10-(3-hydroxypropyl)-1,4,6,8-tetraphenyl-1,4,7,8-tetraaza-5- phosphoniaspiro[4.5]deca-6,9-diene chloride: Synthesis and molecular structure

Article abstract of DOI:10.1023/A:1012753627608

The reaction of 2-(3,4-dihydro-2H-pyran-5-yl)-1,3-diphenyl-1,3-diaza-2λ ³-phospholidine with C,N-diphenylnitrilimine yields 10-(3-hydroxypropyl)-1,4,6,8-tetraphenyl-1,4,7,8-tetraaza-5-phosphoniaspiro[4.5] deca-6,9-diene chloride. Its structure

Full text of DOI:10.1023/A:1012753627608

Russian Chemical Bulletin, International Edition, Vol. 50, No. 8, pp. 1461—1464, August, 2001
1461
10-(3-Hydroxypropyl)-1,4,6,8-tetraphenyl-1,4,7,8-tetraaza-
5-phosphoniaspiro[4.5]deca-6,9-diene chloride:
synthesis and molecular structure
Yu. G. Trishin,a« V. I. Namestnikov,a and V. K. Bel´skiib
aSt.-Petersburg State Technological University of Plant Polymers,
4 ul. Ivan Chernykh, 198095 St.-Petersburg, Russian Federation.
Fax: +7 (812) 186 8600. E-mail: trish@YT4470.spb.edu
bState Research Center of Russian Federation.”L.Ya.Karpov Scientific Research
Physico-Chemical Institute”,
10 ul. Vorontsovo Pole, 103064 Moscow, Russian Federation.
Fax: +7 (095) 975 2450.
The reaction of 2-(3,4-dihydro-2H-pyran-5-yl)-1,3-diphenyl-1,3-diaza-2λ3-phospholidine
with C,N-diphenylnitrilimine yields 10-(3-hydroxypropyl)-1,4,6,8-tetraphenyl-1,4,7,8-tetraaza-
5-phosphoniaspiro[4.5]deca-6,9-diene chloride. Its structure was determined by X-ray dif-
fraction analysis.
Key words: 2-(3,4-dihydro-2H-pyran-5-yl)-1,3-diphenyl-1,3-diaza-2λ3-phospholidine,
C,N-diphenylnitrilimine, 10-(3-hydroxypropyl)-1,4,6,8-tetraphenyl-1,4,7,8-tetraaza-5-phos-
phoniaspiro[4.5]deca-6,9-diene chloride, X-ray diffraction analysis.
Tricyclic spirophosphoranes are of considerable in-
terest as potential physiologically active compounds1
and as objects of investigation into the spatial structures
of phosphorus-containing heterocycles.2 Such com-
pounds can be obtained, for example, by the reactions
of nitrilimines that are the Huisgen 1,3-dipoles with
phosphorus(III) derivatives, in which the phosphorus
atom is included in the heterocycle and simultaneously
bound to the other heterocycle.3 However, while study-
ing the reaction of 2-(4,5-dihydrofuran-3-yl)-1,3-diphe-
nyl-1,3-diaza-2λ3-phospholidine with C,N-diphenylnitril-
imine, we found3 that the closure of a new 1,2,4-diaza-
phosphorine ring in the multi-step process is accompa-
nied by the opening of the both rings in the starting
organophosphorus compound. We assumed that the for-
mation of the final 5-(2-chloroethyl)-4-(N,N´-diphenyl-
ethylenediamino)-1,3-diphenyl-1,4-dihydro-1,2,4λ5-di-
azaphosphorine can occur via a bicyclic spiro com-
pound with a nodal quaternized phosphorus atom. In
the present work, we found that the compound with this
structure is the final product in the reaction of C,N-di-
phenylnitrilimine with 2-(3,4-dihydro-2H-pyran-5-yl)-
1,3-diphenyl-1,3-diaza-2λ3-phospholidine (1), which
differs from the aforementioned 2-(4,5-dihydrofuran-3-
yl)-1,3-diphenyl-1,3-diaza-2λ3-phospholidine in the size
of the oxygen-containing heterocycle bound to the phos-
phorus atom.
Results and Discussion
Compound 1 was obtained from 5-dibromophos-
phino-3,4-dihydro-2H-pyran (2) and N,N´-diphenyl-
ethylenediamine in the presence of triethylamine. 1,3-Di-
aza-2λ3-phospholidine (1) reacts with C,N-diphenylnitril
imine (generated in situ from N-phenylbenzohydrazonoyl
chloride under the action of an excess of triethylamine)
under mild conditions (benzene, 20 °C). As for a
dihydrofuryl analog, the reaction seems to occur stepwise.
Apparently, the initial nucleophilic attack of the phos-
phorus atom on the carbonium atom of nitril imine gives
bipolar ion A (Scheme 1). Then the negatively charged
–
N atom of the P+CNN betaine fragment attacks the
dihydropyran ring at position 6 activated by the phos-
phonium group. This results in the C—O bond cleavage
and in the formation of a six-membered P,N-containing
–
heterocycle B with the P+CCCCO betaine fragment.
Subsequent protonation of the alkoxide ion of betaine B
with triethylamine hydrochloride yields the final
10-(3-hydroxypropyl)-1,4,6,8-tetraphenyl-1,4,7,8-tetra-
aza-5-phosphoniaspiro[4.5]deca-6,9-diene chloride (3).
Thus, unlike an analogous reaction of 2-(4,5-di-
hydrofuran-3-yl)-1,3-diphenyl-1,3-diaza-2λ3-phosphol-
idine, the alcoholic OH group in spirophosphonium salt
3 does not interact with the quaternized phosphorus
atom to give the oxaphosphorinane ring, which could
result, in turn, in the opening of the diazaphospholidine
ring followed by the decomposition of the phosphonium
salt. Apparently, the six-membered 1,2-oxaphosphorinane
ring is less stable thermodynamically than the five-
membered 1,2-oxaphospholane one.
The goal of the present work was to study the
reaction of 2-(3,4-dihydro-2H-pyran-5-yl)-1,3-diphenyl-
1,3-diaza-2λ3-phospholidine (1) with C,N-diphenylnitril
imine as a possible method for the synthesis of a new
P,N-containing compound of bi- or tricyclic structure.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1390—1393, August, 2001.
1066-5285/01/5008-1461 $25.00 ©ꢀ2001 Plenum Publishing Corporation

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Russ.Chem.Bull., Int.Ed., Vol. 50, No. 8, August, 2001
Trishin et al.
Scheme 1
C(23)
C(22)
C(17)
C(21)
C(16)
Ph
N
NH Ph
C(Cl)
+
Et3N
+
C(24)
+
C
–
C(15)
C(14)
C(12)
Et3N•HCl
Ph
N
N
Ph
C(19)
N(1)
C(18)
C(20)
C(13)
C(26)
Ph
C(30)
H(1O)
C(25)
P(1)
+
N
O
N(3)
–
C(11)
+
Ph
C
N
N
Ph
N(2)
P
O
N(4)
C(7)
N
C(28)
Ph
C(32)
C(31)
C(6)
C(27) C(29)
C(1)
ꢀ
C(8)
Cl(1)
C(9)
C(10)
Ph
O
C(2)
C(3)
C(5)
N
+
P
–
N
C
N
N
Ph
C(4)
Ph Ph
Fig. 1. General view of 10-(3-hydroxypropyl)-1,4,6,8-tetra-
phenyl-1,4,7,8-tetraaza-5-phosphoniaspiro[4.5]deca-6,9-diene
chloride (3) (solvate with a CHCl3 molecule).
)
–
O
The structure of compound 3 (in the form of its
solvate with a chloroform molecule) was proved by
X-ray diffraction analysis (Figs. 1, 2; Tables 1, 2). The
six-membered ring in the bicyclic spiro system is planar
with an accuracy of 0.020 Å, while the five-membered
heterocycle has an envelope conformation, in which the
atoms are coplanar within 0.015 Å, except for the C(25)
Ph
N
+ Et3N•HCl
+
P
N Ph
– Et3N
C
N
N
Ph
Ph
*
OH
Ph
N
+
P
–
N Ph
Cl
C
N
N
z
Ph
Ph
y
!
0
Chloride 3 is an uncommon example of bicyclic
spirophosphonium compounds. It is a colorless crystal-
line substance moderately soluble in chloroform and
acetone and insoluble in benzene and THF. The
31P NMR spectrum of compound 3 shows a signal at
δP 4.1 characteristic of cyclic phosphonium salts, and its
IR spectrum contains an absorption band from the OH
–1
group (3260 cm ). In the 1H NMR spectrum of
x
spirophosphonium compound 3, the doublet of the
alkenyl proton is significantly shifted downfield (δ 9.17,
3JP,H = 27.2 Hz) compared to the spectra of analogous
diazaphosphorine rings with the phosphoryl P atom,4
which also confirms the quaternization of phospho-
rus. The protons of all the five methylene groups
(CH2CH2CH2, =CCH2, OCH2 and two NCH2) mani-
fest themselves by the corresponding multiplets (δ 1.70,
2.88, 3.56, 3.99, 4.74).
Fig. 2. Crystal structure of 10-(3-hydroxypropyl)-1,4,6,8-
tetraphenyl-1,4,7,8-tetraaza-5-phosphoniaspiro[4.5]deca-6,9-
diene chloride (3) (solvate with a CHCl3 molecule).

Synthesis of new phosphoniaspiro chloride
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 8, August, 2001
1463
Table 1. Selected bond lengths (d) in 10-(3-hydroxypropyl)-
1,4,6,8-tetraphenyl-1,4,7,8-tetraaza-5-phosphoniaspiro[4.5]de-
ca-6,9-diene chloride (3) (solvate with a CHCl3 molecule)
Experimental
The IR spectra of compounds 1—3 were recorded on an
IKS-29 instrument (in KBr pellets). 1H NMR spectra were
recorded on a Bruker AM-500 instrument (500.1 MHz, inner
stabilization relative to the 2H resonance line). 31P NMR
spectra were recorded on a Bruker AC-200 instrument
(81.4 MHz) with 85% H3PO4 as the standard.
N,N´-Diphenylethylenediamine (Aldrich), 3,4-dihydro-2H-
pyran (Merck) were used without additional purification. PBr3
(Ural PO Galogen, technical specifications 6-09-30-79-88) was
preliminarily distilled at reduced pressure (10 Torr) in a flow of
argon. N-Phenylbenzohydrazonoyl chloride (m.p. 130—131 °C)
was prepared as described earlier.5 Diethyl ether, THF, and
triethylamine were dried over NaOH and distilled over sodium.
Benzene was dried with azeotropic removal of water and dis-
tilled over sodium.
Bond
d/Å
Bond
d/Å
P(1)—N(2)
P(1)—N(1)
P(1)—C(32)
P(1)—C(30)
ΗÑ(29)
N(1)—C(19)
N(1)—C(26)
N(2)—C(1)
N(2)—C(25)
N(3)—C(30)
1.648(2)
1.649(2)
1.733(2)
1.780(2)
1.415(5)
1.431(3)
1.472(3)
1.444(3)
1.469(3)
1.306(3)
N(3)—N(4)
N(4)—C(31)
N(4)—C(7)
C(13)—C(30)
C(25)—C(26)
C(27)—C(32)
C(27)—C(28)
C(28)—C(29)
C(31)—C(32)
1.349(3)
1.366(3)
1.452(3)
1.498(3)
1.501(5)
1.514(3)
1.532(4)
1.518(4)
1.359(3)
Compounds 1 and 2 were synthesized and the reaction of
phospholidine 1 with C,N-diphenylnitrilimine was carried out
in an atmosphere of argon with dried solvents and triethyl-
amine.
Table 2. Selected bond angles (ω) in 10-(3-hydroxypropyl)-
1,4,6,8-tetraphenyl-1,4,7,8-tetraaza-5-phosphoniaspiro[4.5]de-
ca-6,9-diene chloride (3) (solvate with a CHCl3 molecule)
2-(3,4-Dihydro-2H-pyran-5-yl)-1,3-diphenyl-1,3-diaza-
2λ3-phospholidine (1). A solution of 5-dibromophosphino-3,4-
dihydro-2H-pyran (2) (13.6 g, 50 mmol) in 20 mL of THF was
added dropwise with stirring at 0—5 °C to a solution of
N,N´-diphenylethylenediamine (10.6 g, 50 mmol) and triethyl-
amine (10.1 g, 100 mmol) in 150 mL of THF. The reaction
mixture was stirred at 0—5 °C for 0.5 h and at 20 °C for 0.5 h.
Triethylamine hydrobromide was filtered off and washed with
50 mL of THF. The filtrate was concentrated at reduced
pressure. The solid residue was recrystallized from benzene to
give compound 1 (11.4 g, 70%), m.p. 182—184 °C. Found (%):
C, 70.51; H, 6.29; P, 9.73. C19H21N2OP. Calculated (%):
C, 70.36; H, 6.53; P, 9.55. IR, ν/cm–1: 1595 (C=C). 1H NMR
(C6D6), δ: 1.07 (m, 2 H, CH2CH2CH2); 1.57 (m, 2 H,
=CCH2); 3.19, 3.27 (both m, each 2 H, CH2N); 3.33 (m, 2 H,
OCH2); 7.12 (d, 1 H, =CH, 3JP,H = 10.4 Hz); 6.80—7.25 (m,
10 H, Ph). 31P NMR (CDCl3), δ: 90.4.
5-Dibromophosphino-3,4-dihydro-2H-pyran (2). 3,4-Di-
hydro-2H-pyran (18.5 g, 220 mmol) in 25 mL of ether was
added dropwise at 20 °C to a solution of PBr3 (59.5 g, 220 mmol)
in 100 mL of ether. The reaction mixture was stirred at the
same temperature for 12 h. Then triethylamine (24.3 g,
240 mmol) was added, and stirring was continued at 20 °C for
3 h. Triethylamine hydrobromide was filtered off, and the ether
was removed at reduced pressure. The residue was fractionated
Angle
ω/deg Angle
ω/deg
N(2)—P(1)—N(1)
95.02(10) C(8)—C(7)—N(4)
119.4(2)
N(2)—P(1)—C(32) 114.09(11) C(12)—C(7)—N(4) 119.1(2)
N(1)—P(1)—C(32) 114.70(11) C(18)—C(13)—C(30)122.0(2)
N(2)—P(1)—C(30) 116.22(11) C(14)—C(13)—C(30)119.3(2)
N(1)—P(1)—C(30) 115.09(11) C(20)—C(19)—N(1) 122.0(2)
C(32)—P(1)—C(30)102.43(11) C(24)—C(19)—N(1) 119.7(3)
C(19)—N(1)—C(26)120.3(2)
C(19)—N(1)—P(1) 125.46(16) N(1)—C(26)—C(25) 107.8(2)
C(26)—N(1)—P(1) 113.34(19) C(32)—C(27)—C(28)112.5(2)
N(2)—C(25)—C(26) 107.5(2)
C(1)—N(2)—C(25) 120.4(2)
C(1)—N(2)—P(1) 123.39(17) O—C(29)—C(28)
C(29)—C(28)—C(27)112.9(3)
111.1(3)
C(25)—N(2)—P(1) 112.62(18) N(3)—C(30)—C(13) 115.4(2)
C(30)—N(3)—N(4) 122.44(19) N(3)—C(30)—P(1) 123.80(17)
N(3)—N(4)—C(31) 125.94(19) C(13)—C(30)—P(1) 120.74(17)
N(3)—N(4)—C(7) 113.87(18) C(32)—C(31)—N(4) 125.3(2)
C(31)—N(4)—C(7) 120.16(19) C(31)—C(32)—C(27)121.9(2)
C(6)—C(1)—N(2) 119.5(2)
C(2)—C(1)—N(2) 120.0(3)
C(31)—C(32)—P(1) 120.00(18)
C(27)—C(32)—P(1) 118.06(17)
atom deviating from their plane by 0.283 Å. The angle
between the mean planes of these rings is 89.4°, i.e.,
they make a near-right angle.
in vacuo to give compound 2 (32.3 g, 54%), b.p. 80—82 °C
18
(0.7 Torr), nD
1.6362. Found (%): C, 21.71; H, 2.44;
P, 11.17. C5H7Br2OP. Calculated (%): C, 21.93; H, 2.58;
P, 11.31. IR, ν/cm–1: 1590 (C=C). 1H NMR (CDCl3), δ: 2.02
(m, 2 H, CH2CH2CH2); 2.54 (m, 2 H, =CCH2); 4.12
The configuration of the phosphorus atom is a
strongly distorted tetrahedron (the XPY angles vary
from 95.02° to 116.22°). The C(7)—C(12) benzene ring
is rotated relative to the six-membered heterocycle plane
by 43.0°, while the C(13)—C(18) ring makes a torsion
angle of 34.6°. The C(1)—C(6) and C(19)—C(24) ben-
zene rings are rotated relative to the five-membered
heterocycle plane by 50.9° and 12.8°, respectively. The
intermolecular hydrogen bond involving the OH group
and the chlorine atom has the following parameters:
3
(m, 2 H, OCH2); 7.25 (d, 1 H, =CH, JP,H = 12.7 Hz).
31P NMR (CDCl3), δ: 159.2.
10-(3-Hydroxypropyl)-1,4,6,8-tetraphenyl-1,4,7,8-tetra-
aza-5-phosphoniaspiro[4.5]deca-6,9-diene chloride (3). A so-
lution of 1,3-diaza-2λ3-phospholidine (1) (1.62 g, 5 mmol),
N-phenylbenzohydrazonoyl chloride (1.15 g, 5 mmol), and
triethylamine (2 mL) in 20 mL of benzene was kept at 20 °C for
24 h. The precipitate (2.64 g) was filtered off, washed with
benzene (5 mL), and recrystallized from CHCl3. The yield was
2.53 g (75% from crystal solvate 3•CHCl3), m.p. 151—153 °C.
Found (%): C, 58.70; H, 5.43; P, 4.36. C33H35Cl4N4OP.
Calculated (%): C, 58.59; H, 5.22; P, 4.58. IR, ν/cm–1: 3260
(OH), 1570 (C=C). 1H NMR (CDCl3), δ: 1.70 (m, 2 H,
CH2CH2CH2); 2.88 (m, 2 H, =CCH2); 3.56 (m, 2 H, OCH2);
Bond
ΗÍ
H...Cl
O...Cl
d/Å
Angle
ω/deg
168.0
0.90
2.22
3.104
ΗÍ...Cl

1464
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 8, August, 2001
Trishin et al.
3.99, 4.74 (both m, each 2 H, CH2N); 5.28 (s, 1 H, OH);
6.90—7.65 (m, 20 H, Ph); 9.17 (d, 1 H, =CH, 3JP,H = 27.2 Hz).
31P NMR (CHCl3), δ: 4.1.
2. V. A. Naumov and L. V. Vilkov, Molekulyarnye struktury
fosfororganicheskikh soedinenii [Molecular Structures of Orga-
nophosphorus Compounds], Nauka, Moscow, 1986, 277 (in
Russian).
3. Yu. G. Trishin, V. I. Namestnikov, and V. K. Bel´skii, Izv.
Akad. Nauk, Ser. Khim., 2000, 125 [Russ. Chem. Bull., Int.
Ed., 2000, 49, 129].
4. M. R. Erofeeva, Yu. G. Trishin, and V. N. Chistokletov,
Zh. Obshch. Khim., 1989, 59, 2146 [J. Gen. Chem. USSR,
1989, 59 (Engl. Transl.)]; V. I. Namestnikov, Yu. G. Trishin,
L. A. Tamm, and V. N. Chistokletov, Zh. Obshch. Khim.,
1990, 60, 510 [J. Gen. Chem. USSR, 1990, 60 (Engl. Transl.)];
S. M. Senyukh, V. I. Namestnikov, Yu. G. Trishin, and
V. N. Chistokletov, Zh. Obshch. Khim., 1990, 60, 1926
[J. Gen. Chem. USSR, 1990, 60 (Engl. Transl.)]; Yu. G.
Trishin, A. F. Afanasov, I. A. Litvinov, V. A. Naumov, and
V. N. Chistokletov, Zh. Obshch. Khim., 1990, 60, 2446
[J. Gen. Chem. USSR, 1990, 60 (Engl. Transl.)].
X-ray diffraction analysis of the solvate crystals of
(3)•CHCl3 was carried out on a CAD-4 diffractometer
(Mo-Kα radiation, θ/2θ scan mode). The crystals are mono-
clinic, C33H33Cl4N4OP, a = 13.523(3) Å, b = 13.008(4) Å,
c = 18.908(5) Å, β = 91.954(8)°, V = 3324.2(15) Å3; space
group P 21/c, Z = 4, dcalcd = 1.348 g cm–3. The structure was
solved by the direct method; R = 0.0545, Rw = 0.1395 (from
22 116 reflections with I > 2σ(I)). The atomic coordinates and
complete tables of bond lengths and angles were deposited with
the Cambridge Crystallographic Database (No. CCDC 161181).
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 00-03-
32797).
5. R. Huisgen, M. Seidel, G. Wallbillich, and H. Knupfer,
Tetrahedron, 1962, 17, 3.
References
1. I. V. Martynov, V. I. Fetisov, and V. B. Sokolov, in Itogi
Nauki Tekh., Ser. Org. Khim. [Achievements of Science and
Technology, Organic Chemistry], VINITI, Moscow, 1989,
11, 3 (in Russian).
Received December 22, 2000;
in revised form April 30, 2001