Reactions of phenylenedioxytrihalophosphoranes with arylacetylenes: XIII. Reaction of 5-tert-butyl-2,2,2-trihalo-1,3,2λ5- benzodioxaphospholes with acetylenes

Article abstract of DOI:10.1134/S1070428014060190

Reactions of 5-tert-butyl-2,2,2-trichloro-, 2,2,2-tribromo-5-tert-butyl-, and 2,2-dibromo-5-tert-butyl-2-fluoro-1,3,2λ⁵- benzodioxaphospholes with aryl- and alkylacetylenes lead to quantitative formation of 2-halo-1,2λ⁵-benzoxaphosph

Full text of DOI:10.1134/S1070428014060190

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 6, pp. 864–887. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © V.F. Mironov, A.V. Nemtarev, E.N. Varaksina, A.A. Shtyrlina, A.T. Gubaidullin, I.A. Litvinov, A.B. Dobrynin, 2014, published in
Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 6, pp. 880–902.
Dedicated to Full Member of the Russian Academy of Sciences
O.N. Chupakhin on his 80th anniversary
Reactions of Phenylenedioxytrihalophosphoranes
with Arylacetylenes: XIII.* Reaction of 5-tert-Butyl-
2,2,2-trihalo-1,3,2λ5-benzodioxaphospholes with Acetylenes
V. F. Mironov, A. V. Nemtarev, E. N. Varaksina, A. A. Shtyrlina, A. T. Gubaidullin,
I. A. Litvinov, and A. B. Dobrynin
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
e-mail: mironov@iopc.ru
Received April 24, 2014
Abstract—Reactions of 5-tert-butyl-2,2,2-trichloro-, 2,2,2-tribromo-5-tert-butyl-, and 2,2-dibromo-5-tert-butyl-
2-fluoro-1,3,2λ5-benzodioxaphospholes with aryl- and alkylacetylenes lead to quantitative formation of 2-halo-
1,2λ5-benzoxaphosphinine 2-oxides which may be regarded as phosphorus analogs of natural heterocyclic
compounds, coumarin and chromene. The major products (>70%) are 4-aryl-7-tert-butyl-2,6-dichloro-, 4-aryl-
2-bromo-7-tert-butyl-, and 4-aryl-7-tert-butyl-2-fluoro-1,2λ5-benzoxaphosphinine 2-oxides. Hydrolysis of these
compounds and their treatment with amines gives the corresponding 2-hydroxy and 2-amino derivatives, as
well as ammonium salts. The structure of some compounds was proved by X-ray analysis.
DOI: 10.1134/S1070428014060190
As we showed previously [2], reactions of aryl-
acetylenes with 2,2,2-trichloro- and 2,2,2-tribromo-
1,3,2λ5-benzodioxaphospholes provide a convenient
synthetic approach to 1,2λ5-benzoxaphosphinine deriv-
atives. The reaction direction did not change than the
initial 2,2,2-trichloro-1,3,2λ5-benzodioxaphospholes
contained donor (5-methyl [3]) or acceptor substituent
(5-chlorocarbonyl [4]) or halogen atoms (5-bromo,
5,6-dibromo, 4-fluoro [5–7]) in the aromatic ring; on
the other hand, the regioselectivity in the substitution
of oxygen atom and halogenation of the benzene ring
was found to clearly depend on the substituent nature.
The products of these reactions, 1,2λ5-benzoxaphos-
phinine 2-oxide derivatives, were formed in high
yields; they may be regarded as phosphorus-containing
analogs of natural heterocycles, coumarin and
chromene [8–12], whose chemical, biological, and
other properties were extensively studied [13]. There-
fore, interest in phosphorus analogs of coumarins ap-
preciably increases [14–18], though these compounds
remain so far difficultly accessible.
In this paper we report the results of our studies on
reactions of aryl- and alkylacetylenes with 5-tert-butyl-
2,2,2-trihalo-1,3,2λ5-benzodioxaphospholes containing
a bulky tert-butyl group in the para position with
respect to one of the endocyclic oxygen atoms.
The reaction of 5-tert-butyl-2,2,2-trichloro-1,3,2λ5-
benzodioxaphosphole (I) with arylacetylenes in meth-
ylene chloride (10–20°C) was accompanied by libera-
tion of hydrogen chloride (taking into account possible
addition of the latter to multiple bond, 2 equiv of aryl-
acetylene was used). The 31P NMR spectra of the reac-
tion mixtures contained doublets in the region δP 17–
2
20 ppm with geminal coupling constants JPH of 23.4–
25.5 Hz) typical of four-coordinate phosphorus deriv-
atives, 1,2λ5-benzoxaphosphinine 2-oxides. No pos-
sible products of classical electrophilic addition to the
triple bond with unchanged configuration of the phos-
phorus atoms or other reaction paths were detected.
The product structure was assigned by analysis of the
1H, 13C, and and 13C–{1H} NMR spectra of the product
mixtures dried under reduced pressure. The reactions
of I with arylacetylenes gave mainly (70–73%) 4-aryl-
* For communication XII, see [1].
864

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES ... XIII.
865
Scheme 1.
1
O
O
8
5
2
t-Bu
8a
4a
7
6
P
Cl
3
CH
Cl
t-Bu
4
O
O
CH2Cl2
9
+
PCl3
10
11
14
13
R
12
R
I
IIa–IIc
Cl
O
O
O
O
P
Cl
P
Cl
+
+
t-Bu
Cl
C6H4R-4
C6H4R-4
IVa–IVc
IIIa–IIIc
R = H (a), Cl (b), Me (c).
7-tert-butyl-2,6-dichloro-1,2λ5-benzoxaphosphinine
2-oxides IIa–IIc (Scheme 1).
The cyclic structure of IIa–IIc is confirmed by the
presence in their 13C–{1H} NMR spectra of doublet
signals from C4a, C8a, and C8 (see Experimental)
coupled with phosphorus, which is possible only when
cyclic oxaphosphinine fragment is formed. The multi-
plicity of the same signals in the proton-coupled 13C
NMR spectrum indicated substitution at positions 6
and 7 of the heterocycle. The relative position of the
tert-butyl group and chlorine atom introduced into the
benzo fragment may be determined by comparing the
chemical shifts of C6, C7 with account taken of substit-
uent effects. The chlorine atom was thus localized on
IIa
1JPC
*
*
IVa
IIIa
1JPC
1JPC
**
**
o
o
IVa
IIIa
1JCH
IIa
*
1JCH
*
*
*
**
** **
o
o
**
o
o
116.5
115.5
114.5
113.5
δC, ppm
Fig. 1. Fragments of the 13C and 13C–{1H} NMR spectra of the reaction mixture obtained from benzodioxaphosphole I and phenyl-
acetylene (mixture of compounds IIa–IVa).
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MIRONOV et al.
866
Scheme 2.
Cl
O
O
O
t-Bu
O
O
O
H2O
P
OH
+
P
OH
P
OH
II–IV
+
–HCl
Cl
t-Bu
Cl
C6H4R-4
C6H4R-4
VIa–VIc
C6H4R-4
VIIa–VIIc
Va–Vc
R = H (a), Cl (b), Me (c).
Scheme 3.
O
O
Cl
O
17
17
16, 15
O
O
18
18
t-Bu
O
O
PhH
P
N
P
N
IIa–IVa
+
+
N
SiMe3
–Me3SiCl
16, 15
t-Bu
Cl
O
O
O
Ph
VIIIa
Ph
IXa
O
15
O
16
O
P
N
+
Cl
O
Ph
Xa
C6. The C3, C4, and C9 signals characteristically ap-
peared in the spectrum as doublets due to coupling
with the phosphorus nucleus. Figure 1 shows typical
13C and 13C–{1H} NMR patterns for compounds IIa–
IVa in the C3 resonance region.
coupling constant for C8 (d.d.d, δC 128.83 ppm, JPC
=
3
8.2, 2JCH = 5.4, 4JCH = 1.4 Hz) confirms the presence of
chlorine in the ortho position with respect to the endo-
cyclic oxygen atom. Another minor reaction path in-
volves substitution of the tert-butyl group by chlorine.
In our case, only the tert-butyl group in the para posi-
tion to the endocyclic oxygen atom is replaced; prod-
ucts of substitution of the 7-tert-butyl group by
chlorine were not detected. The 13C and 13C–{1H}
NMR spectra of IVa and IVb (recorded from product
mixtures) were consistent with those reported for
4-aryl-2,6-dichloro-1,2λ5-benzoxaphosphinines syn-
thesized previously by reaction of 2,2,2-trichloro-
1,3,2λ5-benzodioxaphosphole with arylacetylenes [2].
Compound IVc was also synthesized independently by
reaction of 2,2,2-trichloro-1,3,2λ5-benzodioxaphos-
phole with 4-methylphenylacetylene.
Minor 1,2λ5-benzoxaphosphinine 2-oxides III and
IV were formed at a ratio of ~1:1 in the reactions with
phenyl- and 4-methylphenylacetylenes and at a ratio of
2 : 1 in the reaction with 4-chlorophenylacetylene.
Their structure was assigned mainly on the basis of the
chemical shifts of C6 and C8, as well as of the multi-
plicities of the C4a, C5, C6, C7, C8, and C8a signals.
In the 13C NMR spectrum of IIIb, the doublet signal of
3
C4a (δC 122.62 ppm, JPC = 17.7 Hz) is additionally
split only into a doublet due to coupling with the 3-H
proton (3JCH = 8.2 Hz), indicating that the substituents
are attached to C6 and C8. The lack of a direct 13C–1H
Scheme 4.
Cl
O
O
O
t-Bu
O
O
O
Dioxane
P
O
P
O
P
O
Vb–VIIb
+
Et2NH
+
+
Et2NH2
Et2NH2
Et2NH2
Cl
t-Bu
Cl
C6H4Cl-4
XIb
C6H4Cl-4
XIIb
C6H4Cl-4
XIIIb
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES ... XIII.
With a view to isolating pure compounds, product
867
C22
mixtures II–IV were subjected to hydrolysis in ben-
zene and, after removal of volatile compounds, were
treated with diethyl ether (Scheme 2). By prolonged
storage of hydroxyphosphinines V–VII in diethyl ether
we succeeded in isolating crystalline cyclic hydrogen
phosphonates VII. Their structure was confirmed by
NMR spectroscopy, as well as by comparison of their
spectral parameters with those given in [2]. We failed
to separate isomeric compounds V and VI by crystal-
lization from different solvents; therefore, we tried
other chemical modification methods for II–IV to
obtain isolable derivatives.
C21
O4
N1
O3
O2
O1
P2
C19
C20
C3
C8a
C10
C4
C9
C8
C6
C18
C4a
C11
C12
C7
C16
By treatment of mixture IIa–IVa in benzene with
N-(trimethylsilyl)succinimide (Scheme 3) and subse-
quent fractional crystallization from diethyl ether we
isolated compound VIIIa and a mixture of amides
VIIIa and Xa at a ratio of 12:1; the structure of these
compounds was determined by 13C and 13C–{1H}
NMR. Hydrogen phoshonates Vb–VIIb reacted with
diethylamine to produce a mixture of ammonium salts
Xb–XIIb; by fractional crystallization of the latter we
succeeded in isolating pure salt XIb (Scheme 4).
C5
C15
C14
C17
C13
Cl6
Cl12
Fig. 2. Structure of diethylammonium 7-tert-butyl-6-chloro-
4-(4-chlorophenyl)-2-oxo-1,2λ5-benzoxaphosphinin-2-olate
hydrate (XIb) in crystal according to the X-ray diffraction
data (hereinafter, non-hydrogen atoms are shown as thermal
vibration ellipsoids with a probability of 30%).
The structure of XIb was proved by X-ray analysis
(Fig. 2). Compound XIb in crystal is represented by
the phosphorus-containing anion, diethylammonium
cation, and one solvation water molecule. The oxa-
phosphinine heterocycle has a distorted boat con-
formation with the planar [within 0.001(6) Å]
O1C8aC4aC4 four-atom fragment; the P2 and C3 atoms
deviate from that plane toward one side by 0.803(2)
and 0.400(6) Å, respectively. The negative charge is
delocalized over the O2 and O3 atoms; the correspond-
ing P–O bond lengths are leveled and are within the
range typical of such bonds. The endocyclic bond
angle at the phosphorus atom is 100.4(3)°. The chloro-
phenyl substituent on C4 is turned with respect to the
C3=C4 bond through a dihedral angle of 44(1)°, which
weakens its conjugation with that π-bond.
lization afforded calcium salt XIVb. The 1,2-oxaphos-
phinine heterocycle in VIIb tured out to be unstable to
hydrolysis in DMSO, and compound VIIb underwent
partial opening with formation of acyclic phosphonic
acid XVb (Scheme 5)
As with arylacetylenes, the reaction of benzodioxa-
phosphole I with terminal alkylacetylenes, namely
pent-1-yne, hex-1-yne, and hept-1-yne, gave exclu-
sively 1,2λ5-benzoxaphosphinine derivatives
1
(Scheme 6). According to the 31P, H, and 13C NMR
data, four products XVI–XIX were formed, and only
three of them contained a tert-butyl group. As in the
O4
H
H
O1
The crystal structure of XIb is stabilized by clas-
sical N–H···O and O–H···O intermolecular hydrogen
bonds. The hydrogen bonds N1–H1b · · · O2 and
N1–H1a···O2′ link molecules XIb to form centrosym-
metric dimers (including two anionic and two cationic
species; Fig. 3). The dimers are linked through solva-
tion water molecules by classical O–H···O hydrogen
bonds, leading to infinite chains along one crystallo-
graphic axis, and these chains give rise to a layered
structure with so-called chlorine channels.
H
O3
H
P2
O2
H
N1
H
Fig. 3. Structure of centrosymmetric dimer formed by di-
ethylammonium 7-tert-butyl-6-chloro-4-(4-chlorophenyl)-2-
oxo-1,2λ5-benzoxaphosphinin-2-olate hydrate (XIb) in crys-
tal according to the X-ray diffraction data.
Treatment of a mixture of hydrogen phosphonates
Vb–VIIb with calcium oxide and subsequent crystal-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

MIRONOV et al.
868
Scheme 5.
15, 16
t-Bu
O
O
OH
P
O
P(O)(OH)2
H2O
CaO, dioxane
Vb–VIIb
Ca2+
VIIb
Cl
Cl
C6H4Cl-4
XIVb
C6H4Cl-4
XVb
2
Scheme 6.
Cl
Cl
O
O
O
O
t-Bu
O
R
O
O
R
t-Bu
O
R
CH2Cl2
P
Cl
P
Cl
P
Cl
P
Cl
I + R
CH
+
+
+
Cl
Cl
t-Bu
R
XVId–XVIf
XVIId–XVIIf
XVIIId–XVIIIf
XIXd–XIXf
R = Pr (d), Bu (e), C5H11 (f).
Scheme 7.
Cl
O
O
P
Cl
O
O
O
O
O
t-Bu
t-Bu
O
H2O
P
OH
P
OH
OH
P
OH
XVI–XIX
+
+
+
Cl
Cl
t-Bu
R
R
R
R
XXd–XXf
XXId–XXIf
XXIId–XXIIf
XXIIId–XXIIIf
R = Pr (d), Bu (e), C5H11 (f).
above considered reaction, the major products were
4-alkyl-7-tert-butyl-2,6-dichloro-1,2λ5-benzoxaphos-
phinine 2-oxides XVId–XVIf with the chlorine atom
occupying the para position with respect to the endo-
cyclic oxygen atom. The C8 signals of XVId–XVIf in
the 13C NMR spectra were doublets of doublets
Hydrolysis of XVI–XIX with water gave mixtures
of hydrogen phosphonates XX–XXIII (Scheme 7),
from which pure compounds XXIIe, XXIIf, and XXf
were isolated by fractional crystallization. Prolonged
(4 months) storage of a solution of XXIIf in aqueous
DMSO resulted in its partial (40%) conversion into
phosphonic acid XXIV via opening of the oxaphos-
phinine ring (Scheme 8).
1
(3JPC, JCH), and the C8a signals, double doublets of
doublets (2JPC, 3JCH, 2JCH), indicating substitution at the
6,7-positions.
Scheme 8.
The position of the tert-butyl group on C7 is con-
firmed by the downfield shift of the C7 resonance due
to deshielding ipso effect of the tert-butyl group.
Analysis of the 1H and 13C NMR spectra of the product
mixture revealed formation of minor amounts of
isomeric 6- and 7-tert-butyl-2,8-dichloro-4-alkyl-
1,2λ5-benzoxaphosphinine 2-oxides XVIIId–XVIIIf
and XIXd–XIXf, as well as products of substitution of
the tert-butyl group in the para position with respect to
the endocyclic oxygen atom, 4-alkyl-2,6-dichloro-
1,2λ5-benzoxaphosphinine 2-oxides XVIId–XVIIf; the
Cl
8
OH
H2O, DMSO
P(O)(OH)2
XXIIf
6
t-Bu
Bu
XXIV
2,2,2-Tribromo-5-tert-butyl-1,3,2λ5-benzodioxa-
phosphole (XXV) reacted with arylacetylenes more
selectively than did trichloro analog I. Among two
oxaphosphinine derivatives XXVI and XXVII, the
major product (>80%) was 4-aryl-2-bromo-7-tert-
butyl-1,2λ5-benzoxaphosphinine XXVI (δP 9–10 ppm,
2JPH = 26.0–28.0 Hz; Scheme 9). Bromine liberated
1
aromatic region of the H NMR spectra of XVIId–
XVIIf was typical of 1,2,4-substituted benzenes: 8-H
(d, 3JHH), 7-H (d.d, 3JHH, 4JHH), 5-H (d, 4JHH).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES ... XIII.
869
Scheme 9.
15, 16
t-Bu
1
O
O
8
5
2
8a
4a
7
P
Br
3
CH
6
O
t-Bu
O
4
O
O
CH2Cl2
P
Br
9
+
+
PBr3
10
11
–ArBrC=CHBr
14
13
R
t-Bu
C6H4R-4
12
R
XXV
XXVIa–XXVIc
XXVIIa–XXVIIc
R = H (a), Cl (b), Me (c).
Scheme 10.
O
O
t-Bu
O
O
P
NEt2
P
NEt2
Et2NH
XXVIb/XXVIIb, XXVIc/XXVIIc
+
t-Bu
C6H4R-4
XXVIIIb, XXVIIIc
C6H4R-4
XXIXb, XXIXc
R = Cl (b), Me (c).
during the reaction adds to the initial acetylene yield-
ing 1-aryl-1,2-dibromoethenes. These results are con-
sistent with the lower migrating ability of the bromine
atom, which was noted previously in the reactions of
2,2,2-tribromo-1,3,2λ5-benzodioxaphosphole with
arylacetylenes [2]. However, in our case, no bromine
migration was observed at all, which may be due to
steric effect of the tert-butyl substituent. Furthermore,
unlike reactions of I with arylacetylenes, there was no
ipso-substitution of the tert-butyl group by bromine.
In the 13C NMR spectra of XXVI the doublet signal
of C8 (3JPC = 8.0–8.1 Hz) is additionally split into
doublets due to couplings with 8-H (1JCH = 161.5–
162.0 Hz) and 6-H (3JCH = 6.5–7.0 Hz). The C8 signals
of minor 6-tert-butyl derivatives XXVII were doublets
1
of doublets with the coupling constants JCH = 164.9–
165.0 and 3JPC = 8.1–8.3 Hz.
From 2-bromo-1,2-benzoxaphosphinines XXVI
and XXVII and diethylamine we obtained amides
XXVIII and XXIX (Scheme 10), and the structure of
Cl1A
Cl1B
C11A
C17A
C12A
C6A
C5A
C10A
C9A
C16A
C12B
C13A
C15A
C11B
C4aA
C7A
C8A
C18A
C4A
C3A
C10B
C9B
C4aB
C13B
C14B
C8aA
O1A
O2A
P2A
C5B
C6B
C4B
C3B
C21A
C21B
C16B
N1A
C8aB
C22A
C22B
P2B
N1B
C7B
C8B
C15B
O1B
O2B
C17B
C19A C20B
C20A
C19B
C18B
Fig. 4. Structure of two independent molecules A and B of 7-tert-butyl-4-(4-chlorophenyl)-2-diethylamino-1,2λ5-benzoxaphos-
phinine 2-oxide (XXVIIIb) in crystal according to the X-ray diffraction data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

MIRONOV et al.
870
C20B
C18A
C16A
C11B
O2B
C19B
C10B
4B C9B
C12B
C13B
C23B
C17A
N1B
C3B
C15A
C7A
C
P2B
C21B
C22B O1B
C6A
C8aB
C4aB
C8A
C14B
C5B
C6B
C5A
C8B
C7B
C22A
C8aA
O1A
C10A
C4aA
C21A
N1A
C11A
C9A
C3A
C16B
C18B
C4A
C23A
C12A
C15B
P2A
C19A
C17B
C20A
O2A
C13A
C14A
Fig. 5. Structure of two independent molecules A and B of 7-tert-butyl-2-diethylamino-4-(4-methylphenyl)-1,2λ5-benzoxaphos-
phinine 2-oxide (XXVIIIc) in crystal according to the X-ray diffraction data.
XXVIIIb and XXVIIIc in crystal was determined by
X-ray analysis. The unit cell of compound XXVIIIb
contains two independent molecules (Fig. 4). The six-
membered heterocycles in both independent molecules
A and B adopt a distorted boat conformation with
planar O1C8aC4aC4 and P2C3C4C4a four-atom fragments
(within 0.02 and 0.03 Å for molecules A and B,
respectively); the P2 and N2 atoms appear at different
sides with respect to the planar fragment, the corre-
sponding deviations being –0.310(2) and 0.062(6) (A)
and –0.324(1) and 0.072(4) Å (B). Intermolecular
C–H···O interactions involving the phosphoryl group
and diethylamine fragment give rise to cylindrical
structures along the 0c crystallographic axis.
which form a dihedral angle of –22(1) (A) or –25(1)°
(B) with respect to each other. The C3 and P2 atoms
deviate from the first plane by –0.19(2) and
–0.576(6) Å (A) and –0.18(2) and –0.542(6) Å (B),
respectively; i.e., these atoms appear at the same side
of the plane. The O1 and C8a atoms also deviate from
the C4aC4C3P2 plane toward the same side but by dif-
ferent distances [0.53(1) and 0.29(2) Å in A and
0.47(1) and 0.11(2) Å in B]. These data suggest a dis-
torted boat conformation of the oxaphosphinine
heterocycle as well. The exocyclic O2 and N2 atoms
deviate from the O1C8aC4aC4 plane by –2.00(1) and
0.45(2) Å in molecule A and by –1.94(1) and
0.39(2) Å, respectively, in molecule B, and the corre-
sponding deviations from the C4aC4C3P2 plane are
–1.32(1) and 1.21(2) Å in A and –1.31(1) and 1.14(2) Å
in B. Thus the diethylamino group occupies equatorial
position, and the phosphoryl oxygen atom is oriented
Amide XXVIIIc in crystal is also represented by
two independent molecules (Fig. 5). The heterocycle in
A and B contains two planar fragments O1AC8aAC4aAC4A
(O1BC8aBC4aBC4B) and C4aAC4AC3AP2A (C4aBC4BC3BP2B)
Scheme 11.
O
O
t-Bu
O
O
P
OH
P
OH
H2O, Et2O
–HBr
XXVIa/XXVIIa, XXVIc/XXVIIc
+
t-Bu
C6H4R-4
XXXa, XXXc
C6H4R-4
XXXIa, XXXIc
O
t-Bu
O
P
O– H3NPr-i
H2O, Et2O
–HBr
XXXa, XXXc
+
i-PrNH2
C6H4R-4
XXXIIa, XXXIIc
R = H (a), Me (c).
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REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES ... XIII.
871
C19B
N1A
C17B
C18B
C21B
C20A
N1B
C20B
O50
C19A
C15B
O3A
O1B
H
C18A
C8B
O2B
O3B
C21A
C7B
C16B
C8aB
C4aB
P2A
O1A
C8aA
P2B
C3B
O2A
C3A
C8A
C15A
C7A
C17A
C16A
C6B
C4aA
C5B
C4B
C14A
C6A
C4A
C5A
C9A
C10A
C11A
C14B
C9B
C13A
C12A
C10B
C11B
C13B
C12B
Fig. 6. Structure of two independent molecules A and B of 2-bromo-6-tert-butyl-4-phenyl-1,2λ5-benzoxaphosphinine 2-oxide hydrate
(XXXIIa) in crystal according to the X-ray diffraction data.
axially. The phenyl substituent on C4 is turned with
respect to the C3=C4 bond so that the torsion angle
C3C4C13C17 is 55(2)° (mean value); therefore, conjuga-
tion between these fragments is hardly probable. The
sum of the bond lengths at the nitrogen atom
(∠P2N2C16, P2N2C2, C2N2C16) is 359(1)° (A, B); i.e.,
the nitrogen atom has a planar–trigonal configuration.
The crystal packing of compound XXVIIIc is deter-
mined by van der Waals interactions.
crystallization, allowed us to separate hydrogen phos-
phonates XXX from minor isomers XXXI. The struc-
ture of the hydrolysis products was determined by
13C NMR spectroscopy and by X-ray analysis of am-
monium salt XXXIIa obtained from XXXa and iso-
propylamine.
Compound XXXIIa crystallizes as hydrate (Fig. 6),
and its unit cell includes two independent phosphorus-
containing anions, two isopropylammonium cations
(the isopropyl group in one of which is disordered by
two positions with equal populations; only one posi-
Hydrolysis of mixtures of benzoxaphosphinines
XXVI and XXVII (Scheme 11), followed by fractional
(a)
(b)
Fig. 7. Hydrogen bond system formed by 2-bromo-6-tert-butyl-4-phenyl-1,2λ5-benzoxaphosphinine 2-oxide hydrate (XXXIIa) in
crystal according to the X-ray diffraction data; views along the (a) 0a and (b) 0b axes.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

MIRONOV et al.
The crystal structure of XXXIIa is stabilized by
872
C12
C11
a hydrogen bond system involving the oxygen atoms
in the anionic species and water molecules and all NH
hydrogen atoms in the ammonium cations and hydro-
gen atoms in water molecules. The hydrogen bonds
give rise to H-columns along the 0a crystallographic
axis. The inner part of the columns contains hydro-
philic parts of molecules, including ammonium cations
and solvation water molecules, while the outer shell of
the columns is composed of hydrophobic tert-butyl
and aromatic fragments (Fig. 7a, b). On the whole, the
crystal structure of XXXIIa may be represented as
hexagonal packing of similar H-columns.
C10
C9
C14
C5
C6
C7
C4
C4a
C3
P2
H
O2
C13
C8a
C8
O1
Tribromophosphorane XXV reacted with hex-1-yne
to give two products XXXIII and XXXIV at a ratio of
2.8:1 (Scheme 12). Here, the major product was that
containing tert-butyl group on C7. Hydrolysis of mix-
ture XXXIII/XXXIV and subsequent fractional crys-
tallization afforded pure hydrogen phosphonate XXXV
(Scheme 13). Figure 8 shows the structure of molecule
XXXV according to the X-ray diffraction data. Like
the above examined structures, the phosphorus atom in
XXXV has a distorted tetrahedral configuration. The
six-membered heteroring adopts a flattened distorted
boat conformation with two planar fragments
C4C4aC8aO1 and P2C3S4O4a [within 0.017(2) and
0.006(2) Å, respectively] with the dihedral angle
11.6(1)° between them. The P2 and C3 atoms deviate
from the first plane toward one side by –0.5466(5) and
–0.235(2) Å, respectively, and the O1 and C8a atoms
deviate from the second planar fragment by 0.471(2)
and 0.193(2) Å respectively. These deviations are
consistent with the distorted boat conformation of the
heterocycle. The O2 atom occupies equatorial position:
the distances from O2 to the C4C4aC8aO1 and P2C3C4O4a
C15
C16
O3
Fig. 8. Structure of the molecule of 4-butyl-7-tert-butyl-2-
hydroxy-1,2λ5-benzoxaphosphinine 2-oxide (XXXV) in
crystal according to the X-ray diffraction data.
tion is shown in Fig. 6), and one water molecule. The
six-membered heterocycles in both independent
molecules A and B have a distrorted boat conforma-
tion; the O1C8aC4aC4 fragments are planar within 0.02
(A) and 0.01 Å (B), and the P2 and C3 atoms deviate
from these planes toward one side by –0.722(1) and
–0.330(4) (A) and 0.871(1) and 0.390(4) Å (B),
respectively. Also, there is one more planar fragment,
P2C3C4C4a. The P2–O1 bond lengths in molecules A
and B do not differ from the corresponding reference
values. The negative charge in the anionic species is
delocalized over the O2 and O3 atoms, and the P2–O2
and P2–O3 bonds have similar lengths which fall into
the range typical of such bonds. The endocyclic bond
angle at the phosphorus atom is 100.6(2) (A) and
99.5(1)° (B).
Scheme 12.
O
O
t-Bu
O
O
CH2Cl2
P
Br
P
Br
XXV
+
Bu
CH
+
t-Bu
Bu
Bu
XXXIII
XXXIV
Scheme 13.
13–16
t-Bu
O
O
O
O
H2O
P
OH
P
OH
XXXIII, XXXIV
+
–HBr
t-Bu
9–12
Bu
Bu
XXXVI
XXXV
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REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES ... XIII.
(a)
873
(b)
Fig. 9. Hydrogen bond system formed by molecules of 4-butyl-7-tert-butyl-2-hydroxy-1,2λ5-benzoxaphosphinine 2-oxide (XXXV)
in crystal according to the X-ray diffraction data; views along the (a) 0b and (b) 0a axes.
planes are 0.335(2) and 1.088(2) Å, respectively; the
O3 atom in the phosphoryl group is axial: its deviations
from the C4C4aC8aO1 and P2C3C4O4a planes are
–1.960(2) and –1.309(1) Å, respectively.
Unlike compound XXXIIa, molecules XXXV in
crystal are linked through only one classical hydrogen
bond involving the phosphonate oxygen atoms and
leading to formation of infinite H-bonded chains along
the 0a axis (Fig. 9a). These H-chains are packed anti-
parallel in a tetragonal mode (Fig. 9b) which ensures
fairly high calculated packing factor (67.1%).
1,2λ5-benzoxaphosphinine 2-oxides XXXVIII and
XXXIX at a ratio of 3:1 (Scheme 14). The structure of
XXXVIII and XXXIX was determined on the basis of
their 13C and 13C–{1H} NMR spectra in which the
signals from these compounds were well resolved, so
that their complete assignment was possible. Figure 10
shows the downfield fragments of the 13C–{1H} NMR
spectrum of a mixture of compounds XXXVIII and
XXXIX. Hydrolysis of the latter produced cyclic hy-
drogen phosphonates XXXa and XXXIa, and com-
pound XXXa was isolated by fractional crystallization.
It was expected that replacement of one bromine
atom on the phosphorus in XXXV by fluorine (com-
pound XXXVII) should led to the formation of
1,2-benzoxaphosphinine derivatives containing bro-
mine in the aromatic fragment, as was observed in the
reaction of 2,2-dibromo-2-fluoro-1,3,2λ5-benzodioxa-
phosphole with phenylacetylene [2]. However, dibro-
mofluorophosphorane XXXVII reacted with phenyl-
acetylene in methylene chloride at 10°C to produce
a mixture of 7- and 6-tert-butyl-2-fluoro-4-phenyl-
In summary, the reaction of 5-tert-butyl-2,2,2-tri-
chloro-, 2,2,2-tribromo-5-tert-butyl-, and 2,2-dibromo-
5-tert-butyl-2-fluoro-1,3,2λ5-benzodioxaphospholes I,
XXV, and XXVII with substituted acetylenes provides
a convenient synthetic route to tert-butyl-substituted
1,2λ5-benzoxaphosphinine 2-oxide derivatives. The
presence of a bulky tert-butyl group in the aromatic
fragment does not prevent introduction of a chlorine
atom into that fragment with formation of 4-aryl-7-
tert-butyl-2,6-dichloro-1,2λ5-benzoxaphosphinine
Scheme 14.
1
O
O
8
2
t-Bu
8a
4a
7
P
F
3
6
O
t-Bu
O
O
4
5
CH2Cl2
P
F
9
+
+
PFBr2
Ph
CH
10
11
–PhBrC=CHBr
14
13
O
t-Bu
Ph
12
XXXVII
XXXVIII
XXXIX
H2O
XXXa
+ XXXIa
–HBr
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MIRONOV et al.
874
XXXVIII
XXXIX XXXVIII
C3 C3
C7
XXXVIII
1JPC
2JCF
1JPC
2JCF
3JPC
XXXVIII
C8
3JCF
2JPC
XXXVIII
XXXIX
XXXVIII
XXXIX
C4
3JPC
C4a
2JPC
C8a
XXXIX
108
107
106
3JCF
2JPC
C4
C4
C8
3JPC
C4a
XXXIX XXXIX
C6
2JPC
XXXIX
C8a
C4
160.2
159.8
158
120
119
118
117
160
156
154
152
150
149
δC, ppm
Fig. 10. Fragments of the 13C–{1H} NMR spectrum (100.6 MHz, CDCl3) of a mixture of compounds XXXVIII and XXXIX.
2-oxides. The minor processes in the reactions of tri-
chlorophosphole I with aryl- and alkylacetylenes are
replacement of the tert-butyl group by chlorine to give
4-aryl-2,6-dichloro-1,2λ5-benzoxaphosphinine 2-ox-
ides and replacement of the oxygen atom in the meta
position with respect to the tert-butyl group with sub-
sequent chlorination of the ortho position relative to
the endocyclic oxygen atom. The main direction in
the reactions of bromobenzophospholes XXV and
XXXVII with substituted acetylenes is the formation
of 4-aryl-2-bromo(fluoro)-7-tert-butyl-1,2λ5-benzoxa-
phosphinine 2-oxides having no bromine in the fused
benzene ring.
10-mm glass ampules; otherwise, 5-mm glass ampules
were used. The IR spectra were measured on UR-20,
Bruker Vector-22, and Specord 75-IR instruments from
samples dispersed in mineral oil. The mass spectra
(electron impact, 70 eV) were obtained on Finnigan
MAT TRACE MS and MKh-1310 high-resolution
mass spectrometers (ion source temperature 200°C,
direct sample admission into the ion source) coupled
with an SM-4 computer. The mass spectra were pro-
cessed using Xcalibur program.
5-tert-Butyl-2,2,2-trichloro-1,3,2λ5-benzodioxa-
phosphole (I). 4-tert-Butylbenzene-1,2-diol, 33.6 g
(0.20 mol), was added in portions under stirring to
a solution of 51.7 g (0.25 mol) of phosphorus(V)
chloride in 350 mL of benzene. After 24 h, excess PCl5
crystallized from the solution; the liquid phase was
separated by decanting, the solvent was distilled off,
and the residue was distilled under reduced pressure.
Yield 20 g (33%), yellowish transparent liquid,
bp 168°C (0.5 mm). 31P–{1H} NMR spectrum
(CH2Cl2): δP –25.3 ppm. Found, %: C 40.11; H 4.07;
P 10.19. C10H12Cll3O2P. Calculated, %: C 39.80;
H 3.98; P 10.28.
EXPERIMENTAL
1
The H, 13C, 13C–{1H}, 31P, and 31P–{1H} NMR
spectra were recorded on Bruker WM-250 (250 MHz,
1H), Bruker MSL-400 (100.6 MHz, 13C; 162.0 MHz,
1
31P), Bruker Avance-600 (600 MHz, H; 150.9 MHz,
1
13C), Bruker Avance-400 (400 MHz, H; 100.6 MHz,
13C; IIc–IVc), Bruker Avance-500 (500 MHz, 1H), and
Bruker CXP-100 spectrometers (36.48 MHz, 31P) at
25°C (CDCl3, CH2Cl2) or 45°C (DMSO-d6); the chem-
ical shifts were determined relative to hexamethyldisil-
oxane (1H, internal reference), solvent (13C), or H3PO4
(31P, external reference). The 13C NMR spectra were
recorded on a Bruker MSL-400 instrument using
4-Phenyl-1,2λ5-benzoxaphosphinine 2-oxides
IIa–IVa. A solution of 4.7 mL (0.043 mol) of phenyl-
acetylene in 5 mL of methylene chloride was added at
10–20°C in a stream of argon (which was intensely
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REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES ... XIII.
875
Crystallographic parameters of compounds XIb, XXVIIIb, XXVIIIc, XXXIIa, and XXXV and conditions of X-ray diffrac-
tion experiments
Parameter
Color, habit
XIa
XXVIIIb
XXVIIIc
Colorless prismatic
C23H30NO2P
XXXIIa
XXXV
Formula
C18H16Cl2O3P·
C4H12N+·H2O
(C22H30Cl2NO4P)
C22H27ClNO2P
2(C18H18O3P–)·
2(C3H10N+)·H2O
(C42H58N2O7P2)
C16H23O3P
Crystal system
Space group
Unit cell parameters
a, Å
Monoclinic
Rhombic
Rhombic
Triclinic
Rhombic
P21/a
Pna21
P212121
P–1
Pbca
14.039(4)
09.949(2)
17.704(5)
090.00(0)
104.97(3)
090.00(0)
2389.1(5)
4
17.262(6)
21.828(7)
11.885(4)
90
12.010(2)
09.319(3)
15.367(3)
16.248(3)
69.38(2)
82.14(3)
87.38(3)
2157.4(9)
2
008.8633(6)
17.012(1)
20.658(1)
90
b, Å
17.083(5)
c, Å
21.933(6)
α, deg
90
β, deg
90
90
90
γ, deg
Volume, Å3
90
90
4500(2)
8
90
4478(3)
8
3114.9(4)
8
Z
Temperature, K
Molecular weight
dcalc, g/cm3
μ, cm–1
294(2)
296(2)
403.87
1.198
2.58
294(2)
294(2)
764.84
1.177
296(2)
294.31
1.255
1.81
474.34
383.45
1.319
1.132
3.66
1.38
1.49
F(000)
1000
1712
1648
820
1264
Radiation source
θ range, deg
hkl range
MoKα, λ 0.71073 Å
2.12 ≤ θ ≤ 24.63
2.21 ≤ θ ≤ 27.0
2.78 ≤ θ ≤ 22.77 2.21 ≤ θ ≤ 26.23 1.97 ≤ θ ≤ 28.71
0 ≤ h ≤ 16,
–11 ≤ k ≤ 9,
–20 ≤ l ≤ 20
–22 ≤ h ≤ 22,
–27 ≤ k ≤ 27,
–15 ≤ l ≤ 15
–13 ≤ h ≤ 7,
–16 ≤ k ≤ 18,
–23 ≤ l ≤ 21
0 ≤ h ≤ 11,
–18 ≤ k ≤ 19,
–18 ≤ l ≤ 20
–11 ≤ h ≤ 11,
–22 ≤ k ≤ 22,
–26 ≤ l ≤ 25
Total number of
reflections
6825
247830
9213
7098
314910
Number of independent
reflections
1811
9415
4624
6767
3927
Number of reflections
1811
4557
1699
4776
2484
with I > 2σ(I)
[I > 3σ(I)]
R
0.050
0.0693
0.0828
0.0485
0.0515
(F ≥ 3σ)
Rw (F2 ≥ 2σ)
0.047
1.131
271
0.1525
0.9790
498
0.1807
0.9590
440
0.1270
1.0370
500
0.1420
1.0020
188
Goodness of fit
Number of variables
CCDC entry no.
982941
982943
982940
982939
982942
bubbled through the mixture using a capillary) to a so-
lution of 6.5 g (0.022 mol) of compound I in 10 mL of
methylene chloride. Evolution of hydrogen chloride
was observed. After 12 h, the mixture was evaporated
under reduced pressure (12 mm and 0.1 mm) at 120°C,
and the glassy residue, a mixture of compounds IIa–
IVa at a ratio of 14 :3 :3 was analyzed by spectral
methods.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

MIRONOV et al.
876
7-tert-Butyl-2,6-dichloro-4-phenyl-1,2λ5-benz-
oxaphosphinine 2-oxide (IIa). H NMR spectrum
mixture of compounds IIb–IVb at a ratio of 7:2:1.
31P–{1H} NMR spectrum (162.0 MHz, CH2Cl2), ppm:
δP 17.1 (IIb), 17.0 (IIIb), 16.9 (IVb).
1
(250 MHz, CDCl3), δ, ppm (J, Hz): 1.49 s (t-Bu),
2
6.30 d (3-H, JPH = 24.0), 7.22 br.s and 7.37 br.s (5-H,
7-tert-Butyl-2,6-dichloro-4-(4-chlorophenyl)-
8-H); 7.34 m, 7.49 m, 7.50 m (C6H5). 31P–{1H} NMR
spectrum (162.0 MHz, CDCl3): δP 16.9 ppm. 13C NMR
spectrum (100.6 MHz, CDCl3), δC, ppm (J, Hz) (here-
inafter, the multiplicity of the corresponding signal in
the proton-decoupled 13C NMR spectrum is given in
1
1,2λ5-benzoxaphosphinine 2-oxide (IIb). H NMR
spectrum (400 MHz, CDCl3), δ, ppm (J, Hz): 1.49 s
2
(t-Bu), 6.29 d (3-H, JPH = 23.5), 7.16 s (8-H), 7.37 s
3
(5-H), 7.31 m and 7.48 m (10-H, 11-H, AA′BB′, JAB
=
3JA′B′ = 8.6). 13C NMR spectrum (100.6 MHz, CDCl3),
1
1
parentheses): 114.58 d.d (d) (C3, JPC = 154.1, JCH
=
δC, ppm (J, Hz): 114.86 d.d (d) (C3, JPC = 154.4,
1
171.3), 155.23 m (d) (C4, JPC = 1.7), 120.08 d.d.d (d)
2
1JCH = 171.5), 153.92 m (d) (C4, JPC = 1.8),
2
(C4a, JPC = 17.8, JC,3-H = 8.7, JC,8-H = 6.0), 132.12 d.d
3
3
3
119.72 d.d.d (d) (C4a, JPC = 18.0, JC,3-H = 8.4, JC,8-H
=
3
3
3
(d) (C5, 1JCH = 167.6, 4JPC = 1.3), 129.61 d.d.d (d) (C6,
5.9), 131.76 d.d (d) (C5, JCH = 166.4, JPC = 1.3),
1
4
3JCH = 11.1, JCH = 4.5, JPC = 1.3), 151.91 m (s) (C7),
2
5
129.70 d.d (s) (C6, 2JC,8-H = 11.2, 2JC,5-H = 3.9), 152.07 m
119.17 d.d (d) (C8, JCH = 163.9, JPC = 8.2),
1
3
(s) (C7), 119.28 d.d (d) (C8, JCH = 163.7, JPC = 8.6),
1
3
2
3
2
149.36 d.d.d (d) (C8a, JPC = 9.8, JCH = 10.0, JCH
=
3
2
2
149.22 d.d.d (d) (C8a, JCH = 10.1, JPC = 9.8, JCH
=
5.4), 136.40 d.t.d.t (d) (C9, JPC = 20.7, JC,11-H = 7.5,
3
3
5.5), 134.91 d.t.d (d) (C9, JPC = 21.1, JC,11-H = 7.8,
3
3
3JC,3-H = 6.7, JCH = 1.1), 128.24 br.d.d.d (s) (C10,
2
1
3
3JC,3-H = 6.1), 129.65 d.d (s) (C10, JCH = 163.5, JCH
=
1JCH = 162.1, JC,14-H = 7.8, JC,12-H = 7.7–7.8),
3
3
7.0), 129.26 d.d (s) (C11, JCH = 166.9, JCH = 5.3),
136.21 t.t (s) (C12, 3JCH = 10.4, 2JCH = 3.4), 36.52 m (s)
(C15), 29.09 q.sept (s) (C16, 1JCH = 126.9, 3JCH = 4.6).
1
3
128.97 br.d.d (s) (C11, JCH = 161.9, JCH = 6.5),
130.00 d.t (s) (C12, 1JCH = 161.9, 3JCH = 7.9), 36.53 m (s)
(C15), 29.20 q.sept (s) (C16, 1JCH = 126.7, 3JCH = 4.9).
1
3
7-tert-Butyl-2,8-dichloro-4-phenyl-1,2λ5-benz-
oxaphosphinine 2-oxide (IIIa). H NMR spectrum
7-tert-Butyl-2,8-dichloro-4-(4-chlorophenyl)-
1,2λ5-benzoxaphosphinine 2-oxide (IIIb). 1H NMR
spectrum (250 MHz, CDCl3), δ, ppm (J, Hz): 1.30 s
1
(250 MHz, CDCl3), δ, ppm (J, Hz): 1.51 s (t-Bu),
(t-Bu), 6.35 d (3-H, 2JPH = 23.9), 7.57 d.d (7-H, 4JCH
=
2
4
6.35 d (3-H, JPH = 24.4), 7.16 br.d (5-H, JHH = 2.3),
5
2.1, JPH = 2.0). 13C NMR spectrum (100.6 MHz,
7.56 d.d (7-H, JHH = 2.3, JPH = 2.0). 31P–{1H} NMR
spectrum (162.0 MHz, CDCl3): δP 16.8 ppm. 13C NMR
spectrum (100.6 MHz, CDCl3), δC, ppm (J, Hz):
4
5
1
CDCl3), δC, ppm: 115.20 d.d (d) (C3, JPC = 152.6,
1JCH = 171.5), 155.20 br.m (br.s) (C4), 120.32 m (d)
3
1
(C4a, JPC = 19.0), 125.02 br.d.d (d) (C5, JCH = 161.0,
114.65 d.d (d) (C3, JPC = 155.5, JCH = 172.4),
1
1
3JCH = 7.2, JPC = 1.2), 148.37 m (s) (C6), 128.95 (s)
4
156.71 m (d) (C4, JPC = 1.6), 122.62 d.d (d) (C4a,
2
(C7), 124.25 d.d (d) (C8, JPC = 7.5, JCH = 3.7),
3
2
3
1
3JPC = 17.7, JCH = 8.2), 125.39 d.d.d (d) (C5, JCH
=
136.29 m (s) (C12), 145.05 m (d) (C8a, JPC = 9.0),
2
160.7, JCH = 7.1, JPC = 1.6), 148.27 m (s) (C6),
3
4
134.89 m (d) (C9, JPC = 21.3), 34.48 m (s) (C15),
3
128.87 d.d (s) (C7), 124.22 d.d.d (d) (C8, JPC = 8.2,
3
30.73 q.sept (s) (C16, JCH = 126.8, JCH = 4.0); signals
1
3
3JCH = 5.4, JCH = 1.4), 144.72 d.d.d (d) (C8a, JPC
=
4
2
from C10 and C11 were not identified because of overlap.
10.0, 3JCH = 10.0, 10.0), 136.38 m (d) (C9, 3JPC = 21.3),
128.38 (s) (C10), 128.82 (s) (C11), 130.14 (s) (C12),
2,6-Dichloro-4-(4-chlorophenyl)-1,2λ5-benzoxa-
34.47 m (s) (C15), 39.73 q.sept (s) (C16, JCH = 126.0,
1
1
phosphinine 2-oxide (IVb). H NMR spectrum
3JCH = 4.3 Hz); the coupling constants for C7, C10, C11,
2
(250 MHz, CDCl3): δ 6.37 ppm, d (3-H, JPH
=
and C12 were not determined because of signal overlap.
23.4 Hz). 13C NMR spectrum (100.6 MHz, CDCl3), δ,
1
1
ppm (J, Hz): 115.77 d.d (d) (C3, JPC = 154.4, JCH
=
The NMR spectra of IVa were identical to those
reported in [2].
172.3), 155.35 m (d) (C4, JPC = 1.5), 122.40 m (d)
2
(C4a, JPC = 17.5), 129.68 d.d (s) (C5, JCH = 167.0,
3
1
4-(4-Chlorophenyl)-1,2λ5-benzoxaphosphinine
2-oxides IIb–IVb. A solution of 7.3 g (0.053 mol) of
4-chlorophenylacetylene in 15 mL of methylene chlo-
ride was added at 10–20°C in a stream of argon (which
was intensely bubbled through the mixture using a cap-
illary) to a solution of 8.9 g (0.03 mol) of compound I
in 20 mL of methylene chloride. After 12 h, the mix-
ture was evaporated under reduced pressure (0.1 mm)
at 150°C. The residue was a light yellow thick oily
3JCH = 6.0), 130.32 m (s) (C6), 132.31 d.d (s) (C7,
3
1
1JCH = 169.6, JCH = 5.9), 121.21 d.d (d) (C8, JCH
=
160.7, JPC = 7.9), 149.41 m (d) (C8a, JPC = 10.3),
135.55 m (d) (C9, 3JPC = 20.9), 129.68 (s) (C10), 129.32
(s) (C11), 136.31 m (s) (C12).
3
2
4-(4-Methylphenyl)-1,2λ5-benzoxaphosphinine
2-oxides IIc–IVc. A solution of 5.32 g (0.046 mol) of
4-methylphenylacetylene in 20 mL of methylene
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REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES ... XIII.
877
chloride was added to a solution of 6.8 g (0.023 mol)
of compound I in 20 mL of methylene chloride while
bubbling argon through the mixture using a thin capil-
lary. Evolution of hydrogen chloride was observed.
After 12 h, the mixture was evaporated under reduced
pressure (0.1 mm) at 150°C to obtain a light yellow
thick oily mixture of compounds IIc–IVc at a ratio of
15:4:1. 31P–{1H} NMR spectrum (162.0 MHz,
CH2Cl2): δP 17.4 (IIc), 17.3 (IIIc), 17.2 ppm (IVc).
acetylene in methylene chloride at 10–20°C. Yield
98%, light yellow oily substance. 31P NMR spectrum
(36.48 MHz, CH2Cl2): δP 17.9 ppm, d (2JPH = 24.5 Hz).
1H NMR spectrum (600 MHz, CDCl3), δ, ppm (J, Hz):
2
2.37 s (CH3), 6.29 d (3-H, JPH = 24.3), 7.05 d (5-H,
3
4JHH = 2.7), 7.36 br.d (7-H, JHH = 8.5), 7.20–7.22 m
(8-H, 10-H, 11-H). 13C NMR spectrum (150.9 MHz,
1
CDCl3), δC, ppm (J, Hz): 114.66 d.d (d) (C3, JPC
=
154.3, JCH3 = 171.3), 155.46 m (s) (C4), 122.65 d.d.d
1
(d) (C4a, JPC = 17.6, JC,3-H = 8.5, JC,8-H = 5.8),
3
3
7-tert-Butyl-2,6-dichloro-4-(4-methylphenyl)-
129.10 d.d (s) (C5, 1JCH = 163.9, 3JCH = 6.2), 130.06 m
1
1,2λ5-benzoxaphosphinine 2-oxide (IIc). H NMR
(s) (C6, JPC = 0.6), 131.86 d.d (s) (C7, JCH = 167.4,
5
1
spectrum (400 MHz, CDCl3), δ, ppm: 1.50 s (t-Bu),
1
3
3JCH = 6.5), 120.86 d.d (d) (C8, JCH = 166.1, JPC
=
=
=
2
2.43 s (CH3), 6.27 d (3-H, JPH = 24.3 Hz), 7.26–
8.0), 149.32 d.d.d.d (d) (C8a, JPC = 10.0, JC,7-H
2
3
7.28 m (10-H, 11-H), 7.36 br.s and 7.28 br.s (5-H,
2
3
3JC,5-H = 10.0, JCH = 4.2), 133.43 d.t.d (d) (C9, JPC
8-H). 13C NMR spectrum (100.6 MHz, CDCl3), δC,
3
3
1
1
20.7, JC,11-H = 7.3, JC,3-H = 6.5), 128.03 d.d (s) (C10,
ppm (J, Hz): 113.71 d.d (d) (C3, JPC = 154.6, JCH
=
3
1
2
1JCH = 160.2, JCH = 6.4), 129.50 d.d.q (s) (C11, JCH
=
171.1), 155.38 m (d) (C4, JPC = 4.0), 120.05 m (d)
3
3
3
159.5, JC,13-H = 6.4, JC.Me = 5.1), 140.18 m (s) (C12),
3
3
(C4a, JP1C = 17.9, JC,3-H = 8.2, JC,8-H = 5.4), 132.10 d
21.06 q.t (s) (C23, 1JCH = 126.9, 3JCH = 4.2).
(s) (C5, JCH = 166.7), 129.49 d.d (s) (C6, JCH = 11.0,
3
2-Hydroxy-4-phenyl-1,2λ5-benzoxaphosphinine
2-oxides Va–VIIa. Glassy mixture IIa–IVa, 1.62 g,
was dissolved in 10 mL of benzene, 0.1 mL of water
was added, the mixture was evaporated, the residue
was dissolved in diethyl ether, and the solution was
kept for 21 days at 20°C. The precipitate of 6-chloro-2-
hydroxy-4-phenyl-1,2λ5-benzoxaphosphinine 2-oxide
(VIIa) was filtered off and dried in air. Yield 0.20 g
(21%), mp 240–242°C; the spectral parameters of
VIIa coincided with published data [2]. After separa-
tion of VIIa, the filtrate was evaporated under reduced
pressure (12 mm) to isolate a yellowish oily mixture of
compounds Va and VIa at a ratio of 14:3.
2JCH = 3.9), 151.54 m (s) (C7), 119.03 d.d (d) (C8,
1JCH = 163.2, JPC = 8.3), 149.17 d.d.d (d) (C8a, JPC
=
=
3
2
9.7, JCH = 9.7, JCH = 5.2), 133.50 m (d) (C9, JPC
3
2
3
20.9, JC,11-H = 7.5, JC,3-H = 6.5), 128.10 d.d (s) (C10,
3
3
1JCH = 160.2, JCH = 6.0), 129.26 d.d.q (s) (C11, JCH
=
3
1
3
3
159.1, JC,13-H = 6.0, JC,Me = 5.0–6.0), 140.22 m (s)
(C12, JCH = 6.0, JCH = 6.0), 36.38 m (s) (C15),
3
2
29.04 q.sept (s) (C16, JCH = 127.0, JCH = 4.0),
1
3
21.19 q.t (s) (C23, 1JCH = 126.6, 3JCH = 4.0).
6-tert-Butyl-2,8-dichloro-4-(4-methylphenyl)-
1,2λ5-benzoxaphosphinine 2-oxide (IIIc). 1H NMR
spectrum (400 MHz, CDCl3), δ, ppm (J, Hz): 1.21 s
(t-Bu), 2.33 s (CH3), 6.32 d (3-H, 2JPH = 24.7), 7.55 d.d
7-tert-Butyl-6-chloro-2-hydroxy-4-phenyl-1,2λ5-
benzoxaphosphinine 2-oxide (Va). 13C NMR spec-
trum (100.6 MHz, CDCl3), δ, ppm (J, Hz): 112.02 d.d
4
5
(7-H, JHH = 3.2, JPH = 2.8). 13C NMR spectrum
(100.6 MHz, CDCl3), δC, ppm (J, Hz): 113.80 d.d (d)
1
1
(C3, JPC = 154.2, JCH = 170.4), 156.67 m (s) (C4),
1
1
(d) (C3, JPC = 177.2, JCH = 165.1), 154.06 m (br.s)
122.07 d.d (d) (C4a, 3JPC3 = 17.9, 3JCH = 8.2), 125.25 d.d
(C4), 120.21 d.d.d (d) (C4a, JPC = 16.7, JC,3-H = 8.2,
3
3
(s) (C5, JCH = 160.7, JCH = 8.1), 147.92 m (s) (C6),
1
3JC,8-H = 6.7), 131.37 d (s) (C5, JCH = 165.5),
1
129.74 d.d (s) (C7, JCH = 163.2, JCH = 8.4),
1
3
128.05 d.d (s) (C6, JCH = 11.0, JCH = 4.1), 150.27 m
3
2
123.82 br.d.d (d) (C8, 3JPC = 7.7, 2JCH = 3.7–3.8, 4JCH
=
(s) (C7), 118.82 d.d (d) (C8, JCH = 162.6, JPC = 8.2),
1
3
1.7), 144.29 d.d.d (d) (C8a, JPC = 8.8, JC.5-H = 9.0,
2
3
149.27 d.d.d (d) (C8a, JPC = 6.3, JCH = 9.8, JCH
=
2
3
2
3JC,7-H = 9.0), 133.35 m (d) (C9, JPC = 21.0),
3
5.2), 137.64 d.t.d (d) (C9, JPC = 19.6, JC,11-H = 7.3,
3
3
128.07 d.d (s) (C10, JCH = 160.2, JCH = 6.0),
1
3
3JC,3-H = 6.3), 128.13 br.d.d.d (s) (C10, JCH = 160.2,
1
129.20 d.d.q (s) (C11, JCH = 160.0, JC,13-H = 6.0,
1
3
3JC,14-H = 6.0, 3JC,12-H = 5.5–6.0), 128.55 br.d.d (s) (C11,
3JC,Me = 6.0), 140.05 m (s) (C12), 34.38 m (s) (C15),
1JCH = 162.3, JCH = 6.2), 129.11 d.t (s) (C12, JCH
=
3
1
30.59 q.sept (s) (C16, JCH = 127.0, JCH = 4.0),
1
3
160.9, JCH = 7.2), 36.16 m (s) (C15, JCH = 3.2),
3
2
21.00 q.t (C23, 1JCH = 126.5, 3JCH = 4.0–5.0).
29.07 q.sept (s) (C16, JCH = 126.5, JCH = 4.6).
31P–{1H} NMR spectrum (162.0 MHz, ethanol-d6):
δP 10.0 ppm.
1
3
2,6-Dichloro-4-(4-methylphenyl)-1,2λ5-benzoxa-
phosphinine 2-oxide (IVc) was synthesized according
to the procedure described in [1] from 2,2,2-trichloro-
1,3,2λ5-benzodioxaphosphole and 4-methylphenyl-
6-tert-Butyl-8-chloro-2-hydroxy-4-phenyl-1,2λ5-
benzoxaphosphinine 2-oxide (VIa). 13C NMR spec-
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MIRONOV et al.
878
trum (100.6 MHz, CDCl3), δ, ppm (J, Hz): 112.68 d.d
(d) (C3, 1JPC = 177.5, 1JCH = 164.3), 155.16 m (s) (C4),
122.38 d.d (d) (C4a, 3JPC = 16.6, 3JCH = 8.3), 124.67 d.d
(100.6 MHz, DMSO-d6), δC, ppm (J, Hz): 116.89 d.d
1
1
(d) (C3, JPC = 168.4, JCH = 63.5), 150.52 m (d) (C4,
3
2JPC = 1.7), 123.71 d.d.d.d.d (d) (C4a, JPC = 16.3,
3
2
4
3JC,3-H = 8.9, JC,8-H = 6.0, JCH = 1.2–1.3, JCH = 0.6),
1
3
(d) (C5, JCH = 159.5, JCH = 7.6), 146.56 m (s) (C6),
129.10 br.d.d (s) (C5, JCH = 165.5, JCH = 5.8, JPC
=
=
1
3
4
1
3
130.83 d.d (s) (C7, JCH = 166.5, JCH = 6.2),
0.9–1.0), 127.01 d.d.d.d.d (s) (C6, JCH = 11.4, JCH
3
2
123.58 d.d (d) (C8, 3JPC = 7.0, 3JCH = 4.6), 144.81 d.d.d
5
5
(d) (C8a, JPC = 5.8–6.0, JC,5-H = 9.0, JC,7-H = 8.3),
2
3
3
4.5, 3.5, JPC = 1.1–1.2, JCH = 0.9–1.0), 131.57 br.d.d
(d) (C7, JCH = 169.7, JCH = 6.1, JPC = 0.4),
1
3
4
137.92 m (d) (C9, JPC = 19.5), 128.19 d.d.d (s) (C10,
3
121.31 d.d (d) (C8, JCH = 167.5, JPC = 7.0),
1
3
1JCH = 160.0, 3JCH = 6.0–7.0, 6.0–7.0), 128.61 (s) (C11,
149.83 d.d.d.d (d) (C8a, JPC = 7.3, JCH = 10.5, 8.7,
2
3
1JCH = 162.0, JCH = 6.0–6.5), 129.05 d.t (s) (C12,
3
2JCH = 3.8), 135.00 d.t.d (d) (C9, JPC = 18.4, JC,11-H
=
3
3
1JCH = 160.0, 3JCH = 7.3), 34.36 m (s) (C15, 2JCH = 3.6),
7.2, JC,3-H = 6.7), 128.26 br.d.d (d) (C10, JCH = 160.2,
3
1
30.84 q.sept (s) (C16, JCH = 125.9, JCH = 4.6).
31P–{1H} NMR spectrum (162.0 MHz, ethanol-d6):
δP 9.8 ppm.
1
3
3JCH = 6.2–6.3, JPC = 0.9–1.0), 129.44 d.d.q (s) (C11,
4
3
3
1JCH = 159.3, JC,13-H = 6.0, JC,Me = 5.1), 138.74 br.t.q
(s) (C12, JCH = 6.0–7.0, JCH = 6.0), 20.86 q.t (s) (C23,
3
2
6-Chloro-4-(4-chlorophenyl)-2-hydroxy-1,2λ5-
benzoxaphosphinine 2-oxide (VIIb). Water, 0.5 mL,
was added to a solution of 6.8 g of a mixture of
compounds IIb–IVb in 30 mL of dioxane. After 24 h,
the precipitate was filtered off and dried in air. Yield
4.4% (0.4 g), mp 294°C. IR spectrum, ν, cm–1: 3436,
3051, 2924, 2855, 2541 v.br, 2255 v.br, 1657, 1596,
1548, 1488, 1468, 1401, 1377, 1337, 1249, 1193, 1113,
1095, 1015, 962, 913, 884, 832, 807, 741, 714, 657,
1JCH = 126.6, JCH = 4.2). Mass spectrum, m/z: 306
3
[M]+, 291 [M – Me], 290 [M – Me – H], 289 [M –
OH], 271 [M – Cl], 243 [M – PO2], 242 [M – PO2H]
(C5H11O), 207 [M – PO2H – Cl]. Found, %: C 58.65;
H 4.07; Cl 11.33; P 10.29. C15H12ClO3P. Calculated,
%: C 58.73; H 3.92; Cl 11.58; P 10.14. M 306.69.
1-(6-Chloro-2-oxo-4-phenyl-1,2λ5-benzoxaphos-
phinin-2-yl)pyrrolidine-2,5-diones VIIIa and Xa.
A solution of 5.5 g of mixture IIa–IVa and 2.84 g of
N-(trimethylsilyl)succinimide in 20 mL of benzene
was heated for 3 h under reflux. The mixture was
evaporated at a bath temperature not exceeding 110°C,
the residue was cooled and dissolved in 15 mL of
diethyl ether, and the solution was kept for 3 days.
A crystalline solid gradually separated and was filtered
off, washed with diethyl ether, and dried under reduced
pressure (12 mm) to obtain 6.3 g of a mixture of com-
pounds VIIIa and Xa at a ratio of 12:1. Compound
VIIIa was isolated by repeated crystallizations from
diethyl ether.
1
631, 558, 484, 454. H NMR spectrum (250 MHz,
2
DMSO-d6), δ, ppm (J, Hz): 6.42 d (1H, 3-H, JPH
=
4
17.0), 7.00 d (1H, 5-H, JHH = 2.6), 7.41 d and 7.57 d
(4H, 10-H, 11-H, AA′BB′, 3JAB = 3JA′B′ = 8.5). 13C NMR
spectrum (100.6 MHz, DMSO-d6), δC, ppm (J, Hz):
117.60 d.d (d) (C3, JPC = 168.2, JCH = 163.3),
1
1
149.18 m (d) (C4, 2JPC = 1.6), 123.11 m (d) (C4a, 3JPC
=
16.0), 127.19 d.d (s) (C5, JCH = 165.9, JCH = 5.5),
1
3
130.32 d.d.d.d (s) (C6, 3JCH = 9.5, 2JC,5-H = 4.3, 2JC,7-H
=
4.3, JPC = 1.1–1.3), 130.41 d.d (s) (C7, JCH = 169.5,
5
1
1
3
3JCH = 6.4), 121.52 d.d (d) (C8, JCH = 168.5, JPC
=
6.4), 149.88 m (d) (C8a, JPC = 7.3), 136.47 m (d) (C9,
2
1-(7-tert-Butyl-6-chloro-2-oxo-4-phenyl-1,2λ5-
benzoxaphosphinin-2-yl)pyrrolidine-2,5-dione
(VIIIa). Yield 0.18 g (14%), mp 173–176°C. IR spec-
trum, ν, cm–1: 3147, 1704, 1590, 1195, 1115, 1069,
993, 867, 807, 760, 700, 639, 602, 548, 520, 454, 426.
1H NMR spectrum (250 MHz, CDCl3), δ, ppm (J, Hz):
1.46 s (t-Bu, 9H), 2.74 s (4H, CH2), 6.35 d (1H, 3-H,
2JPH = 18.7), 7.10 s and 7.33 s (2H, 5-H, 8-H), 7.40–
7.41 m (2H, 9-H), 7.54–7.56 m (3H, 10-H, 11-H).
13C NMR spectrum (100.6 MHz, CH2Cl2, D2O in
an inner capillary), δC, ppm (J, Hz): 111.44 d.d (d) (C3,
1
3
3JPC = 19.3), 129.96 d.d (s) (C10, JCH = 164.3, JCH
=
7.0), 129.32 d.d (s) (C11, JCH = 168.5, JCH = 5.1),
1
3
136.31 t.t (s) (C12, JCH = 11.0, JCH = 4.0). 31P NMR
3
2
spectrum (162.0 MHz, dioxane): δP 6.3 ppm, d (2JPH
=
17.0 Hz). Found, %: C 51.48; H 2.75; P 9.82.
C14H9Cl2O3P. Calculated, %: C 51.38; H 2.75; P 9.48.
6-Chloro-2-hydroxy-4-(4-methylphenyl)-1,2λ5-
benzoxaphosphinine 2-oxide (VIIc) was synthesized
by hydrolysis of compound IVc in diethyl ether. Yield
1
97%, mp >250°C. H NMR spectrum (600 MHz,
1
2
1JPC = 156.2, JCH = 169.7), 155.02 m (d) (C4, JPC
=
DMSO-d6), δ, ppm (J, Hz): 2.38 s (CH3), 6.32 d (3-H,
4
2JPH = 17.5), 7.03 d (5-H, JHH = 2.6), 7.48 d.d.d
2.2), 120.07 d.d.d (d) (C4a, JPC = 17.5, JC,3-H = 8.4,
3
3
3
4
5
3JC,8-H = 6.8), 131.78 d.d (d) (C5, JCH = 166.0, JPC
=
1
4
(7-H, JHH = 8.7, JHH = 2.6, JPH = 1.3), 7.31 d (8-H,
3JHH = 8.7), 7.26 m and 7.31 m (10-H, 11-H, AA′BB′,
3JHH = 8.1), 6.85 v.br.s (OH). 13C NMR spectrum
1.3), 128.78 d.d (s) (C6, JCH = 11.6, JCH = 4.4),
3
2
151.24 m (s) (C7), 119.22 d.d (d) (C8, JCH = 162.8,
1
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REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES ... XIII.
879
2
3
1
3JPC = 8.7), 149.71 d.d.d (d) (C8a, JPC = 8.4, JCH
=
528, 491, 455, 414. H NMR spectrum (400 MHz,
10.5, JCH = 5.5), 137.57 m (d) (C9, JPC = 19.7),
DMSO-d6), ppm (J, Hz): 1.14 t (6H, CH3, JHH = 7.2),
2
3
3
128.39 br.d.d.d (s) (C10, JCH = 160.9, JCH = 6.0–7.0,
1.42 s (9H, t-Bu), 2.83 q (4H, CH2, 3JHH = 7.2), 6.10 d
1
3
6.0–7.0), 128.91 br.d.d (s) (C11, JCH = 161.0, JCH
=
(1H, 3-H, JPH = 15.9), 6.86 s (1H, 8-H), 7.07 s (1H,
1
3
2
7.1), 129.66 d.t (s) (C12, JCH = 161.0, JCH = 7.6),
1
3
5-H), 7.32 m and 7.59 m (4H, 10-H, 11-H, AA′XX′,
36.50 m (s) (C15, JCH = 3.3), 29.11 q.sept (s) (C16,
2
3JAX = JA′X′ = 8.4). 13C NMR spectrum (100.6 MHz,
3
1JCH = 126.0, JCH = 4.6), 177.16 m (d) (C17, JPC
=
3
2
DMSO-d6), δC, ppm (J, Hz): 125.08 d.d (d) (C3, 1JPC
=
1.3), 30.12 t.d.t (d) (C18, JCH = 135.5, JPC = 5.0,
2JCH = 4.2). 31P–{1H} NMR spectrum (162.0 MHz,
CH2Cl2): δP 1.6 ppm. Found, %: C 60.23; H 5.18;
Cl 8.14; N 3.52; P 6.98. C22H21ClNO4P. Calculated, %:
C 61.47; H 4.92; Cl 8.25; N 3.26; P 7.21.
1
3
162.2, JCH3 = 156.5), 147.23 m (s) (C4), 122.59 d.d.d
1
(d) (C4a, JPC = 14.9, JC,3-H = 8.4, JC,8-H = 6.1),
3
3
129.59 d (s) (C5, JCH = 162.7), 124.37 d.d (s) (C6,
1
3JCH = 11.3, JCH = 3.8), 143.08 m (s) (C7), 118.85 d.d
2
(d) (C8, JCH = 159.7, JPC = 5.0), 152.06 m (d) (C8a,
1
3
2JPC = 6.5), 138.40 br.d.t.d (d) (C9, JPC = 16.6,
3
1-(6-Chloro-2-oxo-4-phenyl-1,2λ5-benzoxaphos-
phinin-2-yl)pyrrolidine-2,5-dione (Xa). H NMR
3JC,11-H = 7.8–8.0, JC,3-H = 6.8), 130.12 d.d (s) (C10,
3
1
1JCH = 164.3, JCH = 6.8), 128.73 d.d (s) (C11, JCH
=
3
1
spectrum (250 MHz, CDCl3): δ 6.39 ppm, d (3-H,
2JPH = 18.7 Hz). 13C NMR spectrum (100.6 MHz,
CH2Cl2, D2O in an inner capillary), δC, ppm (J, Hz):
168.2, JCH = 5.0), 133.01 t.t (s) (C12, JCH = 10.7,
3
3
2JCH = 3.1), 35.64 m (s) (C15, JCH = 3.6), 29.31 q.sept
2
(s) (C16, JCH = 126.4, JCH = 4.6), 41.29 br.t.m (C19,
1
2
112.35 d.d (d) (C3, JPC = 156.1, JCH = 170.4),
1
1
1JCH = 142.1), 10.85 br.q.m. (C20, JCH = 127.7, JCH
=
1
2
156.36 m (d) (C4, JPC = 2.2), 122.70 d.d.d (d) (C4a,
2
3.3). 31P NMR spectrum (36.48 MHz, DMSO-d6):
δP –1.2 ppm, d (2JPH = 15.7 Hz). Found, %: C 57.84;
H 6.39; Cl 15.99; N 3.05; P 6.15. C22H28Cl2NO3P. Cal-
culated, %: C 57.89; H 6.14; Cl 15.57; N 3.07; P 6.80.
3JPC = 17.5, JC,3-H = 8.4, JC,8-H = 6.5–6.8), 128.96 (s)
3
3
(C5), 129.44 d.d.d (s) (C6, 3JCH = 12.3, 2JC,5-H = 2JC,7-H
=
4.0), 131.71 d.d (s) (C7, JCH = 169.3, JCH = 6.5),
1
3
121.08 d.d (d) (C8, 1JCH = 167.7, 3JPC = 8.4), 149.99 m
(d) (C8a, JPC = 8.6), 137.55 m (d) (C9, JPC = 19.7),
2
3
Calcium bis[7-tert-butyl-6-chloro-4-(4-chloro-
phenyl)-2-oxo-1,2λ5-benzoxaphosphinin-2-olate]
(XIVb). Calcium oxide, 0.2 g, was added to a solution
of 1.8 g of mixture Vb–VIIb (after partial separation
of VIIb) in 25 mL of dioxane, the mixture was heated
to the boiling point and cooled, and the white precipi-
tate was filtered off and dried. Yield 0.5 g, mp >350°C.
IR spectrum, ν, cm–1: 3530, 3039, 2960, 2925, 2855,
2346, 2251, 1918, 1655, 1601, 1561, 1528, 1480,
1464, 1398, 1372, 1334, 1247, 1214, 1185, 1117, 1073,
1005, 992, 923, 876, 851, 812, 758, 738, 715, 665,
636, 614, 597, 583, 571, 547, 531, 491, 479, 461, 411.
1H NMR spectrum (250 MHz, DMSO-d6), δ, ppm
128.44 br.d.d.d (s) (C10, JCH = 161.0, JC,14-H
=
1
3
3JC,12-H = 6.0–7.0), 128.96 br.d.d (s) (C11, 1JCH = 161.0,
3JCH = 7.1), 129.74 d.t (s) (C12, JCH = 161.1, JCH
=
1
3
7.6), 177.18 m (d) (C15, 2JPC = 1.3), 30.12 t.d.t (d) (C16,
1JCH = 135.5, JPC = 5.0, JCH = 4.2). 31P–{1H} NMR
3
2
spectrum (162.0 MHz, CDCl3): δP 1.1 ppm.
Diethylammonium 7-tert-butyl-6-chloro-4-
(4-chlorophenyl)-2-oxo-1,2λ5-benzoxaphosphinin-2-
olate (XIb) was isolated by evaporation under reduced
pressure (0.1 mm) of the dioxane filtrate obtained after
hydrolysis of mixture IIb–IVb and partial separation
of compound VIIb (see the procedure for the synthesis
of VIIb). The filtrate contained 7-tert-butyl-6-chloro-
and 6-tert-butyl-8-chloro-4-(4-chlorophenyl)-2-hy-
droxy-1,2λ5-benzoxaphosphinine 2-oxides Vb and
VIb [31P NMR spectrum (162.0 MHz), δP, ppm: 6.6 d
(2JPH = 18.0 Hz) (Vb); 6.2 d (2JPH = 18.0 Hz) (VIb)]
and compound VIIb. The glassy residue, 4.1 g, was
dissolved in 30 mL of dioxane, 10 mL of diethylamine
was added while bubbling argon through the mixture
using a thin capillary, and the precipitate was filtered
off, washed with dioxane, and dried under reduced
pressure (12 mm). Yield 1.9 g (13%), mp 172°C. IR
spectrum, ν, cm–1: 3493, 3415, 3287, 2925, 2855,
2518, 1635, 1591, 1563, 1461, 1397, 1371, 1333,
1258, 1217, 1195, 1139, 1116, 1072, 1015, 988, 917,
898, 872, 847, 807, 757, 735, 716, 650, 616, 597, 546,
2
(J, Hz): 6.24 d (1H, 3-H, JPH = 16.4), 6.92 s (1H,
8-H), 7.33 d and 7.50 d (4H, 10-H, 11-H, AA′BB′,
3JAB = JA′B′ = 8.4). 13C NMR spectrum (100.6 MHz,
3
DMSO-d6), δC, ppm (J, Hz): 125.09 d.d (d) (C3, 1JPC
=
162.2, JCH = 156.5), 147.23 m (s) (C4), 122.60 d.d.d
1
3
2
3
(d) (C4a, JPC = 14.9, JCH = 8.3, JCH = 6.2), 129.59 d
(s) (C5, JCH = 162.7), 124.37 d.d (s) (C6, JCH = 11.3,
1
3
2JCH = 3.2), 143.08 m (s) (C7), 118.85 d.d (d) (C8,
1JCH = 159.7, JPC = 5.2), 152.06 m (d) (C8a, JPC
=
3
2
6.4), 138.41 br.d.t.d (d) (C9, 3JPC = 16.6, 3JC,11-H = 6.8–
7.2, JC,3-H = 6.4–6.6), 128.73 d.d (s) (C10, JCH
=
3
1
168.1, JCH = 5.0), 130.12 d.d (s) (C11, JCH = 164.1,
3
1
3JCH = 7.0), 133.01 m (s) (C12, 3JCH = 10.5, 2JCH = 3.6),
35.64 m (s) (C15), 29.31 q.sept (s) (C16, JCH = 126.4,
1
2JCH = 4.8). 31P NMR spectrum (36.48 MHz,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

MIRONOV et al.
880
DMSO-d6): δP 0.4 ppm, d (2JPH = 15.3 Hz). Found, %:
C 53.63; H 3.98; Cl 17.36; P 7.36. C36H32CaCl4O6P2.
Calculated, %: C 53.73; H 3.98; Cl 17.66; P 7.71.
129.24 d.d (s) (C5, 1JCH2 = 164.3, 4JPC = 1.2), 129.66 d.d
3
(s) (C6, JCH = 11.0, JCH = 4.5), 151.34 m (s) (C7),
1
3
119.13 d.d (d) (C8, JCH = 163.3, JPC = 8.3),
149.09 d.d.d (d) (C8a, JCH = 10.1, JPC = 9.8, JCH
=
3
2
2
2-(5-Chloro-2-hydroxyphenyl)-2-(4-chlorophe-
nyl)prop-1-en-1-ylphosphonic acid (XVb). Phos-
phonic acid XVb was formed when compound VIIb
was kept in aqueous DMSO. It was characterized by
5.3), 36.21 t.d.m (d) (C9, JPC = 19.2, JCH = 128.0,
3
1
2JCH = 5.6), 20.97 t.m (s) (C10, JCH = 127.8, JCH
=
1
2
4.5), 13.62 q.t (s) (C11, JCH = 125.9, JCH = 3.9),
1
2
36.43 br.s (s) (C12), 29.16 q.m (s) (C13, JCH = 126.8,
1
1
spectral methods. H NMR spectrum (600 MHz,
2JCH = 4.7).
2
DMSO-d6), δ, ppm (J, Hz): 6.28 d (3-H, JPH = 13.0),
3
4
6-tert-Butyl-2,8-dichloro-4-propyl-1,2λ5-benz-
6.79 d (8-H, JHH = 8.5), 7.14 d (5-H, JHH = 2.7),
3
4
oxaphosphinine 2-oxide (XVIIId). 1H NMR spectrum
7.17 d.d (7-H, JHH = 8.5, JHH = 2.7), 7.22 m and
3
3
3
7.34 m (10-H, 11-H, AA′MM′, JAM = JA′M′ = 8.7).
13C NMR spectrum (150.9 MHz, DMSO-d6), δC, ppm
(J, Hz): 122.48 d.d (d) (C3, 1JPC = 183.8, 1JCH = 149.4),
(600 MHz, CDCl3), ppm (J, Hz): 0.87 t (11-H, JHH
=
7.3), 1.33 s (t-Bu), 1.51 m (10-H, overlapped by the
10-H signal of XVId), 2.53 m (9-H, 3JHH = 7.8), 6.09 d
150.34 m (d) (C4, 2JPC = 5.4), 128.12 m (d) (C4a, 3JPC
=
2
4
(3-H, JPH = 23.4), 7.34 d (7-H, JHH = 2.1), 7.37 s
7.2), 129.31 d.d (s) (C5, JCH = 165.1, JCH = 6.0),
1
3
4
(5-H, JHH = 2.1). 13C NMR spectrum (150.9 MHz,
122.39 d.d.d (s) (C6, JCH = 11.5–12.0, JC,7-H = 3.6,
3
2
CDCl3), δC, ppm (J, Hz): 112.65 d.t.m (d) (C3, JPC
=
1
2JC,5-H = 3.6), 131.06 d.d.d.d (d) (C7, JCH = 165.2,
1
1
3
158.6, JCH = 156.2, JCH = 5.4), 156.56 m (s) (C4),
3JCH = 6.2, JCH = 2.5, JPC = 1.3), 117.53 d (s) (C8,
2
6
121.79 m (d) (C4a, JPC = 19.1, JCH = 3.3), 121.72 d.d
3
3
1JCH = 160.9), 154.08 br.d.d (s) (C8a, JC,5-H = 10.5,
3
(s) (C5, JCH = 161.2, JCH = 7.4), 151.45 m (s) (C6),
1
3
3JC,7-H = 10.5–11.0), 140.00 d.t.d (d) (C9, JPC = 21.6,
3
121.86 d.d (s) (C7, JCH = 158.1, JCH = 7.4),
1
3
3JC,11-H = 7.4, JC,3-H = 6.7), 128.70 br.d.d (s) (C10,
3
124.15 d.d.d (d) (C8, JPC = 7.8, JCH = 7.4),
3
2
3
1
1JCH = 162.8, JCH = 7.7), 128.83 d.d (s) (C11, JCH
=
144.45 d.d.d (d) (C8a, JC,7-H = 9.0–9.5, JC,5-H = 9.0–
3
3
168.8, JCH = 4.7), 133.71 t.t (s) (C12, JCH = 11.1,
2JCH = 3.3–3.4). 31P NMR spectrum (162.0 MHz,
DMSO-d6): δP 10.1 ppm, d (2JPH = 13.0 Hz).
3
3
9.5, JPC = 9.5), 36.75 d.m (s) (C9, JPC = 19.7, JCH
=
2
3
1
128.0), 21.27 t.m (s) (C10, JCH = 128.0, JCH = 4.4),
1
2
13.66 m (s) (C11, overlapped by the C11 signal of
XVId), 34.76 br.s (s) (C12), 29.40 q.m (s) (C13, JCH
=
1
2-Chloro-4-propyl-1,2λ5-benzoxaphosphinine
2-oxides XVId–XIXd. Pent-1-yne, 2.1 mL (1.9 g,
28.0 mmol), was added to a solution of 4.2 g
(14.0 mmol) of compound I in 10 mL of methylene
chloride, argon was bubbled through the mixture over
a period of 20 min, the mixture was evaporated by half
under atmospheric pressure and was evaporated to
dryness under reduced pressure (15 mm). The residue
was a brown glassy mixture of compounds XIVd–
XIXd at a ratio of 3.6:1.5:1.07:1. 31P NMR spectrum
(36.48 MHz, CH2Cl2), δ, ppm: 19.9 d (2JPH = 24.5 Hz),
126.9, 2JCH = 4.8).
7-tert-Butyl-2,8-dichloro-4-propyl-1,2λ5-benz-
1
oxaphosphinine 2-oxide (XIXd). H NMR spectrum
(600 MHz, CDCl3), δ, ppm (J, Hz): 0.85 t (11-H,
3JHH = 7.5), 1.13 s (t-Bu), 1.50 m (10-H, overlapped by
3
the 10-H signal of XVId), 2.62 m (9-H, JHH = 7.8),
2
3
6.12 d (3-H, JPH = 24.5), 7.21 d (6-H, JHH = 8.7),
7.31 s (5-H, JHH = 8.7). 13C NMR spectrum
3
(150.9 MHz, CDCl3), δC, ppm (J, Hz): 113.30 d.t.m (d)
1
1
3
(C3, JPC = 156.3, JCH = 156.2, JCH = 5.6), 156.85 m
19.2 d (2JPH = 22.3 Hz) (XVId, XVIId); 19.6 d (2JPH
=
(s) (C4), 120.18 m (d) (C4a, JPC = 18.5), 124.09 d (s)
3
23.4 Hz), 19.4 d (2JPH = 24.5 Hz) (XVIIId, XIXd).
The spectral parameters of XVIId were consistent with
those reported in [1].
1
1
(C5, JCH = 163.3), 123.19 d (s) (C6, JCH = 163.9),
149.2 m (s) (C7), 124.65 d.d (d) (C8, 3JPC = 8.0, 3JCH
=
9.6), 147.56 d.d (d) (C8a, JCH = 9.5, JPC = 9.0),
3
2
36.80 d.m (s) (C9, JPC = 19.5; overlapped by the C9
3
7-tert-Butyl-2,6-dichloro-4-propyl-1,2λ5-benz-
signal of XVId), 21.20 t.m (s) (C10, JCH = 127.5,
1
1
oxaphosphinine 2-oxide (XVId). H NMR spectrum
2JCH = 4.4), 13.65 m (s) (C11, JCH = 127.0), 35.04 br.s
1
(600 MHz, CDCl3), δ, ppm (J, Hz): 0.87 m (11-H,
(s) (C12), 31.32 q.m (s) (C13, 1JCH = 130.8, 2JCH = 4.8).
3
3JHH = 7.5), 1.17 s (t-Bu), 1.50 m (10-H, JHH = 7.4),
3
2
4-Butyl-2-chloro-1,2λ5-benzoxaphosphinine
2-oxides XVIe–XIXe. A solution of 2.85 mL (2.04 g,
33.2 mmol) of hex-1-yne in 10 mL of methylene
chloride was added to a solution of 5 g (16.6 mmol) of
benzodioxaphosphole I in 10 mL of methylene
2.49 m (9-H, JHH = 7.8), 6.07 d (3-H, JPH = 24.5),
7.12 s (8-H), 7.38 s (5-H). 13C NMR spectrum
(150.9 MHz, CDCl3), δC, ppm (J, Hz): 112.88 d.d.t (d)
1
1
3
(C3, JPC = 155.6, JCH = 156.2, JCH = 5.7), 155.43 m
(s) (C4), 119.75 m (d) (C4a, JPC = 19.2, JCH = 3.3),
3
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES ... XIII.
881
chloride. 31P NMR spectrum of the reaction mixture
3JHH = 7.3–7.5), 6.20 d (3-H, 2JPH = 17.5), 7.26 d (6-H,
3
(36.48 MHz, CH2Cl2), δP, ppm: 19.1 d (2JPH
=
3JHH = 8.5), 7.52 d (5-H, JHH = 8.5). 13C NMR spec-
23.6 Hz), 18.5 d (2JPH = 23.6 Hz) (XVIe, XVIIe); 18.9 d
(2JPH = 23.9 Hz), 18.6 d (2JPH = 23.6 Hz) (XVIIIe,
XIXe). The mixture was evaporated under reduced
pressure (15 mm) to obtain a brown glassy mixture of
compounds XVIe–XIXe at a ratio of 4.8:2.1:1.9:1.
trum (100.6 MHz, DMSO-d6), δC, ppm (J, Hz):
113.83 d.t.m (d) (C3, 1JPC = 170.9, 1JCH = 162.0, 3JCH
=
5.4), 151.33 m (s) (C4), 123.24 m (d) (C4a, 3JPC = 17.2),
131.85 d (s) (C5, 1JCH = 162.4), 124.37 d (s) (C6, 1JCH
=
=
=
3
162.1), 148.69 m (s) (C7), 122.52 d.d (d) (C8, JPC
3
2
3
7.0, JCH = 3.4), 147.82 d.d (d) (C8a, JPC = 7.2, JCH
2-Chloro-4-pentyl-1,2λ5-benzoxaphosphinine
2-oxides XVIf–XIXf. A solution of 3.3 mL (2.4 g,
33.2 mmol) of hept-1-yne was added to a solution of
5 g (16.6 mmol) of compound I in 10 mL of methylene
chloride. 31P NMR spectrum of the reaction mixture
(36.48 MHz, CH2Cl2), δ, ppm: 19.4 d (2JPH = 24.5 Hz),
6.6), 36.37 t.d.m (s) (C9, JPC = 17.6, JCH = 125.1),
3
1
21.21 t.m (s) (C10, JCH = 125.1, JCH = 3.7), 13.68 m
1
2
(s) (C11, JCH = 124.6, JCH = 3.7), 36.02 m (s) (C12),
1
2
29.39 q.m (s) (C13, JCH = 126.0, JCH = 4.2–4.4).
31P NMR spectrum (162 MHz, DMSO-d6): δP 7.30 ppm,
d (2JPH = 17.5 Hz).
1
2
19.2d (2JPH = 22.3 Hz) (XVIf, XVIIf); 19.6 d (2JPH
=
4-Butyl-6-tert-butyl-8-chloro-2-hydroxy-1,2λ5-
benzoxaphosphinine 2-oxide (XXIIe). Water, 2 mL,
was added to a solution of 5.5 g of mixture XVIe–
XIXe in 10 mL of acetone. After 7 days, the white
crystalline precipitate was filtered off. Yield 0.56 g
(53%), mp 74–76°C. IR spectrum (KBr), ν, cm–1:
3530, 2312, 1605, 1563, 1467, 1365, 1172, 1005, 934,
23.4 Hz), 19.4 d (2JPH = 24.5 Hz) (XVIIIf, XIXf). The
mixture was evaporated under reduced pressure at
a bath temperature of 130°C. The residue was a brown
glassy mixture of benzoxaphosphinine oxides XVIf–
XIXf at a ratio of 7.4:2.6:2.1:1.
7-tert-Butyl-6-chloro-2-hydroxy-3-propyl-1,2λ5-
benzoxaphosphinine 2-oxide (XXd) and 7-tert-
butyl-8-chloro-2-hydroxy-3-propyl-1,2λ5-benzoxa-
phosphinine 2-oxide (XXIIId). Water, 2 mL, was
added to a solution of 4.3 g of compounds XVId–
XIXd in 10 mL of dioxane. After several days, a white
solid precipitated and was filtered off. Yield 1.85 g,
a mixture of compounds XXd and XXIIId at a ratio of
3.5:1.0.
1
843, 718, 615, 588, 506, 416. H NMR spectrum
(400 MHz, DMSO-d6), δ, ppm (J, Hz): 0.86 t (12-H,
3
3JHH = 6.5), 1.31 m (11-H, JHH = 6.7–7.0), 1.47 m
3
3
(10-H, JHH = 6.7–7.0), 2.63 br.t (9-H, JHH = 7.0),
2
6.20 d (3-H, JPH = 17.6), 7.31 br.s (5-H), 7.51 br.d
(7-H, JHH = 2.0). 13C NMR spectrum (100.6 MHz,
4
DMSO-d6), δC, ppm (J, Hz): 114.32 d.d.t (d) (C3,
1JPC = 171.3, JCH = 162.1, JCH = 5.1), 151.20 m (s)
1
3
1
(C4), 123.83 m (d) (C4a, JPC = 16.5, JC,3-H = 8.1,
3
3
Compound XXd. H NMR spectrum (400 MHz,
3
3JC,9-H = 3.7), 123.70 d.d (s) (C5, JCH = 167.3, JCH
=
=
1
3
DMSO-d6), δ, ppm (J, Hz): 0.92 t (11-H, JHH = 7.0),
3
4.4), 137.03 m (s) (C6), 127.39 d.d (s) (C7, JCH
1
1.42 s (t-Bu), 1.52 m (10-H, JHH = 7.6), 2.58 m (9-H,
2
3JHH = 7.5), 6.16 d (3-H, JPH = 17.5), 7.18 s (8-H),
3
3
164.3, JCH = 6.6), 126.84 d.d (d) (C8, JPC = 4.4,
7.55 s (7-H). 13C NMR spectrum (100.6 MHz,
2JCH = 4.4), 148.87 d.d.d (d) (C8a, 3JC,7-H = 3JC,5-H = 8.4,
DMSO-d6), δC, ppm (J, Hz): 114.10 d.d.t (d) (C3,
2JPC = 8.4), 34.12 t.d.m (d) (C9, JCH = 126.1, JPC
=
1
3
1
3
1JPC = 170.2, JCH = 161.4, JCH = 5.9), 150.32 m (s)
17.6, JCH = 4.4), 27.29 t.m (s) (C10, JCH = 124.8,
2
1
(C4), 120.96 m (d) (C4a, JPC = 17.6, JCH = 3.7),
3
3
2JCH = 4.4), 21.84 t.m (s) (C11, JCH = 125.5, JCH
=
1
2
128.80 d (s) (C5, JCH = 164.3), 126.85 d.d (s) (C6,
1
4.4), 13.72 q.m (s) (C12, JCH = 124.7), 34.85 m (s)
1
3JCH = 11.0, JCH = 4.4), 148.62 m (s) (C7, JCH = 3.7),
2
2
(C13), 29.30 q.m (s) (C14, JCH = 126.1, JCH = 4.4).
31P NMR spectrum (36.48 MHz, CH2Cl2): δP 5.9 ppm,
d (2JPH = 17.6 Hz). Found, %: C 57.83; H 6.94;
Cl 10.02; P 9.32. C16H22ClO3P. Calculated, %:
C 58.45; H 6.74; Cl 10.78; P 9.42.
1
2
118.85 d.d (d) (C8, JCH = 162.1, JPC = 7.0),
1
3
149.70 d.d.d (d) (C8a, 3JCH = 7.2–7.3, 2JPC = 7.3, 2JCH
=
5.1), 35.43 t.d.m (d) (C9, JPC = 17.6, JCH = 125.2,
3
1
2JCH = 3.7), 20.90 t.m (s) (C10, JCH = 124.7, JCH
=
1
2
3.7), 13.69 q.m (s) (C11, JCH = 124.6, JCH = 3.7),
1
2
7-tert-Butyl-6-chloro-2-hydroxy-4-pentyl-1,2λ5-
benzoxaphosphinine 2-oxide (XXf) and 6-tert-butyl-
8-chloro-2-hydroxy-4-pentyl-1,2λ5-benzoxaphos-
phinine 2-oxide (XXIIf). Glassy mixture XVIf–XIXf,
6 g, was subjected to hydrolysis in moist diethyl ether.
The white precipitate of compound XXIIf was filtered
off, the filtrate was evaporated, and 10 mL of dioxane
36.00 m (s) (C12, 2JCH = 3.0), 29.16 q.m (s) (C13, 1JCH
=
126.3, JCH = 4.2–4.4). 31P NMR spectrum (162 MHz,
2
DMSO-d6): δP 7.16 ppm, d (2JPH = 17.5 Hz).
1
Compound XXIIId. H NMR spectrum (400 MHz,
3
DMSO-d6), δ, ppm (J, Hz): 0.91 t (11-H, JHH = 7.0),
3
1.32 s (t-Bu), 1.52 m (10-H, JHH = 7.5), 2.60 m (9-H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

MIRONOV et al.
882
was added to the oily residue. After several days, the
white precipitate of XXf was filtered off.
C17H24ClO3P. Calculated, %: C 59.56; H 7.06;
Cl 10.34; P 9.04.
2-(5-tert-Butyl-3-chloro-2-hydroxyphenyl)hex-
1-en-1-ylphosphonic acid (XXIV). Phosphonic acid
XXIV was formed when compound XXIIf was kept in
aqueous DMSO. The product was characterized by
spectral data. 1H NMR spectrum (400 MHz,
Compound XXf. Yield 1.5 g (47%), mp 123°C.
IR spectrum (mineral oil), ν, cm–1: 2176, 1661, 1596,
1561, 1203, 1176, 1134, 1034, 999, 954, 882, 853,
822, 789, 613, 536, 478. 1H NMR spectrum (400 MHz,
3
DMSO-d6), δ, ppm (J, Hz): 0.86 t (13-H, JHH = 6.5),
3
3
3
DMSO-d6), δ, ppm (J, Hz): 0.75 t (12-H, JHH = 6.5),
1.29 m (12-H, JHH = 5.5), 1.31 m (11-H, JHH = 5.5),
3
2
1.43 br.s (t-Bu), 1.51 br.s (10-H, JHH = 7.0), 2.68 m
6.00 d (3-H, JPH = 18.6), 6.98 br.s (5-H), 7.21 br.d
3
2
(2H, 9-H, JHH = 7.5), 6.16 d (1H, 3-H, JPH = 17.5),
7.18 s (8-H), 7.55 s (5-H). 13C NMR spectrum
(150.9 MHz, CDCl3), δC, ppm (J, Hz): 113.75 d.d.t (d)
(7-H). 13C NMR spectrum (100.6 MHz, DMSO-d6), δC,
ppm (J, Hz): 121.05 d.d.m (d) (C3, 1JPC = 183.0, 1JCH
=
2
162.0), 150.77 d (s) (C4, JCH = 10.3), 122.32 m (d)
(C3, JPC = 170.2, JCH = 161.4, JCH = 5.9), 150.33 m
(C4a), 123.91 d (s) (C5, JCH = 155.2), 128.34 d.d (s)
1
1
3
1
(s) (C4), 120.71 m (d) (C4a, JPC = 17.2, JCH = 3.7),
3
2
2
2
(C6, JC,7-H = JC,5-H = 4.0–4.5), 127.39 d.d (s) (C7,
128.55 d (s) (C5, JCH = 164.3), 126.58 d.d (s) (C6,
1
1JCH = 155.3), 116.24 m (br.s) (C8), 155.72 m (d) (C8a,
3
3
3JC,7-H = 11.0, JC,5-H = 3.7), 148.36 m (s) (C7, JCH
=
4JPC = 2.5), 31.36 t.d.m (d) (C9, JPC = 18.0, JCH
=
3
1
2.9), 118.59 d.d (d) (C8, JCH = 162.1, JPC = 7.3),
1
3
126.0), 26.29 t.m (s) (C10, JCH = 124.5), 21.94 t.m (s)
1
149.46 d.d.d (d) (C8a, 3JCH = 7.2–7.3, 2JP1C = 7.3, 2JCH
=
1
1
(C11, JCH = 125.4), 13.71 q.m (s) (C12, JCH = 124.5),
4.4), 33.20 d.t.m (s) (C9, JPC = 17.6, JCH = 125.2),
3
35.59 m (s) (C13), 29.84 q.m (s) (C14, JCH = 126.0).
1
30.75 t.m (s) (C10, JCH = 124.9, JCH = 4.4), 27.11 t.m
1
2
31P NMR spectrum (36.48 MHz, CH2Cl2): δP 14.6 ppm,
d (2JPH = 18.6 Hz).
(s) (C11, JCH = 122.5, JCH = 3.7), 21.82 t.m (s) (C12,
1
2
2
1
1JCH = 125.4, JCH = 3.7), 13.84 q.t (s) (C13, JCH
=
2,2,2-Tribromo-5-tert-butyl-1,3,2λ5-benzodioxa-
phosphole (XXV). A mixture of 20 g (0.12 mol) of
4-tert-butylbenzene-1,2-diol, 12.6 mL (35.9 g,
0.13 mol) of phosphorus(III) bromide, and several
drops of water was stirred for 1 h at 100–120°C. Dis-
tillation gave 20.1 g (55%) of 2-bromo-5-tert-butyl-
1,3,2-benzodioxaphosphole as a colorless transparent
liquid with bp 93°C (2 mm). 31P–{1H} NMR spectrum
(CH2Cl2): δP 196.7 ppm.
124.7, JCH = 3.7), 35.77 m (s) (C14, JCH = 2.9),
2
2
28.91 q.m (s) (C15, 1JCH = 126.2, 2JCH = 4.4). 31P NMR
spectrum (36.48 MHz, CH2Cl2): δP 7.2 ppm, d (2JPH
=
17.5 Hz). Found, %: C 59.03; H 7.98; Cl 9.74; P 8.77.
C17H24ClO3P. Calculated, %: C 59.56; H 7.06;
Cl 10.34; P 9.04.
Compound XXIIf. Yield 0.2 g (22%). mp 156°C.
IR spectrum, ν, cm–1: 3448, 2926, 2854, 2724, 2287,
1655, 1596, 1560, 1461, 1377, 1333, 1302, 1271,
1203, 1176, 1134, 1070, 1034, 1011, 1000, 954, 907,
881, 853, 822, 789, 737, 725, 648, 613, 584, 536, 493.
1H NMR spectrum (600 MHz, DMSO-d6), δ, ppm
A solution of 7.18 g (0.026 mol) of 2-bromo-5-tert-
butyl-1,3,2-benzodioxaphosphole in 20 mL of methy-
lene chloride was cooled to –40°C, and a solution of
1.33 mL (0.026 mol) of bromine in 15 mL of methy-
lene chloride was added while bubbling argon through
a capillary. Tribromobenzodioxaphosphole XXV thus
formed was used in further syntheses without isolation.
31P–{1H} NMR spectrum (36.48 MHz, CH2Cl2):
δP –188.6 ppm.
3
(J, Hz): 0.86 t (3H, 13-H, JHH = 3.8), 1.31–1.34 m
3
(4H, 11-H, 12-H), 1.52 m (2H, 10-H, JHH = 3.8),
3
2
2.69 m (2H, 9-H, JHH = 7.8), 6.23 d (1H, 3-H, JPH
=
18.2), 7.48 d (1H, 7-H, 4JHH = 1.9), 7.55 br.s (1H, 5-H).
13C NMR spectrum (150.9 MHz, CDCl3), δC, ppm
(J, Hz): 114.18 d.d.t (d) (C3, 1JPC = 170.9, 1JCH = 157.1,
3JCH = 5.7), 151.83 m (s) (C4), 122.42 m (d) (C4a,
2-Bromo-7(6)-tert-butyl-2-oxo-4-phenyl-1,2λ5-
benzoxaphosphinine 2-oxides XXVIa and XXVIIa.
Phenylacetylene, 6.7 mL (0.06 mol), was added drop-
wise under argon to 13.1 g (0.03 mol) of freshly
prepared compound XXV in 20 mL of methylene
chloride. After 24 h, the mixture was evaporated under
reduced pressure (0.1 mm) to obtain a light brown
mixture of compounds XXVIa and XXVIIa at a ratio
of 4:1.
3JPC = 16.9), 121.67 d.d (s) (C5, JCH = 158.0, JCH
=
=
1
3
7.5), 146.14 m (s) (C6), 127.71 d.d (s) (C7, JCH
1
163.7, JCH = 8.0), 122.29 d.m (d) (C8, JPC = 6.7),
3
3
144.60 d.d.d (d) (C8a, 3JC,7-H = 3JC,5-H = 7.2, 2JPC = 6.5),
33.98 d.t.m (s) (C9, JPC = 17.9, JCH = 126.2),
3
1
30.81 t.m (s) (C10, JCH = 126.2), 27.47 t.m (s) (C11,
1
1JCH = 126.2), 21.78 t.m (s) (C12, JCH = 125.0),
1
1
2
13.66 m (s) (C13, JCH = 124.5, JCH = 3.3). 31P NMR
1
spectrum (36.48 MHz, CH2Cl2): δP 5.9 ppm, d (2JPH
18.2 Hz). Found, %: C 58.97; H 7.34; Cl 10.12; P 8.89.
=
Compound XXVIa. H NMR spectrum (250 MHz,
CDCl3), δ, ppm (J, Hz): 1.32 s (t-Bu), 6.26 d (3-H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES ... XIII.
883
2JPC = 26.4). 13C NMR spectrum (100.6 MHz, CDCl3),
chloride. After 8 h, the solvent was distilled off, and
volatile impurities were then removed at 150°C under
reduced pressure (0.1 mm). The residue was a mixture
of compounds XXVIc and XXVIIc at a ratio of 9:1.
31P NMR spectrum (36.48 MHz, CH2Cl2), δP, ppm:
8.3 d (2JPH = 26.0 Hz) (XXVIc); 9.4 d (2JPH = 27.5 Hz)
(XXVIIc).
δ, ppm (J, Hz): 115.43 d.d (d) (C3, 1JPC = 142.1, 1JCH
=
2
171.5), 156.03 m (d) (C4, JPC = 2.0), 118.76 m (d)
(C4a, JPC = 18.0), 129.67 br.d (d) (C5, JCH = 162.4,
3
1
4JPC = 1.3), 122.33 d.d (s) (C6, JCH = 160.7, JCH
=
=
=
1
3
7.1), 157.35 m (s) (C7), 116.58 d.d.d (d) (C8, JCH
1
161.5, 3JPC = 8.0, 3JCH = 6.5), 151.34 m (d) (C8a, 3JPC
3
2
4
8.0, JCH = 9.1, JCH3 = 5.7, JCH = 1.7), 137.41 m (d)
7- and 6-tert-Butyl-4-(4-chlorophenyl)-2-diethyl-
amino-1,2λ5-benzoxaphosphinine 2-oxides XXVIIIb
and XXIXb. Diethylamine, 7 mL, was added under
stirring to a solution of 10 g of mixture XXVIb/
XXVIIb in 45 mL of benzene. The precipitate was
filtered off, combined with the precipitate obtained
after partial evaporation of the filtrate under reduced
pressure (12 mm), washed with a solution of sodium
carbonate with pH 8.0 and with water, and dried in air
to obtain a mixture of compounds XXVIIIb and
XXIXb at a ratio of 9:1. Repeated recrystallization
from aqueous acetone gave pure compound XXVIIIb.
(C9, JPC = 21.1, JC,11-H = 7.5, JC,3-H = 6.0–7.0),
3
3
128.49 br.d.d.d (s) (C10, JCH = 160.5, JC,12-H = 6.8,
1
3
3JC,14-H = 6.5–6.8), 128.88 br.d.d (s) (C11, 1JCH = 161.8,
3JCH = 6.8), 129.82 d.t (s) (C12, JCH = 161.5, JCH
=
1
3
7.6), 35.33 m (s) (C15, JCH = 3.3), 31.07 q.sept (s)
2
(C16, JCH = 126.1, JCH = 4.5). 31P NMR spectrum
1
3
(36.48 MHz, CH2Cl2): δP 9.2 ppm, d (2JPH = 26.5 Hz).
Compound XXVIIa. 1H NMR spectrum (250 MHz,
CDCl3), ppm (J, Hz): 1.20 s (9H, t-Bu), 6.29 d (3-H,
2JPH = 26.2). 13C NMR spectrum (100.6 MHz, CDCl3),
1
δC, ppm (J, Hz): 116.21 d.d (d) (C3, JPC = 142.5,
2
1JCH = 171.3), 156.54 m (d) (C4, JPC = 1.6), 120.95 m
Compound XXVIIIb. mp 173°C. IR spectrum, ν,
cm–1: 3426, 2127, 1664, 1614, 1591, 1536, 1344, 1244,
1223, 1202, 1174, 1086, 1033, 1008, 976, 918, 878,
837, 788, 636, 547, 530, 509, 476, 451. 1H NMR spec-
trum (250 MHz, DMSO-d6), δ, ppm (J, Hz): 1.07 t
3
1
(d) (C4a, JPC = 18.6), 126.92 br.d.d (s) (C5, JCH
=
162.5, JCH = 5.0–6.0), 148.19 m (d) (C6, JPC = 1.4),
3
5
129.99 (s) (C7), 119.31 d.d (d) (C8, 1JCH = 164.9, 3JPC
=
8.1), 149.11 m (d) (C8a, 3JPC = 10.5), 137.37 m (d) (C9,
3JPC = 20.9), 128.57 (s) (C10), 128.88 (s) (C11), 129.80
2
2
(CH3, JHH = 7.1), 1.27 s (t-Bu), 3.05 d.q (CH2, JPH
=
(s) (C12), 34.70 m (s) (C15), 31.47 q.sept (s) (C16, 1JCH
=
12.3, 2JHH = 7.0), 6.04 d (3-H, 2JPH = 17.5), 7.15 m and
126.7, JCH = 4.4); the coupling constants for C7, C10,
C11, and C12 were not determined because of signal
overlap. 31P NMR spectrum (36.48 MHz, CH2Cl2):
δP 9.4 ppm, d (2JPH = 26.4 Hz).
3
3
7.09 m (5-H, 6-H, AB, JAB = 8.3), 7.52 m and 7.40 m
(10-H, 11-H, AA′BB′, JAB = JA′B′ = 8.4). 13C NMR
3
3
spectrum (100.6 MHz, CDCl3), δC, ppm (J, Hz):
1
1
116.75 d.d (d) (C3, JPC = 143.0, JCH = 171.0),
156.64 m (d) (C4, 2JPC = 2.2), 117.75 m (d) (C4a, 3JPC
=
7- and 6-tert-Butyl-4-(4-chlorophenyl)-2-(diethyl-
amino)-1,2λ5-benzoxaphosphinine 2-oxides XXVIb
and XXVIIb. A solution of 12 g (0.09 mol) of
4-chlorophenylacetylene in 30 mL of methylene
chloride was added to a solution of 17.2 g (0.04 mol)
of freshly prepared compound XXV in 30 mL of
methylene chloride, and the mixture was stirred for
1.5 h by bubbling argon through a capillary. After
3 days, the mixture was evaporated, and the residue
was dried under reduced pressure (0.1 mm) to obtain
a brown oily mixture of compounds XXVIb and
XXVIIb at a ratio of 9 : 2. 31P NMR spectrum
(36.48 MHz, CH2Cl2), δP, ppm: 8.6 d (2JPH = 25.8 Hz)
(XXVIb); 9.7 d (2JPH = 28.0 Hz) (XXVIIb).
17.8), 129.63 d (s) (C5, JCH = 163.4), 121.54 d.d (s)
1
(C6, JCH = 160.1, JCH = 6.5), 156.22 m (s) (C7),
1
3
116.47 d.m (d) (C8, JCH3 = 160.0, JPC = 8.1, JCH
=
1
3
3
8.0), 151.01 m (d) (C8a, JPC = 9.8), 136.77 m (d) (C9,
3JPC = 21.0), 129.71 d.d (s) (C10, JCH = 163.3, JCH
=
1
3
7.9), 128.87 d.d (s) (C11, JCH = 168.5, JCH = 5.4),
1
3
135.52 m (s) (C12), 34.85 m (s) (C15), 30.84 q.sept (s)
(C16, JCH = 126.1, JCH = 4.4). 31P–{1H} NMR spec-
trum (36.48 MHz, DMSO-d6): δP 12.0 ppm. Found, %:
C 64.82; H 7.04; N 3.93; P 7.48. C22H27ClNO2P. Cal-
culated, %: C 65.42; H 6.74; 3.47; P 7.67.
1
3
1
Compound XXIXb. H NMR spectrum (250 MHz,
2
DMSO-d6), δ, ppm: 5.95 d (3-H, JPH = 17.7 Hz).
31P–{1H} NMR spectrum (36.48 MHz, DMSO-d6):
δP 12.5 ppm.
2-Bromo-7- and -6-tert-butyl-4-(4-methylphe-
nyl)-1,2λ5-benzoxaphosphinine 2-oxides XXVIc and
XXVIIc. A solution of 6.64 mL (0.052 mol) of
4-methylphenylacetylene in 30 mL of methylene
chloride was added dropwise to a solution of 11.4 g
(0.026 mol) of compound XXV in 35 mL of methylene
7-tert-Butyl-2-diethylamino-4-(4-methylphenyl)-
1,2λ5-benzoxaphosphinine 2-oxide (XXIXc). Di-
ethylamine, 12 mL, was added to 10.43 g of a mixture
of compounds XXVIc and XXVIIc in 30 mL of ben-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

MIRONOV et al.
884
zene. The precipitate was filtered off, combined with
the precipitate obtained after partial evaporation of the
filtrate under reduced pressure (12 mm), washed with
a solution of sodium carbonate with pH 8.0 and with
water, and dried in air. Yield 6.4 g (70%), mp 163°C.
IR spectrum, ν, cm–1: 2926, 2858, 1926, 1615, 1591,
1539, 1502, 1463, 1406, 1381, 1345, 1302, 1281,
1247, 1224, 1204, 1180, 1133, 1106, 1087, 1039, 969,
919, 876, 840, 795, 773, 716, 693, 673, 643, 626, 598,
4JHH = 1.6). 13C NMR spectrum (100.6 MHz, CDCl3),
1
δC, ppm (J, Hz): 110.86 d.d (d) (C3, JPC = 180.1,
2
1JCH = 165.0), 155.88 m (d) (C4, JPC = 2.6), 119.09 m
3
1
(d) (C4a, JPC = 16.8), 129.03 d (s) (C5, JCH = 161.6),
120.90 d.d (s) (C6, 1JCH = 159.5, 3JCH = 7.0), 155.72 m
(s) (C7), 116.63 d.d.d (d) (C8, JCH = 159.7, JPC = 7.9,
1
3
3JCH = 6.3), 151.43 m (d) (C8a, JPC = 6.8, JCH = 8.7,
3
3
2JCH = 5.2, JC,6-H = JC,3-H = 1.2), 138.99 m (d) (C9,
4
4
3JPC = 19.6), 128.60 br.d.d.d (s) (C10, JCH = 160.9,
1
1
548, 510, 473, 431. H NMR spectrum (400 MHz,
3JC,14-H = 3JC,12-H = 7.1–7.2), 128.68 d.d (s) (C11, 1JCH
=
=
3
1
CDCl3), ppm (J, Hz): 1.31 s (9H, t-Bu), 1.15 t (6H,
161.5, JCH = 8.2–8.3), 129.09 d.t (s) (C12, JCH
3
3
CH2CH3, JHH = 7.2), 2.42 s (3H, CH3), 3.14 q.d and
159.1, JCH = 7.7), 35.15 m (s) (C15), 31.18 q.sept (s)
3.16 q.d (4H, NCH2, 3JPH = 8.9–9.0, 3JHH = 7.2), 5.88 d
(C16, JCH = 126.1, JCH = 4.7). 31P NMR spectrum
(36.48 MHz, CDCl3): δP 12.6 ppm, d (2JPH = 17.5 Hz).
Found, %: C 68.46; H 6.37. C18H19O3P. Calculated, %:
C 68.78; H 6.05.
1
3
2
3
(1H, 3-H, JPH = 18.1), 7.04 d.d (1H, 6-H, JHH = 8.4,
4JHH = 1.9), 7.15 d (1H, 5-H, JHH = 8.4), 7.22 d (1H,
3
4
8-H, JHH = 1.9), 7.26 m (4H, 10-H, 11-H, AA′BB′,
3JAB = JA′B′ = 8.3). 13C NMR spectrum (100.6 MHz,
3
b. Compound XXXa was synthesized in a similar
way from mixture XXXVIII/XXXIX. The product
showed no depression of the melting point on mixing
with a sample obtained as described in a.
CDCl3), δC, ppm (J, Hz): 113.31 d.d (d) (C3, JPC
=
1
160.4, JCH = 160.8), 155.12 m (d) (C4, JPC = 1.9),
1
2
118.82 br.d.d.d.d (d) (C4a, 3JPC = 15.2, 3JC,3-H = 8.0–9.0,
3JC,8-H = JC,6-H = 6.5–7.0), 128.64 d (s) (C5, JCH
=
3
1
7-tert-Butyl-2-hydroxy-4-(4-methylphenyl)-
1,2λ5-benzoxaphosphinine 2-oxide (XXXc). Water,
0.16 mL, was added to 3.28 g of a mixture of com-
pounds XXVIc and XXVIIc in 20 mL of methylene
chloride while bubbling argon through a capillary. The
solvent was removed by distillation, the thick viscous
residue was dried under reduced pressure (12 mm) at
150°C and treated with diethyl ether, and the white
precipitate was filtered off. Yield 1.73 g (70%),
mp 217°C. IR spectrum, ν, cm–1: 3448, 3026, 2924,
2855, 2366, 1660, 1615, 1583, 1535, 1506, 1462,
1404, 1364, 1344, 1301, 1230, 1199, 1134, 1085,
1003, 918, 876, 842, 822, 792, 768, 717, 673, 631,
599, 546, 508, 469, 435. 1H NMR spectrum (250 MHz,
DMSO-d6), δ, ppm (J, Hz): 1.34 s (9H, t-Bu), 2.44 s
161.1), 120.13 d.d (s) (C6, JCH = 159.4, JCH = 7.4),
1
3
155.10 m (s) (C7), 116.56 br.d.d.d (d) (C8, JCH
=
1
159.9, JPC = 7.1, JCH = 6.7), 152.18 br.d.d.d (d) (C8a,
3
3
3JCH = 9.1, 2JPC = 8.5, 2JCH = 3.9), 136.56 d.t.d (d) (C9,
3JPC = 18.3, JC,11-H = 7.7, JC,3-H = 6.8), 128.49 d.d (s)
3
3
(C10, JCH = 159.8, JCH = 5.7), 129.25 d.d.q (s) (C11,
1
3
1JCH = 158.1, 3JC,13-H = 3JC,Me = 5.4), 138.69 t.q (s) (C12,
3JCH = 6.4, JCH = 6.4), 35.00 m (s) (C15), 31.16 q.sept
2
(s) (C16, JCH = 126.0, JCH = 4.6), 39.21 t.d.q (d) (C17,
1
3
1JCH = 136.7, JPC = 5.3, JCH = 4.0), 14.70 q.d.t (d)
2
2
(C18, 1JCH = 126.0, 3JPC = 2.0, 2JCH = 2.0–2.2), 21.33 q.t
(s) (C23, JCH = 126.5, JCH = 4.1). 31P NMR spectrum
(36.48 MHz, C6H6): δP 11.1 ppm, d.q (2JPH = 14.1,
3JPH = 9.0 Hz). Found, %: C 71.84; H 8.02; N 3.53;
P 7.96. C23H30NO2P. Calculated, %: C 72.04; H 7.89;
N 3.65; P 8.08.
1
3
2
(3H, CH3), 6.13 d (1H, 3-H, JPH = 18.3), 7.14 d and
3
4
7.17 d.d (2H, 5-H, 6-H, AB, JAB = 8.7, JHH = 1.6),
7.29 m (4H, 10-H, 11-H, AA′BB′), 7.32 d (2H, 8-H,
4JHH = 1.6). 13C NMR spectrum (100.6 MHz,
7-tert-Butyl-2-hydroxy-4-phenyl-1,2λ5-benzoxa-
phosphinine 2-oxide (XXXa). a. A mixture of 4.1 g
of compounds XXVIa and XXVIIa was treated with
0.2 mL of water in diethyl ether on cooling. The white
precipitate was filtered off, recrystallized from diethyl
ether, and dried. Yield 1.9 g (20%), mp 215–218°C. IR
spectrum, ν, cm–1: 3322 v.br, 3076, 3028, 2960, 2925,
2857, 2600, 2385, 2354, 2287, 1843, 1753, 1616,
1585, 1537, 1463, 1405, 1368, 1344, 1234, 1194,
1085, 1008, 981, 932, 878, 838, 807, 786, 759, 701,
DMSO-d6), δC, ppm (J, Hz): 120.44 d.d (d) (C3, 1JPC
=
1
2
178.6, JCH = 165.6), 155.88 m (d) (C4, JPC = 2.8),
3
3
119.20 d.d.d.d (d) (C4a, JPC = 16.5, JC,3-H = 8.5,
3JC,8-H = 6.5–7.0, JC,6-H = 4.8–5.0), 129.06 d (s) (C5,
3
1JCH = 161.7), 120.79 d.d (s) (C6, JCH = 159.2, JCH
=
=
=
1
3
7.0), 155.72 m (s) (C7), 116.58 d.d.d (d) (C8, JCH
1
159.2, 3JPC = 8.1, 3JCH = 7.2), 151.42 m (d) (C8a, 2JPC
3
2
4
6.6, JCH = 10.5, JCH = 2.6, JCH = 1.0), 136.07 m (d)
(C9, 3JPC = 19.9, 3JC,11-H = 7.4, 3JC,3-H = 6.8), 128.53 d.d
1
671, 640, 574, 543, 508, 465, 437. H NMR spectrum
(s) (C10, JCH = 160.0, JCH = 5.3), 129.32 d.d.q (s)
1
3
(250 MHz, CDCl3), δ, ppm (J, Hz): 1.33 s (9H, t-Bu),
6.13 d (1H, 3-H, 2JPH = 18.0), 7.10 d and 7.14 d.d (2H,
5-H, 6-H, AB, 3JAB = 8.7, 4JHH = 1.7), 7.31 d (1H, 8-H,
(C11, JCH = 158.1, JC,13-H = 6.0, 5.2), 139.07 m (s)
1
3
(C12, 3JCH = 7.0, 2JCH = 6.5), 34.88 m (s) (C15, 3JC,8-H
=
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES ... XIII.
885
2
1
1
3
3JC,6-H = 4.2, JCH = 3.8), 31.15 q.sept (s) (C16, JCH
=
(C10, JCH = 159.6, JCH = 5.5), 129.05 d.d.q (s) (C11,
126.2, JCH = 4.6), 21.38 q.t (s) (C23, JCH = 125.5,
3JCH = 4.2). 31P NMR spectrum (36.48 MHz, CDCl3):
δP 13.0 ppm, d (2JPH = 18.4 Hz). Found, %: C 69.38;
H 6.22. C19H21O3P. Calculated, %: C 69.51; H 6.41.
3
1
1JCH = 158.0, 3JC,13-H = 5.2, JC,Me = 5.2), 138.48 t.q (s)
3
3
2
(C12, JCH = JCH = 6.4–6.6), 34.81 m (s) (C15),
30.96 q.sept (s) (C16, JCH = 126.0, JCH = 4.7),
1
3
21.13 q.t (s) (C23, JCH = 126.8, JCH = 3.8). 31P NMR
spectrum (36.48 MHz, DMSO-d6): δP –0.6 ppm, d
(2JPH = 16.7 Hz). Found, %: C 68.01; H 7.46; N 3.64;
P 8.22. C22H30NO3P. Calculated, %: C 68.21; H 7.75;
N 3.61; P 8.01.
1
3
Isopropylammonium 7-tert-butyl-2-oxo-4-
phenyl-1,2λ5-benzoxaphosphinin-2-olate (XXXIIa).
Isopropylamine, 0.2 mL, was added to a solution of
0.6 g of compound XXXa in 15 mL of diethyl ether.
After 3 days, the colorless crystals were filtered off.
Yield 76% (0.52 g), mp 202°C. IR spectrum, ν, cm–1:
3366, 2924, 2854, 2574, 2346, 2161, 1959, 1895,
1752, 1720, 1642, 1612, 1591, 1572, 1548, 1522,
1492, 1461, 1406, 1385, 1378, 1359, 1344, 1296,
1280, 1258, 1228, 1200, 1170, 1131, 1078, 1066,
1036, 1000, 965, 929, 908, 878, 845, 834, 824, 810,
778, 753, 718, 700, 669, 641, 625, 602, 576, 554, 541,
518, 475, 441, 420. H NMR spectrum (250 MHz,
CDCl3), δ, ppm (J, Hz): 1.20 m (i-Pr), 1.23 s (t-Bu),
3.47 q (CH), 6.17 d (3-H, JPH = 18.2), 6.94 d.d and
7.02 d (5-H, 6-H, AB, JAB = 8.3, JHH = 1.8), 7.16 d
(8-H, JHH = 1.8), 7.34 s (5H, C6H5). Found, %:
C 67.26; H 7.89; N 3.93; P 8.32. C21H28NO3P. Cal-
culated, %: C 67.56; H 7.51; N 3.75; P 8.31.
2-Bromo-4-butyl-7- and -6-tert-butyl-1,2λ5-benz-
oxaphosphinine 2-oxides XXXIII and XXXIV. A so-
lution of 4.6 mL (3.29 g, 0.04 mol) of hex-1-yne was
added to a solution of 8.65 g (0.0199 mol) of freshly
prepared benzodioxaphosphole XXV in 200 mL of
31
methylene chloride. P NMR spectrum of the reaction
mixture (36.48 MHz, CH2Cl2), δP, ppm: 10.3 d (2JPH
=
25.8 Hz) (XXXIII), 9.3 d (2JPH = 27.9 Hz) (XXXIV).
The mixture was evaporated under reduced pressure
(water-jet pump) at a bath temperature of 130°C. The
residue was a brown glassy mixture of compounds
XXXIII and XXXIV at a ratio of 2.8:1.0.
1
2
3
4
4
Compound X X X III. 13C NMR spectrum
(150.9 MHz, CDCl3), δC, ppm (J, Hz): 113.76 d.d.t (d)
(C3, JPC = 144.2, JCH = 144.8, JCH = 6.6), 156.75 m
1
1
3
(s) (C4), 118.21 m (d) (C4a, JPC = 18.6), 126.4 d (s)
3
Isopropylammonium 7-tert-butyl-4-(4-methyl-
phenyl)-2-oxo-1,2λ5-benzoxaphosphinin-2-olate
(XXXIIc). Isopropylamine, 0.2 mL, was added to a so-
lution of 1.1 g of compound XXXc in 15 mL of diethyl
ether; a white solid immediately precipitated. Yield
0.53 g (49%), mp 187°C. IR spectrum, ν, cm–1: 3449,
2924, 2854, 2758, 2665, 2580, 2346, 2175, 1925,
1736, 1719, 1637, 1613, 1591, 1562, 1509, 1498,
1460, 1405, 1396, 1379, 1338, 1301, 1280, 1260,
1232, 1199, 1171, 1130, 1111, 1081, 1066, 1021, 970,
961, 914, 882, 853, 834, 819, 797, 761, 714, 672, 645,
1
1
(C5, JCH = 159.2), 122.48 d.d (s) (C6, JCH = 159.8,
3JCH = 7.2), 149.25 m (s) (C7), 116.63 d.d (d) (C8,
3JPC = 8.4, 1JCH = 161.0, 3JCH = 7.2), 150.97 m (d) (C8a,
2JPC = 19.8), 34.39 t.d.m (d) (C9, JCH = 127.8, JPC
=
1
3
19.8), 30.17 t.m (s) (C10, JCH = 125.0), 22.3 t.m (s)
1
1
1
(C11, JCH = 125.1), 13.87 q.t (s) (C12, JCH = 125.0,
2JCH = 3.9).
Compound X X X IV. 13C NMR spectrum
(150.9 MHz, CDCl3), δC, ppm (J, Hz): 114.64 d.d (d)
1
1
(C3, JPC = 144.2, JCH = 145.0), 156.50 m (s) (C4),
1
630, 593, 555, 511, 489, 445, 420. H NMR spectrum
(400 MHz, DMSO-d6), δ, ppm (J, Hz): 1.15 d (6H,
120.14 m (d) (C4a, JPC = 18.6), 123.23 d.d (s) (C5,
3
1JCH = 156.8, 3JCH = 7.2), 148.09 m (s) (C6), 129.51 d.d
3
CH3, JHH = 6.5), 1.27 s (9H, t-Bu), 3.17 m (1H, CH,
(s) (C7, JCH = 159.2, JCH = 7.8), 119.3 m (d) (C8,
1
3
3JHH = 6.5), 5.92 d (1H, 3-H, JPH = 16.7), 6.90 m and
2
3JPC = 7.8), 148.77 m (d) (C8a, 2JPC = 10.2), 35.03 t.d.m
2
6.92 m (2H, 6-H, 5-H, AB part of ABM, JAB = 8.2,
(s) (C9, JPC = 18.63, JCH = 127.0), 30.17 m (s)
(C10), 22.34 m (s) (C11), 13.9 q.t (s) (C12, 1JCH = 125.0,
2JCH = 4.2).
3
1
4JBM = 1.9), 6.98 d (1H, 8-H, M part of ABM, JBM
=
4
1.9), 7.17 m and 7.23 m (4H, 10-H, 11-H, AA′BB′,
3JAB = JA′B′ = 8.7). 13C NMR spectrum (100.6 MHz,
3
CDCl3), δC, ppm (J, Hz): 113.11 d.d (d) (C13, JPC
=
4-Butyl-7-tert-butyl-2-hydroxy-1,2λ5-benzoxa-
phosphinine 2-oxide (XXXV). Water, 5 mL, was
added to 7 g of a mixture of compounds XXXIII and
XXXIV in 20 mL of diethyl ether. The white precip-
itate was filtered off and dried. Yield 20%, mp 166°C.
IR spectrum, ν, cm–1: 3435, 2958, 2854, 2725, 2670,
2273, 2150, 1959, 1925, 1702, 1615, 1595, 1539,
1502, 1465, 1401, 1377, 1364, 1302, 1284, 1222,
1
160.5, JCH = 160.5), 154.92 m (d) (C4, JPC = 1.8),
1
2
116.26 m (d) (C4a, 3JPC = 15.2), 128.43 d (s) (C5, 1JCH
=
161.1), 119.93 d.d (s) (C6, JCH = 159.4, JCH = 7.6),
1
3
154.90 m (s) (C7), 116.36 br.d.d.d (d) (C8, JCH
=
1
159.5, JPC = 7.1, JCH = 6.9), 151.99 d.d.d (d) (C8a,
3
3
3JCH = 9.1, JPC = 8.4, JCH = 4.0), 136.36 br.d.t.d (d)
3
2
(C9, JPC = 18.3, JC,11-H = 7.8, JC,3-H), 128.29 d.d (s)
3
3
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

MIRONOV et al.
886
3
2
1194, 1160, 1132, 1094, 1039, 1020, 972, 938, 926,
899, 879, 834, 802, 787, 755, 718, 678, 654, 629, 609,
(d.d) (C4, JCF = 2.9, JPC = 2.4), 118.24 m (d) (C4a,
3JPC = 17.1), 129.36 d (s) (C5, 1JCH = 162.6), 121.68 d.d
546, 537, 514, 480, 451. 1H NMR spectrum (600 MHz,
(s) (C6, JCH = 160.6, JCH = 7.0), 156.82 m (s) (C7),
1
3
3
116.03 d.d.d (d) (C8, JCH = 160.8, JPC = 8.3, JCH
=
1
3
3
DMSO-d6), δ, ppm (J, Hz): 0.92 t (3H, 12-H, JHH
=
=
3
6.0), 150.84 br.d.d.d (d) (C8a, JPC = 8.4, JCH = 8.6,
3
3
5.4), 1.29 br.s (3H, 14-H), 1.37 m (2H, 11-H, JHH
3
2JCH = 5.0, JCH = 1.3–1.5), 137.50 m (d) (C9, JPC
=
4
3
5.6, 5.6), 1.51 m (2H, 10-H, JHH = 5.4, 7.0), 2.63 m
(2H, 9-H, JHH = 7.0), 6.06 d (1H, 3-H, JPH = 18.1),
7.14 br.s (1H, 8-H), 7.23 br.d (1H, 6-H, JHH = 6.0),
3
2
20.6), 127.97 d.d.d (s) (C10, 1JCH = 159.7, 3JC,14-H = 7.6,
3
3JCH = 7.5), 128.52 br.d.d (s) (C11, 1JCH = 161.9, 3JCH
=
7.55 d (1H, 5-H, 3JHH = 6.0).
6.0), 129.47 d.t (s) (C12, JCH = 161.5, JCH = 7.6),
1
3
34.81 m (s) (C15), 30.64 q.sept (s) (C16, JCH = 126.2,
1
2,2-Dibromo-5-tert-butyl-2-fluoro-1,3,2λ5-benzo-
dioxaphosphole (XXXVII). Several drops of water
were added to a mixture of 64.5 g (0.32 mol) of 4-tert-
butylbenzene-1,2-diol and 45 mL (0.51 mol) of PCl3.
The mixture was stirred for 2.5 h at 100–120°C and
distilled to isolate 81.2 g (91%) of 5-tert-butyl-2-
chloro-1,3,2-benzodioxaphosphole with bp 86–89°C
(0.6 mm). 31P–{1H} NMR spectrum (162.0 MHz,
CH2Cl2): δP 173.5 ppm.
3JCH = 4.7). 31P NMR spectrum (162.0 MHz, CDCl3):
δP 5.0 ppm, d.d (1JPF = 1059.1, 2JPH = 19.2 Hz).
Compound X X X IX . 13C NMR spectrum
(100.6 MHz, CDCl3), δC, ppm (J, Hz): 106.94 d.d.d (d)
(C3, 1JPC = 180.6, 1JCH = 167.9, 2JCF = 29.8), 160.18 m
3
2
(d.d) (C4, JCF = 2.9, JPC = 2.5), 120.19 m (d) (C4a,
3JPC = 17.0), 126.48 d.d (s) (C5, JCH = 163.0, JCH
=
1
3
6.8), 147.45 m (s) (C6), 129.83 d.d (s) (C7, 3JCH = 6.9),
118.81 d.d (d) (C8, 1JCH = 164.4, 3JPC = 8.2), 148.72 m
Finely ground antimony trifluoride, 20 g
(0.12 mol), was carefully added on cooling to 30.6 g
(0.133 mol) of 5-tert-butyl-2-chloro-1,3,2-benzodioxa-
phosphole. The mixture was thoroughly mixed and
slowly heated to 60–70°C, kept for 1 h at room tem-
perature, and distilled under reduced pressure using
a capillary to isolate 23.0 g (81%) of 5-tert-butyl-2-
fluoro-1,3,2-benzodioxaphosphole as a colorless trans-
parent liquid, bp 94–98°C (10 mm). 31P–{1H} NMR
spectrum (CH2Cl2): δP 124.3 ppm, d (1JPF = 1299.4 Hz).
(d) (C8a, JPC = 8.4), 137.21 m (d) (C9, JPC = 21.0),
3
3
128.06 (s) (C10), 128.52 (s) (C11), 129.62 (s) (C12),
34.20 m (s) (C15), 30.87 q.sept (s) (C16, JCH = 126.0,
1
3JCH = 4.8); the coupling constants for C7, C10, C11, and
C12 were not determined because of signal overlap.
31P NMR spectrum (36.48 MHz, CDCl3): δP 4.8 ppm,
d.d (1JPF = 1060.8 Hz, 2JPH = 19.3 Hz).
The X-ray diffraction data for single crystals of
XIb, XXVIIIb, XXVIIIc, XXXIIa, and XXXV were
obtained at the X-Ray Analysis Department, Joint
Spectral and Analytical Center, Arbuzov Institute of
Organic and Physical Chemistry, Kazan Scientific
Center, Russian Academy of Sciences. The crystal-
lographic parameters and parameters of X-ray diffrac-
tion experiments and structure refinement are given in
table. The data were obtained on a Nonius B.V. CAD-4
automated four-circle diffractometer at 20°C (MoK
radiation, graphite monochromator) and were prelimi-
narily processed using MolEN program [19] on
an AlphaStation 200 PC. No drop in the intensity of
three control reflections was observed during experi-
ments. The structure of XXVIIIc was solved by the
direct method using SIR program [20] and was refined
first in isotropic and then in anisotropic approximation.
Hydrogen atoms were localized from the difference
electron density maps, and their contributions to struc-
tural amplitudes were included with fixed positional
and temperature parameters in the final refinement
step. All calculations were performed using MolEN
software [19] in an Alpha Station 200 PC. The struc-
tures of XIb and XXXIIa were solved by the direct
A solution of 4.28 g (0.02 mol) of 5-tert-butyl-2-
fluoro-1,3,2-benzodioxaphosphole in 8 mL of methy-
lene chloride was cooled to –40°C, a solution of
1.07 mL (0.02 mol) of bromine in 3 mL of methylene
chloride was added dropwise while bubbling argon
through a capillary, and dibromofluorobenzodioxa-
phosphole XXXVII thus formed was used in further
syntheses without isolation. 31P–{1H} NMR spectrum
(36.48 MHz, CH2Cl2): δP –88.0 ppm (1JPF = 1033.0 Hz).
7- and 6-tert-Butyl-2-fluoro-4-phenyl-1,2λ5-benz-
oxaphosphinine 2-oxides XXXVIII and XXXIX.
Phenylacetylene, 7.1 mL (0.064 mol), was added drop-
wise under argon to 10.2 g (0.032 mol) of freshly
prepared phosphole XXXVII in 30 mL of methylene
chloride. After 24 h, the mixture was evaporated under
reduced pressure (0.1 mm) at a bath temperature of
150°C. The residue was a light brown mixture of com-
pounds XXXVIII and XXXIX at a ratio of 4:1. Mass
spectrum, m/z: 316 [M]+. C18H18FO2P. Found: M 316.31.
Compound XXXVIII. 13C NMR spectrum
(100.6 MHz, CDCl3), δC, ppm (J, Hz): 106.05 d.d.d (d)
(C3, 1JPC = 179.3, 1JCH = 168.3, 2JCF = 28.0), 159.71 m
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES ... XIII.
887
7. Mironov, V.F., Shtyrlina, A.A., Varaksina, E.N., Efre-
mov, Yu.Ya., and Konovalov, A.I., Russ. J. Org. Chem.,
2004, vol. 40, p. 1798.
8. Terpenoidy i kumariny. Trudy Botanicheskogo instituta
imeni V.L. Komarova Akademii Nauk SSSR (Terpenoids
and Coumarins. Proc. Komarov Botanic Institute,
Academy of Sciences of the USSR), Pigulevskii, G.V.,
Ed., Moscow: Nauka, 1965.
9. Coumarins. Biology, Applications, and Mode of Action,
O’Kennedy, R. and Thornes, R.D., Eds., Chichester:
Wiley, 1997.
10. Borges, F., Roleira, F., Milhazes, N., Santana, L., and
Uriarte, E., Curr. Med. Chem., 2005, vol. 12, p. 887.
11. Kostova, I., Curr. Med. Chem. Anti-Cancer Agents,
method using SIR program [20] and were refined first
in isotropic and then in anisotropic approximation
using SHELXL-97 [21] and WinGX [22]. Hydrogen
atoms were visualized by the difference electron den-
sity maps, and their positions were refined according
to the riding model. Intermolecular interactions were
analyzed, and the molecular structures were plotted,
using PLATON program [23].
The coordinates of atoms in structures XIb,
XXVIIIb, XXVIIIc, XXXIIa, and XXXV, and their
temperature factors were deposited to the Cambridge
Crystallographic Data Centre (http://www.ccdc.cam.-
ac.uk; for entry numbers, see table).**
2005, vol. 5, p. 29.
12. Coumarin
Anticoagulant
Research
Progress,
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** Tabulated bond lengths and bond and torsion angles are avail-
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p. 34.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014