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Synthesis of Bis(6-chloro-2-oxo-2H-1,2λ5-benzoxa- phosphinin-4-yl)arenes

A. V. Nemtareva, b, A. S. Aniskina, D. S. Baranovb, Zh. Yu. Makarovab, V. F. Mironova, and S. F. Vasilevskiic

a Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia

e-mail: nemtarev@iopc.ru b Kazan (Volga Region) Federal University, ul. Kremlevskaya 18, Kazan, 420008 Tatarstan, Russia

c Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch, Russian Academy of Sciences, Institutskaya ul. 3, Novosibirsk, 630090 Russia

Received January 27, 2014

SHORT COMMUNICATIONS

Diacetylenic compounds of the aliphatic and espe-cially aromatic series are important reagents in organic synthesis. They are successfully used in the prepara-tion of oligomeric and polymeric compounds with practically useful properties via polymerization and polycondensation reactions [1, 2].

The reaction of 2,2,2-trihalo-1,3,2λ5-benzodioxa-phospholes with terminal acetylenes provides a con-venient method of synthesis of 2H-1,2λ5-benzoxa-phosphinine 2-oxide derivatives [3, 4]. The formation of these compounds involves a number of steps, in particular P–C bond formation, replacement of oxygen in the dioxaphosphole fragment by carbon, etc. Up to now, many data have been obtained on the effect of substituents on the phosphorus atom and in the aro-matic ring of 1,3,2λ5-benzodioxaphospholes and at the triple bond of acetylenic component on the formation of 1,2λ5-benzoxaphosphinine derivatives.

In this work we extended the above reaction to di-acetylenic compounds of the aromatic series, 1,4-di-ethynylbenzene, 4,4′-diethynylbiphenyl, and 1,1′-oxy-bis(4-ethynylbenzene). The reactions of phosphorane I with aromatic diacetylenes were carried out in methy-lene chloride at room temperature, and the subsequent hydrolysis afforded 2-hydroxy-2H-1,2λ5-benzoxaphos-phinine 2-oxides II–IV. The reaction was accom-panied by introduction of a chlorine atom into position 6 of 1,2-benzoxaphosphinine with high selectivity. The nature of the aromatic bridging moiety connecting two 1,2-benzoxaphosphinine fragments did not affect the reaction rate or its selectivity, and compounds II–IV were isolated in high yields.

4,4′-(Benzene-1,4-diyl)bis(6-chloro-2H-1,2λ5-benzoxaphosphinin-2-ol 2-oxide) (II). Yield 81%, colorless powder, mp 362°C (decomp.). IR spectrum, ν, cm–1: 3429 br, 3040 br, 2560 br, 2359, 2266, 1593,

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 4, pp. 601–602. © Pleiades Publishing, Ltd., 2014. Original Russian Text © A.V. Nemtarev, A.S. Aniskin, D.S. Baranov, Zh.Yu. Makarova, V.F. Mironov, S.F. Vasilevskii, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 4, pp. 612–613.

DOI: 10.1134/S1070428014040277

II, X = ; III, X = ; IV, X = . O

OPCl3

O2

I

HC X CH(1)CH2Cl2, 20°C

(2) H2O

PO

Cl

X

O OHP

O

Cl

OHO

II–IV

RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 4 2014

NEMTAREV et al. 602

1551, 1503, 1471, 1403, 1336, 1246, 1211, 1154, 1114, 1015, 956, 908, 884, 869, 838, 827, 797, 744, 730, 650, 635, 585, 545, 478, 449, 432, 412. 1H NMR spec-trum, δ, ppm (J, Hz): 6.49 d (2H, 3-H, 2JPH = 17.6), 7.13 d (2H, 5-H, 4JHH = 2.5), 7.35 d (2H, 8-H, 3JHH = 7.7), 7.52 d.d (2H, 7-H, 3JHH = 7.7, 4JHH = 2.5), 7.54 s (4H, 10-H). 31P NMR spectrum: δP 5.13 ppm, d (2JPH = 17.6 Hz). Found, %: C 51.48; H 3.02; Cl 14.07; P 11.87. C22H14Cl2O6P2. Calculated, %: C 52.10; H 2.78; Cl 13.98; R 12.21.

4,4′-(Biphenyl-4,4′-diyl)bis(6-chloro-2H-1,2λ5-benzoxaphosphinin-2-ol 2-oxide) (III). Yield 99%, colorless powder, mp >360°C (decomp.). IR spectrum, ν, cm–1: 3421 br, 3034 br, 2542 br, 2268 br, 1652, 1591, 1550, 1495, 1470, 1398, 1337, 1245, 1223, 1206, 1113, 1012, 962, 909, 889, 869, 848, 824, 798, 751, 671, 635, 614, 585, 565, 544, 450, 419. 1H NMR spectrum, δ, ppm (J, Hz): 6.38 d (2H, 3-H, 2JPH = 17.2), 7.13 d (2H, 5-H, 4JHH = 2.6), 7.23 m (4H, 11-H, AA′ part of AA′XX′ spin system, 3JHH = 8.5), 7.33 d (2H, 8-H, 3JHH = 8.7), 7.46 m (4H, 10-H, AA′ part of AA′XX′ spin system, 3JHH = 8.5), 7.50 d.d.d (2H, 7-H, 3JHH = 8.7, 4JHH = 2.6, 5JPH = 1.4). 31P NMR spectrum: δP 5.32 ppm, d (2JPH = 17.2 Hz). Found, %: C 56.98; H 3.86; Cl 12.73; P 10.14. C28H18Cl2O6P2. Calculated, %: C 57.66; H 3.11; Cl 12.16; P 10.62.

4,4′-[Oxybis(benzene-4,1-diyl)]bis(6-chloro-2H-1,2λ5-benzoxaphosphinin-2-ol 2-oxide) (IV). Yield 62%, colorless powder, mp 306°C (decomp.). IR spec-trum, ν, cm–1: 3436 br, 3061, 3010, 2835, 2543 br, 2266 br, 1600, 1552, 1489, 1471, 1457, 1431, 1399, 1335, 1253, 1236, 1218, 1201, 1123, 1102, 1051, 1007, 957, 942, 906, 852, 820, 772, 751, 725, 666, 653, 614, 574, 535, 484, 449, 415. 1H NMR spectrum, δ, ppm (J, Hz): 6.38 d (2H, 3-H, 2JPH = 17.2), 7.13 d (2H, 5-H, 4JHH = 2.6), 7.24 m (4H, 11-H, AA′ part of AA′XX′ spin system, 3JHH = 8.6), 7.33 d (2H, 8-H, 3JH = 8.7), 7.46 m (4H, 10-H, AA′ part of AA′XX′ spin

system, 3JHH = 8.6), 7.50 d.d.d (2H, 7-H, 3JHH = 8.7, 4JHH = 2.6, 5JPH = 1.1). 31P NMR spectrum: δP 4.16 ppm, d (2JPH = 17.2 Hz). Found, %: C 55.34; H 3.68; Cl 12.21; P 10.09. C28H18Cl2O7P2. Calculated, %: C 56.12; H 3.03; Cl 11.83; P 10.34.

The 1H and 31P NMR spectra were recorded on a Bruker Avance-400 spectrometer at 400.0 and 162.0 MHz, respectively, using DMSO-d6 as solvent. The chemical shifts were determined relative to hexa-methyldisiloxane (internal standard) or residual proton signal of the solvent (1H) or H3PO4 (31P, external standard). The IR spectra were measured in KBr on a Bruker Vector-22 spectrometer. Initial phosphorane I was prepared according to the procedure described in [5]. The reactions with arylacetylenes were carried out in methylene chloride under argon, followed by hydrolysis, under the conditions described previously for the reaction of I with phenylacetylene [6].

This study was performed under financial support by the Russian Foundation for Basic Research (project nos. 12-03-90 703-mob_st, 10-03-00 525).

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