Reaction of (phenylenedioxy)trihalophosphoranes with arylacetylenes: VI. Regiochemistry of the reaction of 2,2,2-trihalo-5-methylbenzo[d][1,3,2] dioxaphospholes with arylacetylenes

Article abstract of DOI:10.1007/s11176-005-0108-2

NMR and IR spectroscopy and X-ray diffraction were used to show that the reaction of 2,2,2-trichloro- and 2,2,2-tribromo-5-methylbenzo[d][1,3,2] dioxaphospholes with para-substituted arylacetylenes proceeds with regioselective formation of 4-aryl-2-halo-7

Full text of DOI:10.1007/s11176-005-0108-2

Russian Journal of General Chemistry, Vol. 74, No. 12, 2004, pp. 1841 1860. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 12, 2004,
pp. 1953 1972.
Original Russian Text Copyright
2004 by Mironov, Shtyrlina, Varaksina, Gubaidullin, Azancheev, Dobrynin, Litvinov, Musin, Konovalov.
Reaction of (Phenylenedioxy)trihalophosphoranes
with Arylacetylenes:
VI.1 Regiochemistry of the Reaction
of 2,2,2-Trihalo-5-methylbenzo[d][1,3,2]dioxaphospholes
with Arylacetylenes
V. F. Mironov, A. A. Shtyrlina, E. N. Varaksina, A. T. Gubaidullin, N. M. Azancheev,
A. B. Dobrynin, A. I. Litvinov, R. Z. Musin, and A. I. Konovalov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received April 4, 2003
Abstract NMR and IR spectroscopy and X-ray diffraction were used to show that the reaction of 2,2,2-tri-
chloro- and 2,2,2-tribromo-5-methylbenzo[d][1,3,2]dioxaphospholes with para-substituted arylacetylenes
proceeds with regioselective formation of 4-aryl-2-halo-7-methyl-2- oxobenzo[e][1,2]oxaphosphorines. With
the trichlorophosphole, selective chlorination of the phenylene fragment in the para position to the endocyclic
oxygen atom occurs. With the tribromophosphole, 6-bromo- and unsubstituted benzo[e][1,2]oxaphosphorines
are formed as major products. The molecular and supramolecular structure of some of the obtained oxa-
phosphorines was studied by X-ray diffraction.
We recently showed [2] that the reaction of 2,2,2-
trichlorobenzo[d][1,3,2]dioxaphosphole (I) with aryl-
acetylenes unexpectedly provides 4-aryl-2,6-dichloro-
sively) to a phosphonate product. The product gives a
singlet at 17 18 ppm in the 31P {1H} NMR spectrum,
that convents into a doublet (2JPCH 23 24 Hz) in the
proton-coupled spectrum. The 1H NMR spectrum
diplays a downfield ( 6.28 6.34 ppm) doublet with
the same constant, belonging to the P CH=C(Ar)
proton. Considering the mass and 13C NMR spectral
data (see below) we identified the product as benzo-
phosphorine IV.
5
benzo[e][1,2 ]oxaphosphorine 2-oxides. This me-
chanistically rather complex reaction involves facile
formation of the phosphoryl group and carbon phos-
phorus bond, ipso substitution of the oxygen atom,
and regioselective chlorination of the phenylene sub-
stituent in the para position to the oxygen atom of
the foming benzo[e][1,2]oxaphosphorine ring. Intro-
duction of one, two, or four halogen atoms in the o-
phenylene fragment of starting phosphole I does not
alter the reaction pathway [3 5], but the regioselective
chlorination of the benzo fragment to form 4-aryl-
2,6,7-trihalobenzo[e][1,2]oxaphosphorines takes place
only if it bears only one halogen substituent.
1
O
7
7a
2
6
5
PCl3
3
O
Me
4a
4
II
1
1M5 e
Cl
7
O
2
P
8
8a O
ArC CH
In this work we present the results of investigation
of the effect of the electron-donor methyl substituent
in the phenylene fragment of 2,2,2-trichloro- and 2,2,2-
tribromo-5-methylbenzo[d][1,3,2]dioxophospholes (II,
III) on the synthetic result of their reaction with
arylacetylenes. It was found that the reaction of com-
pound II with arylacetylenes proceeds with a high
degree of regioselectivity and leads mainly (or exclu-
Cl
6
4a
ArCCl=CH2
3
4
5
9
Ar
10 12
IV
Ar = Ph (a), 4-Cl C6H4 (b), 4-Me C6H4 (c).
The structure of the obtained compounds was
confirmed by electron impact mass spectrometry,
using the example of compound IVb. The mass spec-
1
For communication V, see [1].
1070-3632/04/7412-1841 2004 MAIK Nauka/Interperiodica

1842
MIRONOV et al.
trum of the latter contains ion peaks at m/z 358, 360,
and 362, that relate to the molecular ion (M+ ) with
the formula C15H10Cl3O2P. The intensity ratio of
these peaks is 1.0:0.97:0.32 and agrees with
the intensity ratio of the isotope peaks for the M+ ion
of IVb, calculated from its empirical formula. The
first stage of fragmentation of compound IVb under
electron impact involves elimination of the chlorine
atom from the phosphorinane phosphorus atom. This
process gives rise to an m/z 323 ion. The latter easily
loses an HCl molecule to form an m/z 287 ion. The
loss of hydrogen chloride evidently proceeds from the
chlorine-substituted benzo fragment. An intense peak
at m/z 241 belongs to ion A of the composition
C14H10O2P, which lacks all the three chlorine atoms
and the methyl group.
accompanied by rearrangement of the aromatic sub-
stituent in the 4 position. Such processes forming
of polyphenyl ions and involving rearrangement of aro-
matic rings under electron impact are also characteris-
tic of organophosphorus compounds with several
aromatic substituents [6]. Other fragment ions at low
m/z values in the mass spectrum of compound IVb
are likely to be formed by consecutive fragmentation
of the above-mentioned ions.
Hence, the chlorination attendant in the formation
of benzophosphorines probably involves the phenylene
fragment of the molecule. The fact that the chlorine
atom is present just in this fragment is proved by the
1H NMR spectra. Hence, the aromatic resonance
region contains, together with two complex multi-
plees of phenyl protons, two singlets related to the
tetrasubstituted phenylene ring (see Experimental).
Therewith, the lack of any signal splitting is un-
ambiguous evidence for a para position of the corre-
sponding protons. In this case, it is evident that the
methyl group and the chlorine atom locate para to the
carbon and oxygen atoms of the annelated phospho-
rine heteroring.
+
O
O
P
+
Cl
A
B
To establish mutual location of the chlorine atom
and the methyl group, i.e. regiochemistry of the ipso
substitution of the oxygen atom, we performed a more
detailed structural study of the benzophosphorines
The base peak in the mass spectrum is at m/z 176.
It can be evidently assigned to chloronaphthalene ion
B resulting from complex rearrangements. This ion is
evidently formed from the m/z 287 ion via cleavage
of the C O and C C bonds in the phosphorinane ring,
obtained by means of 13C NMR spectroscopy, using
the example of compound IVa (see Table 1).
Table 1. 13C {1H} NMR spectral data (100.6 MHz, CDCl3) for benzophosphorines IV, V, VII XII, XV, and XVI
(parenthesized is the shape of the signal in the 13C NMR spectrum), C, ppm (J, Hz)
Atom
C3
IVa (25 C, CDCl3)
Vca (40 C, DMSO-d6) VIIbb (50 C, DMSO-d6) VIIcc (50 C, DMSO-d6)
114.02 d (d.d) (154.6, PC3; 115.19 d (d.d) (169.0, 117.09 d (d.d) (155.4, 116.10 d (d.d) (156.4,
171.4, HC3)
PC3; 163.5, HC3)
PC3; 162.5, HC3)
PC3; 161.6, HC3)
151.30 s (m)
C4
155.49 d (m) (2.0, PC3C4) 150.24 d (m) (1.8,
PC3C4)
149.94 d (m) (1.5,
PC3C4)
151.30 s (m)
C4a
120.32
HC3CC4a; 7.7, PC3CC4a; 5.9, PC3CC4a; 8.4, HC3CC4a; PC3CC4a; 8.9, HC3CC4a; PC3CC4a)
HC8CC4a) 6.0, HC8CC4a) 6.1, HC8CC4a)
HC8CC4a) 128.72 s (d) 127.51 s (d) (163.9, HC5)
d
(br.d.d.d) (17.9,
121.03 d (br.d.d.d) (16.4, 120.21 d (br.d.d.d) (17.7, 120.55
d
(m) (17.8,
C5
C6
129.27 d (br.d) (1.6, POCCC5; HC8CC4a) 127.37
d
166.8, HC5)
(br.d) (1.0, POCCC5; (164.7, HC5)
164.7, HC5)
130.37 d (m) (1.5, POCCCC6; 126.93 d (br.d. q) (1.1, 127.15 s (d.q.d) (10.6, 127.04 s (m)
10.1, HC8CC6; 5.0, H3CCC6; POCCCC6; 10.2,
5.0, HC5C6) HC8CC6; 5.5,H3CCC6; 4.6, HC5C6)
4.5, HC5C6)
HC8CC6; 6.6, H3CC7C6;
C7
141.10 s (d.q) (6.3, HC5CC7; 138.26 s (d.q) (6.3 6.4, 138.81 s (q.d) (6.3, 138.64 s (q. d) (6.2,
6.3, H3CC7)
HC5CC7; 6.3 6.4, H3CC7) H3CC7; 6.3, HC5CC7) HC5CC7; 6.2, H3CC7)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

REACTION OF (PHENYLENEDIOXY)TRIHALOPHOSPHORANES WITH ARYLACETYLENES: VI.
1843
Table 1. (Contd.)
Atom
C8
IVa (25 C, CDCl3)
Vca (40 C, DMSO-d6) VIIbb (50 C, DMSO-d6) VIIcc (50 C, DMSO-d6)
121.53 d (d.d.q.d) (8.1, POCC8; 121.17 d (d.d.q) (164.0, 121.58 d (d.d.q) (163.1, 121.57 d (d.d.q) (161.6,
164.6,
HC8;
5.0,
HC8; 7.1, POCC8; 5.2
5.3,
H3CCC8)
HC8; 6.6, POCC8; 4.7 HC8; 6.9 7.0, POCC8; 5.5,
4.8,
HC15CC8; 1.2, HC5CCC8)
H3CC7C8)
H3CCC8)
C8a
C9
149.10 d (d.d.d) (10.1, POC8a; 149.44 d (d.d.d) (9.2, 149.85 d (d.d.d) (9.3
10.1, HC5CC8a; 4.4, HC8C8a) HC5CC8a; 7.2, POC8a; 9.5, HC5CC8a; 7.8,
149.95 d (d.d.d) (9.2 9.3,
HC5CC8a; 7.7, POC8a;
4.0, HC8C8a)
POC8a; 3.8, HC8C8a) 3.7, HC8C8a)
136.60
d
(br.d.t.d) (20.6,
134.72 d (d.t.d) (18.5, 136.68
d
(br.d.t.d)
135.05 d (br.d.t.d) (17.8,
PCCC9; 7.1, HC11CC9; 6.0, PCCC9; 7.5, HC11CC9; (17.8, PCCC9; 7.3 7.5, PCCC9; 7.8, HC11CC9;
HC3CC9)
128.03 s (br.d.m) (162.0, HC10; 127.61 s (d.d) (160.0, 128.73 s (d.d) (168.3, 127.99 s (d.d) (159.1,
5.7 6.1, HCCC10) HC10; 6.1, HCCC10) HC10; 5.3, HCCC10) HC10; 6.6,HCCC10)
128.74 s (d. m) (163.0, HC11; 128.86 s (d.d.q) (160.0, 130.00 s (br.d.d) (164.6, 129.25 s (d.d. q) (159.0,
6.2, HC3CC9)
HC11CC9; 6.3, HC3CC9) 6.5, HC3CC9)
C10
C11
6.4 6.7, H3CCC11)
HC11; 6.1, HCCC11; 5.0, HC11; 7.1, HCCC11) HC11; 6.2, HCCC11; 5.1,
H3CCC11)
H3CCC11)
C12
129.75 s (d.t) (161.9, HC12; 7.1, 138.13
s
(t.q) (6.7,
133.70 s (t.t) (11.0, 138.47 s (q.t) (6.4,
HC10CC12)
HC10CC12; 6.3, H3CC12) HC10CC12; 3.2 3.3,
HC11C12)
H3CC12; 6.4, HC10CC12)
CH3C7 19.97 s (q.d) (128.7, HC; 4.7, 18.87 s (br.q.d) (128.6, 19.27 s (q. d) (128.4, 19.31 s (q.d) (128.8, HC;
HC8CC)
VIIIad (50 C, DMSO-d6)
HC; 4.7, HC8C7C)
HC13; 4.5, HC8C7C)
4.8, HC8CC)
Atom
C3
VIIce (50 C, DMSO-d6)
IX (25 C, CDCl3)
X (25 C, CDCl3)
123.49 d (d.d) (163.6, PC3; 123.61 d (d.d) (163.8, 114.89 d (d.d) (142.6, 116.18 d (d.d) (142.0,
156.9, HC3)
144.67 d (m)
PC3; 155.7, HC3)
144.42 s (m)
PC3; 171.7, HC3)
PC3; 171.7, HC3)
C4
155.80 d (m) (2.0, 154.47 d (m) (1.7,
PC3C4)
PC3C4)
C4a
122.83 d (m) (15.3, PC3CC4a; 123.11 d (d.d.d) (15.3, 118.54
d
(br.d.d.d)
120.49 d (br.d.d.d) (18.1,
9.2, HC3CC4a; 5.9, HC8CC4a) PC3CC4a; 8.7, HC3CC4a; (18.0, PC3CC4a; 7.8 7.9, PC3CC4a; 7.8 7.9,
6.1, HC8CC4a)
HC3CC4a;
HC8CC4a)
5.4 5.6, HC3CC4a; 5.4 5.6,
HC8CC4a)
C5
C6
126.75 s (d) (164.1, HC5)
126.85 s (d) (162.9, HC5) 129.40 d (br.d) (162.5, 132.48 d (br.d) (168.0,
HC5; 1.6, POCCC5)
HC5; 1.4, POCCC5)
125.04 s (m) (10.5, HC8CC6; 124.97 s (d.d.q) (10.5, 125.70 d (d.m) (1.6, 120.24 d (m) (1.7,
5.1, H3CC7C6; 5.0, HC5C6) HC8CC6; 5.0, H3CC7C6; POCCCC6; 162.4, HC6; POCCCC6; 10.1, HC8CC6;
5.0, HC5C6)
6.1, HC8CC6; 5.0,
H3CCC6)
4.7 5.0, HC5C6; 5.0 6.0,
H3CCC6)
C7
C8
136.40 s (q.d) (6.1, H3CC7; 6.1, 136.25
s
(q.d) (6.2,
143.61 s (d.q) (8.7, 143.01 s (d.q) (6.4,
HC5CC7)
HC5CC7; 6.2, H3CCC7) HC5CC7; 6.1, H3CC7) HC5CC7; 6.4, H3CC7)
121.41 d (d.d.q) (161.4, HC8; 121.49 d (d.d.q) (161.5, 128.49 s (d. m) (162.3, 121.41 d (d.m) (8.1,
5.5, POCC8; 4.3, H3CC7C8) HC8; 5.4, POCC8; 5.4 5.5, HC11; 6.6 6.7, HCCC11) POCC8; 5.1 5.2, H3CCC8;
H3CCC8)
1.1, HC5CCC8)
C8a
151.79 d (m) (7.1, POC8a; 3.3, 152.03 d (d.d.d) (9.1, 119.79 d (d.m) (162.4, 149.64 d (d.d.d) (10.5,
HC8C8a)
HC5CC8a; 6.9, POC8a; HC8; 8.0, POCC8; 6.3 POC8a; 10.5, HC5CC8a;
3.7 3.8, HC8C8a)
6.5, H3CCC8; 1.1,
HC5CCC8)
4.3,
HC8C8a)
5.0 5.5, HC3CC9)
C9
139.47 d (d.t.d) (16.7, PCCC9; 136.76 d (d.t.d) (16.2, 150.62 d (m) (10.6, 136.20 d (m) (20.9,
7.6, HC11CC9; 5.5, HC3CC9) PCCC9; 7.7, HC11CC9; POC8a; 10.6, HC5CC8a; PCCC9; 7.4, HC11CC9;
6.5, HC3CC9)
4.3, HC8C8a)
C10
127.98 s (br.d.d.d) (160.7, 127.98 s (d.d) (159.0, 136.91 d (m) (20.9, 127.98 s (br.d. m) (161.7,
HC10; 6.9, HCCC10; 6.9 7.1, HC10; 6.6, HCCC10)
HC12CC10)
PCCC9; 7.6, HC11CC9; HC10; 7.5, HCCC10; 6.2
5.0 5.5, HC3CC9) 6.6, H12CCC10)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

1844
MIRONOV et al.
Table 1. (Contd.)
Atom
C11
VIIIad (50 C, DMSO-d6)
VIIce (50 C, DMSO-d6)
IX (25 C, CDCl3)
(br.d. m)
X (25 C, CDCl3)
128.40 s (br.d.d) (162.3, HC11; 129.06 s (d.d.q) (158.3, 128.08
7.8, HCCC11)
s
128.74 s (d.m) (162.2,
HC11; 6.7, HCCC11)
HC11; 6.0, HCCC11; 5.4, (161.7, HC10; 7.5,
H3CCC11)
HCCC10;
H12CCC10)
6.2 6.6,
C12
127.89 s (d.t) (160.3, HC10; 8.0, 137.33
HC10CC12)
s
(q.d) (6.4,
129.47 s (d.t) (161.8, 129.82 s (d.t) (161.5,
H3CC12; 6.4, HC10CC12) HC12; 7.8, HC10CC12) HC12; 7.0, HC10CC12)
CH3C7 19.06 s (q.d.d) (128.2, HC; 4.0, 19.20 s (q.d) (128.2, HC; 21.18 s (q.d.d) (127.5, 22.89 s (q.d) (128.9, HC;
HC8C7C; 1.1, HC5C6C7C)
4.8, HC8CC)
HC; 4.4, HC6CC; 4.4, 4.5, HC8CC)
HC8CC)
Atom
C3
XI (25 C, CDCl3)
XII (50 C, CDCl3)
XVf (50 C, DMSO-d6) XVIcg (50 C, DMSO-d6)
116.03 d (d.d) (142.1, PC3; 116.36 d (d.d) (141.9, 117.02 d (d.d) (155.8, 118.47 d (d.d) (155.0,
171.2, HC3)
PC3; 171.0 173.0, HC3) PC3; 161.7, HC3)
PC3; 162.1, HC3)
C4
155.82 d (m) (1.8, PC3C4) 154.76 d (m) (1.6,
151.40 d (m) (2.0, 150.08 d (m) (1.6,
PC3C4)
120.80 d (m) (17.8, PC3CC4a) 120.85 d (m) (17.9,
PC3CC4a)
PC3C4)
PC3C4)
C4a
119.14 d (m) (15.5,
PC3CC4a)
121.53 d (m) (16.0,
PC3CC4a; 7.4 7.5,
HC3CC4a;
HC8CC4a
6.0 7.0,
C5
C6
129.73 d (d.m) (162.0 164.0, 129.67 d (m) (1.3,
128.30 d (br.d) (161.0 131.17 br.s (br.d) (165.7,
HC5; 1.6, POCCC5)
POCCC5)
162.0, HC5; 1.2,
POCCC5)
HC5)
134.54 d (m) (1.5, POCCCC6; 134.52
6.3 6.6,
d
(m) (1.3,
123.81 s (d.m) (161.3, 117.33 d (m) (10.7,
H3CCC6)
POCCCC6; 6.0 6.5,
HC8CC6; 5.0, H2CC6)
HC3; 6.7, HC8CC6; 4.7 HC8CC6; 4.8, H3CC7C6;
5.0, H3CC7C6)
4.3 4.5, HC5C6; 1.0,
POCCCC6)
C7
C8
132.90 s (d.d.q) (161.2, HC7; 132.64 s (d.m) (161.2, 141.54 s (d.q.d) (9.0, 140.74
7.7, HC5CC7; 4.8, H3CCC7) CH7; 7.7, HC5CC7; 6.4, HC5CC7;
5.5 5.7,
H2CCC7) H3CC7; 0.7, HCC)
119.18 d (d.d) (165.0, HC8; 8.0, 119.61 d (d.d) (164.7, 119.66 d (d.m) (160.0, 121.73 d (d.m) (163.6,
s
(q.d) (6.4,
HC5CC7; 6.4, H3CC7)
POCC8)
HC8; 8.0, POCC8)
HC8; 6.9 7.1, HC6CC8; HC8; 6.8, POCC8; 5.7 5.8,
8.0, POCC8; 5.2,
H3CCC8)
H3CC7C8)
C8a
C9
149.84 d (m) (10.8, POC8a; 150.13 d (m) (10.8,
10.5, HC5CC8a; 10.3, HC7CC8a; POC8a)
3.5 4.0, HC8C8a)
151.63 d (m) (9.0 10.0, 150.81 d (br.d.d.d) (10.2,
HC5CC8a; 8.0, POC8a; HC5CC8a; 7.9, POC8a;
3.8 4.0, HC8C8a)
4.2, HC8C8a)
136.42 d (m) (20.8, PCCC9)
136.22
d
(m) (20.7,
139.77 d (m) (17.9, 138.62 d (m) (17.6,
PCCC9; 6.5 7.0,
PCCC9; 6.8 7.2,
PCCC9; 6.8 7.2,
HC11CC9;
HC3CC9)
5.0 5.5,
HC11CC9; 6.5, HC3CC9) HC11CC9; 6.5, HC3CC9)
C10
128.09 s (br.d. m) (161.6,
HC10; 7.4, HCCC10; 6.3 6.7,
H12CCC10)
128.28 s (br.d.m) (160.1, 128.24 s (br.d.m) (160.5,
HC10; 6.8 7.0, HCCC10; HC10; 6.8 7.0, HCCC10;
5.9 6.3, HCCC10)
5.9 6.3, HCCC10)
C11
C12
128.54 s (d.m) (162.0, HC11;
6.5 6.7, HCCC11)
128.68 s (br.d.d) (162.0, 128.88 s (br.d.d) (161.3,
HC11; 7.2 7.4, HCCC11) HC11; 7.4, HCCC11)
128.97 s (d.t) (161.3, 128.63 s (d.t) (160.9,
HC12; 7.4, HC10CC12) HC12; 7.3, HC10CC12)
129.50 s (d.t) (161.3, HC12; 7.2,
HC10CC12)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

REACTION OF (PHENYLENEDIOXY)TRIHALOPHOSPHORANES WITH ARYLACETYLENES: VI.
1845
Table 1. (Contd.)
Atom
XI (25 C, CDCl3)
XII (50 C, CDCl3)
XVf (50 C, DMSO-d6) XVIcg (50 C, DMSO-d6)
CH3C7 20.54 s (q.d.d) (127.0, HC; 4.5, BrCH2, 31.65 s (t.d.d) 20.69 s (q.d.d) (127.1, 22.18 s (q. d) (128.6, HC;
HC6CC; 4.4, HC7CC)
(154.0, HC; 5.1, HC7CC; HC13; 4.6, HC8CC; 4.3, 4.8, HC8CC)
5.1, HC5CC)
HC6CC),
NCH
(CH3)3
51.22 d (m) (1.9, PNC) 51.41 d (m) (1.8, PNC)
31.36 s (q.m) (125.9, 31.56 s (q.m) (125.9, HC;
HC; 4.8, PNCC; 2.4, 4.8, PNCC; 2.4, HCCH)
HCCH)
a
12
11 12
b
CH C , 20.27 s (q.t) (126.4, HC; 4.3, HC
C C). NCH, 42.74 br.s (br.d.m) (135.8 136.1, HC; 3.9 4.0, HCC). (CH ) , 25.01 d
3
3 2
11 12
c
12
(q.m) (125.4, HC; 5.7, PNCC), 24.81 d (q.m) (126.6, HC; 5.1, PNCC). CH C , 20.69 s (q.t) (126.4, HC; 4.9 5.0, HC
C
C).
3
NCH, 43.24 d (d.m) (138.7, HC; 1.4, PNC). (CH ) , 24.83 d (q.m) (125.3, HC; 4.6, PNCC), 25.03 d (q.m) (125.2, HC; 6.1, PNCC).
3 2
d
e
12
NCH , 42.48 s (br.t) (143.5, HC). OCH , 63.02 s (br.t.m) (145.5, HC; 2.4 2.5, HCOC; 2.4 2.5, HCC). CH C , 20.69 s (q.t)
2
2
3
11 12
f
(126.4, HC; 4.9 5.0, HC
(1.9, PNC). (CH ) , 31.36 s (q.m) (125.9, HC; 4.8, PNCC; 2.4, HCCH).
C
C). NCH, 42.76 br.s (br.d.m) (145.5, HC). (CH ) , 20.24 br.s (br.q) (127.1, HC). NCH, 51.22 d (m)
3 2
g
NCH, 51.41 d (m) (1.8, PNC).
3 3
As seen from Table 1, the spectrum contains six
signals of carbon atoms bound with hydrogen and six
signals of carbon atoms bearing no protons. Taking
only if the methyl group is ortho to C8. From that it
follows that the reaction involves selective migration
of the chlorine atom into the para position to the
endocyclic oxygen atom of the phosphorinane hetero-
ring. This process is analogous to chlorine migration
in the reaction of unsubstituted trichlorobenzophos-
phole I with arylacetylenes [2]. The ipso substitution
of the oxygen atom, too, regioselectively proceeds
para to the methyl group. This result resembles that
of the reaction of 5-chloro- or 5-bromo-2,2,2-trichlo-
robenzo[d][1,3,2]dioxaphospholes with arylacetylenes
[4].
into account the pair equivalence of the C10 and C11
atoms of the phenyl substituent, we can conclude that
the chlorine atom locates in the phenylene fragment.
The multiplicity of the C4a and C8a signals (d.d.d) is
consistent with the presence of substituents in the 6
and 7 positions. Of C8 and C5, the first atom is
shielded stronger because of the strong ortho effect of
oxygen; moreover, the C8 signal appears as a doublet
due to coupling with phosphorus with a noticeable
2JPOCC constant (8.1 Hz). In the proton-coupled spec-
trum, the C8 signal is a complex multiplet whose
shape is determined by coupling of C8 with H8 (1JHC
164.6 Hz), H5 (4JHCCC 1.2 Hz), and methyl protons
(3JHCCC 5.2 Hz). Such a multiplet structure is possible
The above conclusions were completely confirmed
by a single-crystal X-ray diffraction study of compound
IVa. The resulting coordinates, selected bond lengths,
and bond and torsion angles are listed in Tables 2 and
3. Figure 1 gives a general view of the molecule.
C15
C7
C8
Cl2
P2
Cl6
C8a
C4a
O1
C3
C6
O2
C5
C4
H3
C9
C10
C14
C13
C11
C12
Fig. 1. Molecular geometry of compound IVa in crystal and scheme of dimer formation by intermolecular C H O hydrogen
bonds (shown by dashed lines).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

1846
MIRONOV et al.
Table 2. Atomic coordinates in molecule IVa, equivalent
isotropic thermal parameters of non-hydrogen atoms B =
The phosphorine heteroring in molecule IVa
contains two planar fragments O1C8aC4aC4 and
P2C3C4C4a, which form a dihedral angle of 15.8(3)
with each other. The C3 and P2 atoms of the hetero-
ring deviate from the O1C8aC4C4a plane by 0.375(3)
and 0.739(1) , i.e. these atoms are located on the
same side of the plane. From the second planar frag-
ment (P2C3C5C4a), the heteroring O1 and C8a atoms,
too, deviate to the same side by different distances
( 0.543(2) and 0.286(2) , The fact that two of the
six atoms deviate to the same side but by different
distances suggests that the conformation of the phos-
phorine ring is distorted bath. The O2 and Cl2 atoms
of the exocyclic substituents deviate from the
O1C8aC4aC4 plane by 0.419(2) and 2.6864(7)
and from the P2C3C4C4a plane, by 0.674(2) and
1.8942(7) , respectively. These deviate point to an
axial location of the chlorine atom and to an equato-
rial location of the phosphoryl oxygen atom. The
3
3
4/3
(aiaj)B(i, j) ( 2) and thermal parameters of
i=1 j=1
2
hydrogen atoms Biso
(
)
Atom
x
y
z
B or Biso
Cl2
Cl6
P2
1.46891(8) 0.42542(8) 0.13773(8) 2.33(2)
0.74055(8) 0.71543(8) 0.30376(8) 2.31(2)
1.43291(8) 0.23435(8) 0.16522(8) 1.68(2)
O1
1.3855(2) 0.3024(2)
1.5846(2) 0.1152(2)
1.2483(3) 0.1864(3)
1.0982(3) 0.2513(3)
1.0886(3) 0.3753(3)
0.9378(3) 0.4775(3)
0.9325(3) 0.5909(3)
1.0712(3) 0.6097(3)
1.2271(3) 0.3977(3)
1.2206(3) 0.5096(3)
0.9441(3) 0.1987(3)
0.9187(3) 0.1608(3)
0.7774(3) 0.1113(3)
0.6569(3) 0.0943(3)
0.6809(3) 0.1275(3)
0.8231(3) 0.1791(3)
1.0627(3) 0.7388(3)
0.3134(2)
0.1862(2)
0.0226(3)
0.0383(3)
0.1753(3)
0.1794(3)
0.3092(3)
0.4390(3)
0.3050(3)
0.4344(3)
0.0764(3)
0.2290(3)
0.3374(3)
0.2935(3)
0.1430(3)
0.0345(3)
0.5771(3)
0.049(2)
0.515(3)
0.097(3)
0.252(3)
0.442(3)
0.365(3)
0.112(3)
0.073(2)
0.651(3)
0.560(3)
0.618(3)
1.71(4)
2.31(5)
1.67(6)
1.33(6)
1.32(6)
1.56(6)
1.59(6)
1.61(6)
1.46(6)
1.63(6)
1.40(6)
1.86(7)
2.40(8)
2.27(7)
1.86(7)
1.69(7)
2.05(7)
0.1(4)
O2
C3
C4
C4a
C5
C6
C7
P Cl bond length in this molecule is 2.024(1)
,
C8a
C8
which is slightly larger than in 2,5,6,7,8-pentachloro-
4-phenylbenzo[e][1,2 5]oxaphosphorine 2-oxide
(IVd) [2.018(1) ] we studied previously [5]. Since
compounds IVa and IVd have the same substituents
in the heteroring, it is expedient to compare their other
geometric parameters. The P=O bond lengths are
equal within the experimental error: 1.451(2) and
C9
C10
C11
C12
C13
C14
C15
H3
1.456(3)
in IVa and IVd, respectively. The endo-
cyclic bonds at the phosphorus atom in this molecule
appreciably differ from each other: the O1 P2 bond in
IVa (1.589(2) ) is shorter than IVd [1.597(3) ]. The
same relates to the P2 C3 bond lengths: 1.742(2) in
1.259(2)
1.310(3)
0.839(3)
0.987(3)
0.751(3)
0.555(3)
0.607(3)
0.847(3)
0.118(2)
0.517(3)
0.475(2)
0.173(2)
0.087(3)
0.068(3)
0.107(3)
0.203(2)
0.734(3)
0.841(3)
0.735(3)
H8
1.5(5)
1.4(5)
1.6(6)
3.2(7)
1.8(6)
3.2(7)
1.5(5)
2.9(7)
H5
H10
H11
H12
H13
H14
IVa vs. 1.750(4)
in IVd. Such bond length re-
distribution provides evidence showing that the hyper-
conjugation of the lone electron pair of the endocyclic
oxygen atom with the antibonding orbital of the P Cl
bond (the anomeric effect) in IVa is stronger than in
IVd. These difference in bond angles on phosphorus,
too, is also consistent with these interactions: The
endocyclic O1P2C3 angle in molecule IVa [103.9(1) ]
H151 1.169(3)
H152 1.038(3)
H153 0.987(3)
3.2(7)
3.8(7)
Table 3. Selected bond angles
(deg), bond lengths d ( ), and torsion angles
(deg) in molecule IVa
Angle
Angle
Angle
Cl2P2O1
Cl2P2O2
Cl2P2C3
O1P2O2
O1P2C3
O2P2C3
P2O1C8a
P2C3C4
101.93(8)
P2C3H3
116(1)
123(1)
O1C8aC8
C4aC8aC8
C8aC8C7
C9C14C13
C8C7C6
115.7(2)
110.9(1)
107.9(1)
112.0(1)
103.9(1)
118.7(1)
119.3(2)
121.5(2)
C4C3H3
C3C4C4a
C3C4C9
123.3(2)
120.6(2)
120.6(3)
116.8(2)
121.5(2)
119.7(2)
117.4(2)
119.2(2)
121.2(2)
122.2(2)
121.6(2)
116.1(2)
121.1(2)
C4C4aC8a
C4C4aC5
C8aC4aC5
O1C8aC4a
C8C7C15
Cl6C6C8
Cl6C6C5
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

REACTION OF (PHENYLENEDIOXY)TRIHALOPHOSPHORANES WITH ARYLACETYLENES: VI.
1847
Table 3. (Contd.)
Bond
Cl2 P2
d
Bond
d
Bond
d
2.024(1)
1.743(2)
1.589(2)
1.451(2)
1.742(2)
1.407(3)
1.347(4)
0.80(2)
C4 C4a
C4 C9
C4a C8a
C4a C5
C8a C8
C8 C7
C7 C6
C6 C5
1.485(3)
1.478(3)
1.379(3)
1.400(3)
1.377(3)
1.384(3)
1.378(3)
1.383(3)
C9 C10
C9 C14
C10 C11
C11 C12
C12 C13
C13 C14
C5 H5
1.384(4)
1.395(5)
1.369(3)
1.392(5)
1.369(4)
1.382(3)
0.93(2)
Cl6 C6
P2 O1
P2 O2
P2 C3
O1 C8a
C3 C4
C3 H3
C7 C15
1.513(3)
Angle
Angle
Angle
Cl2P2O1C8a
O2P2O1C8a
C3P2O1C8a
Cl2P2C3C4
Cl2P2C3H3
O1P2C3C4
O1P2C3H3
O2P2C3C4
72.9(2)
168.5(2)
39.2(2)
86.4(2)
99(1)
21.2(2)
153(1)
146.4(2)
O2P2C3H3
P2O1C8aC4a
P2O1C8aC8
P2C3C4C4a
P2C3C4C9
28(2)
32.5(3)
149.2(2)
4.7(3)
173.8(2)
179(2)
1(2)
C3C4C4aC5
C9C4C4aC8a
C9C4C4aC5
C3C4C9C10
C3C4C9C14
C4aC4C9C10
C4aC4C9C14
C4C4aC8aO1
161.0(3)
160.2(2)
20.4(4)
39.1(4)
138.0(3)
142.3(2)
40.6(3)
0.3(4)
H3C3C4C4a
H3C3C4aC8a
C3C4C4aC8a
18.3(4)
is increased compared with the respective angle in
IVd [101.8(1) ], whereas the exocyclic O1P2Cl2 angle
is decreased [101.93(8) in IVa against 103.6(1) in
IVd]. The differences in the O1 C8a [1.407(3) and
1.382(5) ], C3=C4 [1.347(4) and 1.358(5) ], and
C4 C4a [1.485(3) and 1.474(5) ] in IVa and IVd are
also worthy of mention. The shortening of these
bonds in IVd compared with IVa is evidently con-
nected with the electron-acceptor perchloro effect of
the condensed aromatic fragment. Probably, the
attenuated anomeric effect in molecule IVd, too, is
0 . At the same time, the benzo fragment of the
molecule, too, takes part in such interactions with the
benzo fragments of molecules bound with it by the
center of symmetry and translations by +1 and
1
along the 0z axis, with the shortest distance between
the ring centers of 4.61(1) and the dihedral angle of
0 ; as a result, inclined stacks of molecules bound by
such contacts are formed. Contacts of the
H type
are also observed in the crystal, as well as multiple
Cl H contacts with distances spanning the range
2.91 3.69 . The most significant effect on the
caused by the same electron-acceptor effect. The ortho- molecular packing is produced by a C H O inter-
chlorine substituents in the benzo fragment of struc-
ture IVd may also be responsible for the above-
described structural differences in the molecules in
question. It is this effect that explains the noticeable
increase of the C4C4aC5 angle [124.8(3) ] in IVd as
compared with IVa [121.6(2) ]. Therewith, a short
molecular contact o between H3 and O2 (1 x, y, 2
z), with the following parameters: d(H3 O2)
2.51(2)
and C3 H3 O2 angle 155.0(2) ; this leads
to formation of centrosymmetric dimers (Fig. 1). In
whole, the intermolecular contacts present in the
crystal give rise to a 3D supramolecular structure and
a sufficiently tight molecular packing (packing coef-
ficient 69.2%).
intramolecular
Cl5-C11
contact
is
observed
[3.000(3) ; sum of van der Waals radii 3.45 ]. The
opposite O1C8aC8 angle is much decreased in both
molecules [115.7(2) in IVa and 116.2(3) IVa]. The
phenyl substituent is strrongly turned about the C3=C4
double bond [the C3C4C9C10 torsion angle is 39.1(4) ],
which unfavors conjugation of these two fragments.
Hydrolysis of benzophosphorines IV under mild
conditions gave hydroxyphosphorines V with pre-
served heterocyclic structure.
The structure of compounds V was established by
1
Such location of the phenyl substituent occurs to
means of H, 13C, 31P NMR and IR spectroscopy (see
be favorable for
of a neighboring molecule, with the distance between
the ring centers of 4.85(1) and the dihedral angle of
contacts with the same fragment
Experimental). The cyclic structure of the products
was confirmed by X-ray diffraction on an example of
benzophosphorine Vc. The atomic coordinates and
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

1848
MIRONOV et al.
O O
O
SOCl2
Me
Cl
O
OH
Me
Cl
O
O
Me
Cl
O
H2O
HCl
SOCl2
P
P
(or PCl5)
P
IVa IVc
IVa IVc
HCl,
SO2
SO2
( POCl3)
Ar
Ar
Ar
Va Vc
VI
H21
O3
P2
C15
7C8
C
C8a
Cl6
C6
O1
C5
C3
C10
C4 H3
C9
C11
C12
C14
C13
5
C16
Fig. 2. Molecular geometry of compound Vc in crystal and scheme of dimer formation by intermolecular C H O hydrogen
bonds (shown by dashed lines).
selected geometric parameters of the latter (bond
lenghts, bond and torsion angles) are listed in Tab-
les 4 and 5. The molecular geometry and scheme of
hydrogen bonds in the crystal are shown in Fig. 2.
which completely agrees with published data for
analogous structures studied [2, 4, 5]. The principal
geometric parameters of the heteroring in these com-
pounds are almost the same. The 4-phenylmethyl and
P2C3C4C54a planes are almost orthogonal to each
other. The torsion angle between them is 65.3(5) .
Like in above-described case, the heteroring in
compound Vc has two planar fragments, O1C8aC4aC4
and P2C3C4C4a, that form a dihedral angle of 9.9(6)
with each other. The heteroring C3 and P2 atoms
deviate from the O1C8aC4aC4 plane by 0.232(3) and
0.4751(8) , respectively, i.e. to the same side of the
plane. From the second planar fragment (P2C3C4C4a),
the O1 and C8a atoms, too, deviate to the same side
(by 0.407(2) and 0.174(3) , respectively). The fact
that the above-mentioned atoms deviate to the same
side but by different distances suggests a distorted
boat conformation of the phosphorinane ring. The O2
and O3 atoms of the exocyclic substituents deviate by
0.279(2) and 1.956(2) from the P2C3C4C4a plane
and by 0.947(2) and 1.394(2) from the P2C3C4C4a
plane, respectively. Such deviations of the O3 and O2
atoms point to an axial position of the hydroxy group
and an equatorial position of the phosphoryl oxygen,
Analysis of intermolecular interactions in the crys-
tal of compound Vc, carried out by means of the
PLATON program [6], shows that here, unlike the
above-described compound IVa, there are no short
contacts, except for the classical hydrogen bond
between the hydroxyl proton and O2 ( 1 + x, y, z),
with the parameters: d(H31 O2 1.88(2)
and O3
H3 O2 angle 170(3) . Each molecule is involved into
two such hydrogen bonds (as a donor and as an ac-
ceptor), which results in formation of supramolecular
structures having the shape of infinite chains of the
hydrogen-bonded molecules, running along the 0x
crystallographic axis (Fig. 2).
Treatment of phosphonic acids V with thionyl
chloride or phosphorus pentachloride permits to pre-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

REACTION OF (PHENYLENEDIOXY)TRIHALOPHOSPHORANES WITH ARYLACETYLENES: VI.
1849
Table 4. Atomic coordinates in molecule Vc, equivalent
isotropic thermal parameters of non-hydrogen atoms B =
thionyl chloride and slowly transforms to chlorophos-
phonate IV. On treatment with phosphorus penta-
chloride, complete and rather fast conversion to final
reaction product IV occurs.
3
3
4/3
(aiaj)B(i, j) ( 2) and thermal parameters of
i=1 j=1
2
hydrogen atoms Biso
(
)
By treatment of chlorophosphorines IV with
amines we obtained corresponding amides VIIa, VIIb,
and VIIc. In their 31P and 31P {1H} NMR spectra,
the signals of starting benzophosphorines IV are
Atom
x
y
z
B or Biso
Cl1
P2
0.6711(2) 0.14710(7) 0.55663(7) 5.73(2)
shifted upfield to
8.0 10.0 ppm and acquire a
characteristic multipPlicity (d.d) due to additional
coupling through three bonds with the amido proton
(3JPCH 10.0 11.0 Hz) (compounds IVb and IVc). In
0.0402(2) 0.31378(7) 0.21336(6)
3.96(2)
4.50(5)
5.84(6)
4.79(5)
4.41(8)
3.82(7)
3.47(7)
3.81(7)
3.92(7)
4.08(8)
4.10(8)
3.67(7)
4.00(8)
7.8(1)
O1
0.0008(5) 0.3542(2)
0.3169(4) 0.3430(2)
0.1967(4) 0.3750(2)
0.0053(7) 0.1711(3)
0.1138(7) 0.1215(2)
0.2145(6) 0.1890(2)
0.3736(7) 0.1454(2)
0.4710(7) 0.2086(2)
0.4112(7) 0.3204(2)
0.2540(7) 0.3643(2)
0.1599(6) 0.3009(2)
0.1431(7) 0.0019(2)
0.3364(2)
0.1968(2)
0.1592(2)
0.1774(2)
0.2377(2)
0.3404(2)
0.3965(2)
0.4918(2)
0.5366(2)
0.4810(2)
0.3855(2)
0.2010(2)
0.1160(3)
0.0803(3)
0.1246(3)
0.2106(3)
0.2533(3)
O2
O3
the 13C NMR spectra of the amides, all coupling
constants with phosphorus (except for the direct one)
are characteristically decreased by 1 3 Hz; therewith,
the long-range constants for C5 and C6 disappear.
Note that the methyl carbon atoms of the amide frag-
ment are nonequivalent. For example, in the spectrum
C3
C4
C4a
C5
C6
C7
of compound VIIb they appear as upfield doublets of
C8
3
equal intensity ( 24.91 and 24.72 ppm, JPNCC 5.7
C8a
C9
C
and 5.0 Hz, respectively).
C10
C11
C12
C13
C14
C15
C16
H3
0.321(1)
0.341(1)
0.0487(3)
0.1636(3)
Morpholide VIIa proved to be the least resistant to
hydrolysis. It converts to salt VIIIa just when washed
with water during isolation. Amidophosphonates VIIb
and VIIc are more stable, but on treatment with water
in DMSO they yield salts VIII. Therewith, their
9.0(1)
5.8(1)
8.3(1)
6.9(1)
0.1852(9) 0.2351(3)
0.012(1) 0.1868(3)
0.0102(9) 0.0711(3)
0.5146(8) 0.3915(3) 0.6414(3)
5.56(9)
9.2(1)
2.5(5)
2.3(5)
3.2(5)
7.6(9)
6.1(8)
4.1(6)
13(1)
2.5(5)
11(1)
8.5(9)
9(1)
11(1)
11(1)
18(2)
phosphorus signals are shifted even more upfield (
P
0.205(1)
0.047(5)
0.422(4)
0.220(5)
0.428(7)
0.444(6)
0.071(5)
0.14(1)
0.3621(3)
0.133(2)
0.077(2)
0.433(2)
0.001(2)
0.185(2)
0.216(2)
0.038(3)
0.370(2)
0.0839(3)
0.119(2)
0.369(1)
0.510(2)
0.085(2)
0.028(2)
0.247(2)
0.323(3)
0.165(2)
0.696(3)
0.654(2)
0.640(2)
0.131(3)
0.025(3)
0.099(4)
2.0 to 1.0 ppm).
H5
Me
O
NHR
O
HNR(R )
P
H8
IV
R(R )NH HCl Cl
H10
H11
H13
H14
H31
R
Ar
VII
O
O
Me
O
+
0.328(5)
H2O
P
H2NR
H151 0.436(8 ) 0.355(3)
Cl
H152 0.462(8)
H153 0.683(8)
H161 0.111(8)
H162 0.214(9)
H163 0.35(1)
0.459(3)
0.392(3)
0.395(3)
0.382(3)
0.376(4)
R
Ar
VIIIa VIIIc
R + R = O(C2CH2)2N, Ar = Ph (VIIa, VIIIa); R =
CH(CH3)2, R = H, Ar = 5-Cl C6H4 (VIIb), 4-Me C6H4
(VIIc, VIIIc).
pare starting chlorophosphorines IV. Unlike phos-
phorus pentachloride, thionyl chloride fairly slowly
reacts with compounds V. In the course of the reaction
we could detect a pyrophosphonate intermediate VI.
This compound becomes a single product if the ratio
of the starting components is 1:1. In the 31P NMR
spectrum, this product gives a broadened doublet at
2.0 to 1.0 ppm (2JPCH 17.0 18.1 Hz). It is interesting
to note that pyrophosphonate VI is rather inert to
Noticeable changes in the 13C NMR spectra are
observed in going from amides to corresponding salts.
Figures 3 and 4 shows fragments of the 13C {1H}
NMR spectra of amide VIIb and ammonium salt
VIIIa. As seen from these figures and Table 1, the
phosphorine ring in these salts remains unchanged (as
2
3
3
8a
8
4a
judged from the JPOC , JPOCC , and JPCCC con-
stants). The transfer to the salt form causes a strong
downfield shift (
6 7 ppm). At the same time, a
C
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

1850
MIRONOV et al.
(deg), bond lenghts d ( ), and torsion angles
Angle
Table 5. Selected bond angles
(deg) in molecule Vc
Angle
Angle
O1P2O2
O1P2O3
O1P2C3
O2P2O3
O2P2C3
O3P2C3
P2O1C8a
P2O3H31
P2C3C4
P2C3H3
109.6(1)
C4C3H3
C3C4C4a
C3C4C9
C4aC4C9
C4C4aC5
C4C4aC8a
C5C4aC8a
C4aC5C6
C5C6C7
C6C7C8
120(2)
C6C7C15
C8C7C15
C7C8C8a
O1C8aC4a
O1C8aC8
C4aC8aC8
C4C9C10
C4C9C14
C10C9C14
C9C10C11
122.1(3)
107.4(1)
103.0(1)
109.6(1)
115.7(1)
111.0(1)
124.4(2)
119(2)
120.2(3)
120.6(3)
119.2(3)
122.2(3)
121.9(3)
115.9(2)
122.3(3)
121.0(3)
116.9(3)
121.0(3)
121.6(3)
121.2(2)
116.6(3)
122.2(3)
121.3(3)
120.8(3)
117.9(3)
121.1(4)
124.1(2)
116(2)
Bond
d
Bond
d
Bond
d
Cl1 C6
P2 O1
P2 O2
P2 O3
P2 C3
O1 C8a
O3 H31
C3 C4
1.736(4)
C3 H3
C4 C4a
C4 C9
C4a C5
C4a C8a
C5 C6
C6 C7
C7 C8
0.83(2)
C7 C15
C8 C8a
C9 C10
C9 C14
C10 C11
C11 C12
C12 C13
C13 C14
1.514(4)
1.591(2)
1.461(2)
1.525(2)
1.736(3)
1.396(4)
0.64(2)
1.475(4)
1.491(4)
1.382(5)
1.387(4)
1.377(4)
1.393(4)
1.372(5)
1.375(4)
1.346(5)
1.370(5)
1.382(5)
1.331(6)
1.346(5)
1.398(5)
1.334(5)
Angle
Angle
Angle
O2P2O1C8a
O3P2O1C8a
C3P2O1C8a
O1P2O3H31
O2P2O3H31
C3P2O3H31
O1P2C3C4
149.5(2)
O1P2C3H3
O2P2C3C4
O2P2C3H3
O3P2C3C4
O3P2C3H3
P2O1C8aC4a
P2C3C4C9
166(2)
133.1(3)
46(2)
101.1(3)
80(2)
P2O1C8aC8
P2C3C4C4a
C3C4C4aC8a
C3C4C9C10
C3C4C9C14
C4aC4C9C10
C4aC4C9C14
158.7(2)
91.4(2)
25.8(3)
56(2)
175(2)
55(2)
2.4(4)
10.5(5)
65.3(5)
115.0(4)
112.9(4)
66.8(4)
22.4(4)
179.5(2)
13.5(3)
noticeable downfield shift of the C8a signal (
1.0
ca.
2-oxide (XI), and 2-bromo-6-(bromomethyl)-4-phe-
nylbenzo[e][1,2 ]oxaphosphorine 2-oxide (XII) in an
88:45:22:9 ratio.
C
5
1.2 ppm) and an upfield shift of the C6 atom (
2 ppm) are observed. It is interesting to note thaCt the
acids themselves can form sodium salts on treatment
with aqueous sodium hydrocarbonate. For example,
benzophosphorine Vb was treated with aqueous
sodium hydrocarbonate to obtain, after crystallization
from water, sodium 6-chloro-7-methyl-4-(4-methyl-
phenyl)-2-oxobenzo[e][1,2 5]oxaphosphorin-2-olate
VIIId.
Figure 5 shows the upfield and downfield frag-
ments of the 13C {1H} NMR spectrum of the reaction
mixture of tribromophosphorane III with phenylace-
tylene, obtained after removal of volatile admixtures
in a vacuum. The signals of all the four compounds
are well resolved, have different intensities, and do
not overlap, which allows one to interpret the 13C
NMR spectra in sufficient detail and to make con-
clusions about the structure of the compounds. The
major reaction products, compounds IX and X,
Tribromophosphorane III reacts with phenylace-
tylene not so unambiguously as chlorine-containing
derivative II. The reaction yields a mixture of 2-
bromo-7-methyl-4-phenylbenzo[e][1,2 5]oxaphos-
phorine 2-oxide (IX), 2,6-dibromo-7-methyl-4-phenyl-
gradually crystallize from chloroform in a 2:3 ratio.
1
According to the H NMR (see Experimental) and 13
C
NMR (Table 2) spectral data, they can be considered
as 7-methyl-substituted benzophosphorines, one of
which contains a bromine atom in the phenylene
5
benzo[e][1,2 ]oxophosphorine 2-oxide (X), 2-bromo-
6-methyl-4-phenylbenzo[e][1,2 5]oxaphosphorine
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

REACTION OF (PHENYLENEDIOXY)TRIHALOPHOSPHORANES WITH ARYLACETYLENES: VI.
1851
C10
C11
C3
C5
C4a
C6
C8
129
127
125
123
121
119
117
C, ppm
13
1
Fig. 3. Fragment of the C { H} NMR spectrum of benzophosphorine VIIb.
C11
C10
C3
C12
C5
C4a
C8
C6
128
127
126
125
124
123
122 C, ppm
13
1
Fig. 4. Fragment of the C { H} NMR spectrum of salt VIIIa.
1
3
fragment, probably in the 6 position of the benzo-
phosphorine system. The signal of the carbon atom
bound with bromine appears in an upfield region (due
to the shielding heavy atom effect and the para effect
of oxygen), and has a multiplicity characteristic of the
proposed surrounding (Table 1). Further evidence for
the 6 position of the bromine atom comes from the
multiplicity of the C8 and C4a signals that correspon-
dingly contain a smaller number of lines. Note that
the direct JPC constants of bromophosphorines IX
XII are invariably lower by 12.5 Hz than those of
chlorophosphorines IV, whereas the JHC constants
of these two groups of compounds are equal to each
other, which agrees with the results in [2].
1
3
Analysis of the 1H and 13C NMR spectra shows that
the two minor benzophosphorines are 6-methyl- and
6-bromomethyl-substituted derivatives XI and XII.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

1852
MIRONOV et al.
Me
Br
O
Br
Me
O
Br
O
O
O
PhC CH
P
P
+
PBr3
PhCBr=CH2,
PhCBr=CHBr
O
Ph
Ph
III
IX
X
O
Br
O
Br
O
O
P
P
+
+
Me
BrCH2
Ph
Ph
XI
XII
This conclusion was based primarily of the multipli-
cities of the C8 signals (d.d) split by coupling with
H8 (1JHC) and phosphorus (2JPOCC) and appearing in
characteristic upfield regions (Fig. 5). If there would
be no substituent in the 6 position, the C8 signal
would has been additionally split into a doublet by
coupling with H6, as it is observed for compound IX.
The bromomethyl group in benzophosphorine XII
gives a characteristic upfield triplet of triplets
(31.65 ppm).
Hydrolysis of the mixture of compounds IX and
X gives hydroxyphosphorines XIII and XIV which
crystallize as a 1:4 mixture from dioxane and cannot
1
be separated by recrystallization. The H NMR spec-
trum of this mixture (250 MHz, DMSO-d6) contains
two doublets near 6.16 (2JPCH 17.8 Hz) and 6.28 ppm
(2JPCH 17.8 Hz), characteristic of the P CH=C proton.
Treatment of the mixture of benzophosphorines IX
and X with tert-butylamine gave a 2:3 mixture of tert-
IX
IX
C8a
X
C8a
C8
XI
XII
C8a
C8a
148
147
146
145.2 C, ppm
X
IX
IX
C3
X
XI
X
C8
XI
C3
XII
C4a
XII
X
XI
C6
C3 XII
C8
C4a
C4a
C8
C6
C4a
122
120
119
118
117
116
115
C, ppm
13
1
Fig. 5. Fragments of the C { H} NMR spectrum of the reaction mixture of tribromobenzophosphole III with phenylacetylene
after removal of volatile admixtures.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

REACTION OF (PHENYLENEDIOXY)TRIHALOPHOSPHORANES WITH ARYLACETYLENES: VI.
1853
Me
Br
O
OH
Me
O
OH
O
O
P
H2O
HBr
P
+
Ph
Ph
IX, X
XIII
XIV
Me
O
NH
O
Me
O
NH
O
P
P
+
H2NCMe3, NEt3
Et3N HCl
Br
Ph
XVI
Ph
XV
butylamides XV and XVI, obtained as a crystalline
The heterocyclic skeleton in benzophosphorine
XVI contains two planar fragments, O1C8aC4aC4 and
C4aC4C3P2, which form a dihedral angle of 9.90(8)
with each other. The C3 and P2 atoms deviate from
precipitate. The structure of the products was con-
1
firmed by H, 31P, and 13C NMR spectroscopy (see
Experimental and Table 1). Unlike acids XIII and
XIV, the mixture of amides XV and XVI could be
separated by recrystallization to isolate the major
product, benzophosphorine XVI. Its structure was
confirmed by X-ray diffraction. Table 6 lists the
atomic coordinates in molecule XVI and Table 7, its
selected geometric parameters (bond lengths and bond
and torsion angles). Figure 6 presents a general view
of molecule XVI in crystal.
the O1C8aC4aC4 plane by 0.150(9) and 0.458(2)
,
that is to the same side of it. From the other planar
fragment C4aC4C3P2, the heteroring O1 and C8a
deviate by 0.4353 and 0.2681 , respectively, that
is to the same side but by different distances. These
data suggest that here, too, the phosphorine heteroring
has a distorted boat conformation. The O2 and N2
atoms of the exocyclic substituents deviate from the
Table 6. Atomic coordinates in molecule XVI, equivalent isotropic thermal parameters of non-hydrogen atoms B =
3
3
2
4/3
(aiaj)B(i, j) ( 2) and thermal parameters of hydrogen atoms Biso
(
)
i=1 j=1
Atom
x
y
z
B or Biso
Atom
x
y
z
B or Biso
Br6
P2
0.0291(3)
0.3768(4)
0.4177(9)
0.3410(9)
1.0253(2) 0.8020(3)
0.2404(3) 0.8944(3)
0.3843(8) 0.8669(9)
0.1658(8) 1.0473(8)
0.1015(11) C18
0.0198(10) C19
0.580(2)
0.547(2)
0.57230
0.19259
0.00801
0.45338
0.05932
0.14984
0.30126
0.27934
0.07592
0.42227
0.25339
0.33019
0.79483
0.81323
0.82171
0.47360
0.63302
0.61525
0.44036
0.56611
0.59728
0.3140(18) 0.5708(17) 0.069(7)
0.5769(18) 0.083(9)
0.086(2)
0.03975
0.24616
0.75407
0.59395
0.67808
0.74328
0.61698
0.42260
0.36276
0.83489
0.93001
0.96325
0.02602
0.12225
0.08196
0.36446
0.31893
0.36041
0.13827
0.01708
0.09684
O1
0.021(3)
0.027(2)
H2
0.86111
0.80132
0.80568
0.88681
0.57998
0.49967
0.59231
0.79307
0.88065
0.89396
0.95834
0.79358
0.66888
0.65665
0.52035
0.58269
0.47104
0.61035
0.59221
0.61974
0.47638
0.01(2)
0.04(4)
0.0311
0.0311
0.0305
0.0413
0.0358
0.0447
0.0303
0.0847
0.0847
0.0847
0.1212
0.1212
0.1212
0.1040
0.1040
0.1040
0.1242
0.1242
0.1242
O2
H3
N2
0.5280(11) 0.1313(10) 0.7999(10) 0.027(2)
0.2224(12) 0.3139(12) 0.8228(13) 0.022(4)
0.1442(13) 0.4629(12) 0.7951(11) 0.019(4)
0.1823(13) 0.5692(12) 0.8232(11) 0.018(3)
0.0874(14) 0.7220(12) 0.8175(13) 0.026(3)
0.1366(18) 0.8227(14) 0.8295(14) 0.042(5)
0.2738(14) 0.7816(12) 0.8594(12) 0.019(4)
0.3606(15) 0.6284(12) 0.8687(13) 0.026(3)
0.3183(13) 0.5311(12) 0.8534(11) 0.018(3)
0.0076(14) 0.5093(15) 0.7444(14) 0.030(3)
0.0084(15) 0.6275(12) 0.6241(12) 0.026(4)
0.1328(17) 0.6636(14) 0.5756(14) 0.034(5)
0.2240(14) 0.5907(16) 0.6322(14) 0.030(3)
0.2120(14) 0.4736(17) 0.7510(14) 0.038(5)
0.0891(14) 0.4395(14) 0.8017(13) 0.026(4)
H5
C3
H8
C4
H10
H11
H12
H13
H14
H15a
H15b
H15c
H17a
H17b
H17c
H18a
H18b
H18c
H19a
H19b
H19c
C4a
C5
C6
C7
C8
C8a
C9
C10
C11
C12
C13
C14
C15
C16
C17
0.324(2)
0.6102(14) 0.1529(12) 0.6470(12) 0.025(4)
0.774(2) 0.076(2) 0.621(2) 0.081(7)
0.8866(16) 0.8779(18) 0.056(6)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

1854
MIRONOV et al.
C13
O2
H3
C14
C3
C12
C4
P2
C11
H2
N2
C4a
C8a
C19
C17
C5
C6
C16
Br6
C7
C18
C8
C15
Fig. 6. Molecular geometry of compound XVI in crystal and scheme of dimer formation by intermolecular N H O hydrogen
bonds (shown by dashed lines).
O1C8aC4aC4 plane by 1.854(6) and 0.586(6) and
from the C4aC4C3P2 plane by 1.317(6) and
1.202(6) , respectively. It is readily seen from these
deviations that the tert-butylamino group is equatorial,
while the phosphoryl group is axial. Previously we
studied the structure of an analogous compound,
6-chloro-2-morpholino-4-phenylbenzo[e][1,2 5]oxa-
phosphorine 2-oxide (XVII) [3], in which the mor-
pholine substituent is also equatorial. The principal
geometric parameters of molecules XVI and XVII are
similar, except for the P2=O2 bond that is slightly
longer in XVI [1.485(6) ] compared with XVII
[1.43(1) ]. This difference may be explained by the
involvement of the phosphoryl group of compound
Table 7. Selected bond angles
(deg), bond lengths d ( ), and torsion angles
(deg) in molecule XVI
Angle
Angle
Angle
O1P2O2
O1P2N2
O1P2C3
O2P2N2
O2P2C3
N2P2C3
P2O1C8a
P2N2C16
P2N2H2
113.1(5)
C16N2H2
P2C3C4
117.4(5)
121(1)
119.4
N2C16C17
N2C16C18
N2C16C19
C17C16C18
C17C16C19
Br6C6C5
112(1)
114(1)
105(1)
109(1)
110(1)
123(1)
114(1)
120(1)
116(1)
104.1(6)
102.5(5)
110.9(5)
113.4(6)
112.2(6)
126.1(9)
132.0(8)
110.8(8)
P2C3H3
C4C3H3
119.1
C3C4C4a
C4C4aC5
C4C4aC8a
C5C4aC8a
C4aC5C6
122(1)
123(1)
122(1)
115(1)
120(1)
Br6C6C7
O1C8aC4a
O1C8aC8
Bond
d
Bond
d
Bond
d
Br6 C6
P2 O1
P2 O2
P2 N2
P2 C3
O1 C8a
N2 C16
N2 H2
C3 C4
1.85(1)
1.609(9)
1.487(8)
1.63(1)
1.77(1)
1.39(1)
1.47(1)
0.9681
1.36(2)
C3 H3
C4 C4a
C4 C9
C4a C5
C4a C8a
C5 C6
C6 C7
C7 C8
C7 C15
0.98
1.45(2)
C8 C8a
C9 C10
C9 C14
C10 C11
C11 C12
C12 C13
C13 C14
C16 C17
C16 C18
1.32(2)
1.42(2)
1.31(2)
1.41(2)
1.29(2)
1.40(2)
1.41(2)
1.46(3)
1.52(2)
1.51(2)
1.43(2)
1.41(2)
1.39(2)
1.41(3)
1.42(2)
1.47(2)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

REACTION OF (PHENYLENEDIOXY)TRIHALOPHOSPHORANES WITH ARYLACETYLENES: VI.
1855
Table 7. (Contd.)
Angle
Angle
Angle
O2P2O1C8a
N2P2O1C8a
C3P2O1C8a
O1P2N2C16
O2P2N2C16
O2P2N2H2
C3P2N2C16
C3P2N2H2
O1P2C3C4
O1P2C3H3
97(1)
142.8(9)
26(1)
57(1)
179(1)
4
53(1)
132
16(1)
O2P2C3C4
106(1)
75
H2N2C16C18
H2N2C16C19
P2C3C4C4a
P2C3C4C9
154
90
0(2)
175.6(9)
13(2)
172(1)
133(1)
42.8(2)
52(2)
O2P2C3H3
N2P2C3C4
127(1)
52.4(9)
18(1)
162.8(9)
145(1)
20(2)
96(1)
29
N2P2C3H3
P2O1C8aC4a
P2O1C8aC8
P2N2C16C17
P2N2C16C18
P2N2C16C19
H2N2C16C17
C3C4C4aC8a
C9C4C4aC8a
C3C4C9C10
C3C4C9C14
C4aC4C9C10
C4aC4C9C14
163
132(1)
XVI in an intermolecular hydrogen bond N H O2
(Fig. 6). The plane of the 4-Ph substituent forms a
fairly large torsion angle with the plane of the C3=C4
bond [ 45(1) ], which makes conjugation between
them hardly possible. The phosphoryl group and the
N2 C16 bond are trans to each other [the O2P2N2C16
torsion angle is 180.0(1) ], which is the most fa-
vorable for the bulky tert-butyl substituent. The sum
of bond angles at the nitrogen atom (P2N2C16, P2N2H2,
and H2N2C16) is 359.8(3) , what means that this atom
has a planar trigonal configuiration.
meric systems. In the latter case, such separation gives
rise to lamellar structures whose type differs from the
type of the supramolecular structure formed by inter-
molecular interactions (3D net). Contrary to that, in
the crystal of compound Vc the type of the supra-
molecular structure formed intermolecular hydrogen
bonds (infinite chain of molecules) coincides by its
morphologic type with superstuctures formed as a
result of separation of hydrophilic and hydrophobic
regions, even though the crystal packing here is not
very tight (65.8%). These regions represent cylindrical
hydrophilic associates in a hydrophobic matrix
(Fig. 8). A more detailed analysis of this effect and
classification of the resulting structures for condensed
phosphorus-containing heterocycles will be given
elsewhere.
Intermolecular interactions in the crystal of com-
pound XVI are more diverse than in the above-
described crystal of compound Vc. The interaction of
the H2 atom of the amino group with the O2 atom
(1 x, y, 2 z) of the phosphoryl group [d(H2 O2 )
1.95(2) , N2H2 O2 angle 188(1) ] forms molecular
dimers (Fig. 6). The participation of bromine atoms
in C H Br contacts [d(Br6 H17B ) 2.79(2) , Br6
H17B C6 angle 115(1) ] results in binding of the
molecular dimers in two perpendicular directions to
form a lamellar supramolecular structure (Fig. 7a).
Such lamellar super structures are bound to each other
EXPERIMENTAL
The H, 13C, 13C {1H}, 31P, and 31P {1H} NMR
1
spectra were recorded on Bruker WM-250 (250 MHz,
1H), Bruker MSL-400 (162.0 MHz, 31P; 100.6 MHz,
13C), and Bruker CXP-100 (36.48 MHz, 31P) spec-
trometers in DMSO-d6 and CDCl3 against of residual
proton signals or carbon signals of solvents or against
external H3PO4. All the spectra were recorded at 25 C,
unless otherwise stated. The IR spectra were obtained
for suspensions in Vaseline on UR-20 and Bruker
Vector-22 instruments. The electron impact mass
spectra were measured on a Finnigan-MAT TRACE
MS instrument at an ionizing energy of 70 eV and an
ion source temperature of 200 C. Direct inlet of
samples into the ion source was used, the inlet probe
was programmed from 35 to 150 C with a step of
35 deg/min. The mass spectral data were treated by
means of the XCALIBUR program.
by
interactions of the phenyl rings of mole-
cules relates to each other as x, 1 y, 1 z, with the
distance between the ring centers of 3.91
dihedral angle of 0 .
and the
Inspite of the presence of the bulky tert-butyl
substituents, a fairly tight crystal packing of mole-
cules XVI is achieved (packing coefficient 69.1%)
(Fig. 7b). Note that in this crystal there are
separate regions with mainly hydrophilic and mainly
hydrophobic properties. Previously we showed [3]
that molecular associates formed due to this effect can
be of different type depending on the relative
volumes of the hydrophilic and hydrophobic parts of
the molecules, like microphase separation in poly-
Conditions of the X-ray diffraction experiments
are listed in Table 8.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

1856
MIRONOV et al.
(a)
O2
Br6
H2
O1 N2
H17B
(b)
Fig. 7. (a) Formation of lamellar structures by intermolecular contacts in the crystal of compound XVI (shown by dashed
lines) and (b) crystal packing.
yield 20.2 g (49.6%). 13C NMR spectrum (CDCl3),
,
C
ppm (J, Hz) (parenthesized are signal shapes in the
13C {1H} NMR spectrum): 142.84 d.d.d (d) (C3a,
3
2
2
7
3a
4
3a
3a
JHC CC 7.1, JHC C 3.6, JPOC 0.8); 111.32 d.d.q.d.
(d) (C4, JPOCCC 17.6, JHC CC 7.7, JHCCC 5.1,
3
3
3
4
6
4
4
4
4
3
3
JHC CCC 1.4); 133.81 d.q. (s) (C5, JHHC CC 7.8,
7
4
6
5
JHCCC 6.1); 123.51 d.d.q.d. (s) (C6, JHC 161.4,
1
6
3
2
4
6
6
7 6
JHC CC 7.0, JHCCC 5.1, JHC C 1.1); 110.43 d.d. (d)
(C7, JHC 166.7, JPOCC 17.7); 140.40 m (d) (C7a,
1
3
7
7
2
1
JPOC 0.8); 21.21 q.d.d. (d) CH3, JHC 127.2, 3JHO CC
7a
4
4.7, JHCO CC 4.7). 31P {1H} NMR spectrum
3
6
(36.48 MHz, CH2Cl2):
27.26 ppm.
Fig. 8. Crystal packing of molecules Vc.
P
2,2,2-Tribromo-5-methylbenzo[d][1,3,2]dioxa-
phosphole (III). a. A mixture of 20 g of 4-methyl-
benzene-1,2-diol, 17.5 ml of PBr3, and 5 6 drops of
water was heated with stirring over the course of 30
40 min at 90 C. Strong HBr evolution was observed.
Vacuum distillation gave 30.44 g (81%) of compound
III as a colorless liquid with bp 70 75 C (0.8 mm
2,2,2-Trichloro-5-methylbenzo[d][1,3,2]dioxa-
phosphole (II). To a solution of 39.4 g of PCl5 in
143.7 ml of benzene, 19.47 g of a crystalline 4-me-
thylbenzene-1,2-diol was added in portions with
stirring. Strong foaming and HCl evolution were ob-
served. Benzene was distilled off, and the residue was
distilled in a vacuum. The major fraction of phos-
phorane II, a yellow liquid crystallizing at room
temperature, was collected at 95 100 C (0.8 mm Hg),
Hg). 31P {1H} NMR spectrum (CH2Cl2):
P
189.0 ppm.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

REACTION OF (PHENYLENEDIOXY)TRIHALOPHOSPHORANES WITH ARYLACETYLENES: VI.
1857
Table 8. Crystal parameters of compounds IVa, Vc, and XVI and conditions of X-ray diffraction experimentsa
Parameter
IVab
Vcb
XVIc
Color, habitus
Syngony
Colorless, prysmatic
Triclinic
Space group
P-1
Unit cell parametersd
a 8.011(1), b 9.122(2) a 4.642(1), b 12.546(4) a 10.253(2), b 10.236(2)
c 9.342(1) c 13.334(3) c 10.399(5)
77.7(6) 73.10(3) 70.1(4) 66.4(6) 83.02(2) 67.04(1)
69.9(6)
701.9(3)
2
83.56(2)
747(1)
2
64.05(1)
844.5(2)
2
3
V,
Z
Molecular weight
dcalc, g cm
Absorption coefficient, cm
F(000)
325.13
320.72
1.426
3.643
332
403.24
1.514
23.986
410
3
1.538
5.709
332
1
Radiation ( ,
range
)
MoK ,
2.12 <
0.71073
< 27.4
Scan angle
Standard reflections
Index range
0.68+ 0.4tan
Two control by orientation and three control by intensity every 200 reflections
9 < h < 8,
10 < k < 9,
10 < l < 0
1866
5 < h < 0,
13 < k < 12,
13 < l < 13
1904
12 < h < 11,
12 < k < 11,
12 < l < 9
4911
1211
Reflections measured
Number of observed reflections with
I > 3 (I)
1436
1428
Absorption corrections
Location and and refinement of
hydrogen atoms
Not used
Empirical
Located by difference synthesis, refined isotropically
Final values of divergence factors
Fitting parameter
/
Number of refined parameters
Number of unique reflections
R 0.031, RW 0.037
R 0.035, RW 0.048
R 0.0979, RW 0.2212
1.363
0.00
225
1.732
0.01
246
1.176
0.006
196
1433
1496
2870
a
1
Enraft Nonius CAD-4 diffractometer; /2 scanning, scan rate 1 16.4 deg min by ; no correction for the intensity decay of
b
control reflections was applied; MolEN program, AlphaStation 200 computer [8]. Direct method of structure solution, SIR
2
program [9]; full-matrix least-squares refinement; minimized function w( Fo
Fc ) ; no extinction correction was applied;
2
2
2 2
weight scheme 4F /[ (I) + (0.04F )] . Analysis of intermolecular contacts, including hydrogen bonds in crystals, was carried out
by the PLATON program [7]. Direct method of structure solution, SIR program [9]; refinement by the SHELX program [10].
0
0
c
d
Standard deviations are given in parentheses.
b. To a solution of 11 g of 2-bromo-5-methylben-
wise at 10 15 C under argon. The reaction mixture
was left to stand for a day. Therewith, crystals of 2,6-
dichloro-7-methyl-4-phenylbenzo[e][1,2 5]oxaphos-
phorine 2-oxide (IVa) (yield 70%) formed. The
residual solution was carefully decanted, and the
crystals were washed with cold ( 30 C) methylene
chloride and dried in a vacuum (0.8 mm Hg), mp
140 145 C. 31P NMR spectrum (162.0 MHz, CH2Cl2),
P, ppm: 17.4 d.d (2JPCH 26.3 Hz). Found, %: C 55.73;
H 3.92; P 9.11. C15H11Cl2O2P. Calculated, %: C
55.38; H 3.78;P 8.88. The solvent, excess phenylace-
tylene, and chlorostyrenes were removed in a vacuum,
zo[d][1,3,2]dioxaphosphole in 20 ml of CH2Cl2, 2.4
ml of bromine was added dropwise with stirring under
argon. Phosphorane III was quantitatively formed. It
was further used without isolation as a solution in
methylene chloride. 31P {1H} NMR spectrum
(36.48 MHz, CH2Cl3):
190 ppm.
P
Reaction of phosphole II with phenylacetylene.
To a solution of 7.9 g of phosphorane II in 5 ml of
methylene chloride, a solution of 6.2 g of phenylace-
tylene in 2 ml of methylene chloride was added drop-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

1858
MIRONOV et al.
and the residue was hydrolyzed in acetone to obtain
crystals of 6-chloro-2-hydroxy-7-methyl4-phenyl-6-
C15H11Cl2O3P. Calculated, %: C 52.79; H 3.23; Cl
20.82.
5
benzo[e][1,2 ]oxaphosphorine 2-oxide (Va), yield
Reaction of phosphorane II with 4-methylphe-
nylacetylene was carried out by the above procedure
using 8.1 g of phosphorane II in 6 ml of methylene
chloride and 6.55 g of 4-methylphenylacetylene in
4 ml of methylene chloride. The reaction mixture was
kept in a vacuum (0.8 mm Hg) to remove the solvent,
excess acetylene, and chlorostyrene. The resulting
viscous glassy material containing, according to the
31P NMR spectrum (162.0 MHz, CH2Cl3), 77% of
1
2.45 g, mp 235 240 C. IR spectrum, , cm : 416,
485, 462, 541, 595, 675, 698, 729, 758, 813, 834, 876,
882, 1012, 1036, 1074, 1129, 1167, 1193, 1207,
1248 sh., 1255, 1338, 1377, 1443, 14.84, 1594, 1600,
1
2298 v.br (P OH), 2551 v.br, 3060. H NMR spec-
trum (250 MHz, DMSO-d6, 40 C), , ppm (J, Hz):
2
2.36 s (CH3, 3H), 6.31 d (H3, 1H, JPCH 17.5); 7.00 s
(H8, 1H), 7.34 s (H5, 1H), 7.38 m and 7.52 m (C6H5,
5H). 31P NMR spectrum (163.0 MHz, DMSO-d6),
,
P
2,6-dichloro-7-methyl-4-(4-methylphenyl)-benzo[e]-
ppm: 3.7 d (2JPCH 17.5 Hz). Found, %: C 58.95; H
3.78, P 9.88. C15H12ClO3P. Calculated, %: C 58.73;
H 3.92; P 10.11.
5
[1,2 ]oxaphosphorine 2-oxide (IVc) ( 17.4 ppm,
P
2JPCH 24.6 Hz) was dissolved in 50 ml of dioxane and
hydrolyzed with excess water. After 1 2 h, a preci-
pitate formed and was filtered off, washed with ether,
and dried to give 5.49 g (55%) of 6-chloro-2-hydroxy-
Reaction of trichlorophosphole II with 4-chloro-
phenylacetylene. To a solution of 11.3 g of phos-
phorane II in 10 ml of methylene chloride, 9.0 g of
4-chlorophenylacetylene in 10 ml of methylene chlo-
ride was gradually added under argon at 10 15 C.
After 2 h, the solvent and chlorostyrene were removed
from the reaction mixture in a vacuum, and the re-
sidue was crystallized from CCl4 to isolate 7.6 g
(49%) of 2,6-dichloro-4-(4-chlorophenyl)-7-methyl-
5
7-methyl-4-(4-methylphenyl)benzo[e][1,2 ]oxaphos-
phorine 2-oxide (Vc), mp 245 247 C. IR spectrum,
1
, cm : 445, 461, 515, 525, 545, 579, 638, 667, 736,
746, 800, 820, 847, 883, 922, 1010, 1036, 1129, 1166,
1191, 1203, 1215, 1242, 1255, 1337, 1510, 1541,
1594, 1613, 2324 2300 v.br (P OH), 2588 2520 v.br
1
(P OH). H NMR spectrum (250 MHz, DMSO-d6,
50 C) , ppm (J, Hz): 2.48 s and 2.50 s (CH3, 6H),
5
benzo[e][1,2 ]oxaphosphorine 2-oxide (IVb), mp
2
6.34 d (H3, 1H, JPCH 17.7), 7.15 s and 7.38 s (H5 and
145 147 C. 31P NMR spectrum (162.0 MHz, CDCl3),
H8, 2H), 7.39 7.42 m (H10, H11, 4H, AA BB spectrum,
1
P, ppm: 16.2 d (2JPCH 23.6 Hz). H NMR spectrum
3
3JAB = JA B 8.2). 31P NMR spectrum (162.0 MHz,
(250 MHz, CDCl3), , ppm (J, Hz): 2.44 s (CH3, 3H),
DMF), P, ppm: 3.4 d (2JPCH 17.7 Hz). Found, %:
C 58.54; H 4.33; P 9.87. C16H14ClO3P. Calculated,
%: C 59.91; H 4.37; P 9.67.
2
6.28 d (H3, 1H, JPCH 26.3), 7.15 s (H8, 1H), 7.21 s
(H5, 1H), 7.31 m and 7.48 m (H10, H11, 4H, AA BB
3
3
spectrum, JAB = JA B 8.7). Mass spectrum, m/z (Irel
,
2,6-Dichloro-4-(4-chlorophenyl)-2-(isopropyl-
amino)-7-methylbenzo[e][1,2]oxaphosphorine
(VIIb). A mixture of 2.8 g of phosphonic acid Vb and
2.6 g of phosphorus pentachloride suspended in 12 ml
of benzene was heated for 3 h at 80 C. The solvent
and phosphorus oxychloride were then removed by
distillation, and the solid residue was diluted with 30
ml of benzene. The resulting solution was treated with
excess isopropylamine (1.6 ml) and kept for 1 2 h at
20 C. A precipitate formed and was filtered off, the
filtrate was washed with 10% sodium carbonate and
water and dried over sodium sulfate. After 7 9 days,
a white precipitate formed and was filtered off,
washed with diethyl ether and dried in a vacuum
(12 mm Hg) to give 2.79 g (89%) of oxaphosphorine
%) (peaks of ions containing the most abundant iso-
tope are given): 363 (1.6), 362 (7.8), 3.61 (4.4), 3.60
(24.0), 361 (5.9), 358 (24.9) [M+ ]; 323 (43.1), 287
(34.9), 241 (41.1), 176 (100.0), 105 (44.4), 77 (51.8),]
47 (69.2), 36 (37.8), 35 (10.7). The filtrate containing
about 7 g of chlorophosphorine IVb was hydrolyzed
with excess of water in dioxane (20 ml). A precipitate
formed after two days and was washed with ether and
dried to give 4.0 g (60.2%) of 6-chloro-4-(4-chloro-
5
phenyl)-2-hydroxy-7-methylbenzo[e][1,2 ]oxaphos-
phorine 2-oxide (Vb), mp 238 242 C. IR
1
spectrum, , cm : 414, 451, 519, 543, 565, 617, 714,
737, 804, 824, 849, 871, 887, 923, 1015, 1037, 1093,
1129, 1166, 1182, 1250 1253, 1337, 1398, 1482,
1510, 1600, 2284 2254 v.br, 2600 2500 v.br, 3678,
3843. 1H NMR spectrum (250 MHz, DMSO-d6,
1
VIIb, mp 184 165 C. IR spectrum, , cm : 447, 471,
524, 578, 614, 675, 710, 735, 754, 807, 846, 869, 917,
1016, 1037, 1072, 1093, 1130, 1166, 1213, 1235,
50 C), , ppm (J, Hz):
2.37 s (CH3, 3H),
2
6.31 d (H3, 1H, JPCH 17.6), 7.00 s (H8, 1H), 7.32 s
1
1336, 1399, 1442, 1535, 1562, 1597, 3178. H NMR
(H5, 1H), 7.41 m and 7.57 m (H10, H11, 4H, AA BB
spectrum (250 MHz, DMSO-d6, 40 C), , ppm (J, Hz):
3
spectrum, JAB
=
3JA B 8.7). 31P NMR spectrum
3
1.11 d and 1.17 d [6H, (CH3)2, JHCCH 6.5], 2.38 s
(162.0 MHz, DMSO-d6), P, ppm: 3.2 d (2JPCH
(3H, CH3), 3.32 m (1H, CH), 5.43 d.d (1H, NH,
7.0 Hz). Found, %: C 52.84; H 2.97; Cl 20.47.
2JHNH 10.4, 3JHCNH 10.4), 6.21 d (1H, H3, 2JPCH 17.2),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

REACTION OF (PHENYLENEDIOXY)TRIHALOPHOSPHORANES WITH ARYLACETYLENES: VI.
1859
3
7.02 s (1H, H8), 7.35 s (1H, H5), 7.43 m and 7.59 m
3.89 m (4H, OCH2, JHCCH 4.7), 6.10 d (1H, H3,
(4H, H10, H11, AA BB spectrum, JAB = JA B 8.5). 31P
2JPCH 16.5) 6.88 s and 7.09 s (2H, H5 and H8), 7.31 m
3
3
NMR spectrum (162.2 MHz, DMSO-d6), P, ppm:
and 7.46 m (5H, C6H5, 5H). 31P {1H} NMR spectrum
9.7 d.d (2JPCH 17.2, JPNCH 10.4 Hz). Found, %: C
(162.0 MHz, DMF):
1.0 ppm. 31P NMR spectrum
P
3
56.59; H 4.58; N 3.86. C18H18Cl2NO2P. Calculated,
%: C 56.54; H 4.71; N 3.66.
(162.0 MHz, DMSO-d6), P, ppm: 1.7 d (2JPCH
16.5 Hz). Found,%: C 57.47; H 5.44; Cl 9.28; N 3.51;
P 7.74. C19H21ClNO4P. Calculated,%: C 57.94, H
5.34, Cl 9.02, N 3.56, P 7.88.
6-Chloro-2-(isopropylamino)-7-methyl-4-(4-
methylphenyl)benzo[e][1,2 5]oxaphosphorine
2-oxide (VIIc). A mixture of 3.1 g of phosphonic acid
Vc, 15 ml of benzene, and 3 g of phosphorus penta-
chloride was heated under reflux for 3 h until the
precipitate of compound Vc dissolved completely.
The reaction mixture was kept in a vacuum to remove
volatile admixtures, and the solid residue was dis-
solved in 20 of benzene, treated with 1.8 ml of iso-
propylamine, and stirred for 3 h. The precipitate was
filtered off and washed with 10% sodium carbonate
and water. During washing a white precipitate in-
soluble in water and benzene formed and was filtered
off, washed with ether, and dried in a vacuum
(12 mm Hg) to give 3.0 g (87%) of oxaphosphorine
Isopropylammonium 6-chloro-7-methyl-4-(4-
methylphenyl)-2-oxobenzo[e][1,2 ]oxaphosphorin-
5
2-olate (VIIIc). To a mixture of 1.0 g of hydroxy-
phosphorine Vc in 20 ml of anhydrous ether, 0.3 ml
of isoproipylamine was added. Phosphorine Vc dis-
solved. After 2 4 h, salt VIIIc precipitated and was
filtered off, washed with ether, and dried in a vacuum
(12 mm Hg) to give 1.0 g (85%) of ammonium salt
1
VIIIc, mp 199 C. IR spectrum, , cm : 2743, 2558,
1631, 1812, 1590, 1532, 1509, 1484, 1334, 1245,
1229, 1196, 1168, 1131, 1074, 1018, 964, 914, 894,
877, 832, 799, 732, 666, 640, 584, 546, 527, 475. 464,
1
434, 421. H NMR spectrum (250 MHz, DMSO-d6,
1
3
VIIc, mp 168 189 C. IR spectrum, , cm : 472, 525,
50 C), , ppm (J, Hz): 1.15 d [6H, (CH3)3, JHCCH
6.5], 2.31 s (3H, C7CH3, 3H) and 2.36 s (3H, C12
636, 732, 797, 811, 832, 845, 861, 916, 1020, 1070,
1130, 1165, 1217, 1235, 1337, 1443, 1509, 1535,
1567, 1589, 1610, 3185. 1H NMR spectrum
(250 MHz, DMSO-d6, 40 C), , ppm (J, Hz): 1.10 d
CH3), 5.99 d (1H, H3, JPCH 16.1), 6.68 s (1H, H8),
2
6.98 s (1H, H5), 7.18 m and 7,41 m (4H, H10, H11,
AA BB spectrum, JAB = JA B 8.3). 31P NMR spec-
trum (162.0 MHz, DMSO-d6), P, ppm: 1.4 d (2JPCH
16.2 Hz). Found, %: C 60.12; H 6.21; N 3.77.
C19H23ClNO3P. Calculated, %: C 60.08; H 6.07; N
3.69.
3
3
3
and 1.11d [6H, (CH3)2, JHCCH 6.5], 2.38 s (3H,
2
C7CH3) and (3H, C12CH3), 5.40 d.d (1H, NH, JPNH
3
2
10.8, JHCNH 9.7), 6.12 d (1H, H3, JOCH 17.8), 7.07 s
(1H, H5), 7.31 m (4H, H10, H11, AA BB spectrum,
3JAB = JA B = 8.3). 31P NMR spectrum (162 MHz,
3
DMSO-d6), P, ppm: 10.1 d.d (2JPCH 17.7, JPNH
2
Sodium 6-chloro-7-methyl-4-(4-methylphenyl)-
2-oxobenzo[e][1,2 5]oxaphosphorin-2-olate
(VIIId). Benzophosphorine Vc, 1 g, was treated with
an excess of 10% sodium carbonate. Dissolution of
the precipitate was observed. The reaction mixture
was left to stand for 1.5 2 days. Salt VIIId precipi-
tated as fine crystals, yield 1.0 g (95%), mp > 350 C.
1H NMR spectrum (250 MHz, DMSO-d6, 50 C), ,
ppm (J, Hz): 2.29 s and 2.35 s, (6H, CH3), 5.97 d
(1H, H3, 2JPCH 16.0); 6.86 s (1H, H8), 6.96 s (1H, H5),
7.156 m (4H, H11, AA part of the AA BB spectrum,
10.8 Hz). Found, %: C 62.54; H 5.78; N 3.69.
C19H21ClNO2P. Calculated, %: C 63.07; H 5.81; N
3.87.
Morpholinium 6-chloro-7-methyl-2-oxo-4-
phenylbenzo[e][1,2 5]oxaphosphorin-2-olate
(VIIIa). To a solution of 4 g of benzophosphorine
IVa in 15 ml of methylene chloride, 1.2 g of mor-
pholine and 2 ml of triethylamine were added. After
stirring for 2 h, the reaction mixture was washed with
water, the organic layer was dried over MgSO4, and
the solvent was evaporated. The residue was treated
with ether to obtain a white precipitate that was
filtered off, dried, and crystallized from acetone to
obtain 4.2 g (87%) of benzophosphorine VIIIa, mp
3JAB = JA B 8.2, 2H), 7.246 m (4H, H10, BB part of
3
3
3
the AA BB spectrum, JAB = JA B 8.2, 2H). 31P NMR
spectrum (36.48 MHz, DMSO-d6), P, ppm: 1.0 d
(2JPCH 16.0 Hz). 31P NMR spectrum (162.0 MHz,
DMSO-d6), P, ppm: 1.4 d (2JPCH 16.2 Hz). Found,
%: C 56.12; H 3.91; P 9.11. C16H13ClNaO3P. Cal-
culated, %: C 56.06; H 3.80; P 9.05.
1
192 193 C. IR spectrum, , cm : 2720, 2651, 2559,
2467, 2348, 2293, 2238 (NH+2), 1636, 1592, 1572,
1535, 1338, 1223, 1182, 1164, 1130, 1106, 1073,
1045, 1019, 984, 922, 912, 874, 835, 804, 755, 728,
700, 677, 655, 600, 539, 517, 475, 456, 427. 1H NMR
spectrum (250 MHz, DMSO-d6, 50 C), , ppm (J, Hz):
Reaction of tribromophosphorane III with
phenylacetylene. To 18.5 g of a freshly prepared tri-
bromophosphorane III in 20 ml of CH2Cl2, a solution
of 9.6 g of phenylacetylene in 10 ml of CH2Cl2 was
3
2.32 s (3H, CH3), 3.05 m (4H, NCH2, JHCCH 4.7),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

1860
MIRONOV et al.
added dropwise with stirring at 0 C. After 5 days,
methylene chloride was distilled off, and excess
acetylene and bromostyrenes were removed in a va-
cuum (0.8 mm Hg). The glassy residue was a mixture
of 2-bromo-7-methyl-4-phenylbenzo[e][1,2 5]oxa-
phosphorine 2-oxide (IX), 2,6-dibromo-7-methyl-4-
phenylbenzo[e][1,2 5]oxaphosphorine 2-oxide (X),
2-bromo-6-methyl-4-phenylbenzo[e][1,2 5]oxaphos-
phorine 2-oxide (XI), and 2-bromo-6-(bromomethyl)-
4-phenylbenzo[e][1,2 5]oxaphosphorine 2-oxide
(XII) in an 88:45:22:9 ratio. 31P {1H} NMR spec-
trum (162.0 MHz, CDCl3), P, ppm: 8.0 (IX), 6.8 (X),
7.8 (XI), and 6.6 (XII). 1H NMR spectrum (250 MHz,
CDCl3), , ppm (J, Hz): 2.39 s (CH3), 6.23 d [H3,
2-oxide precipitated and was filtered off, washed with
ether, and crystallized from dioxane. H NMR spec-
1
trum (250 MHz, DMSO-d6, 50 C), , ppm (J, Hz):
compoundXIV: 6.28 d (2JPCH 17.8), 7.17 s and 7.34 s
(H4, H8), 7.39 m and 7.52 m (C6H5), 2.39 s (CH3);
compound XIII: 6.16 d (2JPCH 17.8), 2.36 s (CH3).
31P NMR spectrum (162.0 MHz, DMSO), P, ppm:
3.2 d (2JPCH 17.8) (XIV) and 3.3 d (2JPCH 17.8) (XIII).
ACKNOWLEDGMENTS
The work was financially supported by the Russian
Foundation for Basic Research (project nos. 03-03-
06559 and 03-03-32542).
2
2JPCH 26.5 (IX)]; 2.43 s (CH3), 6.28 d [H3, JPCH 26.1
3
(X)]; 2.24 s (CH3), 6.27 d [H3, JPCH 26.3 (XI)]; 4.36
REFERENCES
2
br.s (CH2Br), 6.33 d [H2, JPCH 26.2 (XII)]. The
1. Mironov, V.F., Shtyrlina, A.A., Gubaidullin, A.T.,
Bogdanov, A.V., Litvinov, I.A., Azancheev, N.M.,
Latypov, Sh.K., Musin, R.Z., and Efremov, Yu.Ya.,
Izv. Akad. Nauk, Ser. Khim., 2004, no. 1, p. 186.
residue was treated with a little CHCl3 and kept at
0 10 C for two weeks. Crystals formed and, after
decantation of the solvent, were washed with cold
( 30 C) CCl4 and dried in a vacuum (0.8 mm Hg) to
obtain a mixture of 2-bromo-7-methyl-4-phenylbenzo-
[e][1,2-oxazaphosphorine 2-oxide IX and 2.6-dibro-
mo-7-methyl-2-oxo-4-phenylbenzo[e][1,2 5]oxaza-
phosphorine in a 2:3 ratio was obtained (1H and 31P
2. Mironov, V.F., Litvinov, A.I., Shtyrlina, A.A., Gu-
baidullin, A.T., Petrov, R.R., Konovalov, A.I., Azan-
cheev, N.M., and Musin, R.Z., Zh. Obshch. Khim.,
2000, vol. 70, no. 7, p. 1117 1132.
1
NMR data). H NMR spectrum (400 MHz, CDCl3), ,
3. Mironov, V.F., Konovalov, A.I., Litvinov, I.A., Gu-
baidullin, A.T., Petrov, R.R., Shtyrlina, A.A., Zyab-
likova, T.A., Musin, R.Z., Azancheev, N.M., and
Il’yasov, A.V., Zh. Obshch. Khim., 1998, vol. 68,
no. 9, pp. 1482 1509.
2
ppm (J, Hz): 6.26 d (H3, JPCH 28.0), 7.13 s and 7.32
3
s [H5 and H8, IX, 6.15 d [H3, JPCH 28.7 X. The
mixture of phosphorines IX and X was dissolved in
40 ml of methylene chloride and treated with excess
tert-butylamine. The reaction mixture was washed
with water, and the organic layer was evaporated to
obtain a crystalline precipitate of a mixture of 2-(tert-
butylamino)-7-methyl-4-phenylbenzo[e][1,2 5]oxa-
phosphorine 2-oxide (XV) and 6-bromo-2-(tert-butyl-
amino)-7-methyl-4-phenylbenzo[e][1,2 5]oxaphos-
phorine 2-oxide (XVI) in a 40:60 ratio. 31P {1H}
NMR spectrum (36.48 MHz, DMF): P, ppm: 9.23
(XV), 9.52 (XVI). The precipitate was subjected to
fractional crystallization from DMSO with a small
admixture of DMF to obtain 0.2 g of benzophosphorine
XVI, mp 185 186 C (from acetone). Found, %: C
56.29; H 5.51; Br 19.27; N 3.39; P 7.81. C19H21Br
NO2P. Calculated,%: C 56.18; H 5.17; Br 19.70, N
3.44; P 7.63.
4. Mironov, V.F., Petrov, R.R., Shtyrlina, A.A., Gu-
baidullin, A.T., Litvinov, I.A., Musin, R.Z., and Ko-
novalov, A.I., Zh. Obshch. Khim., 2001, vol. 71, no. 1,
pp. 74 82.
5. Mironov, V.F., Gubaidullin, A.T., Shtyrlina, A.A.,
Litvinov, I.A., Petrov, R.R., Konovalov, A.I., Zyabli-
kova, T.A., Musin, R.Z., and Varaksina, E.N., Zh.
Obshch. Khim., 2002, vol. 72, no. 11, pp. 1868 1888.
6. Kuile, L., in Advances in Mass Spectrometry, Moscow:
Inostrannaya Literatura, 1963, p. 365.
7. Spek, A.L., Acta Crystallogr., Sect. A, 1990, vol. 46,
no. 1, pp. 34 41.
8. Straver, L.H. and Schierbeek, A.J., MolEN Structure
Determination System, Nonius B.V., 1994, vols. 1
and 2.
A mixture of benzophosphorines IX and X, 3.5 g,
was dissolved in 20 ml of dioxane and treated with
0.7 ml of water. After 3-4 days, a 1:3 mixture of
2-hydroxy-7-methyl-4-phenylbenzo[e][1,2 5]oxa-
phosphorine 2-oxide (XIII) and 6-bromo-2-hydroxy-
7-methyl-4-phenylbenzo[e][1,2 5]oxaphosphorine
9. Altomare, A., Cascarano, G., Ciacovazzo, C., and Vi-
terbo, D., Acta Crystallogr., Sect. A, 1991, vol. 47,
no. 4, pp. 744 748.
10. Sheldrick, G.M., Acta Crystallogr., Sect. A, 1990,
vol. 46, pp. 467 473.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004