Reaction of 4-aryl-2,6-dichlorobenzo[e[1,2]oxaphosphinine 2-oxides with organomagnesium compounds as a convenient synthetic approach to (Z)-dialkyl(aryl)[2-(2-hydroxyaryl)-2-arylethenyl]phosphine oxides

Full text of DOI:10.1134/S1070363208060340

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 6, pp. 1287–1289. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © D.A. Tatarinov, V.F. Mironov, E.N. Varaksina, A.I. Konovalov, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 6,
pp. 1049–1050.
LETTERS
TO THE EDITOR
Reaction of 4-Aryl-2,6-dichlorobenzo[e][1,2]oxaphosphinine
2-Oxides with Organomagnesium Compounds
as a Convenient Synthetic Approach
to (Z)-Dialkyl(aryl)[2-(2-hydroxyaryl)-2-arylethenyl]phosphine
Oxides
D. A. Tatarinov, V. F. Mironov, E. N. Varaksina, and A. I. Konovalov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, Tatarstan, 420088 Russia
Received June 27, 2007
DOI: 10.1134/S1070363208060340
We recently prepared benzo[e][1,2]oxaphosphinine
2-oxides [1, 2], phosphorus analogs of coumarins
which are widespread in nature and possess diverse
biological activity [3]. The chemical behavior of this
class of compounds is comparatively poorly studied.
Thus it was shown that they fairly readily chlorinated
[4] and brominated [5] into the heterocyclic fragment
to form finally 3-halo derivatives. In the present work
we investigated for the first time reactions of 4-aryl-
2,6-dichlorobenzo[e][1,2]oxaphosphinine 2-oxides I
with organomagnesium reagents (Grignard reagents).
Taking into account the data summarized in the mono-
graph [6], we expected that the reactions would lead to
2-alkyl(aryl)-4-aryl-6-chlorobenzo[e][1,2]oxaphosphi-
nine 2-oxides II which attract some interest as
complexing agents for rare metals. However, phos-
phinines I were found to react unambiguously with a
double excess of Grignard reagents to give
functionally substituted phosphine oxides III in
quantitative yields. At an equimolar ratio of the start-
ing reagents, mixtures of phosphinines II, phosphine
oxides III, and 2-hydroxy-4-aryl-6-chlorobenzo[e][1,2]-
oxaphosphinine 2-oxides IV formed. It is obvious that
Grignard reagents almost equally reactive toward
O
O
R
O
O
P
(1) RMgX
P
+ III +
OH
(2) H2O
Cl
Cl
O
O
Ar
P
Ar
OH
4
IV
II
8a
Cl
8
5
O
Cl
7
6
(1) 2 RMgX
(2) H2O
R
Ar
P
I
R
4a
Cl
3
Ar
III
15
12
13
12
10
17
9
12 13
9
14
11
14
Ar = Ph (Ia), 1-naphthyl (Ib); Ar =
, R =
(IIIa), CH2CH3 (IIIb), Ar =
,
13
10
20
21
22
16
18
11
19
R =
(IIIc), CH2
(IIId); X = Cl, Br, I.
1287

1288
TATARINOV et al.
exocyclic P–Cl and endocyclic P–O bonds, which
makes impossible, when using both arylmagnesium
halides and primary alkylmagnesium halides, to direct
the process exclusively to substitution of the chlorine
atom to form compounds II.
Calculated, %: С 74.92, Н 4.58, Р 6.45. 31Р–{1H}
NMR spectrum (162.0 MHz, DMSO-d6), δР, ppm:
16.8. Н NMR spectrum (600 MHz, DMSO-d6, 45°С,
1
3
δ, ppm, J, Hz): 6.49 d (H8, 1Н, JH CCH 8.7), 6.70 d
7
8
(H3, 1Н, JPCH 20.6), 6.96 d.d (H7, 1Н, JH CCH 8.7,
2
3
3
8
7
JH CCCH 2.4), 7.20 d (H5, 1Н, JH CCCH 2.4), 7.38 d
4
4
5
7
7
5
The structure of (Z)-dialkyl(aryl)[2-(2-hydroxyaryl)-
2-arylethenyl]phosphine oxides III was confirmed by
(H9, 1Н, JHCCH 7.0), 7.42–7.44 and 7.46–7.47 m (H10,
H13, H14, H17, H18, 9Н), 7.75 d.d (H16, 4Н, 3JHCCH 11.4,
3JHCCH 7.6), 7.87 d (H15, 1Н, 3JHCCH 8.1), 7.91 d.d (H12,
3
1
31
13
means of H, P and C NMR and IR spectroscopy.
Phosphine oxides III contain a hydroxy group in the δ
position to the phosphoryl group and, therefore, they
can find application as starting compounds for syn-
thesis of chelating phosphines and neutral chelating
ligands for extraction of rare and nonferrous metals.
1Н, JHCCH 6.2, JHCCCH 3.2), 8.17 d.d (H11, 1Н, JHCCH
3
4
3
6.1, 4JHCCCH 3.2), 9.71 s (ОН, 1Н).
Compound IIId. Yield 94%, mp 178–181°С.
Found, %: С 75.34, Н 5.47, Р 6.29. С32H26ClO2P.
Calculated, %: С 75.52, Н 5.11, Р 6.10. 31Р–{1H}
NMR spectrum (162.0 MHz, DMSO-d6), δР, ppm:
30.8. IR spectrum, cm–1: 417, 454, 479, 504, 538, 582,
620, 640, 683, 699, 720, 745, 783, 798, 815, 842, 863,
883, 911, 930, 957, 1019, 1031, 1069, 1118, 1153,
1198, 1229, 1283, 1342, 1377, 1411, 1455, 1495,
1586, 1601, 1710, 1825, 1884, 1958, 2717, 2921,
Compound IIIa. A solution of 10 g (0.0321 mol)
of oxaphosphinine Ia [1] in 10 ml of benzene was
added dropwise with stirring in argon to phenyl-
magnesium bromide prepared from 1.7 g of Mg and
7.8 ml of bromobenzene in 50 ml of ether by a
conventional procedure [7]. The reaction mixture was
heated under reflux for 30 min and cooled, after which
it was neutralized with a solution of 6 ml of conc. HCl
in 35 ml of distilled water. The solution was stirred for
30 min to let it warm to room temperature; therewith,
precipitate formation was observed. The precipitate
was filtered off, washed with 10–15 ml of ether, and
dried in air or in a vacuum (12 mm Hg) to obtain 12 g
(87%) of compound IIIa, mp 185–186°С. Found, %: С
72.65, Н 4.91, Р 7.29. C26H20ClO2P. Calculated, %: С
72.47, Н 4.64, Р 7.20. 31Р–{1H} NMR spectrum
(36.46 MHz, CDCl3), δP, ppm: 22.6. 1Н NMR
spectrum (600 MHz, DMSO-d6, 45°C, d, ppm, J, Hz):
9.17 br.s (ОН, 1Н), 7.70 br.m (Н12, 4Н), 7.49 br.m
1
3030, 3441. Н NMR spectrum (600 MHz, DMSO-d6,
45°С, δ, ppm, J, Hz): 3.27 and 3.33 m (СH2, 4Н, 2JH(A)CH(B)
2
2
13.5–14.0, JPCH(B) 13.5–14.0, JPCH(A) 15.2), 6.12 d
(H3, 1Н, JPCH3 22.8), 6.59 d (H5, 1Н, JH7CCCH5 2.7),
2
4
6.79 d (H8, 1Н, JH7CCH8 8.7), 7.12 d.d (H7, 1Н,
3
JH8CCH7 8.7, JH CCCH 2.7), 7.17 d.d (H9, 1Н, JHCCH
3
4
3
5
7
7.1, JHCCCH 0.9), 7.30–7.35 m (H16–18, 10Н), 7.44 d.d
(H10, 1Н, 3JHCCH 7.2, 3JHCCH 8.1), 7.46 and 7.50 m (H13
and Н14, 2Н; 3JHCCH 8.2, 3JHCCH 6.8, 4JHCCCH 1.4; 3JHCCH
8.2, 3JHCCH 6.8, 4JHCCCH 1.2), 7.85 br.d (H15, 1Н, 3JHCCH
4
8.3), 7.91 and 7.93 br.d (H11 and H12, 2Н, JHCCH 7.3–
3
8.7), 10.01 br.s (ОН, 1Н).
(Н14, 2Н, 3JНС
7.1), 7.40 br.m (Н13, 4Н), 7.30–7.34
The spectra were measured under the conditions
described in [2].
13СН14
m (Н7, Н8, Н9–11, 7Н), 6.33 br.s (H5, 1Н), 7.03 d (Н3,
1Н, 2JPСН 20.5).
3
ACKNOWLEDGMENTS
Compound IIIb. Yield 94 %, mp 75–77°С. Found,
%: С 64.29, Н 6.12, Р 9.41. C18H20ClO2P. Calculated,
%: С 64.57, Н 5.98, Р 9.27. 31Р–{1H} NMR spectrum
(36.46 MHz, CDCl3), δP, ppm: 47.5. 1Н NMR
spectrum (600 MHz, CDCl3, δ, ppm, J, Hz): 1.09 d.t
The work was financially supported by the Russian
Foundation for Basic Research (project nos. 07-03-
000180 and MK-1434.2006.3).
3
3
(Н13, 6Н, JРСCH 17.6, JНСCH 7.5), 1.64–1.70 m (Н12,
3
REFERENCES
4Н, АВ-part of the spectrum АВМХ3, JН(Х)СCH(А) 7.5,
2
3JН(Х)СCH(В) 7.5), 6.32 d (РСН3, JРСH 18.1), 6.92 d (Н5,
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3
4JНССCH 2.6), 7.05 d (Н8, JНСCH 8.7), 7.19 d.d (Н7,
4
3
3JНСCH 8.7, JНССCH 2.6), 7.26 br.m (Н9, 2Н, JНСCH
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3
3
7.1), 7.33 m (Н11, 1Н, 3JНСCH 7.1), 8.57 br.s (ОН, 1Н).
Compound IIIc. Yield 97 %, mp 173–175°С.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 6 2008

REACTION OF 4-ARYL-2,6-DICHLOROBENZO[e][1,2]OXAPHOSPHININE
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