Reaction of salicylalkylenediimines with 2-chloro-4,5-diphenyl-1,3,2- dioxaphospholene

Full text of DOI:10.1134/S1070363210020313

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 2, pp. 366–367. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © R.Kh. Bagautdinova, L.K. Kibardina, A.R. Burilov, M.A. Pudovik, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80,
No. 2, pp. 339–340.
LETTERS
TO THE EDITOR
Reaction of Salicylalkylenediimines
with 2-Chloro-4,5-diphenyl-1,3,2-dioxaphospholene
R. Kh. Bagautdinova, L. K. Kibardina, A. R. Burilov, and M. A. Pudovik
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
fax: (8432) 752253
e-mail: pudovik@iopc.knc.ru
Received July 9, 2009
DOI: 10.1134/S1070363210020313
Reaction of salicyl(cyclo)alkylenediimine Ia–Ic
with 4,5-diphenyl-2-chloro-1,3,2-dioxaphospholene II
was found to occur as a cascade cyclization giving rise
to tetracyclic derivatives IIIa–IIIc of the hexa-
coordinated phosphorus atom of the salt structure
involving intramolecular transannular N→P bond.
H
C
H
C
R
N
N
R
R
N
N
C
C
H
H
Ph
Ph
H2+N
H
O
O
O
O
O
O
Et3N
−B·HCl
HN
H
Ph
Ph
P
+
PCl
P
C
O
C
O
OH
HO
Ph
Ph
O
O
Cl−
Iа−Ic
II
I, III, IV: R = (CH2)2 (а); (CH2)3 (b); cyclohexyl (c).
IIIа−IIIc
IVа
The structure of compounds IIIa–IIIc was proved
IIIc contain poorly resolved signals, therefore only
group analysis of the proton signals was performed on
the basis of chemical shifts without considering the
fine structure of the spectra. The transannular N→P
bond (2.006–2.007 Å) is realized in the compounds
IIIa–IIIc. The intermolecular bonding of similar type
was earlier observed in the series of pentacoordinated
phosphorus derivatives [1–5]. On treating with
triethylamine, the product IIIa undergoes dehydro-
chlorination to give phosphorate IVa of neutral
structure (δР –105.87 ppm).
1
by the IR, Н, and 31Р NMR spectroscopy, mass
spectrometry, and composition, by the elemental
analysis data. The IR spectra of the products IIIa–IIIc
contain absorption bands at 1623–1627 (С=N) and
2590–2724 cm–1 (broadened complex band, NH2+). The
chemical shift of the phosphorus atom at δP from –114
to –122 ppm is characteristic of the hexacoordinated
phosphorus derivatives. Notice that the 31P NMR
spectra of the reaction mixtures of IIIa–IIIc contain
signals indicative of the formation of diastereoisomers
mixture. As a result of fractional crystallization com-
pound IIIa was obtained as the two diastereoisomers
mixture in the ratio 1:1. Compounds IIIb and IIIc
were isolated as individual diastereomers. Due to their
salt structure the 1Н NMR spectra of compounds IIIa–
1,1-Diphenylethenedioxy-3,4,11,12-dibenzo-6-aza-
9-ammonia-2,13-dioxa-1-phospha[8.3.01,10]tridecatri-
3,5,11-ene chloride (IIIa). To a solution of 1.13 g of
salicylethylenediimine Ia in 10 ml of anhydrous
366

REACTION OF SALICYLALKYLENEDIIMINES
367
methylene chloride was added dropwise 1.17 g of
chloroderivative II. After 24 h the precipitate was
separated and washed with diethyl ether. Yield 1.88 g
(82%), light brown powder, mp 165–167°С. IR
spectrum, ν, cm–1: 1607 (Ph), 1627 (C=N), 2597, 2669
1,1-Diphenylethenedioxy-3,4,11,12-dibenzo-6-aza-
9-ammonia-2,13-dioxa-1-phospha[8.3.01,10]tridecatri-
3,5,11-ene (IV). To a suspension of 0.6 g of compound
Ia in 5 ml of anhydrous methylene chloride was added
dropwise 0.2 g of triethylamine. After 5 days the reac-
tion mixture was concentrated and mixed with a small
amount of anhydrous diethyl ether. The precipitate was
filtered off and washed with water to remove tri-
ethylamine hydrochloride. Yield 0.43 g (74%), mp
196–198°С. IR spectrum, ν, cm–1: 1625 (C=N), 3398
(NH2+). Н NMR spectrum (CDCl3), δ, ppm: 3.02 br.s
1
(2H, NH2+), 3.20–3.37 m (1Н, CH2), 3.60 d (1Н, СH2,
2
2JHH 12.29 Hz), 3.77 d (1Н, СH2, JHH 10.25 Hz), 4.10–
4.50 m (1Н, CH2), 4.73 s (1H, PCH), 6.86–7.69 m
(18H, Ph), 8.32 br.s (1H, N=CH). 31Р NMR spectrum
(DMSO-d6), δР, ppm: from –115.98 to –122.60 (1:1).
Mass spectrum (MALDI–TOF), m/z: 507 [M+ – HCl].
Found, %: C 66.44; H 4.92; Cl 6.36; N 5.36; P 5.46.
C30H26ClN2O4Р. Calculated, %: С 66.11; H 4.82; Cl
16.50; N 5.36; P 5.68.
1
(NH). Н NMR spectrum (CDCl3), δ, ppm: 3.11–4.51
m (4H, NCH22), 6.94–7.28 m (18H, Ph), 7.57 d. d (1H,
2
2
PCH, JPH = JHH 7.62 Hz), 8.20 d (1Н, NCH, JHH
4.12 Hz). 31Р NMR spectrum (CDCl3), δР, ppm:
–105.87. Found, %: N 5.73; P 5.97. C30H25N2O4Р.
Calculated, %: N 5.51; P 6.10.
1,1-Diphenylethenedioxy-3,4,11,12-dibenzo-6-aza-
10-ammonia-2,14-dioxa-1-phospha[9.3.01,11]tridecatri-
3,5,12-ene chloride (IIIb). To a solution of 1.23 g of
salicylpropylenediimine Ib in 10 ml of anhydrous
methylene chloride was added dropwise 1.21 g of
chloroderivative II. After 2 days to this reaction
mixture was added 5 ml of anhydrous diethyl ether.
The precipitate was separated and washed with diethyl
ether. Yield 2.0 g (82%), light brown powder, mp 149–
151°С. IR spectrum, ν, cm–1: 1626 (C=N), 2724
(NH2+). 31Р NMR spectrum (CDCl3), δР, ppm: –120.98.
Mass spectrum (MALDI–TOF), m/z: 521 [M+ – HCl].
Found, %: C 66.41; H 5.44; Cl 6.54; N 5.12; P 5.46.
C31H28ClN2O4P. Calculated, %: С 66.59; H 5.66; Cl
6.34; N 5.01; P 5.54.
The IR spectra were recorded on a Vector-22
(Bruker) spectrometer in the range of 400–3600 cm–1
1
from mulls in mineral oil. The Н NMR spectra were
registered on a Avance-600 instrument (600.13 MHz)
relative to signals of the residual protons of deuterated
solvent (chloroform-d). The 31Р NMR spectra were
taken on a Bruker MSL-400 NMR-Fourier spectro-
meter (100.62 MHz). The mass spectra MALDI–TOF
were obtained on a ULTRAFLEX III instrument
(matrix p-nitroaniline).
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Foundation for Basic Research (grant no. 08-03-
00029).
1,1-Diphenylethenedioxy-3,4,11,12-dibenzo-6-aza-
7,8-tetramethyleno-9-ammonia-2,13-dioxa-1-phospha-
[8.3.01,10]tridecatri-3,5,11-ene chloride (IIIc) was
prepared similarly from 1.0 g of salicylcyclohexyl-
diimine Ic and 0.86 g of chloroderivative II. Yield
1.4 g (75%), light brown powder, mp 153.5–154°С. IR
spectrum, ν, cm–1: 1623 (C=N), 2667 (NH2+). 31Р NMR
spectrum (CDCl3), δР, ppm: –105.87. Mass spectrum
(MALDI–TOF), m/z: 561 [M+ – HCl]. Found, %: C
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67.96;
H
5.36; Cl 5.93;
N
4.76;
P
5.06.
C34H32ClN2O4P. Calculated, %: С 68.16; H 5.39; Cl
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 2 2010