Synthesis and Crystal Structure of 2-Substituted 3-Aryl-2-Oxophenylbenzo[E]-1,4,2-Oxazaphosphinanes

Article abstract of DOI:10.1080/10426507.2014.993756

Stereoisomers of 2-substituted 3-aryl-2-oxobenzo[e]-1,4,2-oxazaphosphinane derivatives were obtained by the phosphorylation of 2-arylideneaminophenols with dichlorophenylphosphine in the presence of triethylamine followed by the water treatment, which wer

Full text of DOI:10.1080/10426507.2014.993756

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Phosphorus, Sulfur, and Silicon and the
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Synthesis and Crystal Structure
of 2-Substituted 3-Aryl-2-
Oxophenylbenzo[E]-1,4,2-
Oxazaphosphinanes
Mudaris Dimukhametova, Natalya Belovaa, Vladimir Mironova,
Ekaterina Mironovaa, Dmitry Krivolapova, Petro Onys’kob & Yulia
Rassukanayab
a A.E. Arbuzov Institute of Organic and Physical Chemistry, Russian
Academy of Sciences, Kazan, 420088, Russia
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b Institute of Organic Chemistry, National Academy of Sciences of
Ukraine, Murmanskaya Str. 5, Kiev, 02094, Ukraine
Published online: 01 Jul 2015.
To cite this article: Mudaris Dimukhametov, Natalya Belova, Vladimir Mironov, Ekaterina Mironova,
Dmitry Krivolapov, Petro Onys’ko & Yulia Rassukanaya (2015) Synthesis and Crystal Structure of 2-
Substituted 3-Aryl-2-Oxophenylbenzo[E]-1,4,2-Oxazaphosphinanes, Phosphorus, Sulfur, and Silicon and
the Related Elements, 190:5-6, 943-946, DOI: 10.1080/10426507.2014.993756
To link to this article: http://dx.doi.org/10.1080/10426507.2014.993756
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Phosphorus, Sulfur, and Silicon, 190:943–946, 2015
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2014.993756
SYNTHESIS AND CRYSTAL STRUCTURE OF
2-SUBSTITUTED 3-ARYL-2-OXOPHENYLBENZO[E]-1,4,2-
OXAZAPHOSPHINANES
Mudaris Dimukhametov,1 Natalya Belova,1 Vladimir Mironov,1
Ekaterina Mironova,1 Dmitry Krivolapov,1 Petro Onys’ko,2
and Yulia Rassukanaya2
1A.E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy
of Sciences, Kazan 420088, Russia
2Institute of Organic Chemistry, National Academy of Sciences of Ukraine,
Murmanskaya Str. 5, Kiev 02094, Ukraine
GRAPHICAL ABSTRACT
Abstract Stereoisomers of 2-substituted 3-aryl-2-oxobenzo[e]-1,4,2-oxazaphosphinane
derivatives were obtained by the phosphorylation of 2-arylideneaminophenols with
dichlorophenylphosphine in the presence of triethylamine followed by the water treatment,
which were isolated by column chromatography as pure diastereoisomers. Their structure was
determined by NMR and XRD.
Keywords Aminophosphinic acid; oxazaphosphinane; intramolecular Pudovik reaction; dias-
teroisomer; crystal structure; conformation
Among aminophosphinic acid derivatives, cyclic benzo[e]-1,4,2-oxazaphosphinanes are
studied the least, only several works1 are devoted to the synthesis and properties of some
of their representatives. These compounds, as well as their aminophosphonic analogs, are
of interest from the point of view of their biological activity2. In the present work, we
suggest a new convenient approach to the preparation of aminophosphinic acid derivatives,
viz., 3-aryl-2-R-2-oxobenzo[e]-1,4,2-oxazaphosphinanes (1), based on the stepwise one-
pot reaction of the equimolar amounts of 2-arylideneaminophenols (2) with RPCl2 and
water in the presence of NEt3. The process is likely to include the intermediate formation
of hydrophosphoryl compounds (3) (Scheme 1), which, however, were not detected by
Received 19 August 2014; accepted 23 November 2014.
Address correspondence to Vladimir Mironov, A.E. Arbuzov Institute of Organic and Physical Chemistry,
Russian Academy of Sciences, Arbuzov Str. 8, Kazan 420088, Russia. E-mail: mironov@iopc.ru
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpss.
943

944
M. DIMUKHAMETOV ET AL.
NMR because of their very fast conversion to the final cyclic products (1) through the
intramolecular Pudovik reaction (intermediate 4).
Scheme 1
Compounds (1) are formed as mixtures of diastereoisomers (d1, d2) in the ratio
(d1) : (d2) = 3 : 1 (1a) and (d1) : (d2) = 2 : 1 (1b–e).
The diastereoisomers (1a,b) were isolated by column chromatography 3. Their struc-
tures were confirmed by XRD (Figures 1–3).
The fragment O(1)C(8a)C(4a)N(1) in molecule (1a, d1) is planar within 0.003(3) Å,
atoms P(2) and C(3) deviate by −0.0273(7) and 0.613(3) Å to the opposite sides of this
plane, therefore, the conformation of the six-membered heterocycle can be considered as
a distorted half-chair (Figure 1). The deviation of the phosphorus atom from the plane of
the tetraatomic fragment is small, and the penta-atomic fragment P(2)O(1)C(8a)C(4a)N(4)
in molecule (1a, d1) can be considered to be planar within 0.007(2) Å, from which atom
C(3) of the oxazaphosphine ring deviates by −0.630(3) Å, and, therefore, the conformation
of the heterocycle can be also characterized as the sofa (envelop). Atom O(2) is in the
equatorial position (the deviation from the plane P(2)O(1)C(8a)C(4a)N(4) is −0.778(2)
Figure 1 Crystal structure of (1a, d1).

3-ARYL-2-OXOPHENYLBENZO[E]-1,4,2-OXAZAPHOSPHINANES
945
Figure 2 Crystal structure of (1a, d2).
Å), the phenyl groups at atoms P(2) and C(3) are in the axial positions (the deviation of
atoms C(9) and C(15) from the penta-atomic plane is 1.719(3) and −2.158(1) Å).
The crystal of compound (1a, d2) contains two independent molecules (A, B) (only
one molecule is shown in Figure 2). The conformation of both molecules, a distorted (non-
symmetric) boat, contains a tetra-atomic planar fragment O(1)C(8a)C(4a)N(4). Two atoms
of the heterocycle deviate from this fragment to the same side by different distances (P(2)
and C(3) deviate by −0.615(1) and −0.941(5) Å in molecule A and by −0.601(1), −1.024(5)
Figure 3 Crystal structure of (1b, d1).

946
M. DIMUKHAMETOV ET AL.
Å in molecule B), that secures the conformation of the distorted boat. Atom O(2) occupies
the axial position in both molecules [it deviates from the plane O(1)C(8a)C(4a)N(4) by
1.813(3) Å (A) and 1.752(3) Å(B)]. The phenyl groups at atoms P(2) and C(3) are in the
equatorial positions (atoms C(9) and C(15) deviate from the plane O(1)C(8a)C(4a)N(4) by
0.744(5), −0.852(5) Å (A), and −0.777(4), 1.143(5) Å (B).
In the crystal of compound (1b, d1) (Figure 3), the conformation of the heterocycle dif-
fers from that observed in molecules (1a, d1) and (1a, d2): the fragment O(1)C(8a)C(4a)N(1)
in molecule (1b, d1) is planar within 0.004(2) Å, atoms P(2) and C(3) deviate to the opposite
sides from this plane by −0.1586(5) and 0.677(2) Å, thus, the conformation of the six-
membered heterocycle is a half-chair. At the same time, if to assume that molecule (1b, d1),
like in the structure (1a, d1), has a pentaatomic fragment P(2)O(1)C(8a)C(4a)N(4) planar
within 0.051(1) Å, then here the conformation of the heterocycle can be also described as a
sofa (envelop) (remaining atom of the oxazaphosphine ring C(3) deviates by 0.773(2) Å).
Atom O(2) is in the axial position (its deviation from the plane P(2)O(1)C(8a)C(4a)N(4)
is −1.388(1) Å), the phenyl group at atom P(2) and the para methoxyphenyl substituent at
atom C(3) occupy the equatorial positions (the deviation of atoms C(9) and C(15) from the
five atomic plane is 1.057(2) and 0.777(2) Å, respectively).
Owing to the close values of Rf of diastereoisomers (1с–e), it appeared to be impos-
sible to isolate the other one by column chromatography or by recrystallization. The struc-
ture of the compounds was confirmed by 1Н, 31Р NMR and chromatomass-spectrometry.
There are the doublets corresponding to PCH-fragment in 1Н NMR spectra: 4.62 ppm, 2JHP
18.4 Hz (1c, d1), 4.64 ppm, 2JHP 6.0 Hz (1c, d2), 4.98 ppm, 2JHP 10.3 Hz (1d, d1), 5.01 ppm,
2
2
2JHP 19.3 Hz (1d, d2), 4.86 ppm, JHP 9.9 Hz (1e, d1), 5.03 ppm, JHP 20.5 Hz (1e, d2).
Two singlets correspond to each compound in 31P-{ Н} NMR spectra: δР 39.9 ppm (1с,
1
d1), 45.2 ppm (1с, d2), 10.2 ppm (1d, d1), 11.3 ppm (1d, d2), 17.2 ppm (1e, d1), 21.9 ppm
(1e, d2) ppm. There are the closely situated peaks in chromatograms of diastereoisomers
with the same values of molecular masses [273 (1c), 289 (1d), 316 (1e)].
FUNDING
This study was supported by Russian Foundation for Basic Research (grant no.
13-03-90419).
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