Regiochemistry of reaction of benzo[d]-1,3,2-dioxaphosphorin-2-ylisocyanate with ortho-halophenylcarbonyldiethylphosphonates

Full text of DOI:10.1134/S1070363212100192

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 10, pp. 1748–1750. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © L.M. Burnaeva, V.F. Mironov, A.T. Gubaidullin, G.A. Ivkova, A.B. Dobrynin, 2012, published in Zhurnal Obshchei Khimii, 2012,
Vol. 82, No. 10, pp. 1750–1752.
LETTERS
TO THE EDITOR
Regiochemistry of Reaction
of Benzo[d]-1,3,2-dioxaphosphorin-2-ylisocyanate
with ortho-Halophenylcarbonyldiethylphosphonates
L. M. Burnaevaa, V. F. Mironova,b, A. T. Gubaidullinb, G. A. Ivkovaa, and A. B. Dobryninb
a Kazan (Volga Region) Federal University, Kazan, Tatarstan, Russia
ul. Kremlevskaya 18, Kazan, Tatarstan, 142008 Russia
e-mail: liliya.burnaeva@ksu.ru, mironov@iopc.ru
bArbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received May 15, 2012
DOI: 10.1134/S1070363212100192
Functionally substituted P(III) derivatives contain-
ing an isocyanate group react readily with the activated
carbonyl compounds to give a variety of difficultly ac-
cessible P-heterocycles: spirophosphoranes [1], diaza-
diphosphetidines, 1,3,2-dioxaphosphepines [2]. Thus,
the reactions involving perfluoro-para-quinone [3] and
para-substituted arylcarbonylphosphonates [4] result
in the substituted phosphabicyclononanes containing
phosphorus–oxygen, phosphorus–nitrogen, and phos-
phorus–carbon bonds.
with the carbonyl group. The cyclization process
involving isocyanate group proceeds probably through
the formation of bipolar ions B and C owing to the
cleavage of P–O or P–C bond of oxaphosphirane inter-
mediate A. The intramolecular attack of the alkoxide
anion or carbanion intermediate results in the oxaza-
phospholines D and E that undergo intramolecular
acylation at the nitrogen atom to form the target
compounds III and IV.
The individual crystalline phosphonates IIIb and
IIIc were isolated from the mixtures of regioisomers
III and IV. Their structure was confirmed by the NMR
and XRD analysis. The conformation of six-membered
heterocycles IIIb and IIIc is a distorted boat: the
fragment conjugated with the benzene ring is planar;
the P and N atoms are deflected to one side of the
fragment by different distances. The phosphonate
substituent is axially positioned. The conformation of
the five-membered heterocycle is a twist: the C and P
atoms lie on the opposite sides of the N–C–O fragment
plane.
In this report the isocyanatophosphite I is shown to
react with ortho-bromo- and ortho-chlorophenyl-
carbonyl diethylphosphonates II to give tricyclic com-
pounds, like substituted phosphabicyclononanes III
and IV containing the P–C and P–OC bonds.
According to the 31P–{1H} NMR data, the reactions of
isocyanatophosphite Ia with ortho-chloro- and ortho-
bromophenylcarbonylphosphonates IIa and IIb as well
as the reaction of isocyanatophosphite Ib with com-
pound IIa give rise to isomeric mixtures of four
biphosphorus compounds III and IV. The spectra of
each mixture contain four doublets in the range of δР
7.8–17.3 ppm corresponding to the phosphonate
phosphorus atoms of compound III and two doublets
at δР in the range –0.6 to –1.0 and 9.7 to 11.1 ppm
corresponding to the phosphate and phosphonate
phosphorus atoms of compound IV.
9-(o-Chlorophenyl)-9-diethoxyphosphoryl-6-aza-
3,4-benzo-2,8-dioxa-1-phosphabicyclo[4.3.01.6]nonane-
1,5,7-trione (IIIa) and 8-(o-chlorophenyl)-8-di-
ethoxyphosphoryl-6-aza-3,4-benzo-2,9-dioxa-1-phos-
phabicyclo[4.3.01.6]nonane-1,5,7-trione (IVa). A mix-
ture of 6.81 g (0.03 mol) of isocyanatophosphite Ia
and 9.1 g (0.03 mol) of ortho-chlorophenylcarbonyl-
diethylphosphonate IIa was kept in a sealed tube at
120–130°C for 10 h. A thick oily substance was
Apparently, the reaction starts with the formation of
intermediate spirophosphorane A, which is a product
of the cheletropic interaction of the phosphorus atom
1748

REGIOCHEMISTRY OF REACTION
1749
R
NCO
2
O
NCO
O
O
O
O
Ar
P
O
P
O
RCAr
+
O
1
X
X
IIa, IIb
Ia, Ib
A
O
O
R14 19
A−r
O8
O
P
NCO
O−
10
N
P
O
O
+
3
O
11
12
X
O
9
P
1
4
7
O
N
Ar
5
R
R
6
X
Ar
O
13
X
O
O
O
O
D
B
IIIа−IIIc
O
O
NCO
N
P
O
O
+
HP
O
O
R
O
R
O
P
N
2
R
−
O
Ar
Ar
Ar
X
X
X
O
O
O
O
E
IVа−IVc
C
X = H (Iа), Cl (Ib); X = H, Ar = 2-ClC6H4 (IIа–IVа), 2-BrC6H4 (IIb–IVb); X = Cl, Ar = 2-ClC6H4 (IIIc, IVc); R =
P(O)(OEt)2.
obtained, consisting of a mixture of the isomeric
compounds IIIa and IVa in a ratio of 10.3 (7.8 d1, 2.5
d2): 21.3 (14.2 d3, 7.1 d4). 31Р–{1Н} NMR spectrum
(161.9 MHz, СН2Cl2), δР, ppm (J, Hz): 7.8 and 9.1 two
d (2JРСР 27.5), d1, 8.3 and 16.3 two d (2JРСР 22.9), d2
IIIa; –0.4 and 10.4 two d (2JРОСР 6.1), d3, –0.9 and 9.9
two d (2JРОСР 9.2), d4 IVa. Reprecipitation from a
СН2Cl2 solution into pentane gives a light yellow
powder in 80% yield, mp 145°C (mixture of IIIa and
IVa). IR spectrum, ν, cm–1: 1750, 1660, 1600, 1520,
the ratio of 18.6 (16.1 d1, 2.4 d2):10.9 (6.8 d3, 4.1 d4)]
was characterized by the spectroscopic methods.31Р–
{1Н} NMR spectrum (161.9 MHz, СН2Cl2), δР, ppm
(J, Hz): 7.5 and 9.1 two d (2JРСР 27.5), d1, 8.3 and 16.7
two d (2JРСР 24.7), d2 IIIb; –0.6 and 11.1 two d (2JРОСР
6.9), d3, –1.1 and 10.1 two d (2JРОСР 9.2), d4 IVb.
Reprecipitation of this oily substance from a СН2Cl2
solution into pentane gives a mixture of compounds
IIIb and IVb as a pale yellow powder in 80% yield,
mp 130°C. The maintaining of the pale yellow powder
in СН2Cl2 solution for 10 days yields the crystals of
IIIb as a mixture of two diastereomers d1, d2 in the
ratio of 1:1.2. IR spectrum, ν, cm–1: 1830, 1720, 1605,
1460, 1290, 1030, 760, 570. 1Н NMR spectrum
(acetone-d6), δН, ppm (J, Hz): 1.15–1.41 br.t, 4.8–3.7
br.m, 8.5–7.0 br.m. 31Р–{1Н} NMR spectrum
(161.9 MHz, СН2Cl2), δР, ppm. (J, Hz): 7.9 and 9.7
two d (2JРСР 27.5), d1, 7.8 and 13.8 two d (2JРСР 22.9),
d2. Found, %: С 42.86; Н 3.41; Р 11.59. С19Н18Br·
NО8Р2. Calculated, %: С 43.02; Н 3.40; Р 11.70.
1
1490, 1460, 1250, 1160, 1030, 970, 760. Н NMR
spectrum (300 MHz, acetone-d6), δН, ppm (J, Hz): 1.59
q (3JНССН 5.3), 4.3–3.8 br.m, 8.25–7.2 br.m. Found, %:
С 46.70; Н 3.60; Р 12.40. С19Н18ClNО8Р2. Calculated,
%: С 46.96; Н 3.70; Р 12.77.
9-(o-Bromo)phenyl-9-diethoxyphosphoryl-6-aza-
3,4-benzo-2,8-dioxa-1-phosphabicyclo[4.3.01.6]nonane-
1,5,7-trione (IIIb) and 8-(o-bromo)phenyl-8-di-
ethoxyphosphoryl-6-aza-3,4-benzo-2,9-dioxa-1-phos-
phabicyclo[4.3.01.6]nonane-1,5,7-trione (IVb). A mix-
ture of 9.9 g (0.05 mol) of isocyanatophosphite Ia and
15.2 g (0.05 mol) of o-bromophenylcarbonyldi-
ethylphosphonate IIb was kept in a sealed tube at 120–
130°C for 10 h. The obtained thick oil [IIIb + IVb in
9-(o-Chlorophenyl)-9-diethoxyphosphoryl-6-aza-
2,8-dioxa-3,4-(4-chloro)benzo-1-phosphabicyclo-
[4.3.01.6]nonane-1,5,7-trione (IIIc) and 8-(o-chloro-
phenyl)-8-diethoxyphosphoryl-6-aza-2,9-dioxa-3,4-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 10 2012

1750
BURNAEVA et al.
2
(4-chloro)benzo-1-phosphabicyclo[4.3.01.6]nonane-
1,5,7-trione (IVc). A mixture of 8.1 g (0.03 mol) of
isocyanatophosphite Ib and 9.1 g (0.03 mol) of o-
chlorophenylcarbonyldiethylphosphonate IIa was kept
in a sealed tube at 120–130°C for 10 h. The obtained
thick oily substance was characterized by the spectro-
scopic methods. 31Р–{1Н} NMR spectrum (161.9 MHz,
СН2Cl2), δР, ppm. (J, Hz): 7.6 and 9.0 two d (2JРСР
27.5), d1, 8.2 and 17.4 two d (2JРСР 24.7), d2 IIIc; –1.0
and 10.9 two d (2JРОСР 5.5), d3, –1.4 and 9.7 two d
(2JРОСР 9.2), d4 IVc. Reprecipitation of this oily
substance from a СН2Cl2 solution into pentane gives a
mixture of compounds IIIc and IVc in a ratio of 23
(13 d1, 10 d2):11 (7 d3, 3 d4) in 80% yield, yellow
powder, mp 140°C. The maintaining of the pale yellow
powder in СН2Cl2 solution for 10 days gives the
crystalline diphosphonate IIIc, mp 148°C. IR spec-
trum, ν, cm–1: 1827, 1710, 1617, 1600, 1515, 1467,
1450, 1370, 1246, 1211, 1165, 1094, 1025, 998, 965,
2JHC13 12 3.9, JHC11 12 3.9), 130.34 d.d (s) (С13,
С
CС
3
1JHС13 172.6, JHC11 13 5.7), 126.57 m (d.d) (С14,
СC
2JPCС14 4.2, JPCС14 4.3), 131.83 m (d.d) (С15, JPCСC15
2
2
5.7, JPCCС15 4.2), 130.57 d.d.m (br.s) (С16, JHС16
2
1
166.7, 3JHC18 16 6.5), 131.26 br. d.d (br.s) (С17, 1JHС17
СC
164.9, JHC19 17 8.7), 127.72 d.d.d (d) (С18, JHС18
3
1
СC
3
4
164.4, JHC16 18 7.9, JPC СCC18 1.5), 129.18 d.m (d.d)
9
СC
(С19, 1JHС19 162.5, 3JHC17 19 7.5, 3JPCСC19 7.3, 3JPCСC19
СC
3.6), 66.02 t.d.q (d) (OCH2, 1JHС 150.1, 2JPOC 7.5, 2JHCC
4.2), 65.84 t.d.q (d) (OCH2, 1JHС 150.2, 2JPOC 7.3, 2JHCC
4.3), 16.25 q.d.t (d) (CH3, 1JHС 127.7, 3JPOCC 5.2, 2JHCC
2.5), 16.21 q.d.t (d) (CH3, 1JHС 127.8, 3JPOCC 5.6, 2JHCC
2.5). 31Р–{1Н} NMR spectrum (242.9 MHz, СDCl3),
δР, ppm (J, Hz): 7.7 and 9.0 two d (2JРСР 27.5). Found,
%: С 42.70; Н 3.27; Р 11.80. С19Н17Cl2NО8Р2·H2О.
Calculated, %: С 42.38; Н 3.16; Р 11.52.
The Н, 31Р, 13С NMR spectra were recorded on a
1
Varian Unity-300 and Bruker Avance-600 instruments.
The IR spectra were taken on a Bruker Vector-22
instrument from the suspension of the substance in
mineral oil.
1
820, 760, 670, 540. Н NMR spectrum (600 MHz,
3
СDCl3), δН, ppm (J, Hz): 7.37 d (Н10, JН11 10 8.8),
7.68 d.d (Н11, JН10 11 8.8, JН13
11 2.С7С)Н, 8.17 d
3
4
ССН
(Н13, JН11
13 2.7), 7.51 m (Н16С)С,С7Н.42 m (Н17,18),
4
ACKNOWLEDGMENTS
7.73 d.d.dС.dССН(Н19, 3JН18 19 7.2, 4JН17
19 2.3,
ССН
СССН
This work was financially supported by the Russian
Foundation for Basic Research (grant no 10-03-
00525).
4JР1С3ССН19 1.6, JР2СССН19 1.6), 4.16 m (Н20AB, JРОСН
4
3
3
3
7.4, JНССН 7.1), 4.16 d. q (OСН2, JНССН 7.1, JНССН
7.1), 4.03 m [OСНAНB, В-part of ABM3X system,
2J(НAНB) 10.1, 3J(РОСНB) 7.8, 3J(НBССНM) 7.1], 3.96
REFERENCES
2
m [OСН2, A-part of ABM3X system, J(НBНA) 10.1,
1. Konovalova, I.V., Burnaeva, L.A., Sabirova, L.I., and
Pudovik, A.N., Zh. Obshch. Khim., 1991, vol. 61,
no. 11, p. 2465.
2. Konovalova, I.V., Burnaeva, L.A., Mironov, V.F.,
Khlopushina, G.A., and Pudovik, A.N., Zh. Obshch.
Khim., 1994, vol. 64, no. 1, p. 63.
3. Burnaeva, L.M.. Mironov, V.F., Romanov, S.V., and
Konovalova, I.V., Zh. Obshch. Khim., 1999, vol. 69,
no. 12, p. 2054.
4. Burnaeva, L.M., Mironov, V.F., Azancheev, N.M.,
Konovalova, I.V., Ivkova, G.A., Yashagina, O.V., and
Pudovik, A.N., Zh. Obshch. Khim., 2002, vol. 72, no. 6,
p. 1047.
3J(РОСНA) 9.6, J(НAССНM) 7.1], 1.19 t (СН3, JНССН
3
3
7.1), 1.18 t (СН3, JНССН 7.1). 13С NMR spectrum
3
(150.9 MHz, СDCl3), δC, ppm. (J, Hz) (the multiplicity
of the signal in the 13С–{1H} spectrum is given in the
3
brackets): 149.76 d.d.d.d (d) (C3, JНС11 3 11.2,
СC
2JP1OС3 9.2, JНС13 3 8.6, JНС10 3 4.6), 118.81 d.d (d)
3
2
СC
C
(С4, JHC10 4 5.0, JP1OСC4 1.5), 155.60 d.d.d (d) (С5,
3
3
СC
3JHC13 5 4.5, JP1NС5 3.4, JHC10 5 2.0), 144.07 d (d)
2
4
CС
CCС
(С7, JP1NС7 25.1), 83.39 br.d.d (d.d) (С9, JP1С9 153.0,
2
1
1JP2С9 117.5), 121.67 d.d (d) (С10, JHС10 169.2,
1
3JP1OСС10 9.4), 137.27 d.d (s) (С11, JHС11 169.2,
1
3
3JHC13 11 6.5), 132.37 d.d.d (s) (С12, JHC10 12 11.1,
CС
CС
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 10 2012