reference TMS.
N-(3-Oxa-1,5-pentylene)-N -[bis(chloromethyl)-
phosphinyl]urea IId. Yield 94%, mp 130 132 C. IR
1
Single crystal X-ray diffraction study of XIIb.
Triclinic system; at 20 C: a 10.012(1), b 10.151(3),
spectrum (KBr), , cm : 1240 (P=O), 1650 (C=O),
1560, 3150 (NH). 31P NMR spectrum (acetone):
P
c 15.960(3)
;
77.53(2) , 77.03(1) , 86.88(1) ;
30 ppm. Found, %: C 29.80; H 4.72; N 9.93; P 11.02.
C7H13Cl2N2O3P. Calculated, %: C 30.56; H 4.77;
N 10.19; P 11.26.
3
V 1514.7(5) 3, Z 4, dcalc 1.32 g cm , space group
P1 (two independent molecules). The unit cell param-
eters and the intensities of 5238 reflections, including
3923 reflections with I 3 , were measured on an
Enraf-Nonius CAD-4 automatic four-circle diffrac-
tometer at 20 C ( MoK radiation, graphite mono-
N-(Pentamethylene)-N -[bis(chloromethyl)phos-
phinyl]urea IIe. Yield 94%, mp 125 126 C. IR spec-
1
trum (KBr), , cm : 1255 (P=O), 1665 (C=O), 3100
(NH). 31P NMR spectrum (acetone):
30 ppm.
chromator, /2 scanning,
26.7 ). No decay of
Found, %: C 34.80; H 5.20; N 10.30P; P 11.05.
the intensities of three check reflections was observed
during the experiment; the absorption was small ( Mo
C8H15Cl2N2O2P. Calculated, %: C 35.18; H 5.55;
N 10.26; P 11.34.
1
4.32 cm ) and was therefore neglected.
5
2-Diethylamino-4-oxo-4-chloromethyl-1,3,4
-
The structure was solved by the direct method
using SIR program [18] and refined first in the iso-
oxazaphospholine IIIa. Triethylamine (0.4 g) was
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 7 2002

SYNTHESIS AND STRUCTURE OF 1,3,4-OXAZA(THIAZA)PHOSPHOLINES
1079
added dropwise with stirring to a solution of 1 g of
IIa in 50 ml of dry diethyl ether. The mixture was al-
lowed to stand for a day, triethylamine hydrochloride
was filtered off, the solvent was removed, and the
residue was recrystallized from chloroform. Com-
pound IIIa was obtained; yield 0.45 g (52%), mp
700, 1395 (CH2Cl), 965 (P OPh), 690, 760, 1500,
1590 (Ph), 1250 (P=O), 1680 (C=O), 1615, 3390
1
(NH2), 3200 (NH). H NMR spectrum (CD3CN), ,
2
ppm (J, Hz): 4.1 d (2H, PCH2, JPCH 10), 5.61 br.s
(2H, NH2), 7.37 m (5H, Ph), 8.1 br.s (1H, NH).
31P NMR spectrum (acetone):
16.36 ppm, %:
P
1
156 157 C. IR spectrum, , cm : 1230 (P=O), 1625
C 38.01; H 4.19; Cl 14.13; N 11.31; P 12.64.
C8H10ClN2O3P. Calculated, %: C 38.65; H 4.08;
Cl 14.26; N 11.27; P 12.46.
1
(C=N). H NMR spectrum (CDCl3), , ppm: 1.20 m
(6H, CH3C), 3.40 m (4H, NCH2), 3.40 m (2H,
ClCH2), 4.60 m (OCH2). 31P NMR spectrum (acetone):
N-tert-Butyl-N -[O-phenyl(chloromethyl)phos-
phinyl]urea Vb. tert-Butylamine (1.59 g) was added
dropwise with stirring to a solution of 5.03 g of IV in
10 ml of diethyl ether, cooled to 5 C. The mixture
was allowed to stand for 1 day, after which the sol-
vent was removed in a vacuum. Compound Vb was
obtained; yield 6.32 g (95%), viscous substance. IR
59.43 ppm. Found P, %: 13.15. C7H14ClN2O2P.
P
Calculated P, %: 13.79.
Oxazaphospholines IIIb and IIIc were prepared
similarly.
5
2-Morpholino-4-oxo-4-chloromethyl-1,3,4 -ox-
azaphospholine IIIb. Yield 81%, mp 212 213 C.
1
spectrum (KBr), , cm : 1165, 1210 (POPh), 1230
1
IR spectrum (KBr), , cm : 1240 (P=O), 1635
(P=O), 1590 (Ph), 1690 (C=O), 1550, 3200 3400
(C=N). 31P NMR spectrum (acetone):
59.9 ppm.
Found, %: C 35.45; H 5.26; N 11.0P6; P 12.59.
C7H12ClN2O3P. Calculated, %: C 35.23; H 5.08;
N 11.74; P 12.98.
1
(NH). H NMR spectrum (CCl4), , ppm (J, Hz): 1.2 s
2
(9H, CH3C), 3.87 d (2H, ClCH2P, JPH 9), 5.93 br.s
(1H, NH), 6.97 m (5H, Ph), 7.93 br.s (1H, NHP).
31P NMR spectrum (acetone):
18.5 ppm. Found P,
P
2-Piperidino-4-oxo-4-chloromethyl-1,3,4 5-ox-
%: 9.64. C12H18ClN2O3P. Calculated P, %: 10.16.
azaphospholine IIIc. Yield 63%, mp 179 180 C.
1
N-[Bis(chloromethyl)phosphinyl]urea Vc. Gase-
ous ammonia (0.5 g) was passed through a stirred
solution of 5.51 g of Ia in 50 ml of dry diethyl ether,
cooled to 5 C. The resulting precipitate was filtered
off and washed successively with anhydrous aceto-
nitrile and diethyl ether. Compound Vc was obtained;
yield 4.2 g (70%), mp 141 C. IR spectrum (KBr), ,
IR spectrum (KBr), , cm : 1230 (P=O), 1625 (C=N).
31P NMR spectrum (acetone):
59.15 ppm. Found,
P
%: C 39.85; H 6.08; Cl 15.05; N 11.36; P 12.85.
C8H14ClN2O2P. Calculated, %: C 40.60; H 5.97;
Cl 14.98; N 11.84; P 13.09.
5
2-Morpholino-4-thioxo-4-chloromethyl-1,3,4 -
1
cm : 690, 1390 (CH2Cl), 1240 (P=O), 1620, 3390
thiazaphospholine IIId. A mixture of 1.3 g of mor-
pholine and 2.5 ml of triethylamine was added drop-
wise with stirring to a solution of 3.2 g of Ib in 50 ml
of dry benzene, cooled to 5 C. The mixture was al-
lowed to stand for a day, after which triethylamine hy-
drochloride was filtered off, the solvent was removed,
and the residue was recrystallized from acetonitrile.
Compound IIId was obtained; yield 3.85 g (98%),
(NH2), 1680 (C=O), 3200 (NH). 31P NMR spectrum
(acetone):
26.8 ppm. Found, %: C 17.42; H 3.29;
P
Cl 35.20; N 13.33; P 15.22. C3H7Cl2N2O3P. Cal-
culated, %: C 17.58; H 3.45; Cl 34.59; N 13.67;
P 15.11.
Substituted ureas Vd and Ve were prepared simi-
larly.
1
mp 108 109 C. IR spectrum (KBr), , cm : 665
(P=S), 1565 (C=N). 31P NMR spectrum (acetone):
106 ppm. Found, %: C 30.96; H 4.30; N 9.94;
PP 11.76. C7H12ClN2OPS2. Calculated, %: C 31.05;
H 4.48; N 10.35; P 11.44.
N-tert-Butyl-N -[bis(chloromethyl)phosphinyl]-
urea Vd. Yield 80%, mp 109 112 C. IR spectrum
1
(KBr), , cm : 1240 (P=O), 1690 (C=O), 1560,
3180 3355 (NH). 1H NMR spectrum (Me2SO),
,
ppm (J, Hz): 1.2 s (9H, CH3C), 3.87 d (4H, ClCH2P,
2JPH 7), 6.33 s (1H, NH), 7.76 br.s (1H, NHP). 31P
N-[O-Phenyl(chloromethyl)phosphinyl]urea Va.
Ammonia (0.22 g) was passed through a stirred solu-
tion of 3.08 g of IVa in 50 ml of dry diethyl ether,
cooled to 5 C. The resulting precipitate was filtered
off and washed with anhydrous acetonitrile and di-
ethyl ether. Compound Va was obtained; yield 2.45 g
NMR spectrum (acetone):
28.5 ppm. Found, %:
P
C 32.67; H 6.47; N 10.82; P 12.04. C7H15Cl2N2O2P.
Calculated, %: C 32.20; H 5.80; N 10.73; P 11.86.
N-Phenyl-N -[bis(chloromethyl)phosphinyl]urea
Vd. Yield 82%, mp 170 173 C. IR spectrum (KBr),
1
(74%), mp 148 149 C. IR spectrum (KBr), , cm :
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 7 2002

1080
KHAILOVA et al.
1
, cm : 1240 (P=O), 1590 (Ph), 1670 (C=O), 1540,
N-Phenylisouroniomethyl(chloromethyl)phos-
phinate Xb was prepared similarly from 2.9 g of Vd,
1.1 g of triethylamine, and 0.2 g of water. Yield 1.2 g
(45%), mp 187 189 C. 31P NMR spectrum (acetone):
1
3170, 3310 (NH). H NMR spectrum [(CD3)2SO], ,
2
ppm (J, Hz): 4.17 d (4H, ClCH2P, JPH 8), 7.19 m
(5H, Ph), 8.31 br.s (1H, NHP), 8.92 s (1H, NH). 31P
NMR spectrum (acetone):
28 ppm. Found, %:
24 ppm. Found, %: C 41.41; H 4.69; Cl 13.72;
P 12.28. C9H12ClN2O3P. Calculated, %: C 41.15;
H 4.61; Cl 13.50; P 11.79.
C 39.04; H 4.03; Cl 25.15; N P10.25. C9H11Cl2N2O2P.
Calculated, %: C 38.45; H 3.95; Cl 25.22; N 9.97.
P
5
2-Phenoxy-2,5-dioxo-1,4,2 -diazaphospholidine
2-tert-Butylamino-4-thioxo-4-chloromethyl-1,3,4-
5-thiazaphospholine XIIa. tert-Butylamine (2.05 g)
was added dropwise with stirring to a solution of
3.1 g of Ib in 50 ml of absolute benzene. The mix-
ture was allowed to stand for 1 day, after which
tert-butylamine hydrochloride was filtered off, the
filtrate was washed with water (3 5 ml) and dried
over Na2SO4, and the solvent was removed. The re-
sidue was recrystallized; 1.3 g (38%) of XIIa was
VIa. A mixture of 1.5 g of Va, 0.8 g of triethyl-
amine, and 50 ml of anhydrous acetonitrile was
heated for 8 h at 82 C. The precipitate was filtered,
washed with CCl4, and dried in a vacuum. Com-
pound VIa was obtained; yield 0.85 g (66%),
1
mp 210 212 C. IR spectrum (KBr), , cm : 965
(P OPh), 1220 (P=O), 1595 (Ph), 1720 (C=O), 3200
(NH). 31P NMR spectrum (acetone):
20.7 ppm.
P
1
Found P, %: 14.08. C8H9N2O3P. Calculated P, %:
14.60.
obtained, mp 109 110 C. IR spectrum (KBr), , cm :
680 (P=S), 1570 (C=N), 1515, 3290 (NH). 31P NMR
5
2-Chloromethyl-2,5-dioxo-1,4,2 -diazaphospho-
spectrum (acetone):
107 ppm. Found, % : C 32.98;
P
lidine VIb was prepared similarly. Yield 86%, mp
H 5.41; N 10.57; P 12.00; S 24.81. C7H14ClN2PS2.
Calculated, %: C 32.74; H 5.51; N 10.91; P 12.06;
S 24.97.
1
225 C. H NMR spectrum {[(CD3)2N]3PO}, , ppm
(J, Hz): 3.7 d (2H, ClCH2P, 2JPCH 8.5), 4.18 m (2H,
CH2P). 31P NMR spectrum (acetone):
20.0 ppm.
5
P
2-tert-Butylamino-4-thioxo-4-phenoxy-1,3,4
-
Found P, %: 18.32. C3H6N2ClO2P. Calculated P, %:
18.38.
thiazaphospholine XIIb was prepared similarly from
2 g of XI and 1.1 g of triethylamine; yield 2 g (88%),
5
1
2-tert-Butylamino-4-oxo-4-phenoxy-1,3,4 -ox-
mp 129 130 C. IR spectrum (KBr), , cm : 660
azaphospholine VIIb was prepared similarly to IIIa
from 4.1 g of Vb and 1.4 g of triethylamine;
yield 1.95 g (55%), mp 130 132 C. IR spectrum
(P=S), 1205 (P O Ph), 1575 (C=N), 1590 (Ph),
1530, 3240, 3285 (NH). 31P NMR spectrum (acetone):
119.38 ppm. Found, %: C 47.97; H 5.95; N 9.55;
P
1
(KBr), , cm : 1070, 1210 (POPh), 1240 (P=O);
P 10.89; S 21.48. C12H17N2OPS2. Calculated, %: C
47.97; H 5.72; N 9.33; P 10.31; S 21.35.
1
1590 (Ph), 1660 (C=N), 3195, 3285 (NH). H NMR
spectrum (CCl4), , ppm: (A) 1.30 s (9H, CH3C),
3.97 m (2H, CH2P), 5.05 br.s (1H, NH), 7.16 m (5H,
Ph); (B) 1.25 s (9H, CH3C), 3.01 m (2H, CH2P),
4.49 br.s (1H, NH), 7.16 m (5H, Ph). 31P NMR spec-
ACKNOWLEDGMENTS
The study was financially supported by the Russian
Foundation for Basic Research (project no. 00-03-
32837).
trum (acetone):
53.41, 48.35 ppm. Found, %:
C 54.06; H 6.76; PN 10.39; P 12.08. C12H17N2O3P.
Calculated, %: C 53.72; H 6.40; N 10.44; P 11.54.
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SYNTHESIS AND STRUCTURE OF 1,3,4-OXAZA(THIAZA)PHOSPHOLINES
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