Reactions of 2-(2-chloro-4,5-dihydro-3-furyl)-1,3-diphenyl-1,3-diaza-2λ 3-phospholidine with nitrile imines

Article abstract of DOI:10.1023/A:1019682122993

The multistep reactions of 2-(2-chloro-4,5-dihydro-3-furyl)-1,3-diphenyl-1,3-diaza-2λ ³-phospholidine with nitrile imines afforded phosphorus-containing spiro compounds of a new type, viz., 6,8-disubstituted 9-oxo-10-(2-chloroethyl)-1,4-diphenyl-1,4,7,8-tetraaza-5-phosphaspiro[4.5] -deca-6,10-dienes.

Full text of DOI:10.1023/A:1019682122993

Russian Chemical Bulletin, International Edition, Vol. 51, No. 6, pp. 1045—1050, June, 2002
1045
Reactions of 2ꢀ(2ꢀchloroꢀ4,5ꢀdihydroꢀ3ꢀfuryl)ꢀ1,3ꢀdiphenylꢀ
3
1,3ꢀdiazaꢀ2λ ꢀphospholidine with nitrile imines
a
b
Yu. G. Trishin,a V. I. Namestnikov, and V. K. Belsky
ꢀ
aSt.ꢀPetersburg State Technological University of Plant Polymers,
4 ul. Ivana Chernykh, 198095 St.ꢀPetersburg, Russian Federation.
Fax: +7 (812) 186 8600. Eꢀmail: trish@YT4470.spb.edu
bState Research Center of Russian Federation "L. Ya. Karpov Research PhysicoꢀChemical Institute,"
10 ul. Vorontsovo Pole, 103064 Moscow, Russian Federation.
Fax: +7 (095) 975 2450
3
The multistep reactions of 2ꢀ(2ꢀchloroꢀ4,5ꢀdihydroꢀ3ꢀfuryl)ꢀ1,3ꢀdiphenylꢀ1,3ꢀdiazaꢀ2λ ꢀ
phospholidine with nitrile imines afforded phosphorusꢀcontaining spiro compounds of a new
type, viz., 6,8ꢀdisubstituted 9ꢀoxoꢀ10ꢀ(2ꢀchloroethyl)ꢀ1,4ꢀdiphenylꢀ1,4,7,8ꢀtetraazaꢀ5ꢀ
phosphaspiro[4.5]ꢀdecaꢀ6,10ꢀdienes.
3
Key words: 2ꢀ(2ꢀchloroꢀ4,5ꢀdihydroꢀ3ꢀfuryl)ꢀ1,3ꢀdiphenylꢀ1,3ꢀdiazaꢀ2λ ꢀphospholidine,
nitrile imines, 6,8ꢀdisubstituted 10ꢀ(2ꢀchloroethyl)ꢀ9ꢀoxoꢀ1,4ꢀdiphenylꢀ1,4,7,8ꢀtetraazaꢀ5ꢀ
phosphaspiro[4.5]ꢀdecaꢀ6,10ꢀdienes, Xꢀray diffraction analysis.
The reactions of C,Nꢀdiphenylnitrile imine with
1,3ꢀdiazaꢀ2λ ꢀphospholidine derivatives in which the P
expect another possible pathway of the transformation of
the 1,2,4ꢀdiazaphosphorine cylcoadduct generated in the
course of the reaction. This assumption is based on the
results obtained in our previous investigations3,4 on the
reactions of nitrile imines with 3ꢀdialkoxyphosphinoꢀ
4,5ꢀdihydrofurans, which either contain the Cl atom at
position 2 of the dihydrofuran ring or are deprived of this
atom. Thus in the reactions of nitrile imines with 3ꢀdiꢀ
alkoxyphosphinoꢀ4,5ꢀdihydrofuran, the 1,2,4ꢀdiazaphosꢀ
phorine ringꢀclosure was accompanied by the dihydroꢀ
furan ringꢀopening to yield finally bicyclic compounds
containing the pentacoordinated spiro P atom.3 By conꢀ
trast, the 1,2,4ꢀdiazaphosphorineꢀring closure in the reꢀ
action of 2ꢀchloroꢀ3ꢀdialkoxyphosphinoꢀ4,5ꢀdihydroꢀ
furan with CꢀpꢀnitrophenylꢀNꢀphenylnitrile imine was
accompanied by the replacement of the Cl atom, while
the dihydrofuran ring was retained. In the latter case, a
bicyclic compound in which the tetracoordinated P atom
is not located at the spiro position was obtained as the
final product.4 In the present study, we examined the
3
atom is bound to the 4,5ꢀdihydroꢀ3ꢀfuryl or 3,4ꢀdihydroꢀ
2Hꢀpyranꢀ5ꢀyl heterocyclic fragment are multistep proꢀ
cesses as evidenced by the structures of the resulting
compounds.1,2 The key step of these reactions involves
the formation of the sixꢀmembered 1,2,4ꢀdiazaphosꢀ
phorine ring with the simultaneous opening of the
dihydrofuran or dihydropyran ring due to the nucleoꢀ
philic attack of the anionic N atom of the intermediate
bipolar ion on the sp2ꢀhybridized C atom of the oxygenꢀ
containing heterocycle. The reaction of 2ꢀ(4,5ꢀdihydroꢀ
3
3ꢀfuryl)ꢀ1,3ꢀdiphenylꢀ1,3ꢀdiazaꢀ2λ ꢀphospholidine with
C,Nꢀdiphenylnitrile imine was also accompanied by the
diazaphospholidineꢀring opening giving rise to a monoꢀ
5
cyclic compound, viz., substituted 1,4ꢀdihydroꢀ1,2,4λ ꢀ
diazaphosphorine, as the final product.1 In the analoꢀ
gous reaction with 2ꢀ(3,4ꢀdihydroꢀ2Hꢀpyranꢀ5ꢀyl)ꢀ1,3ꢀ
3
diphenylꢀ1,3ꢀdiazaꢀ2λ ꢀphospholidine, the diazaphosꢀ
pholidine ring was retained, and the bicyclic spiro comꢀ
pound with the quaternized P atom at the spiro position,
viz., 10ꢀ(3ꢀhydroxypropyl)ꢀ1,4,6,8ꢀtetraphenylꢀ1,4,7,8ꢀ
tetraazaꢀ5ꢀphosphoniaspiro[4.5]ꢀdecaꢀ6,9ꢀdiene chloꢀ
ride, was obtained as the final product.2
3
reactions of 1,3ꢀdiazaꢀ2λ ꢀphospholidine 1 with nitrile
imines bearing different electronꢀwithdrawing substituꢀ
ents at the carbenium atom.
As part of continuing studies aimed at developing
new procedures for the synthesis of polycyclic phosphoꢀ
rusꢀcontaining compounds, we examined the reactions
of nitrile imines with 2ꢀ(2ꢀchloroꢀ4,5ꢀdihydroꢀ3ꢀfuryl)ꢀ
1,3ꢀdiphenylꢀ1,3ꢀdiazaꢀ2λ ꢀphospholidine (1). Taking
into account the fact that this compound contains the Cl
atom at position 2 of the dihydrofuran ring, one would
Results and Discussion
3
1,3ꢀDiazaꢀ2λ ꢀphospholidine 1 was prepared as a colꢀ
orless crystalline compound from 2ꢀchloroꢀ3ꢀdichloroꢀ
phosphinoꢀ4,5ꢀdihydrofuran and N,N´ꢀdiphenylethyleneꢀ
diamine in the presence of triethylamine. The 31P NMR
spectrum of compound 1 has a signal at δP 70.4, which is
3
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 960—964, June, 2002.
1066ꢀ5285/02/5106ꢀ1045 $27.00 © 2002 Plenum Publishing Corporation

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Russ.Chem.Bull., Int.Ed., Vol. 51, No. 6, June, 2002
Trishin et al.
C(18)
C(17)
C(2)
C(13)
C(1)
N(1)
C(16)
C(15)
C(9)
C(8)
N(2)
C(14)
C(7)
P
C(10)
C(12)
C(11)
C(3)
C(6)
C(4)
C(5)
Cl
O
Fig. 1. Overall view of the molecule of 2ꢀ(2ꢀchloroꢀ4,5ꢀdihydroꢀ3ꢀfuryl)ꢀ1,3ꢀdiphenylꢀ1,3ꢀdiazaꢀ2λ ꢀphospholidine (1).
3
characteristic of compounds containing the trivalent
tricoordinated P atom and is similar in the chemical
shift to the signal for the P atom in analogous 2ꢀ(4,5ꢀdiꢀ
hydroꢀ3ꢀfuryl)ꢀ1,3ꢀdiphenylꢀ1,3ꢀdiazaꢀ2λ ꢀphospholꢀ
idine.1 The 1H NMR spectrum shows signals for the
C(7)—C(12) and C(13)—C(18) benzene rings form angles
of 26.5 and 19.0°, respectively, with the plane of the
diazaphospholidine ring. The angle between the planes
of the benzene rings is 44.1°. The P atom has a disꢀ
torted pyramidal configuration (the X—P—Y angles are
90.46—103.63°).
3
methylene protons of the =CH2 and OCH2 groups (δ 2.60
3
3
and 4.33) as triplets with JH,H = 9.3 Hz (the spinꢀspin
The reactions of 1,3ꢀdiazaꢀ2λ ꢀphospholidine 1 with
3
coupling constant JP,H for the protons of the =CH2
nitrile imines proceeded under mild conditions (benꢀ
zene or THF, 20 °C) upon the in situ generation of
nitrile imines from the corresponding hydrazonoyl haꢀ
lides under the action of triethylamine. As in the case of
the dihydrofuryl analog, the reaction is, evidently, a mulꢀ
tistep process. Apparently, the nucleophilic attack of the
P atom on the carbonium atom of nitrile imine initially
group is, apparently, close to zero). The protons of both
NCH2 groups are manifested as multiplets (δ 3.73
and 3.82).
According to the data from Xꢀray diffraction analyꢀ
sis, the 1,2,3ꢀdiazaphospholidine ring in crystalline comꢀ
pound 1 (Fig. 1, Tables 1 and 2) adopts an envelope
conformation. The C(1) atom deviates from the plane of
the heterocycle by 0.34 Å, and the remaining atoms are
coplanar to within 0.01 Å. The 2ꢀchloroꢀ4,5ꢀdihydrofuran
ring is planar to within 0.02 Å. The angle between the
planes of two heterocycles is 86.6°. The planes of the
Table 2. Selected bond angles (ω) in molecule 1
Angle
ω/deg
Angle
ω/deg
N(2)—P—N(1)
N(1)—P—C(3)
N(2)—P—C(3)
C(4)—О—C(5)
C(7)—N(1)—C(1) 122.2(3) C(3)—C(4)—Cl
C(7)—N(1)—Р
C(1)—N(1)—Р
C(13)—N(2)—С(2) 121.2(3) C(5)—C(6)—C(3)
C(13)—N(2)—Р
C(2)—N(2)—P
N(1)—C(1)—C(2) 107.3(3) С(14)—C(13)—N(2) 119.9(3)
N(2)—C(2)—C(1) 107.4(3) С(18)—C(13)—N(2) 121.3(3)
90.46(14) C(4)—C(3)—С(6)
103.63(15) C(4)—C(3)—Р
100.74(14) C(6)—C(3)—Р
104.9(3) C(3)—C(4)—О
106.4(3)
123.2(3)
130.0(3)
118.2(3)
129.1(3)
112.8(3)
107.9(3)
102.5(4)
Table 1. Selected bond lengths (d) in molecule 1
Bond
d/Å
Bond
d/Å
Cl—C(4)
P—N(1)
P—N(2)
P—С(3)
О—С(4)
О—С(5)
N(1)—C(7)
1.699(4)
1.705(3)
1.712(3)
1.806(3)
1.345(4)
1.455(5)
1.395(4)
N(1)—C(1)
N(2)—C(13) 1.400(4)
1.459(5)
123.3(2) О—C(4)—Cl
113.0(9) О—C(5)—C(6)
N(2)—C(2)
C(1)—C(2)
C(3)—C(4)
C(3)—C(6)
C(5)—C(6)
1.454(5)
1.495(6)
1.313(4)
1.514(5)
1.502(6)
121.9(2) C(8)—C(7)—N(1) 121.2(3)
115.3(2) C(12)—C(7)—N(1) 121.1(3)

3
Reactions of 1,3ꢀdiazaꢀ2λ ꢀphospholidine
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 6, June, 2002
1047
Scheme 1
2—5
a
b
R
Ph
Ar
Ph
Ph
2—5
c
d
R
Ar
pꢀBrC6H4
Ph
C(O)OEt
C(O)C6H4NO2ꢀp
pꢀNO2C6H4
affords bipolar ion 2a—d (Scheme 1). Then, the N atom
belong to rare bicyclic phosphorusꢀcontaining spiro comꢀ
pounds with the ylide P atom at the spiro position. These
compounds occur as white (compound 5a), yellow (comꢀ
pound 5c), or yellowishꢀbrown (compounds 5b,d) crysꢀ
tals, which are readily soluble in chloroform and THF,
moderately soluble in benzene and acetone, poorly soluble
in ether, and insoluble in hexane.
+
−
of the betaine P CNN fragment bearing a negative charge
attacks position 2 of dihydrofuran activated with the phosꢀ
phonium group. This step is accompanied by the nuꢀ
cleophilic vinyl substitution of the Cl atom bound to the
dihydrofuran ring and the closure of the sixꢀmembered
phosphorusꢀcontaining nitrogen heterocycle to form the
tricyclic phosphonium salt (3a—d). Then, the attack of
the chloride ion on the C atom of the methylene group
bound to the O atom of the heterocycle leads to the
dihydrofuranꢀring opening. The resulting spirocyclic biꢀ
polar ion (4a—d) is stabilized through the formation of
the conjugated system of the P=C—C=O bonds givꢀ
ing rise to the final products, viz., 6,8ꢀdisubstituted
10ꢀ(2ꢀchloroethyl)ꢀ9ꢀoxoꢀ1,4ꢀdiphenylꢀ1,4,7,8ꢀtetraazaꢀ
5ꢀphosphaspiro[4.5]ꢀdecaꢀ6,10ꢀdienes (5a—d). It should
be noted that the reaction follows this pathway regardꢀ
less of the nature of the substituent at the carbenium
atom of nitrile imine. Hence, unlike the analogous reacꢀ
tion involving 2ꢀ(4,5ꢀdihydroꢀ3ꢀfuryl)ꢀ1,3ꢀdiphenylꢀ1,3ꢀ
The 31P NMR spectra of spiro compounds 5a—d have
a signal at δP 17.8—18.4, which differs substantially from
the chemical shift of the P atom in the analogous
spirophosphonium compound (δP 4.1).2 In the IR specꢀ
tra of spiro compounds 5a—d, the absorption band of
the carbonyl group of the ring is substantially shifted to
the longꢀwavelength region (1575—1605 cm–1), which is
indicative of the involvement of this group into the conꢀ
jugated O=C—C=P system. In the 1H NMR spectra
of spiro compounds 5a—d, the signals for the proꢀ
tons of the =CH2 group are observed as doublets of
3
3
triplets (δ 2.64—2.75, JH,H = 7.5—7.9 Hz, JP,H
=
15.3—15.6 Hz), the signals for the protons of the CH2Cl
3
3
diazaꢀ2λ ꢀphospholidine, the diazaphosphorineꢀring cloꢀ
group are observed as triplets (δ 3.26—3.36, JH,H =
sure in the latter reactions is accompanied by the reꢀ
placement of the Cl atom rather than by the dihydrofuranꢀ
ring opening to yield finally products with essentially
different structures.
10ꢀ(2ꢀChloroethyl)ꢀ9ꢀoxoꢀ1,4ꢀdiphenylꢀ1,4,7,8ꢀ
tetraazaꢀ5ꢀphosphaspiro[4.5]ꢀdecaꢀ6,10ꢀdienes 5a—d
7.5—7.9 Hz), and the signals for the protons of two
CH2N groups are manifested as multiplets (δ 3.73—4.05
and 4.00—4.24).
The structures of spiro compounds 5a—d were unꢀ
ambiguously established based on the results of Xꢀray
diffraction analysis of 8ꢀpꢀbromophenylꢀ10ꢀ(2ꢀchloroꢀ

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Trishin et al.
C(14)
C(13)
C(25)
Br
C(24)
C(23)
C(15)
O(2)
C(12)
C(11) N(1)
C(26)
C(9)
C(8)
O(3)
N(2)
C(1)
C(27)
C(16)
C(28)
O(1)
C(10)
N(4)
C(2)
C(7)
P
C(3)
C(5)
C(4)
N(3)
C(6)
C(22)
C(21)
C(17)
Cl
C(18)
C(20)
C(19)
Fig. 2. Overall view of the molecule of 8ꢀpꢀbromophenylꢀ10ꢀ(2ꢀchloroethyl)ꢀ6ꢀethoxycarbonylꢀ9ꢀoxoꢀ1,4ꢀdiphenylꢀ1,4,7,8ꢀtetraazaꢀ
5ꢀphosphaspiro[4.5]ꢀdecaꢀ6,10ꢀdiene (5c).
ethyl)ꢀ6ꢀethoxycarbonylꢀ9ꢀoxoꢀ1,4ꢀdiphenylꢀ1,4,7,8ꢀ
tetraazaꢀ5ꢀphosphaspiro[4.5]ꢀdecaꢀ6,10ꢀdiene (5c)
(Fig. 2, Tables 3 and 4). The sixꢀmembered ring inꢀ
volved in the bicyclic spirane system adopts a halfꢀboat
conformation in which the P, N(2), C(2), and C(3)
atoms are coplanar to within 0.03 Å, whereas the N(1)
and C(1) atoms deviate from this plane in the same
direction by 0.15 and 0.23 Å, respectively. The fiveꢀ
membered heterocycle, like that in the molecule of the
83.3°, i.e., these heterocycles are approximately perpenꢀ
dicular to each other. The P atom has a strongly disꢀ
torted tetrahedral configuration (the X—P—Y angles are
94.5—117.2°). The C(23)—C(28) benzene ring is twisted
with respect to the plane of the sixꢀmembered heteroꢀ
cycle by 52.7°. The C(17)—C(22) and C(11)—C(16) benꢀ
zene rings are twisted relative to the plane of the fiveꢀ
Table 4. Selected bond angles (ω) in molecule 5c
3
starting 1,3ꢀdiazaꢀ2λ ꢀphospholidine 1, adopts an enveꢀ
Angle
ω/deg
Angle
ω/deg
lope conformation in which with the C(4) atom deviates
from the plane passing through the remaining atoms
(which are coplanar to within 0.03 Å) by 0.29 Å. The
angle between the mean planes of the heterocycles is
N(3)—P—N(4)
N(3)—P—C(3)
N(4)—P—C(3)
N(3)—P—C(1)
N(4)—P—C(1)
C(3)—P—C(1)
C(8)—O(3)—C(9) 118.0(7) N(3)—C(4)—C(5)
C(1)—N(1)—N(2) 122.8(6) N(4)—C(5)—C(4)
N(1)—N(2)—C(23) 114.4(6) C(3)—C(6)—C(7)
N(1)—N(2)—C(2) 126.9(6) C(6)—C(7)—Cl
C(23)—N(2)—C(2) 118.7(5) O(2)—C(8)—O(3)
C(17)—N(3)—C(4) 119.8(6) O(2)—C(8)—C(1)
94.5(3) O(1)—C(2)—C(3)
117.2(3) O(1)—C(2)—N(2)
114.4(3) C(3)—C(2)—N(2)
113.2(3) C(2)—C(3)—C(6)
115.1(3) C(2)—C(3)—P
103.1(3) C(6)—C(3)—P
126.7(7)
115.3(6)
117.9(6)
118.4(6)
123.5(6)
118.2(5)
107.3(6)
107.8(7)
114.5(6)
110.2(6)
123.0(7)
126.1(7)
110.8(7)
Table 3. Selected bond lengths (d) in molecule 5c
Bond
d/Å
Bond
d/Å
Br—C(26)
Cl—C(7)
P—N(3)
P—N(4)
P—C(3)
1.893(8) N(2)—C(23)
1.789(9) N(2)—C(2)
1.657(6) N(3)—C(17)
1.664(7) N(3)—C(4)
1.696(7) N(4)—C(11)
1.762(8) N(4)—C(5)
1.216(8) C(1)—C(8)
1.201(9) C(2)—C(3)
1.316(9) C(3)—C(6)
1.453(10) C(4)—C(5)
1.299(9) C(6)—C(7)
1.334(8) C(9)—C(10)
1.437(9)
1.463(9)
1.403(10)
1.469(9)
1.412(10)
1.462(10)
1.480(10)
1.403(10)
1.482(11)
1.498(12)
1.525(11)
1.471(19)
C(17)—N(3)—P
C(4)—N(3)—P
124.0(5) O(3)—C(8)—C(1)
113.0(5) C(10)—C(9)—O(3) 112.5(10)
P—C(1)
O(1)—C(2)
O(2)—C(8)
O(3)—C(8)
O(3)—C(9)
N(1)—C(1)
N(1)—N(2)
C(11)—N(4)—C(5) 121.4(7) C(16)—C(11)—N(4) 119.9(8)
C(11)—N(4)—P
C(5)—N(4)—P
124.1(5) C(12)—C(11)—N(4) 121.1(7)
113.1(5) C(22)—C(17)—N(3) 121.9(6)
N(1)—C(1)—C(8) 113.2(6) N(3)—C(17)—C(18) 120.9(7)
N(1)—C(1)—P
C(8)—C(1)—P
124.1(5) C(24)—C(23)—N(2) 119.3(7)
122.7(5) C(28)—C(23)—N(2) 120.0(7)

3
Reactions of 1,3ꢀdiazaꢀ2λ ꢀphospholidine
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 6, June, 2002
1049
(20 mL) was added dropwise with stirring to a solution of
N,N´ꢀdiphenylethylenediamine (6.4 g, 30 mmol) and triethylꢀ
amine (6.6 g, 65 mmol) in benzene (150 mL) at 0—5 °C. The
reaction mixture was stirred at 0—5 °C for 0.5 h and then at
20 °C for 0.5 h. Triethylamine hydrochloride was filtered off
and washed with benzene (30 mL). The filtrate was concenꢀ
trated under reduced pressure. The residue was treated with
warm diethyl ether (100 mL), the solution was decanted from a
small amount of the precipitate, and the ether was concenꢀ
trated to 30% of the initial volume. The solution was kept at
0 °C for several days and then the precipitate of compound 1
that formed was filtered off. Compound 1 was obtained in a
yield of 7.0 g (68%), m.p. 93—95 °C. Found (%): C, 62.51;
H, 5.39; P, 8.73. C18H18ClN2OP. Calculated (%): C, 62.71;
H, 5.26; P, 8.98. IR, ν/cm–1: 1035, 1259 (C—O—C); 1640
membered heterocycle by 14.1 and 24.5°, respectively.
The ethoxycarbonyl group is planar to within 0.05 Å.
The C(3)—C(6)—C(7)—Cl chain is also planar to within
0.02 Å. The P—C(3) and C(3)—C(2) bond lengths are
indicative of the conjugation in the P=C—C=O system.
Thus, the P—C(3) bond (1.696 Å) in the sixꢀmembered
heterocycle is shortened as compared to the correspondꢀ
ing bonds in the analogous spirophosphonium compound
(1.733 Å)2 and the monocyclic 1,2,4ꢀdiazaphosphorine
compound (1.745 Å).1 At the same time, the C(3)—C(2)
bond (1.403 Å) is substantially elongated as compared to
the corresponding bonds in the spirophosphonium comꢀ
pound (1.359 Å)2 and the monocyclic 1,2,4ꢀdiazaꢀ
phosphorine compound (1.338 Å).1 Apparently, this conꢀ
jugation, which eliminates the ylide character of the P=C
bond, is responsible for high hydrolytic stability of spiro
compounds 5a—d. These compounds can be stored unꢀ
der normal conditions over a long period and are not
hydrolyzed to a noticeable degree upon heating with
water.
3
(C=C). 1H NMR, δ: 2.60 (t, 2 H, =CCH2, JH,H = 9.3 Hz);
3.73 and 3.82 (both m, 2 H each, CH2N); 4.33 (t, 2 H, OCH2,
3JH,H = 9.3 Hz); 6.82—7.31 (m, 10 H, Ph). 31P NMR, δ: 70.4.
6,8ꢀDisubstituted 10ꢀ(2ꢀchloroethyl)ꢀ9ꢀoxoꢀ1,4ꢀdiphenylꢀ
1,4,7,8ꢀtetraazaꢀ5ꢀphosphaspiro[4.5]ꢀdecaꢀ6,10ꢀdienes (5a—d)
3
(general procedure). A solution of 1,3ꢀdiazaꢀ2λ ꢀphospholidine
1 (5 mmol), the corresponding hydrazonoyl halide (5 mmol),
and triethylamine (2 mL) in 20 mL of benzene (in the reaction
with the use of Nꢀphenylbenzohydrazonoyl chloride) or THF
(in the reactions with the use of other hydrazonoyl halides) was
kept at 20 °C for 3 days. Triethylamine hydrohalide (∼100%)
was filtered off and washed with the solvent (5 mL) in which
the reaction was conducted. The solvent was distilled off under
reduced pressure and the virtually crystalline residue was trituꢀ
rated with a 2 : 1 benzene—diethyl ether mixture (5 mL). Comꢀ
pounds 5a—d were filtered off and recrystallized.
Experimental
The IR spectra of compounds 1 and 5a—d were recorded
1
on an IKSꢀ29 instrument in KBr pellets. The H NMR spectra
of solutions in CDCl3 were measured on a Bruker AMꢀ500
spectrometer (500.1 MHz) in the mode of internal stabilization
at the 2H resonance line. The 31P NMR spectra of solutions
in CDCl3 were recorded on a Bruker ACꢀ200 instrument
(81.4 MHz); the chemical shifts were measured relative to a
85% aqueous H3PO4 solution.
The reactions were carried out with the use of N,N´ꢀdiꢀ
phenylethylenediamine (Aldrich), γꢀbutyrolactone (Novoꢀ
cherkassk Plant of Synthetic Products, TU 6ꢀ09ꢀ3610ꢀ79),
phosphorus pentachloride (Plant Gꢀ4904, TU 609ꢀ3179ꢀ78),
and tetraethylammonium iodide (Voikov Plant, TU
6ꢀ09ꢀ05ꢀ485ꢀ76). 2ꢀChloroꢀ3ꢀdichlorophosphinoꢀ4,5ꢀdihydroꢀ
10ꢀ(2ꢀChloroethyl)ꢀ9ꢀoxoꢀ1,4,6,8ꢀtetraphenylꢀ1,4,7,8ꢀ
tetraazaꢀ5ꢀphosphaspiro[4.5]ꢀdecaꢀ6,10ꢀdiene (5a), the yield
was 86%, m.p. 210—212 °C (benzene). Found (%): C, 68.90;
H, 5.43; P, 5.56. C31H28ClN4OP. Calculated (%): C, 69.08;
H, 5.24; P, 5.75. IR, ν/cm–1: 1590 (C=O). 1H NMR, δ: 2.64
3
3
(dt, 2 H, =CCH2, JH,H = 7.7 Hz, JP,H = 15.4 Hz); 3.31 (t,
2 H, CH2Cl, 3JH,H = 7.7 Hz); 3.73 and 4.00 (both m, 2 H each,
CH2N); 6.92—7.51 (m, 20 H, Ph).31P NMR, δ: 17.8.
10ꢀ(2ꢀChloroethyl)ꢀ6ꢀpꢀnitrophenylꢀ9ꢀoxoꢀ1,4,8ꢀtriphenylꢀ
1,4,7,8ꢀtetraazaꢀ5ꢀphosphaspiro[4.5]ꢀdecaꢀ6,10ꢀdiene (5b), the
yield was 75%, m.p. 230—232 °C (acetone). Found (%):
C, 63.90; H, 4.43; P, 5.52. C31H27ClN5O3P. Calculated (%):
C, 63.75; H, 4.66; P, 5.30. IR, ν/cm–1: 1550 (NO2); 1575
furan (b.p. 60—63 °C (0.5 Torr), δ 150.5) was prepared by the
P
reaction of phosphorus pentachloride with γꢀbutyrolactone by
analogy with a known procedure5 followed by reduction of the
resulting complex with tetraethylammonium iodide. NꢀPhenylꢀ
benzohydrazonoyl chloride (m.p. 130—131 °C), pꢀnitroꢀNꢀ
phenylbenzohydrazonoyl chloride (m.p. 158—159 °C), and
pꢀbromophenylhydrazone of ethoxycarbonylformyl chloride
(m.p. 164—165 °C) were synthesized according to procedures
reported previously.6 Phenylhydrazone of pꢀnitrobenzoylformyl
bromide (m.p. 208—210 °C) was prepared analogously to the
corresponding chlorides according to a known procedure.7 Diꢀ
ethyl ether, THF, and triethylamine were dried over NaOH
followed by distillation over sodium. Benzene was dried by
azeotropic distillation with water and then distilled over sodium.
The synthesis of 2ꢀ(2ꢀchloroꢀ4,5ꢀdihydroꢀ3ꢀfuryl)ꢀ1,3ꢀ
3
(C=O). 1H NMR, δ: 2.64 (dt, 2 H, =CCH2, JH,H = 7.5 Hz,
3
3JP,H = 15.4 Hz); 3.34 (t, 2 H, CH2Cl, JH,H = 7.5 Hz); 3.82
and 4.08 (both m, 2 H each, CH2N); 6.90—8.13 (m, 19 H, Ar).
31P NMR, δ: 17.8.
8ꢀpꢀBromophenylꢀ10ꢀ(2ꢀchloroethyl)ꢀ6ꢀethoxycarbonylꢀ9ꢀ
oxoꢀ1,4ꢀdiphenylꢀ1,4,7,8ꢀtetraazaꢀ5ꢀphosphaspiro[4.5]ꢀdecaꢀ
6,10ꢀdiene (5c), the yield was 82%, m.p. 201—202 °C (benzene).
Found (%): C, 54.90; H, 4.33; P, 5.22. C28H27BrClN4O3P.
Calculated (%): C, 54.78; H, 4.43; P, 5.05. IR, ν/cm–1: 1030,
1190 (C—O—C); 1580, 1605 (C=O in the ring); 1695, 1720
3
(C=O in COOEt). 1H NMR, δ: 1.24 (t, 3 H, Me, JH,H
=
=
3
3
3
diphenylꢀ1,3ꢀdiazaꢀ2λ ꢀphospholidine (1) and its reactions with
7.2 Hz); 2.68 (dt, 2 H, =CCH2, JH,H = 7.9 Hz, JP,H
3
nitrile imines were carried out under argon with the use of
anhydrous solvents and triethylamine.
15.6 Hz); 3.26 (t, 2 H, CH2Cl, JH,H = 7.9 Hz); 4.00 and 4.11
3
(both m, 2 H each, CH2N); 4.17 (q, 2 H, CH2O, JH,H
7.2 Hz); 6.92—7.56 (m, 14 H, Ar). 31P NMR, δ: 18.4.
=
2ꢀ(2ꢀChloroꢀ4,5ꢀdihydroꢀ3ꢀfuryl)ꢀ1,3ꢀdiphenylꢀ1,3ꢀdiazaꢀ
2λ ꢀphospholidine (1). A solution of 2ꢀchloroꢀ3ꢀdichloroꢀ
3
10ꢀ(2ꢀChloroethyl)ꢀ6ꢀpꢀnitrobenzoylꢀ9ꢀoxoꢀ1,4,8ꢀtriphenylꢀ
1,4,7,8ꢀtetraazaꢀ5ꢀphosphaspiro[4.5]ꢀdecaꢀ6,10ꢀdiene (5d), the
phosphinoꢀ4,5ꢀdihydrofuran (6.2 g, 30 mmol) in benzene

1050
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 6, June, 2002
Trishin et al.
yield was 68%, m.p. 188—190 °C (acetone). Found (%):
and by the Ministry of Education of the Russian Federaꢀ
tion (Project No. Е 00ꢀ5ꢀ317).
C, 62.90; H, 4.33; P, 5.22. C32H27ClN5O4P. Calculated (%):
C, 62.80; H, 4.45; P, 5.06. IR, ν/cm–1: 1555 (NO2); 1575,
3
1600 (C=O). 1H NMR, δ: 2.75 (dt, 2 H, =CCH2, JH,H
=
7.9 Hz, 3JP,H = 15.3 Hz); 3.36 (t, 2 H, CH2Cl, 3JH,H = 7.9 Hz);
4.05 and 4.24 (both m, 2 H each, CH2N); 6.98—8.15 (m, 19 H,
Ar). 31P NMR, δ: 18.7.
References
3
1. Yu. G. Trishin, V. I. Namestnikov, and V. K. Belsky, Izv.
Akad. Nauk, Ser. Khim., 2000, 125 [Russ. Chem. Bull., Int.
Ed., 2000, 49, 129].
2. Yu. G. Trishin, V. I. Namestnikov, and V. K. Belsky, Izv.
Akad. Nauk, Ser. Khim., 2001, 1390 [Russ. Chem. Bull., Int.
Ed., 2001, 50, 1461].
3. V. I. Namestnikov, Yu. G. Trishin, and V. K. Belsky,
Zh. Obshch. Khim., 1996, 66, 1404 [Russ. J. Gen. Chem.,
1996, 66 (Engl. Transl.)]; Yu. G. Trishin, V. I. Namestnikov,
and V. K. Belsky, Zh. Obshch. Khim., 1999, 69, 767 [Russ.
J. Gen. Chem., 1999, 69 (Engl. Transl.)].
4. V. I. Namestnikov and Yu. G. Trishin, Zh. Obshch. Khim.,
1997, 67, 1923 [Russ. J. Gen. Chem., 1997, 67 (Engl. Transl.)].
5. S. V. Fridland, A. I. Efremov, and R. A. Salakhutdinov,
Zh. Obshch. Khim., 1978, 48, 319 [J. Gen. Chem. USSR, 1978,
48 (Engl. Transl.)].
Xꢀray crystallography study of crystals of 1,3ꢀdiazaꢀ2λ ꢀ
phospholidine 1 and 10ꢀ(2ꢀchloroethyl)ꢀ6ꢀethoxycarbonylꢀ9ꢀ
oxoꢀ1,4ꢀdiphenylꢀ1,4,7,8ꢀtetraazaꢀ5ꢀphosphaspiro[4.5]ꢀdecaꢀ
6,10ꢀdiene (5c) was carried out on a CADꢀ4 diffractometer
(MoꢀKα radiation, θ/2θ scan technique). The crystals of comꢀ
pound 1 are monoclinic, C18H18ClN2OP, a = 10.518(2) Å, b =
18.066(4) Å, c = 9.828(2) Å, β = 113.25(3)°, V = 1715.8(6) Å3;
space group P21/c, Z = 4, dcalc = 1.335 g cm–3. The structure of
1 was solved by direct methods, R = 0.0373, Rw = 0.1395
(3410 reflections with I > 2σ(I )). The selected bond lengths
and bond angles in molecule 1 are given in Tables 1 and 2,
respectively. The crystals of compound 5c are monoclinic,
C28H27BrClN4O3P, a = 16.422(3) Å, b = 10.113(2) Å, c =
18.676(4) Å, β = 113.76(3)°, V = 2838.7(10) Å3; space group
P21/c, Z = 4, dcalc = 1.436 g cm–3. The structure of 5c was
solved by direct methods, R = 0.0437, Rw = 0.1429 (2226 reꢀ
flections with I > 2σ(I )). The selected bond lengths and bond
angles in molecule 5c are given in Tables 3 and 4, respectively.
The atomic coordinates and the complete tables of the bond
lengths and bond angles for compounds 1 and 5c were deposꢀ
ited with the Cambridge Structural Database (CCDC 177905
and CCDC 177904, respectively).
6. R. Huisgen, M. Seidel, G. Wallbillich, and H. Knupfer,
Tetrahedron, 1962, 17, 3; R. G. Dubenko and E. F. Gorbenko,
Zh. Org. Khim., 1968, 4, 634 [J. Org. Chem. USSR, 1968, 4
(Engl. Transl.)].
7. R. G. Dubenko and P. S. Pel´kis, Zh. Obshch. Khim., 1963,
33, 3917 [J. Gen. Chem. USSR, 1963, 33 (Engl. Transl.)].
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 00ꢀ03ꢀ32797)
Received February 15, 2002