Intramolecular cyclization of N-arylphosphinimidic isocyanates - Novel approach to a 4a,8a-dihydro-1,3,2λ5-benzodiazaphosphinin-4(3H) -one system

Article abstract of DOI:10.1002/ejic.200800411

A previously unknown type of 1,3,2λ⁵- benzodiazaphosphinin-4(3H)-ones was obtained by intramolecular heterocyclization of novel N-arylphosphinimidic isocyanates. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Full text of DOI:10.1002/ejic.200800411

FULL PAPER
DOI: 10.1002/ejic.200800411
Intramolecular Cyclization of N-Arylphosphinimidic Isocyanates – Novel
Approach to a 4a,8a-Dihydro-1,3,2λ5-benzodiazaphosphinin-4(3H)-one System
Anatoliy P. Marchenko,[a] Georgiy K. Koydan,[a] Radomyr V. Smaliy,*[a]
Aleksandra A. Chaykovskaya,[a] Aleksandr M. Pinchuk,[a] Andrey A. Tolmachev,[b] and
Oleg V. Shishkin[c]
Keywords: 1,3,2λ5-Benzodiazaphosphinin-4(3H)-one / Heterocyclization / Phosphinimidic isocyanates / Phosphinous iso-
cyanate
A
previously unknown type of 1,3,2λ5-benzodiazaphos-
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
phinin-4(3H)-ones was obtained by intramolecular hetero-
cyclization of novel N-arylphosphinimidic isocyanates.
Introduction
Phosphorus-containing heterocycles are of great interest
as model compounds for fundamental investigations,[1] li-
gands in metal-complex catalysis,[2] and physiologically
active compounds or precursors for their synthesis,[3] and
they are also used in other fields. However, in comparison
to sulfur- and nitrogen-containing analogues, the structural
diversity of numerous phosphorus-containing heterocycles
remains highly limited to date,[4] because of significant
limitations in the known methods of their synthesis. There-
fore, the search for phosphorus analogues that are effective
in the synthesis of other heterocycles is not solely of great
theoretical interest but also of practical importance. Our
attention focused on widely used reactions involving the in-
tramolecular cyclization of imino isocyanates of type 2
(Scheme 1) leading to the corresponding quinazolin-4(3H)-
ones 3. For the first time this conversion was observed when
the corresponding amidines 1 were treated with phosgene
or oxalyl chloride.[5]
Scheme 1.
heterocyclization process was impossible because of the
presence of substituents at both the “ortho” positions of the
phenyl ring. It could be assumed that the conversion, sim-
ilar to the one presented in Scheme 1, would be possible
when the carbon atom adjacent to the isocyanate group is
replaced by a phosphorus atom (see Scheme 2), since elec-
tron-donating properties of the phosphinimine fragment
and C-carbamoylating properties of phosphorus isocyan-
ates are well known.[7–10] The route proposed leads to a
previously unavailable type of 1,3,2λ5-benzodiazaphosphi-
nin-4(3H)-one 5 containing an endocyclic P=N double
bond (for the synthesis of the closest topological analogues
see refs.[11–13]).
The intermediate 2 cannot be isolated as it undergoes
cyclization to 4(3H)-quinazolinone (3) in situ. Later, other
reactions leading to intermediates 2 were found;[6] however,
in all cases the corresponding quinazolin-4(3H)-ones 3 were
the final reaction products, excluding the cases where the
[a] Institute of Organic Chemistry, National Academy of Sciences
of Ukraine,
Murmanska 5, 02094 Kyiv 94, Ukraine
Fax: +380445373253
E-mail: r.smaliy@mail.enamine.net
Scheme 2.
[b] National Taras Shevchenko University,
62 Volodymyrska st., 01033 Kyiv, Ukraine
[c] Department of X-ray Diffraction Study and Quantum Chemis-
try, STC “Institute for Single Crystals”, National Academy of
Science of Ukraine,
Results and Discussion
60 Lenina ave., 61001 Kharkiv, Ukraine
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
It is important to note that compounds 6 belong to the
least studied type of phosphorus isocyanates, i.e. phosphin-
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Intramolecular Cyclization of N-Arylphosphinimidic Isocyanates
imidic isocyanates. There are only a few representatives of
this type of compounds described in the literature,[14–17] and
their properties are little studied. For the synthesis of N-
arylphosphinimidic isocyanates we used an imination reac-
tion with trivalent isocyanate 6, which exists as a monomer
unlike the majority of trivalent phosphorus isocyanates,[18]
probably because of the steric effect of the tert-butyl groups.
The previously unreported compound 6 is a colorless liquid
distillable under vacuum (Scheme 3).
Scheme 3.
We established that the reaction of isocyanate 6 with a
set of aryl azides (Scheme 4, Table 1) in benzene at 20–
25 °C indeed leads to the formation of the corresponding
2,2-di-tert-butyl-4a,8a-dihydro-1,3,2λ5-benzodiazaphosphi-
Scheme 4.
nin-4(3H)-ones. It can be seen from Table 1 that this is a electron effects of the substituents and the steric factors. In
general reaction which proceeds quite easily as in the case the case of halogen-containing aryl azides the reaction
of unsubstituted phenyl azide. In the case of phenyl azide slows down and the yields of the cyclization products de-
derivatives the reaction rate and yield depend on both the crease. According to data on the Staudinger reaction, the
Table 1. Compounds 5a–g: structure, reagents, and reaction conditions.
[a] Isolated yield.
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FULL PAPER
interaction of isocyanate 6 with azides proceeds via the cor-
responding triazenes 7 confirmed by 31P NMR spec-
troscopy, which suggest that steps (i) and (ii) proceed
quickly and that the heterocyclization step (iii) is the rate-
determining one.
Compounds 5a–g are colorless crystalline substances,
slightly soluble in most organic solvents, and melting with
decomposition at 300 °C.
The reaction of isocyanate 6 with 2,4,6-trimethylphenyl
azide (8), which excludes the possibility of further heterocy-
clization, gives stable phosphinimidic isocyanate 9 in high
yield (Scheme 5). Compound 9 is a colorless, distillable li-
quid that is stable under inert conditions. As with other
isocyanates it easily reacts with dimethylamine forming the
corresponding N-phosphorylated urea 11, which was also
synthesized by another route (Scheme 5). The result ob-
tained is an additional confirmation of the intermediate
compounds 4a–g in the transformation of 4.
Figure 1. Structure of compound 5e in the crystal.
Conclusions
Novel di-tert-butylphosphinous isocyanate exists as a
monomer because of steric factors. It was iminated with
a set of aryl azides to give poorly known phosphinimidic
isocyanates that spontaneously cyclized into previously
unknown
4a,8a-dihydro-1,3,2λ5-benzodiazaphosphinin-
4(3H)-one systems. An alternative synthetic approach to
4a,8a-dihydro-1,3,2λ5-benzodiazaphosphinin(e)-4(3H)-(thi)-
ones has been proposed.
Experimental Section
General: NMR spectra were recorded with a Varian VXR-300 spec-
trometer: 1H NMR (300 MHz) spectra were recorded with TMS as
an internal standard; 31P NMR (121 MHz) spectra were recorded
with 85% H3PO4 as an external standard. IR spectra were recorded
with a UR-20 spectrometer for samples in KBr discs. Mass spectra
were recorded with an Agilent 1100 Series LC/MSD system. All
reactions were carried out under dry argon using Schlenk-type
glassware. All solvents, including deuterated solvents used for
NMR spectroscopy, were dried and distilled prior to use.
Scheme 5.
The introduction of the isocyanate group into chloro-
phosphinimide can serve as an alternative method for the
synthesis of phosphinimidic isocyanates, because prolonged
heating of compound 12 in the presence of sodium cyanate
gives compound 5e in high yield; the use of potassium rho-
danide in the reaction allowed us to successfully synthesize
its thio analogue 14 (Scheme 6).
X-ray Crystal Structure Analysis of 5e: The crystals of compound
5e are monoclinic; at 20 °C a = 17.801(2), b = 7.869(1), c =
12.193(2) Å, β = 100.83(1)°, V = 1677.5(4) Å3, Mr = 308.35, Z =
4, space group P21/c, dcalcd.
= =
1.221 g/cm3, µ(Mo-Kα)
0.170 mm–1, F(000) = 664. Unit cell parameters and intensities of
8735 reflections (3845 independent, Rint = 0.047) were measured
with an “Xcalibur-3” diffractometer (Mo-Kα radiation, CCD detec-
tor, graphite monochromator, ω-scanning, 2θmax = 55°). The struc-
ture was solved by direct methods using the SHELXTL[19] pro-
gram. Positions of hydrogen atoms were located from difference
synthesis of electron density. Hydrogen atoms of butyl groups were
refined by the “riding” model with Uiso = 1.5Ueq of the carrier non-
hydrogen atom; the rest of the hydrogen atoms were refined within
an isotropic approximation. The structure was refined against F2
by a full-matrix least-squares procedure with an anisotropic
approximation for the non-hydrogen atoms where wR2 = 0.142 for
3812 reflections [R1 = 0.061 for 2634 reflections with F Ͼ 4σ(F), S
= 1.099]. CCDC-668559 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Scheme 6.
The structure of compound 5e was confirmed by X-ray
Di-tert-Butylphosphinous Isocyanate (6): A mixture of tBu2PCl
diffraction studies (Figure 1).
(3.74 g, 20 mmol) and sodium cyanate (1.95 g, 30 mmol) was
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Intramolecular Cyclization of N-Arylphosphinimidic Isocyanates
stirred at 70 °C for 20 h. The solvent was then evaporated at 25–
30 °C/10 Torr. The residue was distilled into a cold receiver (ca.
–20 °C), b.p. 22–25 °C/0.05 Torr. The pure product was obtained
(300 MHz, CDCl3): δ = 1.33 (d, J = 15.0 Hz, 18 H), 2.24 (s, 3 H),
2.31 (s, 6 H), 6.83 (s, 2 H) ppm. 31P NMR (121 MHz): δ =
54.9 ppm. MS: m/z = 320 [M]+.
by additional distillation under the same conditions. Yield 3.18 g
N-(Dimethylcarbamoyl)-P,P-dimethylphosphinous Amide (10): A
solution of dimethylamine (0.2 g, 4.4 mmol) in C6H6 (5 mL) was
added to a solution of compound 6 (0.7 g, 3.7 mmol) in C6H6
(5 mL). After 20 min, the solvent was removed in vacuo, and the
product was purified by recrystallization from diethyl ether at
–10 °C. M.p. 109–110 °C. Yield 0.67 g (77%). 1H NMR (300 MHz,
CDCl3): δ = 1.14 (d, J = 11.7 Hz, 18 H), 3.00 (s, 6 H), 4.66 (d, J
= 8.7 Hz, 1 H) ppm. 31P NMR (121 MHz): δ = 56.5 ppm.
1
(85%). IR (KBr): ν = 2280 cm–1. H NMR (300 MHz, C D ): δ =
˜
6
6
1.06 (d, J = 12.5 Hz) ppm. 31P NMR (121 MHz): δ = 103.3 ppm.
Compounds 5a–g. General Procedure: A solution of the correspond-
ing aryl azide (3 mmol) in C6H6 (3 mL) was added to a frozen
solution of compound 6 (0.56 g, 3 mmol) in C6H6 (3 mL). During
the melting of the frozen benzene, the evolution of N2 was ob-
served; after a few hours, the reaction product began to precipitate.
After the time noted in Table 1 (31P NMR control) the reaction
mixture was filtered, the product was washed with benzene
(3ϫ1 mL), and dried in vacuo. For additional analytical and spec-
troscopic data of compounds 5a–g see Supporting Information.
P,P-Di-tert-butyl-N-(dimethylcarbamoyl)-NЈ-mesitylphosphinimidic
Amide (11). (a): A solution of dimethylamine (0.1 g, 2.2 mmol) in
C6H6 (1 mL) was added to a solution of compound 9 (0.4 g,
1.25 mmol) in C6H6 (3 mL). After 24 h, the solvent was removed
in vacuo, and the product was purified by recrystallization from
hexane at –15 °C. Yield 0.35 g (78%). (b): A solution of compound
8 (0.43 g, 2.7 mmol) in C6H6 (2 mL) was added to a solution of
compound 10 (0.62 g, 2.7 mmol) in C6H6 (4 mL). The reaction mix-
ture was refluxed for 30 min, and the solvent was then removed in
vacuo. After 15 h, the by-product precipitated and was removed,
the mother liquor was concentrated in vacuo, and the residue was
recrystallized from pentane (3 mL). M.p. 123–124 °C. Yield 0.32 g
1
Compound 5a: H NMR (300 MHz, [D6]DMSO): δ = 1.23 (d, J =
16.2 Hz, 18 H), 6.81 (t, J = 7.8 Hz, 1 H), 6.98 (d, J = 7.8 Hz, 1 H),
7.98 (t, J = 8.1 Hz, 1 H), 7.81 (d, J = 6.9 Hz, 1 H), 8.06 (d, J =
10.8 Hz, 1 H, NH) ppm. 31P NMR (121 MHz): δ = 52.4 ppm.
1
Compound 5b: H NMR (300 MHz, [D6]DMSO): δ = 1.23 (d, J =
15.3 Hz, 18 H), 2.23 (s, 3 H), 6.63 (d, J = 7.9 Hz, 1 H), 6.79 (s, 1
H), 7.68 (d, J = 8.1 Hz, 1 H), 8.10 (d, J = 11.1 Hz, 1 H, NH) ppm.
31P NMR (121 MHz): δ = 51.5 ppm.
1
(33%). H NMR (300 MHz, CDCl3): δ = 1.27 (d, J = 13.6 Hz, 18
1
Compound 5c: H NMR (300 MHz, [D6]DMSO): δ = 1.21 (d, J =
H), 2.18 (s, 6 H), 2.22 (s, 3 H), 2.59 (s, 6 H), 6.81 (s, 2 H), 9.05 (s,
1 H) ppm. 31P NMR (121 MHz): δ = 53.9 ppm. MS: m/z = 366
[M]+.
15.0 Hz, 18 H), 2.16 (s, 3 H), 2.50 (s, 3 H), 6.45 (s, 1 H), 6.68 (s, 1
H), 7.71 (d, J = 6.6 Hz, 1 H, NH) ppm. 31P NMR (121 MHz): δ =
51.3 ppm.
1
P,P-Di-tert-Butyl-N-(3-methoxyphenyl)phosphinimidic Chloride
(12): A solution of 1-azido-3-methoxybenzene (0.88 g, 5.9 mmol) in
C6H6 (2 mL) was added to a solution of di-tert-butylphosphinous
chloride (1.06 g, 5.9 mmol) in C6H6 (3 mL). After the exothermic
reaction had proceeded for 30 min, the solvent was removed in
vacuo, and the product was purified by distillation. B.p. 150 °C/
Compound 5d: H NMR (300 MHz, [D6]DMSO): δ = 1.22 (d, J =
3
4
15.0 Hz, 18 H), 2.09 (s, 3 H), 2.27 (s, 3 H), 6.83 (dd, J = 8.0, J =
2.5, 1 H), 7.34 (t, J = 8.0 Hz, 1 H), 7.47 (br. s, 1 H) ppm. 31P NMR
(121 MHz): δ = 38.6 ppm.
1
Compound 5e: H NMR (300 MHz, [D6]DMSO): δ = 1.22 (d, J =
15.3 Hz, 18 H), 3.74 (s, 3 H), 6.40 (dd, 3J = 8.7, 4J = 2.1, 1 H),
6.53 (d, J = 2.1 Hz, 1 H), 7.73 (d, J = 8.7 Hz, 1 H), 8.23 (d, J =
10.8 Hz, 1 H, NH) ppm. 31P NMR (121 MHz): δ = 52.2 ppm.
1
0.005 Torr. Yield 1.60 g (90%). H NMR (300 MHz, CDCl3): δ =
1.41 (d, J = 17.1, 18 H), 3.76 (s, 3 H), 6.34 (d, J = 7.2 Hz), 6.5 (s),
6.54 (d, J = 7.8), 7.03 (t, J = 8.1 Hz) ppm. 31P NMR (121 MHz):
δ = 51.7 ppm.
1
Compound 5f: H NMR (300 MHz, [D6]DMSO): δ = 1.23 (d, J =
3
14.7 Hz, 18 H), 6.64 (d, J = 11.5 Hz, 1 H), 7.76 (dd, JHF = 11.7,
2,2-Di-tert-butyl-7-methoxy-1,3,2λ5-benzodiazaphosphinine-4(1H)-
thione (14): A mixture of compound 12 (0.75 g, 2.5 mmol), potas-
sium rhodanide (0.5 g, 5.1 mmol), NaI (10 mg), and CH3CN
(8 mL) was heated and stirred in a pressure tube at 125 °C for 4 h.
The reaction mixture was then filtered, and the residue was washed
with CH3CN (3ϫ5 mL). The mother liquor was concentrated in
vacuo, and the product was washed with water (3ϫ10 mL) and
3JHH = 8.7, 1 H), 7.84 (t, JHH
≈
4JHF = 8.7, 1 H), 8.06 (d, J =
3
10.8 Hz, 1 H, NH) ppm. 31P NMR (121 MHz): δ = 52.8 ppm.
1
Compound 5g: H NMR (300 MHz, [D6]DMSO): δ = 1.22 (d, J =
13.5 Hz, 18 H), 6.87 (d, J = 8.1 Hz, 1 H), 7.03 (s, 1 H), 7.43 (d, J
= 8.1 Hz, 1 H), 8.44 (d, J = 10.8 Hz, 1 H, NH) ppm. 31P NMR
(121 MHz): δ = 52.8 ppm.
2,2-Di-tert-butyl-7-methoxy-1,3,2λ5-benzodiazaphosphinin-4(3H)-
one (5e). Procedure 2: A mixture of compound 12 (1.52 g, 5 mmol),
sodium cyanate (0.92 g, 6.1 mmol), NaI (10 mg), and CH3CN
(8 mL) was heated and stirred in a pressure tube at 100 °C for
110 h. The solvent was then removed in vacuo, the residue was
washed with water (4ϫ10 mL), dried, and then washed with C6H6
(3ϫ20 mL). Yield 1.40 g (90%).
1
dried under reduced pressure. M.p. 310 °C. Yield 0.45 g (56%). H
NMR (300 MHz, [D6]DMSO): δ = 1.24 (d, J = 14.1 Hz, 18 H),
3
4
3.77 (s, 3 H, OMe), 6.43 (dd, JHH = 9 Hz, 1 H, JHH = 2.4 Hz, 6-
4
2
H) 6.47 (d, JHH = 2.4, 1 H, 8-H), 8.45 (d, JPH = 9.3 Hz, 1 H,
NH), 8.62 (d, 3JHH = 9.0 Hz, 1 H, 5-H) ppm. 31P NMR (121 MHz):
δ = 46.0 ppm. MS: m/z = 323 [M]+.
Supporting Information (see footnote on the first page of this arti-
cle): C,H,N,P analytical data for compounds 5a–g and crystal
structure description for compound 5e.
P,P-Di-tert-butyl-NЈЈЈ-mesitylphosphinimidic Isocyanate (9): A solu-
tion of azide 8 (0.48 g, 4 mmol) in C6H6 (4 mL) was added to a
frozen solution of compound 6 (0.79 g, 4 mmol) in C6H6 (5 mL).
During the melting of the frozen benzene, the evolution of N2 and
a strong exothermic effect were observed. The temperature of the
reaction mixture was kept in the range 15–20 °C. The reaction was
complete after 15 min, and the solvent was removed in vacuo. The
product was extracted with pentane (2ϫ10 mL), and, after the sol-
vent was removed, the product was purified by vacuum distillation.
B.p. 150–160 °C/0.005 Torr. Yield 1.15 g (90 %). 1H NMR
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Received: December 18, 2007, revised April 22, 2008
Published Online: June 19, 2008
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