The interaction of 2-(5-methyl-2-phenyl-2h-1,2,3-diazaphosphol-4-yl)-4h-benzo[e]-1,3,2-dioxaphosphinin-4-one with activated carbonyl compounds. Synthesis of bis-heterocyclic systems containing di- and tetracoordinated phosphorus

Article abstract of DOI:10.1080/10426507.2017.1390459

The interaction of 2-(5-methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl)-4H-benzo[e]-1,3,2-dioxaphosphinin-4-one with mesoxalic and trifluoropyruvic acids ethyl and diethyl esters, hexafluoroacetone and chloral proceeds with an exclusive participation of P(III) atom and allows to obtain 2-(5-methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl)-derivatives of 1,4,2- and 1,3,2-dioxaphosphepines as well as dichlorovinylphosphonate, being the product of Perkow reaction in the case of chloral.

Full text of DOI:10.1080/10426507.2017.1390459

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
THE INTERACTION OF 2-(5-METHYL-2-
PHENYL-2H-1,2,3-DIZAPHOSPHOL-4-YL)-4H-
BENZO[e]-1,3,2-DIOXAPHOSPHININ-4-ONE WITH
ACTIVATED CARBONYL COMPOUNDS. SYNTHESIS
OF BIS-HETEROCYCLIC SYSTEMS CONTAINING DI-
AND TETRACOORDINATED PHOSPHORUS
Vladimir F. Mironov, Gulnara A. Ivkova, Liliya M. Abdrakhmanova, Rashid Z.
Musin, Ekaterina V. Mironova, Dmitry B. Krivolapov & Aidar T. Gubaidullin
To cite this article: Vladimir F. Mironov, Gulnara A. Ivkova, Liliya M. Abdrakhmanova,
Rashid Z. Musin, Ekaterina V. Mironova, Dmitry B. Krivolapov & Aidar T. Gubaidullin
(2017): THE INTERACTION OF 2-(5-METHYL-2-PHENYL-2H-1,2,3-DIZAPHOSPHOL-4-
YL)-4H-BENZO[e]-1,3,2-DIOXAPHOSPHININ-4-ONE WITH ACTIVATED CARBONYL
COMPOUNDS. SYNTHESIS OF BIS-HETEROCYCLIC SYSTEMS CONTAINING DI- AND
TETRACOORDINATED PHOSPHORUS, Phosphorus, Sulfur, and Silicon and the Related
Elements, DOI: 10.1080/10426507.2017.1390459
To link to this article: http://dx.doi.org/10.1080/10426507.2017.1390459
Accepted author version posted online: 11
Oct 2017.
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THE INTERACTION OF 2-(5-METHYL-2-PHENYL-2H-1,2,3-DIZAPHOSPHOL-4-YL)-
4H-BENZO[e]-1,3,2-DIOXAPHOSPHININ-4-ONE WITH ACTIVATED CARBONYL
COMPOUNDS. SYNTHESIS OF BIS-HETEROCYCLIC SYSTEMS CONTAINING DI-
AND TETRACOORDINATED PHOSPHORUS
Vladimir F. Mironova,b, Gulnara A. Ivkovab, Liliya M. Abdrakhmanovaa, Rashid Z.
Musina, Ekaterina V. Mironovaa,b, Dmitry B. Krivolapova , Aidar T. Gubaidullina
aA. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre, Russian
Academy of Sciences, Arbuzov str. 8, 420088 Kazan, Russian Federation. Fax: 8(843)2731872;
E-mail: mironov@iopc.ru
bKazan Federal University, Kremlevskaya str. 18, 420008, Kazan, Russian Federation. Tel:
8(843)2337397; E-mail: gulnara.ivkova@mail.ru
Abstract
The interaction of 2-(5-methyl-2-phenyl-2H-1,2,3-dizaphosphol-4-yl)-4H-benzo[e]-1,3,2-
dioxaphosphinin-4-one with mesoxalic and trifluoropyruvic acids ethyl and diethyl esters,
hexafluoroacetone and chloral proceeds with an exclusive participation of Р(III) atom and allows
to obtain 2-(5-methyl-2-phenyl-2H-1,2,3-dizaphosphol-4-yl)-derivatives of 1,4,2- and 1,3,2-
dioxaphosphepines as well as dichlorovinylphosphonate, being the product of Perkow reaction in
the case of chloral.
Graphical Abstract
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Keywords
Diazaphosphole; benzodioxaphosphinine; benzodioxaphosphepine; chloral; hexafluoroacetone;
Perkow reaction.
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Introduction
Organophosphorus heterocycles have a high theoretical and practical importance.1-6
Among the wide range of phosphorus-containing heterocycles the reactive trivalent phosphorus
species play a role of precursors in the synthesis of tetracoordinated phosphorus derivatives,
which are usually very stable.3-9 The cyclic mixed anhydrides, obtained from
hydroxy/aminocarboxylic acids and phosphoric / phosphonic acids contain a nucleophilic
phosphorus(III) atom as well as electrophilic carbonyl group and occupy a special position
among trivalent phosphorus heterocycles. The presence of macroergic Р(III)–О–С(О)/P(III)–
N(R)–C(O) fragment in the initial phosphite molecule leads to an appearing of unusual
reactivity, namely, to the possibility that both P(III) atoms react with nucleophiles and
electrophiles, affording a diverse range of heterocycles containing tetracoordinated
phosphorus.10-16
Functionalization of the exocyclic substituent, bonded to the phosphorus(III) atom, by
additional introduction of heterocyclic fragments could lead to new directions, such as cascade
processes allowing to involve both heterocyclic systems into reactions.17-19
In this article the 1,2,3-diazaphospholyl substituent, bearing nucleophilic two-coordinated
phosphorus atom (σ2λ3), was chosen as a second heterocyclic fragment R and was included in the
2-R-benzo[e]-1,3,2-diheterophosphinin-4-one molecule containing a P(σ3λ3)-atom. The literature
data gives for diazaphospholes evidence of high reactivity in various reactions. Substitution at
сarbon, alkylation and substitution at nitrogen or phosphorus, 1,2-additions to C=P- or N=P-bond
and oxidative addition to phosphorus, cycloaddition reactions, including [2+3]-, [1+4]- and
[2+4]-cycloadditions, as well as the coordination to transition metals should be mentioned
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among them.20-27 The frontier orbital crossing calculations showed the ambident reactivity of
P(σ2λ3) systems, containing a P=X double bond.28
The chemical properties of diazaphospholes bearing exocyclic phosphorus atom as a
substituent (with the coordination numbers of 2 and 4, 2 and 3, 2 and 5 as well as 2 and 6) are
reviewed.29 It is known that some reactions of diazaphospholes like interaction with proton
donors appeared to be reversible.30,31 Nevertheless, the information concerning competitive and
cascade reactions of bis-heterocyclic PII,PIII-systems with activated carbonyl compounds is
absent.
The presence of a nucleophilic Р(σ2λ3)-atom in the diazaphosphole molecule can change
not only the reaction pathways in the reaction with various reagents, but also the reactivity of the
Р(σ3λ3)-mojety.
Results and Discussion
The approach to the synthesis of bis-heterocyclic polyfunctional 2-(5-methyl-2-phenyl-
2H-1,2,3-diazaphosphol-4-yl)-4H-benzo[e]-1,3,2-dioxaphosphinin-4-one 1, combining the 5-
methyl-2-phenyl-2H-1,2,3-diazaphosphole and benzo[e]-1,3,2-dioxaphosphinin-4-one fragments
was realized in this work. It is based on the reaction of the 1-trimethylsilyloxy-2-
trimethylsilyloxycarbonylbenzene with 4-(dichlorophosphino)-5-methyl-2-phenyl-2H-1,2,3-
diazaphosphole occurring at room temperature. The 1,3,2-dioxaphosphinin-4-one 1 was obtained
by the procedure, similar to 4-(dichlorophosphino)-2,5-dimethyl-2H-1,2,3-diazaphosphole.32-33
Compound 1 appeared to be stable and does not undergo any transformations at room
temperature. The structure of the isolated phosphonite 1 was proved by spectroscopic methods.
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31
The Р{1H}NMR spectrum contains two doublets with P 238.5 (PII) and 156.3 (PIII) (2JРСР
=
16.6 Hz), the low field doublet of PII being broadened. The 13С and 13С{1H} NMR spectra
contain characteristic carbon signals, showing couplings with one or two phosphorus atoms. The
multiplicity of the C4b signal, belonging to the diazaphosphole cycle (d.d) is in agreement with
1
the formation of the Р=С4b–Р fragment (С 148.5, JРС 63.5 Hz, 1JРС 56.1 Hz); the signals of C4a
3
5
2
2
(С 116.1, JРОСС 11.7 Hz, JРСРОСС 3.3 Hz) and С5b (С 158.4, JРСС 23.8 Hz, JРСС 5.5 Hz) are
also doublets of doublets. The XRD data confirms also the molecular structure of compound 1
(Figure 1).
C12B
C7
C8
N1B
C5B
C4B
O1
C6
C11B
P2
C8A
C4A
C10B
C9B
N2B
C6B
C7B
C5
P3B
C4
O3
C8B
O4
Figure 1. Molecular structure in the crystal and atom labeling scheme for 1 (30 % thermal
ellipsoids). Selected bond lengths (Å), bond and torsion angles (): P(2)–O(1) 1.639(2), P(2)–
O(3) 1.658(2), P(2)–C(4B) 1.801(2), P(3B)–N(2B) 1.688(2), P(3B)–C(4B) 1.704(2), O(1)–
C(8A) 1.376(3), O(3)–C(4) 1.367(3), O(4)–C(4) 1.196(4), N(1B)–N(2B) 1.354(3), N(1B)–C(5B)
1.317(3), C(4)–C(4A) 1.468(3), C(4B)–C(5B) 1.414(3), O(1)–P(2)–O(3) 99.87(8), O(1)–P(2)–
C(4B) 103.05(9), N(2B)–P(3B)–C(4B) 89.1(1), P(2)–O(1)–C(8A) 120.2(1), P(2)–O(3)–C(4)
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124.5(2), N(2B)–N(1B)–C(5B) 108.9(2), P(3B)–N(2B)–N(1B) 116.6(1), C(4)–C(4A)–C(8A)
122.4(2), P(2)–C(4B)–P(3B) 126.7(2), P(2)–C(4B)–C(5B) 123.5(2), N(1B)–C(5B)–C(4B)
116.2(2), P(3B)–C(4B)–C(5B) 109.3(2), C(4B)–P(2)–O(3)–C(4) 68.1(2), C(4B)–P(2)–O(1)–
C(8A) –59.4(2), O(3)–P(2)–O(1)–C(8A) 42.1(2), O(1)–P(2)–O(3)–C(4) –36.9(2), O(1)–P(2)–
C(4B)–P(3B) 113.8(2), O(1)–P(2)–C(4B)–C(5B) –76.1(2), O(3)–P(2)–C(4B)–P(3B) 11.5(2),
O(3)–P(2)–C(4B)–C(5B) –178.4(2), C(7B)–C(6B)–N(2B)–N(1B) –169.8(2), C(11B)–C(6B)–
N(2B)–P(3B) –166.0(2).
According to the literature data, mentioned above, we suggested that the molecule of
compound 1, bearing PII and PIII atoms with different lone pairs of electrons, would easy react
with electron deficient carbonyl compounds like hexafluoroacetone, chloral or ethyl ester of
mesoxalic and trifluoropyruvic acids. 5-Phenyl-5-methyl-1,2,3-diazaphosphole acts as
nucleophile with the highly electrophilic hexafluoroacetone, resulting in fluorinated
diazaphosphole derivatives.2,34 On the other side, 2-R-benzo[e]-1,3,2-dioxaphosphinin-4-ones
easily react with the electrophiles mentioned above, leading to ring enlargement products (from
six- to seven membered heterocycles) as well as to products with pentacoordinated phosphorus –
phosphoranes.35,36 Firstly, the nucleophilic attack of the phosphorus atom to the activated carbon
atom takes place. It involves the intermediate formation of spirophosphoranes, containing
oxaphosphirane cycle.37
Compound 1 proved to be more stable to oxidation in comparison with 5-methyl-2-
phenyl-2H-1,2,3-diazaphosphole and 2-Ph-benzo[e]-1,3,2-dioxaphosphinin-4-one. Derivative 1
was proved to be less reactive to the activated reagents, mentioned above. In all cases the two-
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coordinated phosphorus atom (σ2λ3) remains intact. Taking into account published data38 it can
be assumed, that introduction of the sterically hindered and at the same time weakly electron
withdrawing benzo[e]-1,3,2-dioxaphosphinin-4-one substituent in 4 position of diazaphosphole
changes the electronic situation at the phosphorus atom of the latter. This means, that the lone
pair of electrons becomes less convenient for the attack by an electrophile. The diazaphosphole
fragment in turn is sterically hindered and possesses a weak electron withdrawing effect as well.
It also influences the chemoselectivity of the P(σ3λ3) atom, belonging to the benzo[e]-1,3,2-
dioxaphosphinin-4-oxide.39
The 2-R-benzo[e]-1,3,2-dioxaphosphinin-4-one derivatives usually react with mesoxalic
acid diethyl ester giving the phosphorane derivatives without the participation of the РIII–ОС(О)
bond.40 The interaction of 2-isocyanatobenzo[e]-1,3,2-dioxaphosphinin-4-one with mesoxalic
acid diethyl ester yields products with bicyclononane structure.41 Compound 1 was found to react
with mesoxalic acid diethyl ester with the formation of 1,3,2-dioxaphosphepine 2. The possible
intermediate, bearing a three-membered cycle (А), is the product of the cheletropic reaction of
the phosphorus atom with the carbonyl group. It transforms further via betaine-like transition
state (В) into the 1,3,2-dioxaphosphepine 2 (Scheme 1).
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Scheme 1. The reaction of phosphonite 1 with mesoxalic acid diethyl ester.
1
13
13
31
The structure of 2 was identified by H, C, C{1H}, and Р{1H} NMR spectroscopy.
31
2
The Р{1H} NMR spectrum contains two doublets with P 251.3 (br. d) and 14.9 (d, JРСР 76.3
2
Hz). The 13C{1H} NMR spectrum displays the characteristic upfield (C 88.6, JРОС 8.3 Hz) and
lowfield (C 185.3) signals belonging to the carbon atoms (C4 and С5) of 1,3,2-dioxaphosphepine
cycle. Interpretation of 13C NMR spectra is made taking into account published data.24,32
Thus, 5-methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl substituent is likely to direct the
reaction by the pathway, that is non-characteristic for diethyl ester of mesoxalic acid. This
pathway includes the ring enlargement reaction from a six-membered to a seven-membered P-
heterocycle with high chemo- and regioselectivity. The formation of 1,3,2-dioxaphosphepine
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derivative 2 is the only direction of this reaction, and the two-coordinated phosphorus atom does
not take part in the process.
The reaction of compound 1 with trifluoropyruvic acid ethyl ester proceeds by two
pathways (Scheme 2). The main pathway (> 90 %) includes the formation of 1,3,2-
dioxaphosphepine 3, which is the Р–СO → Р–ОС rearrangement product. Such a behavior of
compound 1 also differs from the similar reaction of 2-R-benzo[e]-1,3,2-dioxaphosphinin-4-one
with trifluoropyruvic acid ethyl ester leading to spirophosphoranes.16,42 The minor pathway (< 8
%) includes the formation of pentacoordinated phosphorus derivative 4, showing characteristic
signals in 31Р{1H} NMR spectrum: –32.3 d, –34.1 d (5 : 1) (PIV), 254.0 br. d (PII) (2JРСР 87.2 Hz).
Scheme 2. The reaction of phosphonite 1 with ethyl ester of trifluoropyruvic acid.
Trifluoropyruvic acid ethyl ester contains prochiral carbonyl group which converts into
C4-asymmetric center during the reaction process. This leads to the formation of two
diastereoisomers of compound 3 in the ratio of 55 to 45. Their structures were confirmed by the
NMR spectroscopy and mass spectrometry. The phosphepine 3 was washed free from
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1
phosphorane 4 impurities and dried of volatile compounds. H, 13С{1H} and 31Р{1H} NMR
spectra of compound 4 contain the double set of signals with closely related integral intensities,
which does not allow the a detailed correlation to each diastereoisomer. The 31Р{1H} NMR
spectrum contains three doublets with corresponding coupling constants through two bonds: P
252.1 (br. d) and P 12.4 (d, 2JРСР 74.1 Hz), 250.1 (br. d) and P 16.1 (d, 2JРСР 82.3 Hz).
The reaction of compound 1 with hexafluoroacetone leads to the formation of 1,3,2-
dioxaphosphepine derivative 5 (Scheme 3). The structure of compound 5 was proved by NMR
13
and IR spectroscopy. The С{1H} NMR spectrum contains characteristic signals for С4 and С5
(C 83.6 and 185.5 ppm), which definitely agree with the 1,3,2-dioxaphosphepine structure. The
characteristic doublet with P 252.9 ppm (2JPCP 82.8 Hz) in the 31Р{1H} NMR spectrum indicates
that the PII-fragment of the molecule has not changed, despite an excess of hexafluoroacetone
and prolonged exposure. This result may be caused by the presence of the bulky six-membered
heterocycle at С4b as well as by the high energetic benefit of the phosphoryl group formation
from the Р(σ3λ3)-atom. The structure of compound 5 was confirmed by single crystal X-ray
diffraction studies (Figure 2).
Scheme 3. The reaction of phosphonite 1 with hexafluoroacetone.
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F103
C10
F112
F113
C8B
C7B
C12B
C5B
F102
N1B
N2B
C9B
C11
O3
F101
C4
C11B
C6B
F111
C10B
C5
O5
C5A
C4B
O1
P2
O2
P3B
C9A
C6
C7
C9
C8
Figure 2. Molecular structure in the crystal and atom-labeling scheme for 5 (30 % thermal
ellipsoids). Selected bond lengths (Å), bond and torsion angles (): P(2)–O(1) 1.587(2), P(2)–
O(2) 1.446(2), P(2)–O(3) 1.602(2), P(2)–C(4B) 1.748(3), P(3B)–N(2B) 1.676(3), P(3B)–C(4B)
1.711(3), O(1)–C(9A) 1.394(3), O(3)–C(4) 1.418(3), O(5)–C(5) 1.205(4), N(1B)–N(2B)
1.364(3), N(1B)–C(5B) 1.323(3), N(2B)–C(6B) 1.438(3), C(4)–C(5) 1.556(4), C(4B)–C(5B)
1.418(3), C(5)–C(5A) 1.495(4), O(2)–P(2)–O(1) 114.7(1), O(2)–P(2)–O(3) 113.5(1), O(1)–P(2)–
O(3) 101.9(1), O(2)–P(2)–C(4B) 117.5(1), O(1)–P(2)–C(4B) 104.1(1), O(3)–P(2)–C(4B)
103.4(1), N(2B)–P(3B)–C(4B) 88.3(1), C(9A)–O(1)–P(2) 123.4(1), C(4)–O(3)–P(2) 122.5(1),
C(5B)–N(1B)–N(2B) 109.0(2), N(1B)–N(2B)–C(6B) 117.7(2), N(1B)–N(2B)–P(3B) 117.4(2),
C(6B)–N(2B)–P(3B) 124.88(19), C(5B)–C(4B)–P(3B) 110.7(2), C(5B)–C(4B)–P(2) 127.9(2),
P(3B)–C(4B)–P(2) 121.5(2), N(1B)–C(5B)–C(4B) 114.6(2), N(1B)–C(5B)–C(12B) 118.8(2),
O(2)–P(2)–O(1)–C(9A) 48.8(2), O(3)–P(2)–O(1)–C(9A) –74.3(2), O(1)–P(2)–O(3)–C(4)
77.2(2), C(4B)–P(2)–O(3)–C(4) –175.1(2), O(1)–P(2)–C(4B)–P(3B) –135.8(1), O(2)–P(2)–
C(4B)–P(3B) –7.8(2), O(1)–P(2)–C(4B)–C(5B) 43.4(2), O(2)–P(2)–C(4B)–C(5B) 171.4(2),
C(7B)–C(6B)–N(2B)–N(1B) 38.8(3), C(11B)–C(6B)–N(2B)–P(3B) 40.6(3).
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The reaction of chloral with compound 1 (20 C) is different from the one with 2-R-4H-
benzo[e]-1,3,2-dioxaphosphinin-4-one.35 It proceeds by two pathways including Perkow reaction
(pathway 1) and ring enlargement reaction (pathway 2) (Scheme 4). The first pathway leads to
the formation of dichlorovinylphosphonate 6 and the second one gives the benzo[f]-1,4,2-
dioxaphospepine 7 in a ratio of 9 : 1. The last compound was obtained as a mixture of
diastereoisomers in a 2 : 1 ratio (P 246.1, br. d, P 26.0 d, 2JРСР 65.7 Hz; P 246.1 br. d, P 29.6
d, 2JРСР 68.1 Hz).
The reaction seems to begin with [1+2]-cycloaddition of the PIII atom to chloral with
formation of the intermediate spirophosphorane bearing three-membered cycle (C). According to
Perkow mechanism, the heterocycle (C) eliminates chloride-anion and forms intermediate
quasiphosphonium salt (D). Susequently cleavage of the cyclic PIIIO–C(O) bond in the
intermediate (D) takes place resulting in the final reaction product 6 (pathway 1). The second
pathway involves the formation of the species (C) and its transformation to the reaction product
7 via a betaine-like transition state (E). The phosphepine 7 was gradually crystallized from the
reaction mixture and isolated.
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Scheme 4. The reaction of phosphonite 1 with chloral.
The introduction of diazaphosphole fragment as exocyclic substituent increases the
sensibility of the compound 1 towards hydrolysis and various transformations during storage.
Compound 6 remains as non-distillable oil after filtration of the reaction mixture from
phosphepine 7. The structure of 6 was established by NMR spectroscopy. The 31Р{1H} NMR
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spectrum contains signals at P 251.9 (br. d) and P 11.3 (d), 2JРСР 84.5 Hz. Thus, PII-fragment of
the molecule 1 remains inactive in this reaction, but strongly affects its synthetic result. It guides
the reaction with chloral predominantly on the way to the dichlorovinylphosphonate 6 (Perkow
pathway).
Crystallization allows to isolate the major isomer of 1,4,2-dioxaphosphepine 7. The
structure of this compound was established by NMR spectroscopy and single crystal X-ray
diffraction studies. The geometry of the molecule 7 is shown in Figure 3.
The X-ray structure of compound 7 was published earlier in our preliminary
communication43 without a detailed discussion. Here comparative analysis of the structures of
the three compounds synthesized (1, 5, 7) is presented. There is one independent molecule of
each compound in the asymmetrical unit.
Cl2
Cl1
Cl3
C12B
N2B
C10
C5B
C4B
O2
O4
C3
N1B
C6B
O5
P2
O1
C7B
C5
C5A
C8B
C9B
P3B
C11B
C9A
C9
C10B
C6
C7
C8
Figure 3. The molecular structure of phosphepine 7 in the crystal (30 % of thermal ellipsoids).
P2–O1 1.596(2), P2–O2 1.462(2), P2–C3 1.853(2), P2–C4B 1.763(2), P3B–N2B 1.684(2), P3B–
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C4B 1.715(2), O1–C9A 1.395(3), O4–C3 1.435(3), O4–C5 1.365(3), O5–C5 1.194(3), N1B–
N2B 1.359(3), N1B–C5B 1.323(3), N2B–C6B 1.435(3), C3–C10 1.528(3), C4B–C5B 1.423(3),
C5–C5A 1.480(3), C5A–C6 1.395(4), C5A–C9A 1.381(3), C5B–C12B 1.497(4), O1–P2–O2
110.6(1), O1–P2–C3 98.27(9), O1–P2–C4B 105.8(1), O2–P2–C3 114.7(1), O2–P2–C4B
115.7(1), N2B–P3B–C4B 88.7(1), P2–O1–C9A 129.2(2), N2B–N1B–C5B 109.3(2), P3B–N2B–
N1B 117.0(2), P3B–N2B–C6B 125.4(2), N1B–N2B–C6B 117.6(2), P2–C3–O4 105.3(1), P2–
C3–C10 118.9(2), O4–C3–C10 105.9(2), P2–C4B–P3B 124.2(1), P2–C4B–C5B 125.9(2), P3B–
C4B–C5B 109.9(2), N1B–C5B–C4B 115.1(2), O2–P2–O1–C9A 152.3(2), C3–P2–O1–C9A
31.9(2), O1–P2–C4B–P3B 26.7(2), P3B–N2B–C6B–C7B 15.4(3), O2–P2–C3–C10 56.9(2).
Diazaphosphole heterocycle of molecules 1, 5, 7 is planar (within 0.007(2) Å for 1, within
0.003(2) Å for 5, within 0.000(2) Å for 7, respectively). The deviations of P(2) and С(12b) atoms
from the plane of the heterocycle are rather small (1: P(2) –0.189(1) Å, С(12b) –0.012(4) Å; 5:
P(2) 0.032(1) Å, С(12b) –0.002(4) Å; 7: P(2) –0.037(1) Å, С(12b) –0.007(3) Å); that is why all
those atoms can be considered lying in heterocycle plane with the only exception of P(2) atom in
molecule 1. Dihedral angles between the phenyl substituent and diazaphosphole plane are:
12.1(1) in 1, 39.5(1) in 5; 14.8(2) in 7. The largest value of corresponding dihedral angle for 5
is probably caused by the presence of sterically hindered benzodioxaphosphepine fragment. In
molecules 5 and 7 the configuration of the other phosphorus atom is tetrahedral, whereas it is
pyramidal one in molecule 1.
In molecule 1 the six-membered phosphorus heterocycle adopts the conformation of a P-
envelope: the atom P(2) deviates from the O(1)C(8a)C(4a)C(4)O(3) plane (planar within
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0.052(2) Å) by 0.5918(6) Å. The dioxaphosphepine heterocycle in molecule 5 adopts a twist-boat
conformation (the heteroatom fragment O(1)C(5a)C(9a)C(5) is planar within 0.002 (2) Å. The
atoms P(2) and C(4) deviate from this plane on one side by 0.5318(6) and 0.792(2) Å, the O(3)
atom deviates to the opposite side by –0.643(1) Å). Molecule 7 has a conformation of a distorted
boat (the fragment O(1)C(5a)C(9a)C(5) is planar within 0.010(2) Å, the atoms P(2), C(3) and
O(4) deviate from this plane on one side by –1.1531(5), –1.853(2) and –0.744(2) Å respectively).
The crystal structure of 1, 5 and 7 is stabilized mainly by C–H···O- hydrogen bonds and
π–π-interactions.
In the crystal the molecules of compounds 1 and 7 form the infinite chains along the а
crystallographic axis (see the Supporting Information file) due to short interactions of C–H···O-
type. The parameters of the interactions are: in 1 bifurcate interaction C(8)–H(8)···O(4), С–H
0.90(3) Å, HО 2.58(3) Å, СО 3.405(5) Å, СHО 152(2)°, symmetry operation 1 + x, y, z; and
C(12b)–H(122)···O(4), С–H 0.98(3) Å, HО 2.60(3) Å, СО 3.560(5) Å,  СHО 168(3)°,
symmetry operation 1 + x, y, z; in 7 C(3)–H(3)···O(2), С–H 0.89(2) Å, HО 2.42(2) Å, СО
3.282(3) Å,  СHО 162(2)°, symmetry operation 1 + x, y, z.
In the crystal of compound 5 the sterically hindered benzodioxaphosphepine fragment
causes the formation of molecular dimers, instead of molecular chains like in 1 and 7 (see the
Supporting Information file). Parameters of the short C(6)–H(6)···O(5)-interaction in 5 are: С–H
0.98(3) Å, HО 2.56(3) Å, СО 3.325(5) Å, СHО 135(2)°, symmetry operation –x, 1 – y, 1 –
z. It is interesting to note an alternation of diazaphosphole cycle with phenyl substituent and
dioxaphosphepine cycle in the crystal of 5 (see the Supporting Information file). The packing of
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the molecules in the crystal is also stabilized by π–π-interactions between С(5а-9a) phenyl
substituents. The distance between the centers of the rings is dc 3.810(4) Å, the dihedral angle
between the corresponding planes is α = 12.9°, the shortest distance between the planes is d –
3.26 Å.
Conclusions
Thus, the ability of bis-heterocyclic 2-(5-methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl)-
4H-benzo[e]-1,3,2-dioxaphosphinin-4-one 1 to react with only one molecule of an activated
carbonyl compound was shown in this work. The synthetic result of the reaction is defined by the
sterical and electronic properties of the exocyclic diazaphosphole substituent at the phosphorin-
4-onic phosphorus atom. The regiochemistry of the reaction with hexafluoroacetone appears to
be the same as in the case of 2-R-benzo[e]-1,3,2-dioxaphosphinin-4-ones (phosphepine
pathway). The reaction of compound 1 with esters of mezoxalic and trifluoropyruvic acids leads
to phosphepines as the result of phosphonate-phosphate rearrangement instead of the expected
phosphoranes. It was found, that the main pathway for the interaction of chloral with compound
1 is a Perkow reaction. In all cases the two-coordinated phosphorus atom remains unchanged.
Experimental
General
Melting points were measured with a Stuart digital SMP10 apparatus. Mass spectra were
recorded with a DFS Thermo Electron Corporation instrument (Germany). The energy of
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ionizing electrons was 120 eV and the temperature of ion source was 200 C. The system of
direct input of substances into the source was used. The temperature of the ampoule and
evaporation ranged from 50 C to 350 C. The IR spectra were measured with a Bruker Vector-
22 instrument in KBr pellets. NMR spectra were recorded with a Bruker Avance-400 instrument
1
13
(400 MHz for H and 100.6 MHz for C) in CDCl3 as a solvent. Chemical shifts are given in
ppm (δ) relative to residual CHCl3 signal and coupling constants (J) are reported in Hertz (Hz).
The elemental analyses were obtained with a Euro Vector-3000 analyzer (C, H, N) and by
burning in a stream of oxygen (Cl, P).
X-ray crystallography
Single crystal XRD experiments were carried out with a Bruker Smart APEX II
automatic diffractometer with a two-dimensional CCD detector at a temperature of 293 K
(МоK, graphite monochromator,  = 0.71073 Å, -scan mode). Absorption correction was
carried out using the SADABS program.44 The structure was solved by the direct methods and
refined first in an isotropic and then anisotropic approximation using the SHELXL-9745 and
WinGX46 programs. The hydrogen atoms were found from difference Fourier maps and refined
isotropically. Data collection, unit cell parameters, indexation and refinement were processed
using the APEX2 software.47 The unit cell parameters, coordinates of the atoms and their
temperature parameters have been deposited with the Cambridge Crystallographic Data Centre
(http://www.ccdc.cam.ac.uk) under no. CCDC 862209 and 862208 for the compounds 1 and 5,
respectively. Crystallorgaphic data of 7 have been reported previously.43 The analysis of the
intermolecular interactions and the figures were made using the PLATON48 and ORTEP49
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programs.
Compound 1 (C16H12N2O3P2): triclinic, space group P-1, a = 7.521(2), b = 8.013(2), c =
15.325(5) Å,  = 77.964(4),  = 76.862(3),  = 62.285(2), V = 790.5(4) Å3, M = 342.22, dcalc
=
1.438 g/cm3, Z = 2. Cell parameters and intensities of 7928 reflections, including 3076
independent reflections, 2440 of which had I  2 (Rint = 0.0233), were measured at a
temperature of 293 K (2.75    26.00, index ranges: –9  h  9, –9  k  9, –18  l  18).
The absorption coefficient Mo = 2.90 cm–1, F (000) = 352. The final divergence factors are R =
0.0369, Rw = 0.1124 from 2440 reflections with F2  4; the goodness-of-fit parameter is 0.841,
256 refined parameters.
Compound 5 (C19H12F6N2O4P2): monoclinic, space group P21/c, a = 20.499(17), b =
14.456(12), c = 6.955(6) Å,  = 91.20(1), V = 2060(3) Å3, M = 508.25, dcalc = 1.638 g/cm3, Z =
4. Cell parameters and intensities of 15238 reflections, including 4046 independent reflections,
2941 of which had I  2 (Rint = 0.0467), were measured at a temperature of 293 K (1.99   
26.00, index ranges: –25  h  24, –17  k  17, –8  l  8). The absorption coefficient Mo =
2.96 cm–1, F (000) = 1024. The final divergence factors are R = 0.0437, Rw = 0.1005 from 2941
reflections with F2  4; the goodness-of-fit parameter is 1.035, 346 refined parameters.
Syntheses and spectroscopic data
2-(5-Methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl)-4H-benzo[e]-1,3,2-dioxaphosphi-
nin-4-one (1)
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4-(Dichlorophosphino)-5-methyl-2-phenyl-2H-1,2,3-diazaphosphole (4.28 g, 0.015 mol)
was added to a mixture of 1-trimethylsilyloxy-2-trimethylsilyloxycarbonylbenzene (4.36 g, 0.015
mol) and CH2Cl2 (3 mL) in argon atmosphere. The reaction mixture was dried in vacuo (1.5
Torr) and 4.77 g (93 %) of a light-yellow powder was isolated. Compound 1 thus obtained was
1
used without further purification. m.p. 97-98 °C. Н NMR (400 MHz, CDCl3):  = 8.05 (dd,
3JНCCH = 8.0, 4JНCСCH = 1.9, 1Н, Н-5), 7.30 (dd, 3JНCCH = 7.6, 3JНСCH = 6.6, 1Н, Н-6), 7.59 (ddd,
3
4
3JНCCH = 7.6, JНСCH = 8.3, JНCСCH = 1.6), 7.10 (d, 3JНCCH = 8.2, 1Н, Н-7, 1Н, Н-8), 7.66 (dd,
3JНCCH = 8.5, 4JPNСCH = 1.6, 1Н, Н-7b), 7.38 (dd, 3JНCCH = 8.6, 3JНСCH = 6.7, 1Н, Н-8b), 7.20 (td,
4
13
3JНCCH = 7.6, JНССCH = 2.0, 1Н, Н-9b), 2.69 (s, 1Н, Н-12b). C NMR (100.6 MHz, CDCl3):
(hereinafter the splitting of the signal in the 13C{1H} NMR spectrum is given in parentheses),  =
3
3
5
162.3 dd (br. s) (2JР ОС = 1.5, JНC CС = 8.4, C-4), 118.1 dd (m) ( JР ОСС = 12.0, JР
=
2
4
5
4
2
4a
3b
4a
СРОСС
3
4
2
3.6, C-4a), 131.5 ddddd (d) (1JНС = 165.6, JНC CС = 8.3, JP OCCС = 2.2, JНC С = 2.1-2.2,
5
7
5
2
5
6 5
4
1
3
1
8
5
6
8
6
7
JHC CCС = 1.0, C-5), 124.6 dd (s) ( JНС = 164.0, JНС СС = 7.9, C-6), 136.9 dddd (d) ( JНС
=
3
4
2
161.7, JНС СС = 9.2, JP OCCС = 2.2, JНC С = 1.0, C-7), 120.3 ddddd (d) (1JНС = 164.9,
5
7
2
7
8 7
8
3
2
4
3
3
6
8
7 8
5
8
7
8a
5
8a
JНС СС = 7.7, JНС С = 1.4, JHC CCС = 1.3, C-8), 155.4 ddddd (d) ( JНС СС = 11.0, JНС СС
=
2
4
1
1
8.3, 2JР ОС = 7.3, JНС С = 3.4, JHC CCС = 1.4, C-8a), 148.5 ddq (dd) ( JР
= 63.5, JР С
2
8a
8 8a
5
8a
3b 4b
2 8b
С
2
2
2
= 56.1, 3JНС
= 2.8, C-4b), 158.4 ddq (dd) ( JР
= 23.8, JР СС = 5.5, JНС
= 6.4,
12b 4b
3b 5b
2
5b
12b 5b
СС
СС
С
3
2
4
C-5b), 143.0 dttdd (dd), (2JР
= 10.7, JНС
= 8.7, JНС
=
3b 6b
8b,10b 6b
7b,11b 6b
9b
= 1.7-2.0, JHC
CCС
6b
NС
СС
С
4
1
3
2
3b 6b
7b,11b
3b
7b,11b
NCС
1.0-1.3, JP CP
= 0.8, C-6b), 120.6 ddm (d) (C-11b, JНС
= 161.4, JP
= 9.5,
NС
3
3
2
4
11b 7b
7b 11b
8b,10b 7b,11b
9b
7b,11b
JНС
= 7.5-8.5, JНС
= 7.5-8.5, JНС
= 2.2, JHC
= 1.3, C-7b),
СС
СС
С
CCС
3
3
2
129.6 ddd (s) (C-10b, 1JНС
= 161.0, JНС
= 7.6-7.7, JНС
= 8.6, JНС
= 1.1,
8b,10b
8b 10b
10b 8b
9b 10b
СС
СС
С
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3
5
2
C-8b), 127.8 dtdd (d) (1JНС = 162.5, JНС
8.8, JP
= 1.7, JНС
= 1.0, C-
9b
7b,11b 9b
СС
3b
9b
10b 9b
С
NСCСС
3
3
2
31
9b), 15.4 qdd (dd) (1JНС = 128.8, JР
= 8.4, JР ССС = 1.0, C-12b). P NMR (162.0
12b
3b
ССС
12b
12b
2
2
2
3b
3b
2
СР
MHz, CDCl3):  = 238.5 (br. d, JР СР = 16.6, P-3b), 156.3 (d, JР
= 16.6, P-2). IR (KBr
pellet): ν = 3440, 3100, 3066, 3027, 3012, 2958, 2914, 1734, 1664, 1606, 1579, 1492, 1475,
1457, 1424, 1383, 1346, 1286, 1227, 1206, 1153, 1129, 1070, 1043, 1014, 960, 930, 904, 880,
869, 787, 767, 754, 748, 686, 656, 632, 586, 543, 527, 496, 473 cm–1. MS: m/z (%) = 342 [(M)+,
61]. Anal. Calcd. for 1 (C16H12N2O3P2) (342.22): C, 56.15; H, 3.53; N, 8.19; P, 18.10. Found: C,
56.03; H, 3.73; N, 8.14; P, 17.96 %.
2-(5-Methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl)-2,5-dioxo-4,4-bis(ethoxycarbonyl)-
benzo[f]-1,3,2-dioxaphosphepine (2)
Mesoxalic acid diethyl ester (0.87 g, 0.005 mol) was added to a solution of compound 1
(1.71 g, 0.005 mol) in CH2Cl2 (10 mL) at –10 С. The reaction mixture was kept for 1 day. Then
the solvent was removed in vacuo (0.1 Torr) and a light-yellow oil was obtained. The oil was
washed with a mixture of CH2Cl2 / hexane and dried in vacuo (0.1 Torr) to afford 2.28 g (89 %)
3
4
of 2. 1Н NMR (400 MHz, CDCl3):  = 8.06 (dd, JНCCH = 7.9, JНCСCH = 1.7, 1Н, Н-6), 7.68 (d,
3JНCCH = 8.2, 1Н, Н-7b), 7.59 (ddd, 3JНCCH = 7.4, 3JНСCH = 8.0, 4JНCСCH = 0.8, 1Н, Н-8), 7.38 (dd,
3
3
3JНCCH = 8.1, JНСCH = 7.3, 1Н, Н-8b), 7.27-7.32 (m, 2Н, Н-9b, Н-7b), 7.10 (ddd, JНCCH = 8.2,
4
4
3
2
JP OСCH =1.2, JНCСCH =1.2, 1Н, Н-9), 4.41 (q, JНCCH = 7.1, 2H, CH2), 4.27 (m, А- and B-parts
of АВX3 system, 3JН H = 12.0, 3JНCCH = 7.1, CHAHB), 2.71 (s, 1Н, Н-12b), 1.33 (t, 3JНCCH = 7.1,
А
В
3
3Н, Н-12), 1.18 (t, JНCCH = 7.1, 3Н, Н-15). 13C NMR (100.6 MHz, CDCl3):  = 88.6 d (d)
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3
3
(2JР ОС = 8.3, C-4), 185.3 d (s), ( JНС СС = 3.3, C-5), 125.9 m (d) ( JР ОСС = 1.8, C-5а), 131.8
2
4
6
5
2
5a
3
5
br. ddd (d) (1JНС = 166.3, JНС СС = 8.4, JР ОСССС = 1.4, C-6), 126.6 ddd (d) (1JНС = 164.4,
6
8
6
2
6
7
3
5
3
2
JНС СС = 8.2, JР ОСССС = 1.0, C-7), 137.0 (dddd (s) (1JНС = 164.1, JНС СС = 8.9, JНС С
=
=
9
7
2
7
8
6
8
9 8
2.0, 2JНС С = 1.2, C-8), 122.3 dddd (d) ( JНС = 159.8, JР ОСС = 5.7, JНС С = 2.3, JНС СCC
1
3
2
4
7 8
9
2
9
8 9
6
9
3
3
2
1.0, C-9), 149.2 dddd (s) (2JР ОС = 8.4, JНС СС = 7.0, JНС СС = 5.2, JНС С = 2.3, C-9a),
2
9a
8
9a
6
9a
9 9a
3
3
163.0 dt (d) (3JР ОСС = 7.4, JНС
= 3.4, C-10), 162.0 dt (d) (3JР ОСС = 8.3, JНС
=
2
10
11 10
2
13
14 13
СС
СС
2
1
2
3.4, C-13), 63.7 tq (s) (1JНС = 149.5, JНС
= 4.4, C-11), 63.5 tq (s) ( JНС = 149.5, JНС
11
12 11
14
15 14
С
С
2
= 4.4, C-14), 13.8 qt (s) (1JНС = 127.4, JНС
= 2.6, C-12), 13.7 qt (s) (1JНС = 127.7,
12
11 12
15
С
2
1
1
3
14 15
3b 4b
2 4b
12b 4b
СС
JНС
= 2.6, C-15), 132.1 ddq (dd) ( JР
= 199.2, JР С = 50.3, JНС
= 2.8, C-4b),
С
С
2
2
2
158.9 ddq (dd) (2JР
= 11.0, JР СС = 5.0, JНС
= 6.6, C-5b), 142.6 td (d) ( JР
=
=
3b 5b
СС
2
5b
12b 5b
3b 6b
С
NС
9.0, 3JНС
= 7.9-8.5, JНС
= 2.8, C-6b), 120.6 ddm (d) ( JНС = 162.2, JP
2
1
3
8b,10b 6b
7b,11b 6b
7b
3b
7b
NCС
СС
С
3
3
2
1
11b 7b
9b 7b
= 7.9, JНС
СС
8b 7b
8b
9.7, JНС
= 7.9-8.1, JНС
= 1.4, C-7b), 129.5 ddd (s) ( JНС = 162.3,
СС
С
3
2
1
3
10b 8b
9b 8b
9b
7b,11b 9b
СС
JНС
= 8.1, JНС
= 1.1, C-8b), 128.1 dt (s) ( JНС = 161.4, JНС
= 7.5, C-9b),
СС
С
31
2
15.6 q (s) (1JНС = 129.6, C-12b). P NMR (162.0 MHz, CDCl3):  = 251.3 (br. d, JР СР
=
12b
2
3b
2
3b
2
76.3, P-3b), 14.9 (d, JР
= 76.3, P-2). IR (film): ν = 3412, 3119, 3058, 2985, 2940, 2874,
СР
2696, 1752, 1690, 1603, 1562, 1545, 1494, 1477, 1452, 1388, 1370, 1268, 1239, 1207, 1156,
1113, 1076, 1056, 1021, 925, 851, 831, 781, 738, 703, 628, 584, 557, 512 cm-1. MS: m/z (%) =
516 [(M)+, 0.3], 487 [М – С2Н4, 0.1], 470 [М – OEt + H, 18], 424 [М – 2 C2H4, 3], 398 [М –
C(C(O)OEt)2, 3], 313 [М – C(C(O)OEt)2 – C(O), 40], 121 [C6H4OHC(O), 41], 92 [C6H4O, 24],
77 [C6H5, 36]. Anal. Calcd. for 2 (С23Н22N2O8P2) (516.38): C, 53.50; H, 4.29; N, 5.42; P, 12.00.
Found: C, 53.21; H, 4.33; N, 5.22; P, 12.07 %.
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2-(5-Methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl)-2,5-dioxo-4-trifluoromethyl-4-
ethoxycarbonylbenzo[f]-1,3,2-dioxaphosphepine (3)
Ethyltrifluoropyruvate (2.21 g, 0.013 mol) was added to a solution of compound 1 (4.44
g, 0.013 mol) and diethyl ether (15 mL) at –5 С under argon atmosphere. The reaction mixture
was allowed to reach 20 С during 30 min and then it was kept at room temperature for one day.
The solvent was removed in vacuo (0.1 Torr), the residue was washed with hexane and was dried
in vacuo (0.1 Torr). Compound 3, light-yellow oil, yield 5.32 g (80 %). It gradually crystallizes
during 2 months under an inert atmosphere, m.p. 72-75 C (mixture of diastereoisomers d1 and
3
4
d2). 1Н NMR (400 MHz, CDCl3):  = 8.02 (dd, JНCCH = 7.9, JНCСCH = 1.7, 1Н, Н-6), 7.91 (dd,
4
3
3
3JНCCH = 7.9, JНCСCH = 1.7, 1Н, Н-6), 7.71 (br. d, JНCCH = 8.2, 1Н, Н-7), 7.56 (br. d, JНCCH
=
3
3
4
8.2, 1Н, Н-7), 7.62 (br. ddd, JНCCH = 8.2, JНCCH = 7.9, JНСCCH = 1.4, 1Н, Н-8), 7.51 (br. ddd,
3
4
3JНCCH = 8.2, JНCCH = 7.9, JНСCCH = 1.7, 1Н, Н-8), 7.36 and 7.34 (m, Н-8b), 7.30-7.35 (m, Н-
3
2
7b, Н-9b), 7.02 and 7.28 (br. d, JНCCH = 8.2, Н-9), 4.43 (m, АВ-part of АВХ3-system, JАВ
=
=
10.7, 3JНCCH = 7.2, 2Н, OCН2), 4.19 and 4.06 (m, АВ-part of АВХ3-system, 2JАВ = 10.7, 3JНCCH
7.2, 2Н, OCНAНB), 2.76 (s, 3Н, Н-12b), 2.63 (s, 3Н, Н-12b), 1.32 (t, 3JНCCH = 7.2, 3Н, OCCH3),
3
13
1.11 (t, JНCCH = 7.2, 3Н, OCCH3). C NMR (100.6 MHz, CDCl3):  = 84.6 qd (qd) (2JР ОС
=
=
2
7.2, JFCС = 28.9, C-4), 84.9 qd (qd) (2JР ОС = 7.3, JFCС = 28.9, C-4), 185.6 dd (s) (3JНС СС
2
2
2
6
5
3
4.3, 4JНС ССС = 1.5, C-5), 182.4 br. d (s) ( JНС СС = 4.0, C-5); 125.9 br. m (br. s) (C-5a), 126.7
7
5
6
5
3
1
br. m (br. s) (C-5a), 131.8 dd (s), (1JНС = 166.4, JНС СС = 8.6, C-6), 131.6 dd (s) ( JНС = 166.8,
6
8
6
6
3
3
JНС СС = 8.2, C-6), 126.7 dd (s) (1JНС = 165.4, JНС СС = 7.7, C-7), 126.6 dd (s), (1JНС
=
8
6
7
9
7
7
23
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1
3
2
164.9, 3JНС СС = 7.6, C-7), 137.9 dd (s) ( JНС = 163.5, JНС СС = 8.8, JНСС = 1.3, C-8), 136.8
9
7
8
6
8
8
3
2
1
br. ddd (s) (1JНС = 161.6, JНС СС = 8.8, JНСС = 2.3, C-8), 121.9 dm (d) ( JНС = 160.0-162.0,
8
6
8
8
9
3
3
JРОСС = 6.1, C-9), 121.88 dm (d) (1JНС = 160.0-162.0, JРОСС = 6.3, C-9), 148.6 ddddd (d)
9
9
9
3
2
2
4
(3JНССС = 10.5, JНССС = 9.0, JР ОС = 8.4, JНС С = 3.9, JНС ССС = 1.7, C-9а), 147.9
9а
9а
2
9а
9 9а
7
9а
3
2
2
4
ddddd (d) (3JНССС = 10.5, JНССС = 9.1, JРОС = 8.4, JНС С = 4.0, JНС ССС = 1.7, C-9а),
9а
9а
9а
9 9а
7
9а
2
120.7 qd (qd) (1JFС = 286.5, JРОС = 13.1, C-10), 121.3 br.q (br.q) (1JFС = 285.5, C-10),
10
10
10
3
3
3
161.1 dt (d) (3JНС
= 3.4-3.5, JРОСС = 1.4, C-11), 160.7 dt (d) ( JРОСС = 3.5, JНС
=
12 11
11
11
12 11
ОС
ОС
2
1
2
3.5, C-11), 64.6 tq (s) (1JНС = 150.1, JНС
= 4.5, C-12), 64.2 tq (s) ( JНС = 150.2, JНС
12
13 12
12
13 12
С
С
2
= 4.5, C-12), 13.4 qt (s) (1JНС = 127.9, JНС
= 2.6, C-13); 13.2 qt (s) (1JНС = 127.9,
13
12 13
13
С
2
1
1
3
12 13
3b 4b
2 4b
12b 4b
СС
JНС
= 2.6, C-13), 131.3 ddq (dd) ( JР
= 205.3, JР С = 49.9, JНС
= 2.8, C-4b),
С
С
1
3
2
130.7 ddq (dd) (1JР
= 197.6, JР С = 49.1, JНС
= 2.8, C-4b), 159.0 dqd (dd) ( JР
3b 4b
2 4b
12b 4b
СС
3b 5b
С
СС
2
2
2
= 6.5-6.6, JР СС = 4.5, C-5b), 158.5 dqd (dd) (2JР
= 10.8, JHC
=
12b 5b
2
5b
3b 5b
12b 5b
С
= 11.2, JHC
С
СС
2
3
6.4-6.5, 2JР СС = 4.2, C-5b), 142.4 br. dt (d) ( JРNС = 11.0, JНС
= 8.9, C-6b), 142.1 br. dt
2
5b
6b
8b 6b
CС
3
1
3
(d) (2JРNС = 10.9, JНС
= 8.9, C-6b), 120.4 dm (d) ( JНС = 162.0, JPNCС = 9.7, C-7b),
6b
8b 6b
7b
7b
CС
3
1
3
120.1 dm (d) (1JНС = 162.0, JPNCС = 9.7, C-7b), 129.4 dd (s) ( JНС = 161.9, JНССС = 7.7,
7b
7b
8b
8b
3
C-8b), 129.3 dd (s) (1JНС = 162.0, JНССС = 7.7, C-8b), 128.1 br. dt (s) (1JНС = 163.3,
8b
8b
9b
3
1
3
7b 9b
9b
7b 9b
СС
JНС
= 7.6, C-9b), 128.0 br. dt (s) ( JНС = 163.3, JНС
= 7.6, C-9b), 15.3 br. qd (br. d)
СС
3
31
2
(1JНС = 129.7, JР
= 3.5, C-12b). P NMR (162.0 MHz, CDCl3):  = 252.1 (br. d, JРСР
10b
3b
10b
ССС
= 74.1, P-3b), 250.1 (br. d, 2JРСР = 82.3, P-3b), 16.1 (d, 2JРСР = 82.3, P-2), 12.4 (d, 2JРСР = 74.1,
P-2). IR (film): ν = 3056, 2986, 2941, 2835, 2694, 1770, 1705, 1603, 1493, 1428, 1451, 1387,
1371, 1282, 1224, 1156, 1141, 1069, 1025, 925, 846, 739, 704, 691, 673, 652, 640, 618 cm–1.
24
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MS: m/z (%) = 512 [(M)+, 2], 484 [М – C2H4, 51], 466 [М – OEt – H, 5], 439 [М – C(O)OEt –
H, 1], 421 [М – C(O)OEt – F + H, 1], 403 [М – C(O)OEt – 2F + 2H, 1], 382 [М – C(O)OEt – 3F
+ 2H, 0.2], 238 [C9H8N2O2P2, 6], 222 [C9H8N2OP2, 10], 178 [C8H3O3P, 10], 121 [C7H4O2 + H,
40], 77 [C6H5, 100]. Anal. Calcd. for 3 (С21Н17F3N2O6P2) (512.31): C, 49.23; H, 3.34; N, 5.47; P,
12.09. Found: C, 49.34; H, 3.41; N, 5.39; P, 12.11 %.
2-(5-Methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl)-2,5-dioxo-4,4-bis(trifluoromethyl)-
benzo[f]-1,3,2-dioxaphosphepine 5
Hexafluoroacetone (1.99 g, 0.012 mol) was condensed into a solution of compound 1 (4.0
g, 0.012 mol) dissolved in a mixture of CCl4 / CH2Cl2 (20 mL, 1 : 1) at –40 °C. The reaction
mixture was slowly (8-10 h) warmed up to 20 °C and kept at that temperature for one day. The
colourless crystals of compound 5 formed were filtered off, washed with CCl4 / CH2Cl2-mixture
1
and dried in vacuo (0.1 Torr). Yield 5.54 g, 93 %, m.p. 173-175 °C. Н NMR (400 MHz,
4
3
CDCl3):  = 7.82 (dd, 3JН CCH = 7.9, JН CСCH = 1.6, 1Н, Н-6), 7.77 (m, JН
= 7.8, 2Н, Н-
7
6
8
6
8b
7b
CCH
3
3
4
5
9
8
7
8
6
8
2
8
7b), 7.64 (dddd, JН CCH = 8.2, JН СCH = 7.4, JН CСCH = 1.6, JP OCСCH = 1.1, 1Н, Н-8), 7.47
3
3
3
7b
8b
9b
8b
3
8b
9b
СCH
(m, JН
= 7.7, JН
= 7.4, 2Н, Н-8b), 7.40 (br. m, JН
= 7.4, 1Н, Н-9b), 7.38
CCH
СCH
(br. m, 3JН CCH = 7.9-8.0 Hz, JН CCH = 7.4, 1Н, Н-7), 7.08 (br. d, JН CCH = 8.2, 1Н, Н-9), 2.76
3
6
7
8
7
8
9
2
(s, 3Н, Н-12b). 13C NMR (100.6 MHz, CDCl3):  = 83.6 sept.d (sept.d) (2JFCС = 30.3, JР ОС
=
4
2
4
3
4
7.6, C-4), 185.5 ddd (d) (3JНС СС = 4.3, JР ОСС = 1.9, JHCCСС = 1.7, C-5), 128.0 br.m (br.s)
6
5
2
5
5
3
2
4
4
(C-5а). 132.4 ddddd (d) (1JНС = 166.4, JНС СС = 8.3, JНC С = 2.6, JР ОССС = 1.2, JНC ССС
=
6
8
6
7 6
2
6
9
6
3
2
4
1.2, C-6), 126.5 dddd (d) (1JНС = 165.2, JНС СС = 8.1, JНС С = 1.1, JP OCСС = 1.1, C-7),
7
9
7
8 7
2
7
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3
2
136.8 ddd (s) (1JНС 163.3, JНС СС = 9.0, JНС С = 2.1, C-8), 121.7 ddddd (d) (1JНС = 165.8,
8
6
8
9 8
9
3
3
2
4
3
2
9
7
9
8 9
6
9
8
9a
JР ОСС = 8.1, JНС СС = 8.0, JНС С = 1.2, JНС ССС = 1.2, C-9), 148.0 ddddd (d) ( JНС СС
=
3
2
2
4
6
9a
2
9a
9 9a
7
9a
10.4, JНC СС = 9.0, JР ОС = 8.2, JНС С = 4.1, JНС ССС = 1.7, C-9а), 120.1 qdq (qdq)
3
4
1
3
(1JFС = 288.3, JР ОСС = 3.0, JFC
= 1.1, C-10), 120.0 qdq (qdq) ( JFС = 290.0, JР ОСС
10
2
10
11 10
11
2
11
CС
1
1
3
= 10.0, 4JFC
= 1.3, C-11), 130.1 ddq (dd) ( JР
= 204.9, JР С = 49.0, JНС
= 2.8,
10 11
3b 4b
2 4b
12b 4b
СС
CС
С
2
2
C-4b), 159.2 ddq (dd) (2JР
= 10.5, JР СС = 4.4, JНС
= 4.2, C-5b), 142.7 dtt (d)
3b 5b
СС
2
5b
12b 5b
С
3
2
(2JР
= 11.1, JНС
= 8.5-9.0, JНС
= 2.7, C-6b), 120.9 dm (d) (1JНС = 162.2,
3b 6b
NС
8b 6b
7b 6b
7b
СС
С
3
3
3JP
= 9.6, JНС
= 6.5-7.5, JНС
= 7.0, C-7b), 129.8 ddd (s) (1JНС = 162.6,
3b
7b
NCС
7b 7b
9b 7b
8b
СС
СС
3
2
1
3
5
8b 8b
8b
9b
7b 9b
3b
9b
NСССС
JНС
= 7.5, JНСС = 1.2, C-8b), 128.7 dtd (d) ( JНС = 162.5, JНС
= 7.6, JР
СС
СС
= 1.6, C-9b), 15.6 q (s) (1JНС = 129.6, C-10b). 31P NMR (162.0 MHz, CDCl3):  = 253.2 (br. d,
2
2
2
3b
3b
2
СР
JР СР = 82.8, P-3b), 15.8 (d, JР
= 82.8, P-2). IR (KBr pellet): ν = 3436, 3103, 3035, 2998,
2926, 2853, 1708, 1693, 1602, 1573, 1493, 1481, 1448, 1427, 1383, 1357, 1277, 1247, 1234,
1210, 1173, 1151, 1124, 1066, 1036, 1020, 980, 945, 931, 891, 878, 849, 786, 767, 754, 739,
712, 677, 651, 602, 579, 565, 543, 517, 500, 481, 457 cm–1. MS: m/z (%) = 481 [MH – CO,
100]+. Anal. Calcd. for 5 (С19Н12F6N2O4P2) (508.25): C, 44.90; H, 2.38; N, 5.51; P, 12.19.
Found: C, 44.95; H, 2.39; N, 5.47; P, 12.07 %.
2-(5-Methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl)-2,5-dioxo-4-trichloromethyl)-
benzo[f]-1,4,2-dioxaphosphepine 7
A mixture of compound 1 (2.74 g, 0.008 mol), CH2Cl2 (10 mL), diethyl ether (10 mL),
and chloral (1.18 g, 0.008 mol) was kept for 5 days. A crystalline precipitate was gradually
26
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formed. Filtration and washing with hexane followed by drying in vacuo (0.1 Torr) afforded 0.32
g (9 %) of compound 7 (d1, d2) as colorless crystals, m.p. 165-171 °C. After recrystallization
1
from CH2Cl2 was obtained 0.18 g (5 %) of compound 7 (d1), m.p. 169-170 °C. Н NMR (400
3
4
MHz, CDCl3, d1):  = 5.11 (d, 2JPCH = 2.8, Н-3), 8.02 (dd, JН CCH = 7.8, JН CCCH = 1.8, Н-6),
3
7
6
8
6
3
4
7.40 (m, H-9b, Н-7), 7.75 (m, Н-7b), 7.68 (dddd, 3JН CCH = 8.3, JН CCH = 7.4-7.5, JН CCCH
=
=
9
8
7
8
6
8
1.8, 5JPOCCCH = 1.0, Н-8), 7.45 (m, Н-8b), 7.07 (ddd, JН CCH = 8.3, JН CCCH = 1.2, JPOCCH
3
4
4
8
8
9
7
9
9
1.0, Н-9), 2.82 (s, Н-12b). 13C NMR (100.6 MHz, CDCl3):  = 86.0 ddd (dd) (1JНС = 146.2,
3
1
3
3
3
3
II
3
6
5
5a
JРС = 104.5, JP СPС = 2.9, C-3), 163.7 br. d (br s) ( JHС CС = 6.0, C-5), 126.4 m (d) ( JPOCС
3
1
= 6.2, C-5a), 133.9 br. dd (d) (1JНС = 166.3, JНС СC = 8.7, C-6), 127.6 br. dd (d) ( JНС = 166.0,
6
8
6
7
3
5
1
3
2
9
7
7
8
6
8
9 8
JНС СC = 7.8, JPOCCCС = 1.7, C-7), 136.1 br. ddd (d) ( JHС = 165.6, JНС CC = 8.4, JHС С
=
1
3
3
1.3, 4JPOCCС = 1.0, C-8), 123.7 br. ddd (d) ( JHС = 165.0-166.0, JНС CC = 8.5, JPOCС = 3.9, C-
8
9
7
9
9
2
1
1
9), 93.5 dd (d) (2JРС C = 6.5, JНС C = 6.5, C-10), 133.0 ddq (dd) ( JР
= 201.6, JP С
=
3 10
3 10
3b 4b
2 4b
С
3
3
= 3.5, C-4b), 159.7 m (dd) (2JР
= 7.8, JP СС = 4.3, C-5b), 142.6 m (d)
12b 4b
3b 5b
СC
2
5b
48.6, JHС
CС
3
(1JР NC = 11.1, C-6b), 120.8 ddm (d) (1JНС = 161.1, JP
= 9.8, C-7b), 129.9 dd (s)
II 6b
7b
3b
7b
NCС
3
3
(1JНС = 161.8, JHС
= 8.0, C-8b), 128.8 br. dt (d) (1JНС = 162.6, JHС
= 7.8,
8b
8b’ 8b
9b
7b 9b
CС
CC
1
31
5JP
= 1.5, C-9b), 16.6 q (s) ( JНС = 130.0, C-12b). P NMR (36.46 MHz, CDCl3):  =
3b
9b
10b
NСCCС
2
2
251.9 (br. d, 2JР СР = 84.5, P-3b), 11.3 (d, JР
= 84.5, P ). IR (KBr pellet): ν = 3421, 3411,
2
3b
3b
2
СР
3397, 2884, 1741, 1602, 1591, 1578, 1490, 1478, 1454, 1430, 1382, 1343, 1288, 1266, 1254,
1236, 1214, 1158, 1133, 1112, 1080, 1057, 1040, 1015, 953, 931, 911, 872, 846, 808, 783, 772,
755, 743, 706, 689, 666, 639, 606, 585, 549, 521, 509 cm–1. Anal. Calcd. for 7
27
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(С18Н13Cl3N2O4P2) (489.61): C, 44.16; H, 2.68; Cl, 21.72; N, 5.72; P, 12.65. Found: C, 43.92; H,
2.74; Cl, 21.33; N, 5.57; P, 12.44 %.
After separation of precipitate 7, the filtrate was dried in vacuo (0.1 Torr) and 3.43 g (88
%) of 2-chlorocarbonylphenoxy-2,2-dichlorovinyloxy-(5-methyl-2-phenyl-2H-1,2,3-diazaphos-
1
phol-4-yl)phosphonate 6 was obtained as a colorless oil. Н NMR (400 MHz, CDCl3):  = 8.15
3
7
6
(br. d, X-part of ABMX-system, JН CCH = 8.0, 1Н, Н-6), 7.77 (br. d, XX’-part of ABB’XX’-
3
3
8b
7b
9
8
system, JН
= 8.0, 2Н, Н-7b), 7.71 (br. dd, B-part of ABMX-system, JН CCH = 8.4,
CCH
3
3
7
8
8
9
JН CCH = 7.7, 1Н, Н-8), 7.55 (br. d, A-part ABMX-system, JН CCH = 8.3, 1Н, Н-9), 7.44 (br.
3
3
dd, 3JН
= 8.1, JН
= 7.9, 2Н, Н-8b), 7.36 (br. dd, M-part ABMX-system, JН CCH =
9b
8b
7b
8b
СCH
8
7
CCH
3
7.6, 3JН CCH = 8.0, 1Н, Н-7), 7.35 (br. t, A-part of ABB’XX’-system, JН
= 8.1, 1Н, Н-9b),
6
7
8b
9b
CCH
7.21 (d, 3JPOCH 6.6, 1H, OCH=), 2.75 (s, 3Н, Н-12b). 13C NMR (100.6 MHz, CDCl3):  = 148.3
3
2
2
4
ddddd (d) (3JНС СС = 10.7, JНС СС = 9.0, JРОС = 8.3, JНС С = 3.2, JНC CСС = 1.7, C-9a),
8
9a
6
9a
9a
9 9a
7
9a
3
3
1
126.1 br. ddd (d) (3JНС СС = 8.0, JРОСС = 5.7, JНС CС = 5.8, C-5a), 134.3 dddd (s) ( JНС
=
7
5a
5a
9
5a
6
3
2
3
165.5, JНС СС = 8.5, JНС С = 2.2, C-6), 126.0 dddd (d) (1JНС = 165.3, JНС СС = 7.8,
8
6
7 6
7
9
7
5
1
3
4
2
7
8
6
8
2
8
JР ОСССС = 1.1, C-7), 136.1 ddd (d) ( JНС = 164.0, JНС СС = 8.9, JР ОССС = 1.4, C-8), 122.3
3
3
ddd (d) (1JНС = 159.4, JНС СС = 8.0, JР ОСС = 3.3, C-9); 164.0 br. dd (s) (3JНС СС = 6.7,
9
7
9
2
9
6
5
4
2
JНСССС = 1.2, C-5), 132.9 dd (d) (1JНС = 201.1, JР ОС = 4.5, C-4), 114.7 dd (d) (2JНСС
=
5
4
2
4
10
3
1
1
3
2
10
3b 4b
2 4b
12b 4b
СС
13.8, JР ОСС = 13.8, C-10), 134.7 ddq (dd) ( JР
= 201.8, JР С = 48.7, JНС
= 2.8,
С
2
2
C-4b), 158.7 ddq (dd) (2JР
= 9.7, JР СС = 4.8, JНС
= 4.7, C-5b), 142.7 br. dm (d)
3b 5b
2
5b
12b 5b
СС
С
3
3
(2JР
= 11.1, JНС
= 8.5, C-6b), 120.7 ddm (d) (1JНС = 162.2, JP
= 9.7,
3b 6b
8b 6b
7b
3b
7b
NCС
NС
СС
3
3
1
3
11b 7b
9b 7b
8b
10b 8b
СС
JHC
= 6.0-8.0, JHC
= 7.0, C-7b), 129.6 dd (s) ( JНС = 162.1, JНС
= 8.1, C-
CС
CС
28
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3
5
8b), 128.3 br. dtd (d) (1JНС = 162.2, JНС
= 7.5, JР
= 1.1, C-9b), 15.6 q (s)
9b
7b 9b
3b
9b
NСССС
СС
31
2
3b
(1JНС = 129.7, C-12b). P NMR (162.0 MHz, CDCl3):  = 251.9 (br. d, JР СР = 84.5, P ),
12b
2
3b
2
= 84.5, P2). IR (film): ν = 3107, 3076, 1774, 1708, 1599, 1496, 1478, 1450,
3b
2
11.3 (d, JР
СР
1384, 1342, 1282, 1214, 1195, 1151, 1133, 1073, 1025, 977, 926, 848, 815, 754, 737, 690, 661,
646, 613, 513 cm–1. MS: m/z (%) = 488 [(M)+, 1], 453 [M – Cl, 10], 418 [М – 2 Cl, 1], 406 [М –
CCl2, 3], 377 [М – OCH=CCl2, 5], 358 [М – OCH=CCl2 – Cl, 23], 330 [М – OCH=CCl2 –
C(O)Cl, 5], 176 [C9H8N2P + H, 88]+, 92 [C6H5O, 92]. Anal. Calcd. for 6 (С18Н13Cl3N2O4P2)
(489.61): C, 44.16; H, 2.68; Cl, 21.72; N, 5.72; P, 12.65. Found: C, 43.87; H, 2.81; Cl, 21.51; N,
5.63; P, 12.57 %.
Funding
The work was supported by Russian Foundation for Basic Research (grant 16-03-00451)
and funded also by the subsidy allocated to Kazan Federal University for the state assignment in
the sphere of scientific activities (No. 4.5888.2017/8.9).
Supporting information
Hydrogen bonds in the molecules of compounds 1, 5, 7 and figures of NMR spectra of
compounds 1-3, 5-7 are included in the Supplemental Materials (Figures S 1 – S 57).
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