Reaction of arylenedioxytrihalophosphoranes with acetylenes 11. Electronic effect of the substituent in arylacetylene on the reaction rate

Article abstract of DOI:10.1007/s11172-013-0008-2

The reactions of 2,2,2-trichlorobenzo-1,3,2-dioxaphosphole and its benzo-substituted derivatives with arylacetylenes containing strong +M-donors and -M-acceptors afford benzo[e]-1,2-oxaphosphinine 2-oxides (phosphacoumarins) in high yields. Studies by the competitive reaction method showed that the reaction rate is sensitive to the electronic nature of the substituent in arylacetylene. Thus, the introduction of +M-donors into the phenyl ring of arylacetylene leads to an increase in the reaction rate, whereas the introduction of -M-acceptors results in its substantial decrease. The molecular and supramolecular structures of selected 2-hydroxyphosphacoumarins and substituted vinylphosphonate, which is generated by the cleavage of the P-heterocycle, were studied by X-ray diffraction.

Full text of DOI:10.1007/s11172-013-0008-2

Russian Chemical Bulletin, International Edition, Vol. 62, No. 1, pp. 55—70, January, 2013
55
Reaction of arylenedioxytrihalophosphoranes with acetylenes
11.* Electronic effect of the substituent in arylacetylene on the reaction rate
A. V. Nemtarev,a V. F. Mironov,a A. S. Aniskin,a D. S. Baranov,b E. V. Mironova,a
D. B. Krivolapov,a R. Z. Musin,a S. F. Vasilevskii,b N. O. Druzhkov,c and V. K. Cherkasovc
aA. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of the Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843) 273 2253. Eꢀmail: mironov@iopc.ru
bInstitute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences,
3 ul. Institutskaya, 630090 Novosibirsk, Russian Federation.
Fax: +7 (383) 330 7350. Eꢀmail: vasilev@kinetics.nsc.ru
cG. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences,
49 ul. Tropinina, 603950 Nizhnii Novgorod, Russian Federation.
Fax: +7 (831) 462 7497. Eꢀmail: cherkasov@iomc.ras.ru
The reactions of 2,2,2ꢀtrichlorobenzoꢀ1,3,2ꢀdioxaphosphole and its benzoꢀsubstituted deꢀ
rivatives with arylacetylenes containing strong +Mꢀdonors and –Mꢀacceptors afford benzo[e]ꢀ
1,2ꢀoxaphosphinine 2ꢀoxides (phosphacoumarins) in high yields. Studies by the competitive
reaction method showed that the reaction rate is sensitive to the electronic nature of the
substituent in arylacetylene. Thus, the introduction of +Mꢀdonors into the phenyl ring of
arylacetylene leads to an increase in the reaction rate, whereas the introduction of –Mꢀaccepꢀ
tors results in its substantial decrease. The molecular and supramolecular structures of selected
2ꢀhydroxyphosphacoumarins and substituted vinylphosphonate, which is generated by the cleavꢀ
age of the Pꢀheterocycle, were studied by Xꢀray diffraction.
Key words: arylacetylene, 2,2,2ꢀtrichlorobenzoꢀ1,3,2ꢀdioxaphosphole, 2,2,2ꢀtrichloroꢀ5ꢀ
methylbenzoꢀ1,3,2ꢀdioxaphosphole, 4,7ꢀbis(tertꢀbutyl)ꢀ2,2,2ꢀtrichlorobenzoꢀ1,3,2ꢀdioxaphosꢀ
phole, ipsoꢀsubstitution of oxygen, benzo[e]ꢀ1,2ꢀoxaphosphorinine 2ꢀoxides, chlorination of
the aromatic ring, reaction rate, electronic effect of the substituent, vinylphosphonate.
The development of facile and efficient methods for
the synthesis of compounds containing the P—C bond is a
topical problem in chemistry of heteroorganic comꢀ
pounds,2—4 because they are widely used in various fields
of chemistry, biology, and industry.5 These compounds
are often considered as phosphate analogs, which exhibit
high and diverse biological activities and which are virtuꢀ
ally not cleaved by hydrolases and transferases.6,7 This is
the reason why the synthesis of P—C analogs of different
natural compounds (e.g., aminophosphonates, P—Cꢀsugꢀ
ars, P—Cꢀnucleosides, and so on) has attracted firm inꢀ
terest.8,9 Earlier,10—14 we have developed a new approach
to the synthesis of compounds containing the P—C bond,
benzo[e]ꢀ1,2ꢀoxaphosphinines (or phosphacoumarins),
which are P—C analogs of coumarin. This approach is
based on the reaction of 2,2,2ꢀtrichlorobenzoꢀ1,3,2ꢀdioxaꢀ
phosphole (1) with arylacetylenes. The reaction involves
the easy formation of the P—C bond, the ipsoꢀsubstitution
of oxygen by carbon, and the chlorination of the phenylꢀ
ene moiety at the para position with respect to the enꢀ
docyclic oxygen atom of the heterocycle. In some cases,
the aboveꢀmentioned transformations are accompanied
by the ipsoꢀsubstitution of the tertꢀbutyl group by chlorine
and the ipsoꢀsubstitution of bromine by chlorine. More
recently, many important features of the reaction, such as
the effect of the nature of the halogen at the PV atom, the
effect of the nature of bulky substituents in the phenylene
ring of 2,2,2ꢀtrihalobenzoꢀ1,3,2ꢀdioxaphosphole, the efꢀ
fect of the increase in the coordination number of the
phosphorus atom from 5 to 6, and other factors have been
elucidated (see the review15). However, no attention was
given to such an important aspect of this multistep reacꢀ
tion as the influence of the electronic effect of substituents
in the aromatic moiety of arylacetylene both on the synꢀ
thetic result and the reaction rate as a whole. The aim of
this work is to investigate the latter aspect.
Results and Discussion
The introduction of both nitro and methoxy groups
into arylacetylene molecules does not cause a hindrance
* For Part 10, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 0056—0070, January, 2013.
1066ꢀ5285/13/6201ꢀ55 © 2013 Springer Science+Business Media, Inc.

56
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
Nemtarev et al.
Scheme 2
to the formation of phosphacoumarins, which substanꢀ
tially extends the synthetic potential of the reaction under
consideration. Thus, the reaction of dioxaphosphole 1 with
pꢀnitrophenylacetylene produces 2,6ꢀdichloroꢀ4ꢀ(4ꢀnitroꢀ
phenyl)benzo[e]ꢀ1,2ꢀoxaphosphinine 2ꢀoxide (2a)
(Scheme 1). According to the 31P NMR spectroscopic
2
data (P 18, JHCP = 25 Hz), the latter compound is the
only phosphorusꢀcontaining reaction product. The mass
spectrum of this product also contains only a molecular
ion peak at m/z 355 corresponding to the molecular forꢀ
mula C14H8Cl2NO4P, which is indicative of the introducꢀ
tion of the chlorine atom into the molecule. The regioꢀ
chemistry of the chlorination of the phenylene moiety was
determined by 13C and 13C—{1H} NMR spectroscopy. The
absence of the coupling constant with the proton H(6) in
the multiplet of the C(8) atom in the 13C NMR spectrum
confirms the presence of the chlorine atom at position 6 of
oxaphosphinine 2a.
a
Scheme 1
10
6
2

b
X = 4ꢀNO2 (a), 4ꢀMeO (b)
10
6
2

After the hydrolysis and treatment with tertꢀbutylꢀ
amine, the corresponding phosphonic acid (3a) and its
salt (4a) were isolated. Their structures were determined
by NMR and IR spectroscopy. It should be noted that the
storage of hydroxyphosphinine 3a in wet DMSO over
a long period of time results not only in the gradual cleavꢀ
age of the Pꢀheterocycle to form the Z isomer of phosphoꢀ
nic acid (Zꢀ5) but also in the isomerization of the latter,
apparently, to the thermodynamically more stable E isoꢀ
c
6
7
5
1
mer (Eꢀ5) (Scheme 2), This was established by H and
31P NMR spectroscopy. The reaction dynamics observed
by 31P NMR spectroscopy during a long period of time
(DMSO, 20 C) is illustrated by Fig. 1.
10
6
2

Fig. 1. Dynamics of the hydrolysis and isomerization of acid 3a
according to the 31P NMR spectroscopic data in aqueous
DMSOꢀd6 (162.0 MHz) after 3 weeks (a), 11 months (b), and
26 months (c).
The reaction of benzodioxaphosphole 1 with pꢀmethꢀ
oxyphenylacetylene follows the same pathway. This reacꢀ
tion also gives the only phosphorusꢀcontaining product,

Arylacetylenes and trichlorobenzodioxaphosphole
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
57
fragment is planar within 0.002(4) Å; the C(3) and P(2)
atoms deviate from this plane by 0.294(4) and 0.598(1) Å,
respectively; the P(2)C(3)C(4)C(4a) fragment is planar
within 0.016(4) Å; the O(1) and C(8a) atoms deviate from
this plane by –0.516(3) and –0.236(4) Å, respectively).
The oxygen atom O(2) substantially deviates from both
planes (by 2.089(3) and –1.396(3) Å, respectively) and
is in the axial position. The oxygen atom O(3) is in the
equatorial position (the deviations are –0.046(3) and
0.897(3) Å, respectively). The dihedral angle between
the O(1)C(8a)C(4a)C(4) and P(2)C(3)C(4)C(4a) planes
is 12.7(2). The dihedral angle between the plane of
the paraꢀmethoxyphenyl substituent at position 4 and
the P(2)C(3)C(4)C(4a) plane (59.1(2)) virtually does
not allow this substituent to be conjugated with the
C(3)=C(4) bond.
In the crystal, the molecules are linked to each other
by O(2)—H(2)...O(3´) hydrogen bonds (see Table 2) to
form chains along the crystallographic 0a axis (Fig. 3).
An analysis of the results of these reactions and a comꢀ
parison of these reaction products with the reaction prodꢀ
ucts of phosphorane 1 with phenylacetylene11 show that
the electronꢀdonating methoxy group and the electronꢀ
withdrawing nitro group in the aromatic moiety of aceꢀ
tylene have no effect on the regiochemistry of the chloriꢀ
nation of the arylene moiety of oxaphosphinines, but afꢀ
fect the reaction rate, which is confirmed by the 31P—{1H}
NMR dynamic experiment. Thus, the reaction with
pꢀmethoxyphenylacetylene occurs virtually immediately
and is accompanied by a strong exo effect, whereas the
reaction with pꢀnitrophenylacetylene is slower, as eviꢀ
denced by the presence of the signal of the starting phosꢀ
phorane (P –26) along with the signal of the reaction
product in the 31P NMR spectrum recorded 5 min after
the mixing of the reagents.
O(2)
P(2)
C(10)
C(3)
C(11)
C(12)
C(4)
C(9)
C(5)
Cl(6)
O(3)
O(1)
C(8a)
C(4a)
C(6)
C(15)
C(14)
O(12)
C(13)
C(8)
C(7)
Fig. 2. Molecular structure of 3b in the crystal and the atomic
numbering scheme (here and in other figures, the thermal ellipꢀ
soids are drawn at the 30% probability level).
2,6ꢀdichloroꢀ4ꢀ(4ꢀmethoxyphenyl)benzo[e]ꢀ1,2ꢀoxaphosꢀ
phinine 2ꢀoxide (2b). After the hydrolysis, phosphonic acid
(3b) was isolated. In the 13C—{1H} NMR spectrum of this
compound, the carbon atoms C(4a), C(8), and C(8a) apꢀ
pear as doublets with coupling constants of phosphorus,
which corresponds to its cyclic nature. The heterocycle of
molecule 3b (Fig. 2, Tables 1—3) adopts a distorted (unsymꢀ
metrical) boat conformation (the O(1)C(8a)C(4a)C(4)
Table 1. Selected geometric parameters for strucꢀ
ture 3b
Parameter
Value
Bond length
d/Å
P(2)—O(1)
P(2)—O(2)
P(2)—O(3)
P(2)—C(3)
O(1)—C(8a)
C(3)—C(4)
C(4)—C(4a)
C(4a)—C(5)
C(4a)—C(8a)
C(5)—C(6)
C(6)—C(7)
C(7)—C(8)
C(8)—C(8a)
1.593(4)
1.519(3)
1.450(3)
1.744(4)
1.375(5)
1.347(6)
1.460(6)
1.399(6)
1.398(6)
1.364(7)
1.366(6)
1.365(7)
1.360(7)
The reaction of 2,2,2ꢀtrichloroꢀ5ꢀmethylbenzoꢀ1,3,2ꢀ
dioxaphosphole (6) with pꢀnitrophenylacetylene is charꢀ
acterized by lower selectivity of the ipsoꢀsubstitution of
the oxygen atom and the chlorination of the arene moiety
O
H
O
P
Bond angle
/deg
O(1)—P(2)—O(2)
O(1)—P(2)—O(3)
O(2)—P(2)—C(3)
O(3)—P(2)—C(3)
P(2)—O(1)—C(8a)
P(2)—C(3)—C(4)
107.9(2)
109.2(2)
111.0(2)
114.8(2)
123.4(3)
121.2(3)
Torsion angle
/deg
O(2)—P(2)—O(1)—C(8a)
O(3)—P(2)—O(1)—C(8a)
P(2)—C(3)—C(4)—C(4a)
C(3)—C(4)—C(4a)—C(8a)
C(3)—C(4)—C(9)—C(10)
85.2(3)
–155.1(3)
3.5(5)
–14.5(6)
–56.8(6)
Fig. 3. Hydrogen bond network in the crystal of compound 3b.

58
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
Nemtarev et al.
Table 2. Hydrogen bond parameters in the crystals of compounds 3b and 24 (D is the donor, A is the
acceptor)
...
D—H
A
d/Å
...
D—H—A angle Symmetry operation
/deg
...
D A
D—H
H
A
3b
O(2)—H(2)...O(3´)
0.92(2)
1.49(2)
2.407(4)
176(6)
1 + x, y, z
24
O(3)—H(3)...O(50)
O(4)—H(4)...O(2´)
O(1)—H(1)...O(2)
0.82(3)
0.84(3)
0.84(3)
1.74(4)
1.71(3)
2.24(3)
2.518(5)
2.557(4)
2.978(4)
160(3)
176(4)
147(5)
1 – x, 1 – y, –z
2 – x, 1 – y, –z
—
annulated to the Pꢀheterocycle (compared to the correꢀ
sponding reaction of phenylacetylene16). Three reaction
products of oxaphosphinine nature, viz., compounds 7, 8,
and 9, are formed in a ratio of 13.8 : 2.8 : 1 (Scheme 3).
Benzoxaphosphinine 7 is the major product characterized
by the molecular ion peak at m/z 369 in the electron imꢀ
pact mass spectrum. The structures of minor compounds
scopy. In the 13C NMR spectrum, compound 9 is characꢀ
terized by a triplet at C 40 assigned to the chloromethylꢀ
benzyl group.
The hydrolysis and fractional crystallization afforded
oxaphosphinine 10 (Scheme 4), whose storage in DMSO
resulted in the gradual cleavage of the oxaphosphinine
ring to form acid 11. The latter is manifested in the
31P NMR spectrum as a doublet with JHC(2)P = 12.6 Hz at
1
8 and 9 were established by H and 13C NMR spectroꢀ
Table 3. Crystallographic parameters of compounds 3b, 24, and 26 and the Xꢀray data collection and structure
refinement statistics
Parameter
3b
24
26
Crystal color, habit
Molecular formula
Colorless, needleꢀlike Colorless, plateletꢀlike
Colorless, prismatic
C23H27Cl2O3P
C15H12ClO4P
C22H27СlO6NP,
C3H6O
Molecular weight
Crystal system
Space group
Unit cell parameters
a/Å
b/Å
с/Å
/deg
/deg
645.33
Monoclinic
P 21/n
525.94
Monoclinic
P 21/n
453.32
Triclinic
Pꢀ1
4.687(5)
25.237(9)
12.370(4)
—
97.60(2)
—
1450(2)
4
1.478
3.86
9.040(2)
9.889(3)
29.157(7)
—
90.673(3)
—
2607(1)
4
1.340
2.52
7.210(2)
10.554(4)
15.342(5)
94.910(4)
95.665(4)
96.244(4)
1149.4(7)
2
/deg
3
V/Å
Z
dcalc/g cm–3
1.310
3.73
476
Absorption coefficient, (Mo)/cm–1
F(000)
664
1112
Number of observed reflections
R(int)
Number of observed
reflections with I > 2(I)
R factors
2847
0.1443
1115
5115
0.0384
3718
4412
0.0322
3089
R = 0.0623,
Rw = 0.0779
0.944
R = 0.0597,
Rw = 0.1480
0.937
R = 0.0514,
Rw = 0.1351
1.046
(I > 2(I))
Goodnessꢀofꢀfit
Number of parameters in refinement
hkl Ranges
195
336
269
–5  h  5,
–31  k  30,
–15  l  15
–11  h  10,
–12  k  12,
–35  l  35
–8  h  8,
–12  k  13,
–18  l  18

Arylacetylenes and trichlorobenzodioxaphosphole
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
59
Scheme 3
lower fields compared to cyclic oxaphosphinines. The conꢀ
stant JPC(2)C(3)C(4) = 7.3 Hz in the multiplet of the C(4)
atom and the absence of the spinꢀspin coupling of the
phosphorus nucleus with the carbon atoms C(8) and C(8a)
in the 13C NMR spectrum are also evidence for the acyclic
nature of acid 11. The treatment of phosphonic acid 10
with triethylamine gave ammonium salt 12, in which the
phosphonate anion retains the cyclic nature.
pꢀMethoxyphenylacetylene reacts with phosphole 6
more selectively than pꢀnitrophenylacetylene. After the
storage over a long period of time (>10 days) or heating,
oxaphosphinine 13 is formed as the only phosphorusꢀconꢀ
taining reaction product. The freshly prepared reacꢀ
tion product contains 12% of the intermediate 2ꢀ(5ꢀchloꢀ
roꢀ4ꢀmethylꢀ6ꢀoxocyclohexaꢀ1,4ꢀdienyl)ꢀ2ꢀ(4ꢀmethoxyꢀ
phenyl) dichlorovinylphosphonate (14), which gives a douꢀ
blet at P 26.6 (2JPCH = 31.0 Hz) in the 31P NMR specꢀ
trum (earlier,17 we have found related intermediates in the
reaction of tetrachloroꢀoꢀbenzoquinone with PCl3 and
arylacetylenes). The heating of vinylphosphonate 14 reꢀ
sulted in the elimination of HCl and the formation of
oxaphosphinine 13 (Scheme 5). The structure of the latter
compound was determined by NMR spectroscopy. After
the hydrolysis, cyclic phosphonic acid (15) was isolated.
The structure of the latter was also established by spectroꢀ
scopic methods.
Scheme 4
It should be noted that the Pꢀheterocycle of acid 15
was not cleaved even after storage in aqueous DMSO over
a long period of time due to the more efficient stabilizaꢀ
tion of the electronꢀdonating methoxy group. Apparently,
the electronꢀwithdrawing nitro group substantially increasꢀ
es the electrophilicity of the phosphorus atom in phosphaꢀ
coumarins, resulting in that it is more easily subjected to
the attack by nucleophiles, even by such weak nucleoꢀ
philes as water.
To qualitatively estimate the effect of the nature of
substituents in the phenylacetylene moiety on the formaꢀ
tion rate of phosphinines, we studied two model competiꢀ
tive reactions of dioxaphosphole 6 with an equimolar mixꢀ
ture of phenylacetylene and pꢀnitrophenylacetylene and
with an equimolar mixture of phenylacetylene and pꢀmethꢀ
oxyphenylacetylene (Scheme 6). The reactions were carꢀ
ried out in dichloromethane in the presence of hexene at
Scheme 5

60
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
Nemtarev et al.
Scheme 6
Scheme 7
20 C. The composition and the ratio of the components
were controlled both based on acetylene and oxaphosꢀ
phinines by 1H and 31P NMR spectroscopy and mass specꢀ
trometry. It appeared that the former reaction proceeds
almost quantitatively with the involvement of phenylacetꢀ
ylene to form 2,6ꢀdichloroꢀ7ꢀmethylꢀ4ꢀphenylbenzo[e]ꢀ
1,2ꢀoxaphosphinine 2ꢀoxide (16) (this compound was
characterized in the study16). In the latter case, the comꢀ
petitive reaction (pꢀmethoxyphenylacetylene/phenylacetꢀ
ylene) gives two phosphorusꢀcontaining compounds, viz.,
oxaphosphinines 13 and 16, in a ratio of ~2 : 1. However,
taking into account the high reactivity of acetylenes in the
latter competitive reaction, it was performed also at lower
temperature (–10 C). In this case, the ratio of oxaphosꢀ
phinines 13 and 16 was 8 : 1. After the hydrolysis of the
reaction mixtures of both competitive reactions, 6ꢀchloroꢀ
2ꢀhydroxyꢀ7ꢀmethylꢀ4ꢀphenylbenzo[e]ꢀ1,2ꢀoxaphosphinꢀ
ine 2ꢀoxide (17) (the constants and spectroscopic paraꢀ
meters of this compound are identical to those reported in
the study16) and compound 15 were isolated in high yields.
The competitive reactions show high selectivity to the
nature of acetylene. The rateꢀdetermining step is very sensitive
to the electronic nature of the group in the aryl substituꢀ
ent. The stronger the electronꢀdonating character of this
substituent, the higher the rate of the process as a whole.
According to the possible mechanism of the reaction
of trihalobenzoꢀ1,3,2ꢀdioxaphospholes with terminal
acetylenes, which has been considered in detail in the
study,15 it can be proposed that the nature of substituents
in phenylacetylene affects the competition for the coordiꢀ
nation with the phosphorus atom of benzoꢀ1,3,2ꢀdiꢀ
oxaphosphole (Lewis donorꢀacceptor interaction) in the
formation of the  complex (18) (Scheme 7). Acetylenes
containing stronger electronꢀdonating groups form more
stable  complexes and, consequently, these complexes
will more readily undergo the reorganization to the  comꢀ
plex (19) followed by the formation of the oxaphosphinꢀ
ine system.
X = 4ꢀOMe, 4ꢀNO2
4,7ꢀdi(tertꢀbutyl)ꢀ2,2,2ꢀtrichlorobenzoꢀ1,3,2ꢀdioxaphosꢀ
phole (20) (P –29.8). On the whole, the reaction is slowꢀ
er due to the steric effect in the molecule of dioxaphosꢀ
phole 20. Thus, the reaction of the latter with pꢀnitrophenꢀ
ylacetylene (Scheme 8) initially gives the intermediate of
the vinylꢀquinoid type, viz., 2ꢀ[3,6ꢀdi(tertꢀbutyl)ꢀ3ꢀchloroꢀ
6ꢀoxocyclohexaꢀ1,4ꢀdienyl]ꢀ2ꢀ(4ꢀnitrophenyl) dichloroꢀ
vinylphosphonate (21), in one day. The content of this
intermediate in the reaction mixture exceeds 80% (P 25.2,
2JPCH = 31.5 Hz) in 3 days. The heating of this compound
or its storage over a long period of time (>10 days) results
in its transformation into the final reaction product, oxꢀ
aphosphinine 22 (P 14.6, 2JPCH = 25.2 Hz). The reaction
dynamics was observed by 31P NMR spectroscopy (CH2Cl2)
and is illustrated by Fig. 4.
The introduction of the nitro group into the phenyl
substituent located at position 4 of the benzoxaphosphinꢀ
ine ring leads to a decrease in the stability of cyclic derivaꢀ
tive 23 to such an extent that the hydrolysis of compound
22 cannot be terminated in the step of the formation of 23,
and the reaction immediately gives acyclic phosphonic
acid 24 (see Scheme 8). The treatment of the latter with
triethylamine afforded salt 25.
The observed characteristic features of the reactions of
P,P,Pꢀtrichlorobenzoꢀ1,3,2ꢀdioxaphospholes with arylꢀ
acetylenes containing an electronꢀdonating or ꢀwithdrawꢀ
ing substituent in the benzene ring were observed also in
the reactions of these acetylenes with sterically hindered
The molecular geometry of compound 24 isolated as
the 1 : 1 acetone solvate was determined by Xꢀray difꢀ

Arylacetylenes and trichlorobenzodioxaphosphole
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
61
a
Cl(6)
21
C(18)
C(6)
C(17)
C(7)
C(8)
C(22)
C(19)
C(15)
C(16)
C(5)
20
22
C(8a)
O(3)
C(4a)
C(21)
O(1)
O(2)
C(20)
C(14)
C(13)
C(12)
O(122)
25 15
0
–30

C(4)
N(12)
b
C(9)
C(3)
21
P(2)
C(10)
C(4)
C(11)
O(121)
Fig. 5. Molecular structure of the acetone solvate of 24 and the
atomic numbering scheme (the acetone molecule is not shown).
22
fraction (Fig. 5, Tables 2—4). The phenylene moiety
C(4A)C(5)C(6)C(7)C(8)C(8a) is planar within 0.024(3) Å.
The deviations of the atoms are as follows: Cl(6), 0.0635(9) Å;
O(1), –0.033(3) Å; C(4), 0.193(3) Å; C(15), 0.061(3) Å;
C(19), 0.051(4) Å. A substantial deviation of the C(4)
atom from the phenylene moiety is apparently associated
with the presence of two bulky substituents, such as
the paraꢀnitrophenyl and phosphorylmethyl groups, at
this atom. The configuration of the substituents at the
C(3)=C(4) double bond is retained (Z) despite the hydrolꢀ
ysis. Figure 6 shows the dimer of compound 24 formed
via hydrogen bonds with the participation of the
P(2)—O(4)—H(4) and O(2´)=P(2´) groups. Each moleꢀ
cule in the dimer is linked by the O(3)—H(3) O(50)
hydrogen bond to the acetone solvent molecule. The hyꢀ
drogen bond parameters are given in Table 2.
pꢀMethoxyphenylacetylene reacts with phosphole 20
more vigorously without the formation of vinylꢀquinoidꢀ
type intermediates at 0 C to form oxaphosphinine 26 in
25 15
0
–30

c
22
...
25 15
0
–30

Fig. 4. Dynamics of changes in the composition of the reaction
mixture of dioxaphosphole 20 and 4ꢀnitrophenylacetylene with
time according to the 31P NMR spectroscopic data (36.48 MHz,
CH2Cl2) after 1 (a), 3 (b), and 12 days (s).
Table 4. Selected geometric parameters for structure 24
Parameter
Value
Parameter
Bond angle
Value
Parameter
Value
Torsion angle
/deg
Bond length
d/Å
/deg
O(2)—P(2)—C(3)—C(4)
O(4)—P(2)—C(3)—C(4)
P(2)—C(3)—C(4)—C(9)
P(2)—C(3)—C(4)—C(4a)
C(3)—C(4)—C(4a)—C(5)
C(3)—C(4)—C(9)—C(14)
C(9)—C(4)—C(4a)—C(8a)
C(4)—C(4a)—C(5)—C(15)
C(4)—C(4a)—C(8a)—O(1)
C(15)—C(5)—C(6)—Cl(6)
C(19)—C(8)—C(8a)—O(1)
–57.9(3)
179.1(3)
176.4(2)
4.3(4)
–103.7(4)
–142.7(3)
–90.3(3)
5.7(5)
P(2)—O(2)
P(2)—O(3)
P(2)—O(4)
P(2)—C(3)
O(1)—C(8a)
C(3)—C(4)
C(4)—C(4a)
C(4)—C(9)
C(4a)—C(5)
C(4a)—C(8a)
C(6)—C(7)
C(7)—C(8)
C(8)—C(8a)
1.480(2)
1.542(3)
1.546(3)
1.775(3)
1.378(4)
1.335(4)
1.514(4)
1.484(4)
1.422(4)
1.403(4)
1.379(4)
1.373(4)
1.393(4)
O(2)—P(2)—O(3)
O(2)—P(2)—O(4)
O(2)—P(2)—C(3)
O(3)—P(2)—C(3)
P(2)—C(3)—C(4)
C(3)—C(4)—C(4a)
C(4a)—C(4)—C(9)
C(4)—C(4a)—C(5)
C(8a)—C(8)—C(19)
C(4a)—C(5)—C(15)
Cl(6)—C(6)—C(5)
114.2(2)
113.1(2)
112.7(1)
103.8(2)
125.8(2)
122.8(3)
116.3(2)
125.4(3)
122.9(3)
125.9(2)
124.1(2)
–6.4(4)
2.6(4)
0.3(4)

62
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
Nemtarev et al.
Scheme 8
high yield (Scheme 9). The characteristic feature of this
compound is higher resistance of the phosphine heteroꢀ
cycle to the hydrolysis and aminolysis compared to comꢀ
pound 22. This fact allowed us to synthesize cyclic
amide 28 and spectroscopically detect phosphonic acid 27
The molecular structure of compound 26 in the crystal
structure was determined by Xꢀray diffraction (Fig. 7,
Tables 3 and 5). The heterocycle of 26 adopts a distorted
(unsymmetrical) boat conformation and contains two plaꢀ
nar groups, O(1)C(8a)C(4a)C(4) (planar within 0.091(2) Å)
and P(2)C(3)C(4)C(4a) (planar within 0.033(2) Å).
The other two atoms deviate from these planar groups by
2
(P 2.1, JPCH = 15.6 Hz), which is rather rapidly hydroꢀ
lyzed to form vinylphosphonic acid 29.
Scheme 9

Arylacetylenes and trichlorobenzodioxaphosphole
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
63
O(50´)
H(3´)
O(1)
H(1)
O(3´)
O(4´)
O(2)
H(4´)
H(4)
P(2´)
H(1´)
O(1´)
P(2)
O(2´)
O(4)
H(3)
O(3)
O(50)
Fig. 6. Hydrogen bond network in the acetone solvate of 24 in the crystal.
–0.398(3) (C(3)) and –0.9487(8) Å (P(2)), 0.898(2)
(O(1)) and 0.629(2) Å (C(8a)), respectively. The fact that
the aboveꢀmentioned atoms deviate from the plane in the
same direction and to a different extent is responsible
for the unsymmetrical boat conformation. The chlorine
atom Cl(2) substantially deviates from both planes (by
–2.7808(9) and –1.7855(9) Å, respectively) and is in the
axial position. The oxygen atom O(2) is in the equatorial
position and is located closer to the aboveꢀmentioned
planes (the deviations are –0.877(2) and 0.511(2) Å, reꢀ
spectively). A substantial deviation of the heterocycle from
planarity is also evidenced by the dihedral angle between
the planes O(1)C(8a)C(4a)C(4) and P(2)C(3)C(4)C(4a)
(21.6(2)). The dihedral angle between the plane
of the paraꢀmethoxyphenyl substituent and the
P(2)C(3)C(4)C(4a) plane is large (43.5(1)) due to which,
as in the case of molecule 3b, the conjugation between
this substituent and the C(3)=C(4) double bond is unꢀ
likely. The molecule of compound 26 contains the pentaꢀ
substituted
sterically
crowded
benzene
ring
C(4a)C(5)C(6)C(7)C(8)C(8a), which is planar within
0.090(3) Å. The character of substitution leads to substanꢀ
tial deviations of the substituents from this plane. Thus,
the Cl(6), O(1), C(4), C(15), and C(19) atoms deviate
from this plane by 0.236(1), –0.086(2), 0.584(2),
–0.611(3), and –0.150(3) Å, respectively. The largest deꢀ
viations of the C(4) and C(15) atoms are associated with
the steric repulsion between the paraꢀmethoxyphenyl and
tertꢀbutyl substituents. It is interesting that the C=C bond
lengths in this benzene ring are also sensitive to the charꢀ
O(2)
Cl(2)
P(2)
C(3)
C(20)
C(21)
O(1)
C(19)
C(4)
C(4a)
C(9)
C(8a)
C(22)
C(8)
C(7)
C(11)
C(10)
C(16)
C(5)
C(12)
C(14)
C(15)
C(6)
C(23)
C(13)
C(18)
Cl(6)
O(23)
C(17)
Fig. 7. Molecular structure of 26 in the crystal and the atomic numbering scheme.

64
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
Nemtarev et al.
Table 5. Selected geometric parameters for structure 26
Parameter
Value
Parameter
Bond angle
Value
Bond length
d/Å
/deg
Cl(2)—P(2)
Cl(6)—C(6)
P(2)—O(1)
P(2)—O(2)
P(2)—C(3)
O(1)—C(8a)
C(3)—C(4)
C(4)—C(4a)
C(4a)—C(5)
C(4a)—C(8a)
C(5)—C(6)
C(6)—C(7)
C(7)—C(8)
C(8)—C(8a)
2.005(2)
1.745(3)
1.582(2)
1.449(2)
1.737(3)
1.395(3)
1.346(4)
1.496(3)
1.417(3)
1.403(3)
1.389(4)
1.388(4)
1.372(4)
1.398(3)
C(4a)—C(5)—C(6)
C(4a)—C(5)—C(15)
Cl(6)—C(6)—C(7)
C(8a)—C(8)—C(19)
113.8(2)
123.2(2)
114.0(2)
123.4(2)
Torsion angle
/deg
Cl(2)—P(2)—O(1)—C(8a)
O(2)—P(2)—O(1)—C(8a)
C(3)—P(2)—O(1)—C(8a)
Cl(2)—P(2)—C(3)—C(4)
O(1)—P(2)—C(3)—C(4)
O(2)—P(2)—C(3)—C(4)
P(2)—O(1)—C(8a)—C(4a)
P(2)—C(3)—C(4)—C(4a)
P(2)—C(3)—C(4)—C(9)
C(3)—C(4)—C(4a)—C(8a)
C(9)—C(4)—C(4a)—C(5)
C(9)—C(4)—C(4a)—C(8a)
C(3)—C(4)—C(9)—C(10)
C(4)—C(4a)—C(5)—C(15)
C(8a)—C(4a)—C(5)—C(6)
C(4)—C(4a)—C(8a)—O(1)
C(5)—C(4a)—C(8a)—C(8)
C(15)—C(5)—C(6)—Cl(6)
C(19)—C(8)—C(8a)—O(1)
–64.6(2)
174.8(2)
47.7(2)
76.9(2)
–30.6(3)
–154.1(2)
–25.7(3)
–6.9(3)
60.7(2)
36.3(3)
40.0(3)
–131.3(2)
41.0(3)
37.1(4)
17.8(3)
–19.9(3)
–12.6(4)
–25.6(4)
–0.2(3)
Bond angle
/deg
Cl(2)—P(2)—O(1)
Cl(2)—P(2)—O(2)
Cl(2)—P(2)—C(3)
O(1)—P(2)—O(2)
O(1)—P(2)—C(3)
O(2)—P(2)—C(3)
P(2)—C(3)—C(4)
C(4)—C(4a)—C(5)
C(4)—C(4a)—C(8a)
102.52(8)
112.0(1)
108.8(1)
112.8(1)
101.1(1)
118.1(1)
118.3(2)
123.1(2)
116.5(2)
spectra were obtained on a DFS Thermo Electron Corporation
instrument (Germany) at the ionizing electron energy of 70 eV
using a direct inlet system. The temperature of the ion source
was 280 C. The vaporizer tube was heated in the temperatureꢀ
programmed mode from 50 to 350 C.
acter of substitution in the ring. Thus, the tetrasubstitutꢀ
ed C(8)=C(8a), C(8a)=C(4a), and C(4a)=C(5) bonds
are much longer than the trisubstituted C(7)=C(8) and
C(6)=C(7) bonds (see Table 5).
To summarize, the present study showed that the naꢀ
ture of the acetylene component plays a considerable role
in the reaction with P,P,Pꢀtrihalobenzoꢀ1,3,2ꢀdioxaphosꢀ
pholes giving phosphacoumarin derivatives. The rateꢀ
determining step of this multistep reaction proved to be
sensitive to the electronic nature of the substituent in the
phenyl ring of arylacetylene. Thus, the presence of the
+Mꢀdonor (OMe) substantially increases the reaction rate,
whereas the introduction of the –Mꢀacceptor (NO2) subꢀ
stantially reduces the rate. The nature of the substituent
also greatly affects the stability of intermediates in this
reaction (vinylꢀquinoidꢀtype phosphonates) and the reꢀ
sistance of the resulting benzo[e]ꢀ1,2ꢀoxaphosphinine deꢀ
rivatives to the hydrolysis.
The Xꢀray diffraction data were collected from crystals of
compounds 3b, 24, and 26 on a Bruker Smart APEX II CCD
automated diffractometer (graphite monochromator, (MoꢀK) =
= 0.71073 Å, ꢀscanning technique, 293 K). The semiempirical
absorption correction was applied using the SADABS program.18
The structures were solved by direct methods using the SIR proꢀ
gram19 and refined first isotropically and then anisotropically
using the SHELXLꢀ97 program package.20 The hydroxy hydroꢀ
gen atoms in the structures of 3b and 24 were located in differꢀ
ence Fourier maps and refined isotropically. The other hydroꢀ
gen atoms in the structures of 3b, 24, and 26 were positioned
geometrically and refined using a riding model. All calculations
were carried out with the use of the WinGX (see Ref. 21) and
APEX2 (see Ref. 22) programs. All figures were prepared and
intermolecular interactions were analyzed using the PLATON
(see Ref. 23) and ORTEP (see Ref. 24) programs. The singleꢀ
crystal Xꢀray diffraction studies of compounds 3b, 24, and 26
were performed at the Federal SpectralꢀAnalytical Center for
Collective Use on the basis of the Laboratory of Research by
Diffraction Methods of the A. E. Arbuzov Institute of Organic
and Physical Chemistry of the Kazan Scientific Center of the
Russian Academy of Sciences. The crystallographic characterisꢀ
tics of the compounds and the Xꢀray data collection and strucꢀ
ture refinement statistics are given in Table 3. The parameters of
Experimental
The NMR spectra were recorded on a Bruker Avanceꢀ400
instrument (400 MHz for 1H, 100.6 MHz for 13C, and 162 MHz
for 31P), unless otherwise mentioned, and on a Bruker CXPꢀ100
instrument (36.48 MHz for 31P). The IR spectra were measured
on a Bruker Vectorꢀ22 spectrometer (Nujol mulls, KBr). Mass

Arylacetylenes and trichlorobenzodioxaphosphole
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
65
intraꢀ and intermolecular interactions (hydrogen bonds) are listꢀ
ed in Table 2.
3J(PCCC(4a)) = 16.5 Hz, 3J(HC(3)CC(4a)) = 8.1 Hz,
3J(HC(8)CC(4a)) = 8.0 Hz); 127.68 (dd (s), C(5), 1J(HC(5)) =
= 165.8 Hz, 3J(HC(7)CC(5)) = 5.1 Hz); 127.68 (ddd (s), C(6),
Reaction of benzodioxaphosphole 1 with 4ꢀnitrophenylacetylꢀ
ene. A solution of hexꢀ1ꢀene (1.7 mL, 13.6 mmol) and 4ꢀnitroꢀ
phenylacetylene (1 g, 6.8 mmol) in CH2Cl2 (20 mL) was slowly
added to a solution of phosphorane 1 (1.68 g, 6.8 mmol) in
CH2Cl2 (5 mL) under a stream of argon. After the removal of
the solvent and volatile products from the reaction mixture
in a vacuum of 12 Torr (the externalꢀheating temperature was
90—100 C), the glassy paleꢀbrown compound, 2,6ꢀdichloroꢀ4ꢀ
(4ꢀnitrophenyl)benzo[e]ꢀ1,2ꢀoxaphosphinine 2ꢀoxide (2a), was
obtained and characterized by spectroscopic methods. MS, m/z:
3J(HC(8)CC(6))
= = 3.6 Hz,
11.4 Hz, 2J(HC(7)C(6))
2J(HC(5)C(6)) = 3.6 Hz); 131.29 (dd (s), C(7), 1J(HC(7)) =
3
= 170.2 Hz, J(HC(5)CC(7)) = 5.9 Hz); 121.82 (dd (d), C(8),
1J(HC(8)) = 168.0 Hz, 3J(POCC(8)) = 6.6 Hz); 150.49 (dddd
(d), C(8a), 2J(POC(8a)) = 7.3 Hz, 3J(HC(5)CC(8a)) = 8.4 Hz,
3J(HC(7)CC(8a)) = 8.4 Hz, 2J(HC(8)C(8a)) = 3.7 Hz); 144.71
(dtd (d), C(9), 3J(PCCC(9)) = 18.7 Hz, 3J(HC(3)CC(9)) =
= 7.3 Hz, 3J(HC(11)CC(9)) = 7.3 Hz); 124.38 (dd (s), C(10),
1J(HC(10)) = 170.6 Hz, 2J(HC(11)C(10)) = 4.0 Hz); 130.36
(dd (s), C(11), 1J(HC(11)) = 166.5 Hz, 2J(HC(10)C(11)) = 6.6 Hz);
355 [M]+ (C14H8Cl235NO4P), 312 [M – Cl]+. 1H NMR
•
3
3
(CDCl3), : 6.46 (d, H(3), J(PCH) = 22.2 Hz); 7.08 (d, H(5),
148.16 (m (s), C(12), J(HC(10)CC(12)) = 9.2 Hz). 31P NMR
4J(H(7)H(5)) = 2.5 Hz); 7.33 (d, H(8), 3J(H(7)H(8)) = 8.3 Hz);
7.50 (d, H(7), 4J(H(5)H(7)) = 2.5 Hz, 3J(H(8)H(7)) = 8.3 Hz);
7.59 (m, H(10), AA´ part of AA´XX´ spectrum, 3J(HCCH) =
= 8.9 Hz); 8.40 (m, H(11), XX´ part of AA´XX´ spectrum,
(DMSOꢀd6, 36.48 MHz),  : 3.3 (d, 2J(PC(3)H) = 16.4 Hz).
P
Zꢀ2ꢀ(5ꢀChloroꢀ2ꢀhydroxyphenyl)ꢀ2ꢀ(4ꢀnitrophenyl)vinylꢀ
phosphonic acid (Zꢀ5) (see the text). 1H NMR (DMSOꢀd6),
: 6.19 (d, H(3), 2J(PC(3)H) = 13.5 Hz); 6.86 (d, H(8),
3J(HC(7)C(8)H) = 8.7 Hz); 7.21 (dd, H(7), 3J(HC(8)C(7)H) =
= 8.7 Hz, 4J(HC(5)CC(7)H) = 2.7 Hz); 7.05 (d, H(5),
4J(HC(7)CC(5)H) = 2.6 Hz); 7.54 (m, H(10), 2J(HCCH) =
= 8.9 Hz, AA´ part of AA´XX´ spectrum); 8.13 (m, H(11),
2J(HCCH) = 8.9 Hz, XX´ part of AA´XX´ spectrum). 31P NMR
3J(HCCH) = 8.9 Hz). 13C NMR (CDCl3),  : 117.13 (dd (d),*
C
C(3), 1J(PC(3)) = 154.4 Hz, 1J(HC(3)) = 171.3 Hz); 153.32
(m (d), C(4), 2J(PCC(4)) = 1.5 Hz); 122.04 (dddd (d), C(4a),
3J(PCCC(4a)) = 18.0 Hz, 3J(HC(3)CC(4a)) = 8.3 Hz,
3J(HC(8)CC(4a)) = 7.0 Hz, 2J(HC(5)C(4a)) = 1.2 Hz); 128.85
(dddd (d), C(5), 4J(PCCCC(5)) = 1.6 Hz, 1J(HC(5)) = 166.9 Hz,
3J(HC(7)CC(5)) = 5.7 Hz, 4J(HC(8)CCC(5)) = 1.5 Hz); 131.01
(dddd (d), C(6), 4J(PCCCC(6)) = 1.5 Hz, 3J(HC(8)CC(6)) =
= 14.1 Hz, 2J(HC(7)C(6)) = 4.6 Hz, 2J(HC(5)C(6)) = 4.6 Hz);
132.99 (ddd (s), C(7), 1J(HC(7)) = 170.5 Hz, 3J(HC(5)CC(7)) =
= 6.3 Hz, 2J(HC(8)C(7)) = 1.0 Hz); 121.65 (dd (d), C(8),
3J(POCC(8)) = 8.1 Hz, 1J(HC(8)) = 169.0 Hz); 149.60 (dddd
(d), C(8a), 2J(POC(8a)) = 9.9 Hz, 3J(HC(7)CC(8a)) = 10.2 Hz,
3J(HC(5)CC(8a)) = 9.9 Hz, 2J(HC(8)C(8a)) = 4.2 Hz); 142.83
(dtd (d), C(9), 3J(PCCC(9)) = 20.9 Hz, 3J(HC(11)CC(9)) = 7.7 Hz,
3J(HC(3)CC(9)) = 6.2 Hz); 124.54 (dd (s), C(10), 1J(HC(10)) =
= 170.4 Hz, 3J(HCCC(10)) = 4.8 Hz); 129.68 (dd (s), C(11),
1J(HC(11)) = 166.9 Hz, 3J(HCCC(11)) = 5.7 Hz); 147.74 (m (s),
(DMSOꢀd6),  : 10.2 (d, 2J(PC(3)H) = 13.5 Hz).
P
Eꢀ2ꢀ(5ꢀChloroꢀ2ꢀhydroxyphenyl)ꢀ2ꢀ(4ꢀnitrophenyl)vinylphosꢀ
phonic acid (Eꢀ5). 1H NMR (DMSOꢀd6), : 6.44 (d, H(3),
2J(PC(3)H) = 13.0 Hz); 6.81 (d, H(8), 3J(HC(7)C(8)H) =
= 8.5 Hz); 7.23 (dd, H(7), 3J(HC(8)C(7)H) = 5.7 Hz,
4J(HC(5)CC(7)H) = 2.9 Hz); 7.25 (dd, H(5), 4J(HC(7)CC(5)H) =
= 2.5 Hz, 5J(PCCCC(5)H) = 2.5 Hz); 7.45 (m, H(10),
2J(HCCH) = 8.9 Hz, AA´ part of AA´XX´ spectrum); 8.15
(m, H(11), 2J(HCCH) = 8.9 Hz, XX´ part of AA´XX´ spectrum).
31P NMR (DMSOꢀd6),  : 9.8 (d, 2J(PC(3)H) = 13.0 Hz).
P
tertꢀButylammonium 6ꢀchloroꢀ4ꢀ(4ꢀnitrophenyl)benzo[e]ꢀ
1,2ꢀoxaphosphinineꢀ2ꢀoxideꢀ2ꢀoate (4a). tertꢀButylamine (0.19 mL,
1.72 mmol) was added to a solution of phosphine 3a (0.29 g,
0.86 mmol) in diethyl ether (20 mL). The white precipitate that
formed was filtered off and washed with diethyl ether (5×3 mL).
Yield 0.33 g (93%), m.p. 237 C. Found (%): C, 51.82; H, 5.13;
Cl, 7.61; N, 6.72; P, 6.49. C18H20ClN2O5P. Calculated (%):
C(12)). 31P NMR (CH2Cl2, 36.48 MHz),  : 16.1 (d, 2J(PCH) =
P
= 22.2 Hz).
6ꢀChloroꢀ2ꢀhydroxyꢀ4ꢀ(4ꢀnitrophenyl)benzo[e]ꢀ1,2ꢀoxaꢀ
phosphinine 2ꢀoxide (3a). A 20 : 1 mixture of water and acetone
(16 mL) was added to phosphine 2a (2.4 g, 6.7 mmol). The white
precipitate that formed was filtered off and washed with a 3 : 1
dioxane—water mixture (4×2 mL) and then with diethyl ether
(5×4 mL). Yield 2.12 g (93%), m.p. 321 C (decomp.). Found (%):
C, 48.20; H, 2.93; Cl, 11.40; N, 4.28; P, 8.97. C14H9ClNO5P.
Calculated (%): C, 49.80; H, 2.69; Cl, 11.40; N, 4.15; P, 9.17.
IR (Nujol mulls), /cm–1: 3435, 2346, 2029, 1976, 1959, 1655,
1638, 1616, 1588, 1572, 1537, 1445, 1394, 1343, 1313, 1243,
1197, 1181, 1166, 1119, 1076, 1006, 966, 929, 880, 862, 820,
761, 748, 701, 668, 629, 601, 588, 570, 537, 511, 434. 1H NMR
(DMSOꢀd6), : 6.53 (d, H(3), 2J(PC(3)H) = 16.4 Hz); 6.97
(d, H(5), 4J(HC(7)CC(5)H) = 2.6 Hz); 7.34 (d, H(8),
3J(HC(7)C(8)H) = 8.7 Hz); 7.52 (ddd, H(7), 3J(HC(8)C(7)H) =
= 8.7 Hz, 4J(HC(5)CC(7)H) = 2.6 Hz, 5J(POCCC(7)H) = 1.4 Hz);
7.68 (m, H(10), AA´ part of AA´XX´ spectrum); 8.33 (m, H(11),
XX´ part of AA´XX´ spectrum). 13C NMR (DMSOꢀd6),
C, 52.63; H, 4.91; Cl, 8.63; N, 6.82; P, 7.54. IR (KBr), /cm–1
:
434, 461, 480, 546, 565, 633, 655, 696, 728, 756, 805, 822, 836,
851, 870, 885, 948, 1016, 1072, 1090, 1113, 1151, 1197, 1223,
1264, 1348, 1376, 1401, 1470, 1519, 1549, 1585, 1638, 1886,
2004, 2169, 2341, 2360, 2539, 2627, 2736, 2913, 2983, 3033,
3451, 3558. 1H NMR (DMSOꢀd6—CDCl3 (9 : 1)), : 1.23
(s, H(16)); 6.23 (d, H(3), 2J(PC(3)H) = 15.1 Hz); 6.82 (d, H(5),
4J(HC(7)CC(5)H) = 2.5 Hz); 7.05 (d, H(8), 3J(HC(7)C(8)H) =
= 8.7 Hz); 7.30 (ddd, H(7), 3J(HC(8)C(7)H) = 8.7 Hz,
5
4J(HC(5)CC(7)H) = 2.5 Hz, J(POCCC(7)H) = 0.9 Hz); 7.57
(d, H(10), AA´ part of AA´XX´ spectrum, 3J(HCCH) = 8.8 Hz);
7.87 (br.m, (NH3+)); 8.27 (d, H(11), XX´ part of AA´XX´ specꢀ
trum, 3J(HCCH) = 8.8 Hz). 13C NMR (DMSOꢀd6—CDCl3
(9 : 1)),  : 127.29 (dd (d), C(3), 1J(PC(3)) = 161.8 Hz,
C
1J(HC(3)) = 157.0 Hz); 143.25 (br.m (s), C(4)); 124.82 (dddm (d),
C(4a), 3J(PCCC(4a)) = 15.0 Hz, 3J(HC(3)CC(4a)) = 5.9 Hz,
3J(HC(8)CC(4a)) = 5.9 Hz); 126.81 (dd (s), C(5), 1J(HC(5)) =
 : 119.70 (dd (d), C(3), 1J(PC(3)) = 167.6 Hz, 1J(HC(3)) =
C
3
= 164.7 Hz); 148.80 (m (s), C(4)); 123.38 (dddm (d), C(4a),
= 164.0 Hz, J(HC(7)CC(5)) = 5.1 Hz); 125.53 (dm (s), C(6),
1
3J(HC(8)CC(6)) = 7.4 Hz); 129.49 (dd (s), C(7), J(HC(7)) =
* Hereinafter, the multiplicities of the signals in the 13C—{1H}
NMR spectra are given in parentheses.
= 163.2 Hz, J(HC(5)CC(7)) = 5.5 Hz); 121.61 (dd (d), C(8),
3
1J(HC(8)) = 161.8 Hz, 3J(POCC(8)) = 5.1 Hz); 152.70 (dddm (d),

66
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
Nemtarev et al.
C(8a), 2J(POC(8a)) = 7.3 Hz, 3J(HC(5)CC(8a)) = 7.7 Hz,
3J(HC(7)CC(8a)) = 7.7 Hz); 146.69 (dm (d), C(9), 3J(PCCC(9))
= 7.3 Hz, 3J(HC(11)CC(9)) = 7.6—7.7 Hz, 3J(HC(13)CC(9)) =
= 7.6—7.7 Hz, 3J(HC(3)CC(9)) = 7.6—7.7 Hz); 130.11 (dd (s),
C(10), 1J(HC(10)) = 165.8 Hz, 2J(HC(11)C(10)) = 6.6 Hz);
124.27 (dd (s), C(11), 1J(HC(11)) = 169.5 Hz, 2J(HC(10)C(11))
= 3.4 Hz); 147.62 (tm (s), C(12), 3J(HC(10)CC(12)) = 8.8 Hz);
51.08 (m (s), C(15), 2J(HCC(15)) = 3.7 Hz); 27.58 (br.q (s),
CDCl3 (1 : 4)),  : 114.80 (dd (d), C(3), 1J(PC(3)) = 171.7 Hz,
C
1J(HC(3)) = 163.2 Hz); 151.18 (m (d), C(4), 2J(PCC(4a)) =
3
= 1.5 Hz); 123.38 (dddm (d), C(4a), J(PCCC(4a)) = 16.1 Hz,
3J(HC(3)CC(4a) = 5.5 Hz, 3J(HC(8)CC(4a)) = 7.7 Hz); 127.86
(dd (s), C(5), 1J(HC(5)) = 166.2 Hz, 3J(HC(7)CC(5)) = 5.5 Hz);
127.47 (ddd (s), C(6), 3J(HC(8)CC(6)) = 11.4 Hz, 2J(HC(7)C(6)) =
= 4.0 Hz, 2J(HC(5)C(6)) = 4.0 Hz); 129.94 (dd (s), C(7),
1J(HC(7)) = 169.1 Hz, 3J(HC(5)CC(7)) = 5.9 Hz); 120.42
1
3
C(16), 1J(HC(16)) = 127.3 Hz). 31P NMR (DMSOꢀd6),  : –3.5
(dd (d), C(8), J(HC(8)) = 166.2 Hz, J(POCC(8)) = 7.4 Hz);
149.76 (dddd (d), C(8a), 2J(POC(8a)) = 7.3 Hz, 3J(HC(5)CC(8a)) =
= 10.2 Hz, 3J(HC(7)CC(8a)) = 10.2 Hz, 2J(HC(8)C(8a)) =
= 4.0 Hz); 129.91 (dt (d), C(9), 3J(PCCC(9)) = 18.7 Hz,
3J(HC(11)CC(9)) = 7.7 Hz); 129.26 (dd (s), C(10), 1J(HC(10)) =
= 159.2 Hz, 2J(HC(11)C(10)) = 7.7 Hz); 113.74 (dd (s),
C(11), 1J(HC(11)) = 160.3 Hz, 2J(HC(10)C(11)) = 4.4 Hz);
159.77 (m (s), C(12)); 54.91 (q (s), C(15), 1J(HC(15)) =
P
(br.d, 2J(PC(3)H) = 15.1 Hz).
Reaction of benzodioxaphosphole 1 with 4ꢀmethoxyphenylꢀ
acetylene. Hexꢀ1ꢀene (2.8 mL, 22.4 mmol) was added to a soluꢀ
tion of phosphorane 1 (2.8 g, 11.4 mmol) in CH2Cl2 (7 mL), and
then a solution of 4ꢀmethoxyphenylacetylene (1.5 g, 11.4 mmol)
in CH2Cl2 (5 mL) was slowly added dropwise under a stream of
argon. After the removal of the solvent and volatile products
from the reaction mixture in a vacuum of 12 Torr (the externalꢀ
heating temperature was 80—90 C), the glassy paleꢀbrown comꢀ
pound, 2,6ꢀdichloroꢀ4ꢀ(4ꢀmethoxyphenyl)benzo[e]ꢀ1,2ꢀoxaphosꢀ
phinine 2ꢀoxide (2b), was obtained and characterized by spectroꢀ
2
= 171.5 Hz). 31P NMR (DMSOꢀd6),  : 4.7 (d, J(PC(3)H) =
P
= 17.8 Hz).
Reaction of benzodioxaphosphole 6 with 4ꢀnitrophenylacetylꢀ
ene. 2,6ꢀDichloroꢀ7ꢀmethylꢀ4ꢀ(4ꢀnitrophenyl)benzo[e]ꢀ1,2ꢀoxaꢀ
phosphinine 2ꢀoxide (7), 2,8ꢀdichloroꢀ7ꢀmethylꢀ4ꢀ(4ꢀnitroꢀ
phenyl)benzo[e]ꢀ1,2ꢀoxaphosphinine 2ꢀoxide (8), and 2ꢀchloroꢀ
6ꢀchloromethylꢀ4ꢀ(4ꢀnitrophenyl)benzo[e]ꢀ1,2ꢀoxaphosphinine
2ꢀoxide (9). A solution of 4ꢀnitrophenylacetylene (1.04 g,
7.07 mmol) in CH2Cl2 (16 mL) was added to a solution of phosꢀ
phorane 6 (1.75 g, 6.64 mmol) and hexꢀ1ꢀene (0.84 mL,
6.7 mmol) in CH2Cl2 (2 mL). The solvent and volatile products
were removed from the reaction mixture in a vacuum of 12 Torr
(the externalꢀheating temperature was 70—90 C), and the glassy
paleꢀbrown substance composed of compounds 7—9 was obꢀ
tained. The latter were characterized by spectroscopic methods.
scopic methods. MS, m/z: 340 [M]+ (C15H11Cl235O3P), 325
•
[M – Me]+, 305 [M – Cl]+. 1H NMR (CDCl3), : 3.90
(s, OMe); 6.34 (d, H(3), 2J(PC(3)H) = 23.6 Hz); 7.04 (m, H(11),
AA´ part of AA´XX´ spectrum); 7.28 (d, H(8), 3J(HC(7)C(8)H) =
= 8.5 Hz); 7.32 (d, H(5), 4J(HC(7)CC(5)H) = 2.4 Hz); 7.33
(m, H(10), XX´ part of AA´XX´ spectrum); 7.45 (dd, H(7),
3J(HC(8)C(7)H) = 8.5 Hz, 4J(HC(5)CC(7)H) = 2.4 Hz,
5J(POCCC(7)H) = 2.4 Hz). 13C NMR (CDCl3),  : 114.31
C
(dd (d), C(3), 1J(PC(3)) = 155.1 Hz, 1J(HC(3)) = 170.9 Hz);
155.48 (m (d), C(4), 2J(PCC(4a)) = 1.8 Hz); 123.04 (ddd (d),
C(4a), 3J(PCCC(4a)) = 17.2 Hz, 3J(HC(3)CC(4a)) = 7.7 Hz,
3J(HC(8)CC(4a)) = 7.7 Hz); 129.46 (dd (s), C(5), 1J(HC(5)) =
= 168.4 Hz, 3J(HC(7)CC(5)) = 5.1 Hz); 129.46 (m (s), C(6),
3J(HC(8)CC(6)) = 11.2 Hz); 132.06 (dd (s), C(7), 1J(HC(7)) =
MS of compounds 7—9, m/z (Irel (%)): 369 [M]+ (10.1)
•
(C15H10Cl235NO4P), 334 [M – Cl]+ (17.3), 288 [M – Cl –
– NO2]+ (9.8), 270 [M – P(O)OH – Cl]+ (3.1), 185 [C13H13O]+
3
1
= 170.2 Hz, J(HC(5)CC(7)) = 6.2 Hz); 121.16 (dd (d), C(8),
(100.0). H NMR of compound 7 (CDCl3), : 2.43 (s, H(15));
1J(HC(8)) = 168.7 Hz, 3J(POCC(8)) = 8.1 Hz); 149.57 (dddd (d),
C(8a), 2J(POC(8a)) = 9.9 Hz, 3J(HC(5)CC(8a)) = 9.9 Hz,
3J(HC(5)CC(8a)) = 9.9 Hz, 2J(HC(8)C(8a)) = 3.7 Hz); 137.77
(m (d), C(9), 3J(PCCC(9)) = 11.4 Hz); 129.93 (dd (s), C(10),
1J(HC(10)) = 159.9 Hz, 2J(HC(11)C(10)) = 7.3 Hz); 114.52
(dd (s), C(11), 1J(HC(11)) = 160.7 Hz, 2J(HC(10)C(11)) = 4.8 Hz);
161.22 (m (s), C(12)); 55.49 (qm (s), OMe, 1J(HC) = 144.5 Hz).
6.38 (d, H(3), 2J(PC(3)H) = 22.6 Hz); 7.06 (s, H(5)); 7.23
(s, H(8)); 7.58 (m, H(10), AA´ part of AA´XX´ spectrum); 8.34
(d, H(11), XX´ part of AA´XX´ spectrum). 13C NMR of comꢀ
1
pound 7 (CDCl3),  : 20.39 (qd (s), CH3, J(HC) = 129.2 Hz,
C
3J(HC(8)CC) = 4.3 Hz); 115.66 (dd (d), C(3), 1J(PC(3)) = 154.8 Hz,
1J(HC(3)) = 171.7 Hz); 153.40 (m (d), C(4), 2J(PCC(4)) =
= 2.3 Hz); 119.65 (m (d), C(4a), 3J(PCCC(4a)) = 18.1 Hz);
31P NMR (CH2Cl2, 36.48 MHz),  : 18.5 (d, 2J(PCH) = 23.6 Hz).
128.88 (dd (d), C(5), J(HC(5)) = 166.6 Hz, J(PCCCC(5)) =
= 1.4 Hz); 131.00 (m (d), C(6), 5J(PCCCCC(6)) = 1.4 Hz);
142.19 (dq (s), C(7), 2J(HCC(7)) = 6.2 Hz, 3J(HC(5)CC(7)) =
= 6.2 Hz); 122.08 (ddm (d), C(8), 1J(HC(8)) = 165.5 Hz,
3J(POCC(8)) = 8.1 Hz); 149.13 (ddd (d), C(8a), 2J(POC(8a)) =
= 10.1 Hz, 3J(HC(5)CC(8a)) = 9.9 Hz, 2J(HC(8)C(8a)) = 4.4 Hz);
142.87 (dt (d), C(9), 3J(PCCC(9)) = 21.1 Hz, 3J(HC(11)CC(9)) =
= 7.9 Hz); 124.27 (dd (s), C(10), 1J(HC(10)) = 170.2 Hz,
2J(HC(11)C(10)) = 4.5 Hz); 129.58 (dd (s), C(11), 1J(HC(11)) =
1
4
P
6ꢀChloroꢀ2ꢀhydroxyꢀ4ꢀ(4ꢀmethoxyphenyl)benzo[e]ꢀ1,2ꢀoxaꢀ
phosphinine 2ꢀoxide (3b). A 20 : 1 mixture of acetone and water
(16 mL) was added to phosphine 2b (3.6 g, 10.9 mmol). The
white precipitate that formed was filtered off and washed with
dioxane (2×2 mL), a 3 : 1 dioxane—water mixture (3×2 mL),
and diethyl ether (5×4 mL). Yield 2.48 g (71%), m.p. 272 C.
Found (%): C, 55.98; H, 4.30; Cl, 10.87; P, 9.54. C15H12ClO4P.
Calculated (%): C, 55.83; H, 3.75; Cl, 10.99; P, 9.60. IR (Nujol
mulls), /cm–1: 441, 449, 537, 565, 585, 641, 721, 776, 801, 829,
886, 908, 960, 1014, 1112, 1151, 1178, 1221, 1247, 1294, 1337,
1377, 1463, 1510, 1551, 1574, 1606, 1667, 2330, 2359, 2675,
2724, 2854, 2923, 2954, 3435. 1H NMR (DMSOꢀd6—CDCl3
(1 : 4)), : 3.58 (s, H(13)); 6.07 (d, H(3), 2J(PC(3)H) = 17.8 Hz);
6.93 (d, H(11), AA´ part of AA´XX´ spectrum); 7.09 (d, H(5),
4J(HC(7)CC(5)H) = 2.2 Hz); 7.10 (d, H(8), 3J(HC(7)C(8)H) =
= 8.3 Hz); 7.22 (m, H(10), XX´ part of AA´XX´ spectrum); 7.26
(ddd, H(7), 3J(HC(8)C(7)H) = 8.3 Hz, 4J(HC(5)CC(7)H) =
= 2.2 Hz, 5J(POCCC(7)H) = 1.6 Hz). 13C NMR (DMSOꢀd6—
2
= 165.9 Hz, J(HC(10)C(11)) = 6.9 Hz); 148.71 (tt (s), C(12),
3J(HC(10)CC(12)) = 9.4 Hz, 2J(HC(11)C(12)) = 3.7 Hz).
31P NMR (CH2Cl2, 36.48 MHz),  : 15.9—16.1 (d, 2J(PCH) =
P
= 22.6—24.0 Hz) (compounds 7—9).
6ꢀChloroꢀ2ꢀhydroxyꢀ7ꢀmethylꢀ4ꢀ(4ꢀnitrophenyl)benzo[e]ꢀ
1,2ꢀoxaphosphinine 2ꢀoxide (10). A 20 : 1 mixture of acetone
and water (16 mL) was added to a mixture of phosphines 7—9
(2.4 g). The white precipitate of compound 10 that formed was
filtered off and washed with diethyl ether (5×4 mL). Yield 1.6 g
(90%), m.p. 324 C (decomp.). Found (%): C, 50.95; H, 3.67;

Arylacetylenes and trichlorobenzodioxaphosphole
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
67
Cl, 9.87; N, 4.01; P, 9.07. C15H11ClNO5P. Calculated (%):
C, 51.23; H, 3.15; Cl, 10.08; N, 3.98; P, 8.81. IR (Nujol mulls),
/cm–1: 436, 462, 549, 566, 699, 730, 752, 809, 854, 869, 889,
1014, 1038, 1129, 1189, 1249, 1259, 1339, 1352, 1376, 1458,
1516, 1587, 1602, 2311, 3480. 1H NMR (DMSOꢀd6), : 2.35
(s, Me); 6.43 (d, H(3), 2J(PC(3)H) = 16.6 Hz); 6.94 (s, H(5)); 7.33
(s, H(8)); 7.66 (m, H(10), AA´ part of AA´XX´ spectrum); 8.32
(m, H(11), XX´ part of AA´XX´ spectrum). 13C NMR (DMSOꢀd6),
= 162.1 Hz, 1J(HC(3)) = 156.3 Hz); 143.16 (m (s), C(4)); 122.72
(m (d), C(4a), 3J(PCCC(4a)) = 15.0 Hz, 3J(HC(3)CC(4a)) =
= 6.2—6.4 Hz, 3J(HC(8)CC(4a)) = 6.2—6.4 Hz); 127.03
(d (s), C(5), 1J(HC(5)) = 162.9 Hz); 125.85 (dq (s), C(6),
3J(HC(8)CC(6)) = 7.4 Hz, 3J(HC(15)CC(6)) = 5.5 Hz); 137.40
(dq (s), C(7), 3J(HC(5)CC(7)) = 5.8—5.9 Hz, 2J(HC(15)C(7)) =
1
= 5.8—5.9 Hz); 122.25 (ddq (d), C(8), J(HC(8)) = 161.8 Hz,
3J(POCC(8)) = 5.5 Hz, 3J(HC(15)CC(8)) = 5.4 Hz); 152.51
(ddd (d), C(8a), 2J(POC(8a)) = 7.0 Hz, 3J(HC(5)CC(8a)) =
= 7.0 Hz, 2J(HC(8)C(8a)) = 3.6 Hz); 146.80 (dt (d), C(9),
3J(PCCC(9)) = 16.5 Hz, 3J(HC(11)CC(9)) = 7.3 Hz); 124.29
(dd (s), C(10), 1J(HC(10)) = 169.8 Hz, 2J(HC(11)C(10)) =
= 4.0 Hz); 130.11 (dd (s), C(11), 1J(HC(11)) = 165.8 Hz,
 : 19.59 (qd (s), Me, 1J(HC) = 128.7 Hz, 3J(HC(8)CC) =
C
= 4.2 Hz); 118.15 (dd (d), C(3), 1J(PC(3)) = 168.0 Hz, 1J(HC(3)) =
= 164.6 Hz); 148.57 (m (br.s), C(4)); 120.82 (m (d), C(4a),
3J(PCCC(4a)) = 16.5 Hz); 127.54 (d (s), C(5), 1J(HC(5)) =
= 164.3 Hz); 127.67 (dq (s), C(6), 3J(HC(8)CC(6)) = 5.2 Hz,
3J(HCCC(6)) = 4.7 Hz); 139.34 (dq (s), C(7), 2J(HCC(7)) =
= 6.2 Hz, 3J(HC(5)CC(7)) = 6.2 Hz); 121.96 (ddq (d), C(8),
1J(HC(8)) = 164.7 Hz, 3J(POCC(8)) = 6.6 Hz, 3J(HCCC(8)) =
= 3.4 Hz); 149.87 (ddd (d), C(8a), 2J(POC(8a)) = 7.0 Hz,
3J(HC(5)CC(8a)) = 9.6 Hz, 2J(HC(8)C(8a)) = 3.8 Hz); 144.45
(dtm (d), C(9), 3J(PCCC(9)) = 18.7 Hz, 3J(HC(11)CC(9)) =
= 7.5 Hz); 124.05 (dd (s), C(10), 1J(HC(10)) = 170.2 Hz,
2J(HC(10)C(11))
= 7.0 Hz); 147.60 (m (s), C(12),
3J(HC(10)CC(12)) = 9.5 Hz, 2J(HC(11)C(12)) = 3.7 Hz); 19.85
(qd (s), C(15), 1J(HC(15)) = 128.4 Hz, 4J(HC(5)CCC(15)) =
= 4.4 Hz); 46.00 (tm (s), C(16), 1J(HC(16)) = 142.7 Hz);
8.94 (qm (s), C(17), 1J(HC(17)) = 127.6 Hz). 31P NMR
(DMSOꢀd6—CDCl3 (3 : 1), 36.48 MHz),  : 0.8 (br.d,
P
2J(PC(3)H) = 15.6 Hz).
1
2J(HC(11)C(10)) = 4.4 Hz); 129.98 (dd (s), C(11), J(HC(11))
Reaction of benzodioxaphosphole 6 with 4ꢀmethoxyphenylꢀ
acetylene. A solution of 4ꢀmethoxyphenylacetylene (1.51 g,
11.4 mmol) in CH2Cl2 (4 mL) was added to a solution of phosꢀ
phorane 6 (2.7 g, 10.2 mmol) and hexꢀ1ꢀene (1.3 mL, 10.4 mmol)
in CH2Cl2 (2 mL). The solvent and volatile products were reꢀ
moved from the reaction mixture in a vacuum of 12 Torr (the
externalꢀheating temperature was 70—90 C), and the glassy
paleꢀbrown compound, 2,6ꢀdichloroꢀ4ꢀ(4ꢀmethoxyphenyl)ꢀ7ꢀ
methylbenzo[e]ꢀ1,2ꢀoxaphosphinine 2ꢀoxide (13), was obtained
and characterized by spectroscopic methods. MS, m/z (Irel (%)):
354 [M]+• (32.5) (C16H13Cl235O3P), 339 [M – Me]+ (1.6), 319
[M – Cl]+ (7.2), 272 [M – Cl – Me]+ (6.3), 234 (100.0), 185
[C13H13O]+ (68.2). 1H NMR of compound 13 (CDCl3), : 2.36
2
= 166.8 Hz, J(HC(10)C(11)) = 6.8 Hz); 147.83 (tt (s), C(12),
3J(HC(10)CC(12)) = 9.5 Hz, 2J(HC(11)C(12)) = 3.5 Hz).
31P NMR (DMSOꢀd6),  : 4.5 (d, 2J(PC(3)H) = 16.6 Hz).
P
Zꢀ2ꢀ(5ꢀChloroꢀ2ꢀhydroxyꢀ4ꢀmethyl)ꢀ2ꢀ(4ꢀnitrophenyl)vinylꢀ
phosphonic acid (11). 1H NMR (DMSOꢀd6), : 2.26 (s, Me);
6.40 (d, H(3), 2J(PC(3)H) = 12.6 Hz); 6.75 (s, H(8)); 7.25
(s, H(5)); 7.47 (m, H(10), AA´ part of AA´XX´ spectrum); 8.16
(m, H(11), XX´ part of AA´XX´ spectrum). 13C NMR (DMSOꢀd6),
 : 19.74 (qd (s), Me, 1J(HC) = 128.0 Hz, 3J(HC(8)CC) =
C
= 4.4 Hz); 125.29 (dd (d), C(3), 1J(PC(3)) = 181.9 Hz, 1J(HC(3)) =
= 150.3 Hz); 149.24 (m (d), C(4), 2J(PCC(4)) = 4.8 Hz); 124.67
(m (d), C(4a), 3J(PCCC(4a)) = 7.3 Hz); 131.24 (d (s), C(5),
1J(HC(5)) = 165.3 Hz); 122.34 (m (s), C(6)); 136.41 (dq (s),
C(7), 2J(HCC(7)) = 6.0 Hz, 3J(HC(5)CC(7)) = 6.0 Hz); 117.97
2
(br.s, C(15)H(3)); 3.80 (s, OMe); 6.21 (d, H(3), J(PC(3)H) =
= 24.5 Hz); 6.95 (m, H(11), AA´ part of AA´XX´ spectrum,
3J(HCCH) = 8.6 Hz); 7.14 (s, H(5)); 7.25 (s, H(8)); 7.25
(m, H(10), XX´ part of AA´XX´ spectrum, 3J(HCCH) = 8.6 Hz).
1
3
(dq (s), C(8), J(HC(8)) = 158.8 Hz, J(HCCC(8)) = 4.6 Hz);
153.50 (dm (s), C(8a), 3J(HC(5)CC(8a)) = 8.80 Hz); 147.64
(m (d), C(9), 3J(PCCC(9)) = 21.6 Hz); 123.63 (dd (s), C(10),
1J(HC(10)) = 169.8 Hz, 2J(HC(11)C(10)) = 4.1 Hz); 127.81
(dd (s), C(11), 1J(HC(11)) = 164.6 Hz, 3J(HC(10)C(11)) =
= 6.8 Hz); 147.19 (tt (s), C(12), 3J(HC(10)CC(12)) = 9.1 Hz,
1
13C NMR (CDCl3),  : 19.91 (dq (s), Me, J(HC) = 128.6 Hz,
C
3J(HC(8)CC) = 4.6 Hz); 55.74 (q (s), MeO, 1J(HC) =
= 144.5 Hz); 115.76 (dd (d), (C(3), 1J(PC(3)) = 169.4 Hz,
1J(HC(3)) = 163.5 Hz); 153.80 (m (d), C(4), 2J(PCC(4)) =
= 1.5 Hz); 122.06 (m (d), C(4a), 3J(PCCC(4a)) = 16.5 Hz);
128.30 (d (s), C(5), 1J(HC(5)) = 164.6 Hz); 127.82 (dq (s), C(6),
2J(HC(5)C(6)) = 5.6 Hz, 3J(HCCC(6)) = 5.0) Hz; 139.22
(dq (s), C(7), 3J(HC(5)CC(7)) = 6.3 Hz, 2J(HCC(7)) = 6.3 Hz);
2J(HC(11)C(12)) = = 3.7 Hz). 31P NMR (DMSOꢀd6),  : 10.2
P
(d, 2J(PC(3)H) = 12.6 Hz).
Triethylammonium 6ꢀchloroꢀ7ꢀmethylꢀ4ꢀ(4ꢀnitrophenyl)ꢀ
benzo[e]ꢀ1,2ꢀoxaphosphinineꢀ2ꢀoxideꢀ2ꢀoate (12). Triethylꢀ
amine (0.084 mL, 0.57 mmol) was added to a solution of phosꢀ
phine 10 (0.10 g, 0.28 mmol) in diethyl ether (5 mL). The white
precipitate that formed was filtered off and washed with diethyl
ether (5×1 mL). Yield 0.1 g (77%), m.p. 157 C. Found (%):
C, 55.27; H, 6.04; Cl, 7.18; N, 6.23; P, 6.45. C21H26ClN2O5P.
Calculated (%): C, 55.70; H, 5.79; Cl, 7.83; N, 6.19; P, 6.84. IR
(KBr), /cm–1: 425, 438, 468, 482, 515, 538, 560, 617, 698, 728,
754, 822, 852, 873, 910, 918, 1014, 1068, 1107, 1129, 1171,
1216, 1247, 1348, 1375, 1389, 1452, 1485, 1521, 1580, 1595,
1803, 2477, 2608, 2918, 2948, 2985, 3037, 3106, 3430. 1H NMR
(DMSOꢀd6—CDCl3 (3 : 1)), : 1.17 (t, H(17), 3J(HC(16)C(17)H) =
= 7.3 Hz); 2.30 (s, H(15)); 3.03 (q, H(16), 3J(HC(17)C(16)H) =
= 7.3 Hz); 6.20 (d, H(3), 2J(PC(3)H) = 15.5 Hz); 6.82 (s, H(5));
7.06 (s, H(8)); 7.58 (m, H(10), AA´ part of AA´XX´ spectrum);
8.28 (m, H(11), XX´ part of AA´XX´ spectrum). 13C NMR
1
122.25 (ddq (d), C(8), J(HC(8)) = 164.3 Hz, 3J(POCC(8)) =
= 7.0 Hz, 3J(HCCC(8)) = 5.6 Hz); 150.31 (ddd (d), C(8a),
2J(POC(8a))
= = 7.0 Hz,
7.0 Hz, 3J(HC(5)CC(8a))
2J(HC(8)C(8a)) = 3.4 Hz); 130.53 (dt (d), C(9), 3J(PCCC(9)) =
3
= 18.7 Hz, J(HC(11)CC(9)) = 7.8 Hz); 130.18 (dd (s), C(10),
1J(HC(10)) = 159.5 Hz, 2J(HC(11)C(10)) = 7.4 Hz); 114.70
(dd (s), C(11), 1J(HC(11)) = 160.5 Hz, 2J(HC(10)C(11)) = 4.7 Hz);
160.35 (m (s), C(12)). 31P NMR (CH2Cl2, 36.48 MHz),  : 16.0
P
(d, 2J(PCH) = 24.5 Hz).
6ꢀChloroꢀ2ꢀhydroxyꢀ4ꢀ(4ꢀmethoxyphenyl)ꢀ7ꢀmethylbenzoꢀ
[e]ꢀ1,2ꢀoxaphosphinine 2ꢀoxide (15). A 20 : 1 mixture of acetone
and water (21 mL) was added to phosphine 13 (3.6 g, 10.1 mmol).
The white precipitate that formed was filtered off and washed
with diethyl ether (5×4 mL). Yield 2.87 g (84%), m.p. 286 C.
Found (%): C, 56.79; H, 4.87; Cl, 10.34; P, 9.05. C16H14ClO4P.
Calculated (%): C, 57.07; H, 4.19; Cl, 10.53; P, 9.20. IR (Nujol
(DMSOꢀd6—CDCl3 (3 : 1)),  : 126.36 (dd (d), C(3), 1J(PC(3)) =
C

68
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
Nemtarev et al.
mulls), /cm–1: 415, 444, 463, 484, 521, 535, 553, 584, 631, 666,
722, 748, 782, 801, 820, 853, 870, 883, 890, 922, 1014, 1033,
1128, 1166, 1179, 1248, 1337, 1376, 1460, 1483, 1510, 1595,
1611, 2290, 2549, 2854, 2924, 2954, 3466. 1H NMR (DMSOꢀd6),
: 2.36 (br.s, Me); 3.83 (s, OMe); 6.23 (d, H(3), J(PC(3)H) =
= 17.8 Hz); 7.07 (m, H(11), AA´ part of AA´XX´ spectrum);
1J(PC(3)) = 165.0 Hz, 1J(HC(3)) = 172.6 Hz); 157.05 (m (d), C(4),
2J(PCC(4)) = 2.4 Hz); 125.01 (ddm (d), C(4a), 3J(PCCC(4a)) =
= 20.0 Hz, 3J(HC(3)CC(4a)) = 8.0 Hz); 147.24 (ddm (d), C(5),
3J(HC(7)CC(5)) = 4.7 Hz, 4J(PCCCC(5)) = 1.4 Hz); 131.70
(dd (d), C(6), 2J(HC(7)C(6)) = 4.2 Hz, 5J(PCCCCC(6)) =
2
1
= 2.0 Hz); 133.00 (d (s), C(7), J(HC(7)) = 165.6 Hz); 138.25
7.08 (s, H(8)); 7.32 (br.s, H(5)); 7.33 (m, H(10), XX´ part of
(ddm (d), C(8), 3J(POCC(8)) = 6.8 Hz, 2J(HC(7)C(8)) =
= 3.6 Hz); 147.50 (dd (d), C(8a), 3J(HC(7)CC(8a)) = 11.7 Hz,
2J(POC(8a)) = 11.6 Hz); 148.16 (dtd (d), C(9), 3J(PCCC(9)) =
= 20.9 Hz, 3J(HC(11)CC(9)) = 7.5 Hz, 3J(HC(3)CC(9)) =
AA´XX´ spectrum). 13C NMR (DMSOꢀd6),  : 115.76 (dd (d),
C
C(3), 1J(PC(3)) = 169.5 Hz, 1J(HC(3)) = 163.5 Hz); 150.78
(m (d), C(4), 2J(PCC(4)) = 1.5 Hz); 121.91 (m (d), C(4a),
3J(PCCC(4a)) = 16.5 Hz); 128.30 (d (s), C(5), 1J(HC(5)) =
= 164.6 Hz); 127.82 (dq (s), C(6), 2J(HC(5)C(6)) = 5.6 Hz,
1
= 6.0 Hz); 124.00 (dm (br.s), C(10), J(HC(10)) = 171.6 Hz);
1
128.84 (dm (s), C(11), J(HC(11)) = 164.2 Hz); 148.31 (tt (s),
3J(H(3)CC(7)C(6))
=
5.0 Hz); 139.22 (dq (s), C(7),
C(12), 3J(HC(10)CC(12)) = 9.0 Hz, 2J(HC(11)C(12)) = 3.0 Hz);
39.38 (m (s), C(15), 2J(HC(16)C(15)) = 3.4 Hz); 30.26 (qqq (s),
C(16), 1J(HC(16)) = 126.9 Hz, 3J(HCCC(16)) = 4.5 Hz); 34.90
(m (s), C(19), 2J(HC(20)C(19)) = 3.5 Hz); 29.60 (qqq (s), C(20),
1J(HC(20)) = 126.7 Hz, 3J(HCCC(20)) = 4.6 Hz). 31P NMR
2J(HC(8)C(7)) = 6.3 Hz, 2J(H(3)CC(7)) = 6.3 Hz); 122.23 (ddq
(d), C(8), 1J(HC(8)) = 163.4 Hz, 3J(H(3)CC(7)C(8)) = 6.1 Hz,
3J(POC(8a)C(8)) = 7.0 Hz); 150.29 (ddd (d), C(8a), 2J(POC(8a))
= 7.0 Hz, 3J(HC(5)CC(8a)) = 7.0 Hz, 2J(HC(8)C(8a)) =
= 3.8 Hz); 130.52 (dm (d), C(9), 3J(PCCC(9)) = 18.7 Hz,
2J(HCC(9) = 7.8 Hz); 130.18 (dd (s), C(10), 1J(HC(10)) =
= 159.5 Hz, 2J(HC(11)C(10)) = 7.4 Hz); 114.70 (dd (s), C(11),
1J(HC(11)) = 160.5 Hz, 2J(HC(10)C(11)) = 4.7 Hz); 160.35
(m (s), C(12)); 19.91 (qd (s), Me, 1J(HC) = 128.7 Hz,
3J(HC(8)CCH) = 4.1 Hz); 55.74 (q (s), OMe, 1J(HC) = 144.5 Hz).
(CH2Cl2, 36.48 MHz),  : 15.27 (d, 2J(PCH) = 27.8 Hz).
P
2ꢀ[2,5ꢀDi(tertꢀbutyl)ꢀ4ꢀchloroꢀ2ꢀhydroxyphenyl]ꢀ2ꢀ(4ꢀnitroꢀ
phenyl)vinylphosphonic acid (24) (1 : 1 acetone solvate). A 20 : 1
mixture of acetone and water (20 mL) was added to a mixture of
phosphine 22 (2.9 g, 5.9 mmol). The crystalline precipitate that
formed overnight was filtered off and washed with diethyl ether
(5×4 mL). Yield 2.1 g (66%), m.p. 164 C. Found (%): C, 54.97;
H, 6.04; Cl, 6.87; N, 2.75; P, 6.58. C25H33ClNO7P. Calculated (%):
31P NMR (DMSOꢀd6),  : 5.4 (d, 2J(PC(3)H) = 17.8 Hz).
P
Competitive reaction of 2,2,2ꢀtrichloroꢀ5ꢀmethylbenzo[d]ꢀ
1,3,2ꢀdioxaphosphole 6 with a mixture of 4ꢀnitrophenylꢀ and
phenylacetylene. A solution of 4ꢀnitrophenylacetylene (0.31 g,
2.1 mmol) and phenylacetylene (0.22 g, 2.1 mmol) in CH2Cl2
(6 mL) was rapidly added to a solution of phosphorane 6 (0.50 g,
1.9 mmol) and hexꢀ1ꢀene (0.24 mL, 1.9 mmol) in CH2Cl2
(2 mL), The 31P NMR spectrum of the reaction mixture (CH2Cl2,
C, 57.09; H, 6.32; Cl, 6.74; N, 2.66; P, 5.89. IR (KBr), /cm–1
:
451, 492, 534, 553, 603, 682, 689, 703, 740, 762, 789, 820, 850,
858, 871, 890, 928, 947, 1000, 1092, 1112, 1178, 1254, 1342,
1362, 1425, 1486, 1521, 1577, 1687, 2341, 2360, 2872, 2961,
3021, 3536. 1H NMR (DMSOꢀd6), : 1.32 (s, ButC(8)); 1.35
(s, ButC(5)); 2.08 (s, 2 Me); 6.88 (d, H(3), 2J(PC(3)H = 13.5 Hz);
7.25 (s, H(7)); 7.31 (br.d, H(10), AA´ part of AA´XX´ system,
3J(HCCH) = 8.8 Hz); 8.17 (br.d, H(11), XX´ part of AA´XX´
36.48 MHz),  : 18.9 (d, 2J(PCH) = 23.1 Hz). This spectrum
P
corresponds to compound 16.
Competitive reaction of benzodioxaphosphole 6 with a mixture
of 4ꢀmethoxyphenylꢀ and phenylacetylene. A solution of 4ꢀnitroꢀ
phenylacetylene (0.32 g, 2.4 mmol) and phenylacetylene (0.25 g,
2.4 mmol) in CH2Cl2 (5 mL) was rapidly added to a solution of
phosphorane 6 (0.58 g, 2.2 mmol) and hexꢀ1ꢀene (0.28 mL,
2.2 mmol) in CH2Cl2 (2 mL) at 20 C. The 31P NMR spectrum of
system, 3J(HCCH) = 8.8 Hz). 13C NMR (DMSOꢀd6),  : 125.95
C
(dd (d), C(3), 1J(PC(3)) = 184.9 Hz, 1J(HC(3)) = 152.2 Hz);
150.97 (ddt (d), C(4), 2J(PCC(4)) = 4.8 Hz, 2J(HC1C(4)) =
= 5.2 Hz, 3J(HC(10)CC(4)) = 4.2 Hz); 130.10 (ddd (d), C(4a),
3J(PCCC(4a)) = 7.0 Hz, 3J(HC(3)CC(4a)) = 10.0 Hz,
4J(HC(7)CCC(4a))
= 0.8 Hz); 151.86 (dd (d), C(8a),
the reaction mixture (CH2Cl2, 36.48 MHz),  : 18.9 (d, 2J(PCH) =
4J(PCCCC(8a)) = 2.2 Hz, 3J(HC(7)CC(8a)) = 9.5 Hz); 138.88
(m (s), C(8), 2J(HC(7)C(8)) = 3.5 Hz); 131.15 (d (s), C(7),
1J(HC(7)) = 161.4 Hz); 126.74 (d (s), C(6), 2J(HC(7)C(6)) =
= 3.7 Hz); 142.29 (m (s), C(5)); 147.56 (dtd (d), C(9),
P
= 23.1 Hz); 19.6 (d, 2J(PCH) = 24.4 Hz). This spectrum correꢀ
sponds to a mixture of compound 16 (24%) and 13 (76%).
Reaction of benzodioxaphosphole 20 with 4ꢀnitrophenylꢀ
acetylene. A solution of 4ꢀnitrophenylacetylene (1.00 g,
6.8 mmol) and hexꢀ1ꢀene (0.77 mL, 6.18 mmol) in CH2Cl2 (1 mL)
was added dropwise to a solution of phosphorane 20 (2.2 g,
6.2 mmol), which was prepared from 3,6ꢀdi(tertꢀbutyl)ꢀ1,2ꢀ
benzoquinone (1.36 g) and phosphorus trichloride (1.1 mL), in
CH2Cl2 (8 mL). The solvent and volatile products were removed
from the reaction mixture in a vacuum of 12 Torr (the externalꢀ
heating temperature was 100 C), and the glassy paleꢀyellow
compound, 5,8ꢀdi(tertꢀbutyl)ꢀ2,6ꢀdichloroꢀ4ꢀ(4ꢀnitrophenyl)ꢀ
benzo[e]ꢀ1,2ꢀoxaphosphinine 2ꢀoxide (22), was obtained and
characterized by spectroscopic methods. MS, m/z (Irel (%)): 467
3J(PCCC(9))
= = 6.5 Hz,
21.6 Hz, 2J(HC(3)C(9))
3J(HC(11)CC(9)) = 6.5 Hz); 124.64 (dd (s), C(10), 1J(HC(10))
= 171.7 Hz, 2J(HC(11)C(10)) = 3.7 Hz); 127.70 (dd (s), C(11),
1J(HC(11)) = 170.4 Hz, 2J(HC(10)C(11)) = 6.2 Hz); 147.59
(tt (s), C(12), 3J(HC(10)CC(12)) = 9.5 Hz, 2J(HC(11)C(12)) =
= 3.3 Hz); 34.64 (m (s), C(19), 2J(HC(20)C(19)) = 3.6—4.0 Hz,
3J(HC(7)CC(19)) = 3.6 Hz); 29.73 (qm (s), C(20), 1J(HC(20)) =
= 125.4 Hz); 206.75 (m (s), C(O), acetone, 2J(HCC) = 5.9 Hz);
30.96 (m (s), Me, acetone, 1J(HC) = 127.2 Hz, 3J(HCC) = 1.5 Hz).
31P NMR (DMSOꢀd6),  : 12.0 (d, 2J(PCH) = 13.5 Hz).
P
Triethylammonium 2ꢀ[2,5ꢀdi(tertꢀbutyl)ꢀ4ꢀchloroꢀ2ꢀhydrꢀ
oxyphenyl]ꢀ2ꢀ(4ꢀnitrophenyl)vinylphosphonate (25). Triethylꢀ
amine (0.077 mL, 0.52 mmol) was added to a solution of phosꢀ
phonic acid 24 (as the 1 : 1 acetone solvate) (0.14 g, 0.26 mmol)
in diethyl ether (5 mL). The reaction mixture was stirred for 3 h.
The white precipitate that formed was filtered off and washed
with diethyl ether (5×1 mL). Yield 0.14 g (97%), m.p. 189 C.
Found (%): C, 58.03; H, 8.11; Cl, 6.02; N, 4.97; P, 5.74.
[M]+ (2.2) (C24H24Cl235NO4P), 452 [M – Me]+ (2.2), 411
•
[M – C4H8]+ (16.2), 269 [C14H7O3N]+ (100). 1H NMR (CDCl3),
: 1.12 (s, ButC(8)); 1.42 (s, ButC(5)); 6.53 (d, H(3), 2J(PC(3)H)
= 27.8 Hz); 7.29 (br.s, C(10)H, AA´ part of AA´XX´ system,
3J(HCCH) = 7.6 Hz); 7.44 (d, H(7), 5J(POCCC(7)H = 1.3 Hz);
8.18 (br.d, H(11), XX´ part of AA´XX´ system, 3J(HCCH) =
= 7.6 Hz). 13C NMR (CDCl3),  : 117.10 (dd (d), C(3),
C

Arylacetylenes and trichlorobenzodioxaphosphole
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 1, January, 2013
69
C28H42ClN2O6P. Calculated (%): C, 59.10; H, 7.44; Cl, 6.23;
N, 4.92; P, 5.44. IR (KBr), /cm–1: 459, 580, 624, 763, 798, 853,
1024, 1086, 1135, 1177, 1229, 1252, 1294, 1326, 1396, 1441,
1462, 1502, 1589, 2047, 2837, 2907, 2934, 2955, 3002, 3081.
1H NMR (DMSOꢀd6), : 0.87 (t, NCMe, 3J(HCCH) = 7.3 Hz);
1.30 (s, ButC(8)); 1.36 (s, ButC(5)); 2.01 (br.q, NH, 3J(HCCH) =
= 7.3 Hz); 6.77 (d, H(3), 2J(PC(3)H) = 11.0 Hz); 7.05 (d.br.d,
C(10)H, AA´ part of AA´XX´ system, 3J(HCCH) = 9.0 Hz);
7.15 (s, H(7)); 8.08 (d.br.d, C(11)H, XX´ part of AA´XX´ system,
= 4.7 Hz); 34.85 (d.dec (s), C(19), 2J(HC(20)C(19)) =
= 3.5 Hz); 29.43 (q.sept (s), C(20), 1J(HC(20)) = 126.5 Hz,
3J(HCCC(20)) = 4.8 Hz). 31P NMR (DMSOꢀd6),  : 18.8
P
(d, 2J(PCH) = 27.7 Hz).
2ꢀ[3,6ꢀDi(tertꢀbutyl)ꢀ5ꢀchloroꢀ2ꢀhydroxy)ꢀ2ꢀ(4ꢀmethoxyꢀ
phenyl)vinylphosphonic acid (29). A 20 : 1 acetone—water mixꢀ
ture (20 mL) was added to phosphine 26 (0.6 g, 1.3 mmol). The
white precipitate of compound 29 that formed was filtered off
and washed with diethyl ether (3×4 mL). Yield 0.48 g (80%),
m.p. 188—190 C. Found (%): C, 58.87; H, 7.01; Cl, 7.78;
P, 6.92. C23H30ClO5P. Calculated (%): C, 60.99; H, 6.68; Cl, 7.83;
P, 6.84. IR (KBr), /cm–1: 470, 491, 513, 526, 546, 568, 621,
640, 695, 718, 754, 811, 858, 912, 1038, 1075, 1113, 1178, 1215,
1254, 1284, 1308, 1367, 1473, 1509, 1595, 2325, 2624, 2678,
2953, 3411. 1H NMR (DMSOꢀd6), : 1.35 (s, ButC(8)); 1.37
3J(HCCH) = 9.0 Hz). 13C NMR (DMSOꢀd6),  : 131.17 (dd (d),
C
C(3), 1J(PC(3)) = 172.0 Hz, 1J(HC(3)) = 147.5 Hz); 147.48
2
(ddt (d), C(4), J(PCC(4)) = 4.4 Hz, 2J(HC(3)C(4)) = 4.8 Hz,
3J(HC(10)CC(4))
=
3.9 Hz); 132.30 (dd (d), C(4a),
3J(PCCC(4a)) = 5.9 Hz, 3J(HC(3)CC(4a)) = 3.9 Hz); 152.83
4
3
(dd (d), C(8a), J(PCCCC(8a)) = 1.7 Hz, J(HC(7)CC(8a)) =
= 9.5 Hz); 139.54 (m (s), C(8)); 130.31 (d (s), C(7), 1J(HC(7)) =
= 161.0 Hz); 126.65 (d (s), C(6), 2J(HC(7)C(6)) = 3.7 Hz);
142.46 (m (s), C(5)); 149.84 (dtd (d), C(9), 3J(PCCC(9)) = 19.8 Hz,
2J(HC(11)C(9)) = 5.9 Hz, 3J(HC(3)CC(9)) = 5.9 Hz); 123.61
(dd (s), C(10), 1J(HC(10)) = 165.1 Hz, 2J(HC(11)C(10)) = 3.7 Hz);
127.07 (dd (s), C(11), 1J(HC(11)) = 163.6 Hz, 2J(HC(10)C(11))
= 6.6 Hz); 146.73 (tm (s), C(12), 3J(HC(10)CC(12)) = 9.5 Hz);
38.37 (m (s), C(15)); 31.23 (qm (s), C(16), 1J(HC(16)) = 126.3 Hz);
34.65 (m (s), C(19)); 29.84 (qm (s), C(20), 1J(HC(20)) =
2
(s, ButC(5)); 6.49 (d, H(3), J(PC(3)H = 12.7 Hz); 6.84 (br.m,
H(11), AA´ part of AA´XX´ spectrum); 6.89 (br.m, H(10), XX´
part of AA´XX´spectrum); 7.17 (br.s, H(7)). 31P NMR (DMSOꢀd6),
 : 10.8 (d, 2J(PC(3)H) = 12.7 Hz).
P
2ꢀtertꢀButylaminoꢀ5,8ꢀdi(tertꢀbutyl)ꢀ6ꢀchloroꢀ4ꢀ(4ꢀmethꢀ
oxyphenyl)benzo[e]ꢀ1,2ꢀoxaphosphinine 2ꢀoxide (28). tertꢀButylꢀ
amine (1.4 mL, 13.2 mmol) was added to a solution of phosꢀ
phine 26 (3.0 g, 6.6 mmol) in diethyl ether (30 mL) under an
atmosphere of dry argon. The white precipitate of compound 28
and tertꢀbutylammonium chloride that formed was washed with
a 5% sodium hydrocarbonate solution (5×10 mL), water (2×10 mL),
and diethyl ether (5×4 mL) and dried in vacuum of 12 Torr.
Yield 2.4 g (75%), m.p. 239 C. Found (%): C, 65.44; H, 7.97;
Cl, 7.13; N, 2.93; P, 6.45. C27H37ClNO3P. Calculated (%):
C, 66.18; H, 7.61; Cl, 7.24; N, 2.86; P, 6.32. IR (Nujol mulls),
/cm–1: 425, 477, 557, 583, 629, 689, 722, 743, 779, 813, 836,
871, 959, 1019, 1037, 1084, 1134, 1179, 1199, 1237, 1313, 1369,
1415, 1453, 1509, 1544, 1580, 1607, 1743, 2342, 2360, 3247.
1H NMR (DMSOꢀd6—CDCl3 (3 : 2)), : 1.11 (s, ButC(8)); 1.34
(s, ButC(5)); 1.42 (s, But(NH)); 5.20 (br.d, NH, 2J(PNH) = 9.6 Hz);
6.10 (d, H(3), 2J(PC(3)H = 23.7 Hz); 6.80 (br.m, H(10),
AA´ part of AA´XX´ system); 6.93 (br.s, H(11), XX´ part of
AA´XX´ system); 7.20 (s, H(7)). 31P NMR (DMSOꢀd6—CDCl3
1
= 126.9 Hz); 45.77 (br.t (s), CH2 (NEt), J(HC) = 143.8 Hz);
8.69 (q (s), Me (NEt), 1J(HC) = 128.0 Hz). 31P NMR (DMSOꢀd6)
 : 9.6 (d, 2J(PCH) = 11.0 Hz).
P
Reaction of benzodioxaphosphole 20 with 4ꢀmethoxyphenylꢀ
acetylene. A solution of 4ꢀmethoxyphenylacetylene (1.26 g,
9.6 mmol) and hexꢀ1ꢀene (1.1 mL, 8.8 mmol) in CH2Cl2 (5 mL)
was added to a solution of phosphorane 20 (3.1 g, 8.7 mmol),
which was prepared from 3,6ꢀdi(tertꢀbutyl)ꢀ1,2ꢀbenzoquinone
(1.91 g) and phosphorus trichloride (3.1 mL), in CH2Cl2 (20 mL).
The solvent and volatile products were removed from the reacꢀ
tion mixture in a vacuum of 12 Torr (the externalꢀheating temꢀ
perature was 100 C), and pentane (15 mL) was added to the
glassy paleꢀyellow residue. The white crystalline precipitate of
5,8ꢀdi(tertꢀbutyl)ꢀ2,6ꢀdichloroꢀ4ꢀ(4ꢀmethoxyphenyl)benzo[e]ꢀ
1,2ꢀoxaphosphinine 2ꢀoxide (26) that formed overnight was filterꢀ
(3 : 2), 36.48 MHz),  : 10.3 (dd, 2J(PCH) = 23.6 Hz,
P
ed off under argon and washed with a cold (0— 5 C) 10 : 1
2J(PNH) = 9.6 Hz).
–
pentane—CH2Cl2 mixture (3×5 mL). Yield 3.2 g (82%), m.p.
111—113 C. MS, m/z (Irel (%): 452 [M]+• (2.2) (C23H27Cl235O3P),
437 [M – Me]+ (3.5), 417 [M – Cl]+ (2.0), 396 [M – C4H8]+
(75.9), 381 [M – C4H8 – Me]+ (30.3), 365 [M – C4H8 – OMe]+
(100.0). 1H NMR (CDCl3), : 1.18 (s, ButC(8)); 1.36 (s, ButC(5));
6.30 (d, H(3), 2J(PC(3)H = 27.7 Hz); 6.83 (br.s, H(10), AA´
part of AA´XX´ system); 6.98 (br.s, C(11)H, XX´ part of AA´XX´
system); 7.42 (d, H(7), 5J(POCCC(7)H = 1.4 Hz). 13C NMR
This study was financially supported by the Russian
Foundation for Basic Research (Project Nos 10ꢀ03ꢀ00525
and 12ꢀ03ꢀ90703ꢀmob_st).
References
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(CDCl3),  : 55.406 (q (s), OMe, J(HC) = 144.3 Hz); 112.64
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Received November 19, 2011;
in revised form December 3, 2011