ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 8, pp. 1617–1621. © Pleiades Publishing, Ltd., 2009. Original Russian Text © S.F. Malysheva, A.V. Artem’ev, N.K. Gusarova, B.V. Timokhin, A.A. Tatarinova, B.A. Trofimov, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 8, pp. 1259–1263.

Synthesis of New Secondary Phosphine Chalcogenides with Bulky Substituents from Aryl(hetaryl)ethenes, Red Phosphorus, Sulfur, and Selenium S. F. Malysheva, A. V. Artem’ev, N. K. Gusarova, B. V. Timokhin, A. A. Tatarinova, and B. A. Trofimov Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, ul. Favorskogo 1, Irkutsk, 664033 Russia e-mail: [email protected] Received Februaty 24, 2009

Abstract—Phosphine generated along with hydrogen from red phosphorus and aqueous potassium hydroxide selectively reacts with aryl(hetaryl)ethenes (α-methylstyrene, 2-vinylnaphthalene and 5-vinyl-2methylpyridine) in superbasic system KOH–DMSO(H2O) to give secondary phosphines. The latter are practically quantitatively oxidized by elemental sulfur or selenium (20–25оС, toluene, 0.5 h), to afford the hitherto unknown secondary phosphine chalcogenides with bulky arylalkyl pyridine and naphthyl substituents.

DOI: 10.1134/S1070363209080052 Secondary phosphine chalcogenides R2P(X)H (X = O, S, Se) due to their ability to exist in a tautomeric form R2P–XH are effective chemolabile ligands in metal complex catalysis [1, 2] of the cross-coupling reactions of Tamao–Kumada–Corriu [3], SuzukiMiyaura [4], Heck, Stiles [5], Sonogashira [6], Negishi [7]). An advantage of hydrochalcogenophosphoryl compounds as ligands in comparison with the conventionally used phosphines is their higher oxidative stability [3]. In the last years the phosphine chalcogenide ligands with sterically bulky substituents were also successfully used for the design of metal complex catalysts. For example, di(tert-butyl)phosphine chalcogenides t-Bu2P(X)H (X = O, S) in conbination with bis(cyclooctadienyl)nickel Ni(COD)2 effectively catalyze the Tamao-Kumada-Corriu reaction of arylchlorides with arylmagnesium halides [8]. However, as a rule, the synthesis of these phosphine chalcogenide ligands is laborious, multistep and ecologically hardly acceptable since it is based on the reactions of toxic and aggressive phosphorus halides with organometal compounds. Recently, a new general convenient approach to the synthesis of secondary phosphine chalcogenides has been developed [9–13]. The approach is based on the selective reaction of nucleophilic addition of phos-

phine PH3 to weakly electrophilic alkenes (arylethenes, vinylpyridines, vinylnaphthalenes) with further oxidation of the secondary phosphines with elemental chalcogenes. Phosphine is generated together with hydrogen (in ~1:1 volume ratio) from red phosphorus and potassium hydroxide in water–toluene medium in a separate flask [14]. In this paper, this effective approach is used for directed synthesis of new sterically hindered secondary phosphine sulfides and phosphine selenides based on hydrophosphination of α-methyl-styrene, 2-vinylnaphthalene and 5-vinyl-2-methylpyridine. For example, the secondary bis(2-phenylpropyl) phosphine selenide was prepared by Scheme 1 including the reaction of red phosphorus with KOH in water– toluene medium at 70–80°С, hydrophosphination of αmethylstyrene with phosphine in a superbasic system KOH–DMSO at 70–75°С with formation of the intermediate secondary phosphine I and subsequent oxidation of the latter (without isolation and purification) with elemental selenium in toluene at room temperature. The yield of phosphine selenide II was 82% (here and hereinafter the yield is calculated on the starting alkene). Similarly, according to Scheme 2, from 2-vinylnaphthalene, elemental phosphorus, and sulfur or

1617

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MALYSHEVA et al. Scheme 1. Me

Me Pn

KOH/H2O PhMe, 70_80oC

PH3/H2

P KOH/DMSO (H2O), 70_75oC

H

Me I

Me

Se

Se

P

PhMe, 20_25oC

Me

H

II Scheme 2.

Pn

KOH/H2O PhMe, 70_80oC

P

PH3/H2

H

KOH/DMSO (H2O), 70_75oC

III X

S8 (Se)

P

PhMe, 20_25oC

H

IV, V X = S (IV), Se (V).

selenium, secondary phosphine sulfide IV and phosphine selenide V with bulky naphthyl substituents were prepared in 88 and 87% yield, respectively. On the example of 5-vinyl-2-methylpyridine it was shown that the developed procedure can be successfully applied for the synthesis of new secondary phosphine chalcogenides VII, VIII with bulky hetarylalkyl substituents (Scheme 3). The yield of secondary phosphine chalcogenides VII, VIII calculated on 5-vinyl-2-methyl-pyridine was 86 and 81%, respectively. Note, that nucleophilic addition of phosphine РН3 to 5-vinyl-2-methylpyridine proceeds under milder conditions (45–50°С , KOH– DMSO) as compared to hydrophosphination of α-

methylstyrene and 2-vinylnaphthalene (Schemes 1 and 2), that can be explained by higher electrophilicity of the double bond of 5-vinyl-2-methylpyridine. Therefore, the hitherto unknown secondary phosphine chalcogenides containing bulky 2-phenylpropyl, 2-(2-naphthyl)ethyl and 2-(2-methylpyrid-5-yl)ethyl fragments were synthesized in high yield from available reagents: red phosphorus, KOH, α-methylstyrene, 2-vinylnaphthalene, 5-vinyl-2-methylpyridine, elemental sulfur and selenium. The obtained secondary phosphine chalcogenides are promising chemolabile ligands for design of metal complex catalysts as well as suitable models for investigation of the diad prototropic tautomerism [15] and reactive synthons for

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SYNTHESIS OF NEW SECONDARY PHOSPHINE CHALCOGENIDES

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Scheme 3.

Me

Pn

Me

KOH/H2O

N

N

P

PH3/H2

PhMe, 70_80oC

Me Me

VI

X

N

S8 (Se)

H

N

KOH/DMSO (H2O), 45_50oC

P

PhMe, 20_25oC

H

N Me VII, VIII X = S (VII), Se (VIII).

atom-saving synthesis of the tertiary phosphine chalcogenides on demand [16–20] based on the reactions of nucleophilic and radical addition of these РН-addends to multiple bonds (C=C, C≡C, C=O). Besides, in the present work the method of synthesis of the intermediate secondary phosphines was improved. The increase of the basicity of the system KOH–DMSO–H2O at the stage of hydrophosphination of the corresponding alkenes allowed to increase the yields of phosphines I, III, and VI with respect to those earlier obtained by 19% [21], 13% [22] and 13% [23], respectively. EXPERIMENTAL IR spectra were recorded on a Bruker IFS-25 in thin layer and in KBr pellets. 1Н, 13С, 31Р and 77Se NMR spectra were registered on a Bruker DPX 400 spectrometer (400.13, 101.61, 161.98 and 76.31 MHz, respectively), with HMDS (1H, 13C) and Me2Se (77Se) as internal standards and 85% Н3РО4 as an external standard (31Р). All experiments were carried out in an inert atmosphere (argon). α-Methylstyrene and 5-vinyl2-methylpyridine were distilled prior to use. 2-Vinylnaphthalene was purified by sublimation under reduced pressure. Phosphine–hydrogen mixture was prepared in a separate flask by adding 50% aqueous solution of KOH (50 g) to the mixture of 20 g of red phosphorus and 50 ml of toluene at 70–80°С . Bis(2-phenylpropyl)phosphine selenide (II). To suspension of 20 g KOH in 50 ml DMSO and 3 ml

H2O flushed with argon and saturated with phosphine– hydrogen mixture 7.0 g of α-methylstyrene in 10 ml DMSO was added dropwise at 70–75°С in the course of 1.5 h upon continuous bubbling of phosphine. The supply of phosphine was stopped, another 3.0 g of αmethylstyrene was added and stirring at this temperature was continued for 30 min, then the reaction mixture was cooled, diluted with water (100 ml), extracted with toluene (100 ml), toluene extracts were washed with water (30 ml×3), dried over potassium carbonate, 3.34 g of amorphous selenium was added. The obtained suspension was stirred at room temperature for 30 min, filtered, solvent was removed, the residue washed with hexane (5 ml×2). 12.11 g (82%) of phosphine selenide II was obtained as a white powder, mp 94–96ºС (hexane). IR spectrum (KBr), cm–1: 3103, 3083, 3061, 2026, 3000, 2959, 2925, 2899, 2869, 2726, 2350, 1948, 1874, 1806, 1751, 1673, 1602, 1583, 1544, 1493, 1453, 1399, 1375, 1358, 1326, 1314, 1305, 1285, 1235, 1196, 1174, 1155, 1089, 1054, 1029, 1011, 997, 934, 914, 881, 846, 819, 804, 763, 699, 663, 620, 579, 555, 542, 531, 491, 440. 1Н NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.23–1.33 m (6H, Me), 2.02-2.33 m (4H, CH2P), 3.19–3.37 m (2H, CH), 5.22 d (PH, 1JPH 439.3), 5.49 d (PH, 1JPH 439.6), 5.87 d (PH, 1JPH 437.7), 7.12–7.30 m (10H, Ph). 13С NMR spectrum (CDCl3), δС, ppm: 22.12 d (Ме 2JPC 16.1 Hz), 22.21 d (Ме, 2JPC 16.4 Hz), 23.67 d (Ме, 2JPC 13.5 Hz), 34.62 (СНРh), 35.07 (СНРh), 35.34 (СНРh), 36.74 d (CH2P, 1JPC 78.0 Hz), 37.18 d (CH2P, 1JPC 78.0 Hz), 38.09 d (CH2P, 1JPC 74.2 Hz), 38.17 d (CH2P, 1JPC 76.3 Hz), 126.46 (C-р), 126.52

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and 126.58 (С-о), 143.39 (C-i, 3JPC 19.4 Hz), 143.44 (C-i, 3JPC 20.4 Hz), 144.59 (C-i, 3JPC 16.1 Hz). 31Р NMR spectrum (CDCl3), δР, ppm: –4.43, –3.75, –2.49 (the ratio of intensities is 13 : 20 : 10). The presence of the three signals in the 31P NMR spectrum can be due to the presence of three asymmetric centers in the molecule. 77Se NMR spectrum (CDCl3), δSe, ppm: –427.54 d (1JPSe 730.0 Hz), –420.96 d (1JPSe 729.6 Hz), –498.36 d (1JPSe 727.5 Hz). Found, %: С 61.55; Н 6.61; Р 8.40; Se 22.96. С18Н23РSe. Calculated, %: С 61.89; Н 6.64; Р 8.87; Se 22.60. Synthesis of phosphine chalcogenides (IV, V). To suspension of 20 g KOH in 45 ml DMSO and 4.5 ml H2O flushed with argon and saturated with phosphine– hydrogen mixture the solution of 3.0 g of 2-vinylnaphthalene in 20 ml DMSO was added dropwise at 70–75°С in the course of 1.5 h upon continuous bubbling of phosphine. The supply of phosphine was stopped, the mixture was stirred at this temperature for 30 min, then cooled, diluted with water (100 ml), extracted with toluene (100 ml), toluene extracts were washed with water (30 ml×3), dried over potassium carbonate, 0.31 g of elemental sulfur or 0.77 g of selenium was added. The suspension was stirred at room tem-perature for 30 min, filtered, the solvent was removed under a reduced pressure, the residue washed with hexane (5 ml×2). Bis[2-(2-naphthyl)ethyl]phosphine sulfide (IV). Yield 3.22 g (88%), yellow powder, mp 99–101ºС (ether). IR spectrum (KBr), cm–1: 3050, 3017, 2924, 2854, 2325, 1918, 1803, 1675, 1628, 1597, 1508, 1467, 1428, 1396, 1367, 1324, 1285, 1271, 1198, 1154, 1143, 1123, 1013, 963, 948, 899, 857, 815, 763, 739, 643, 630, 620, 600, 533, 476. 1Н NMR spectrum (CDCl3), δ, ppm (J, Hz): 2.14–2.29 m (2H, CH2Р), 2.43–2.50 m (2H, CH2Р), 3.01–3.24 m (4H, CH2Nаph), 6.05 d (1Н, РН, 1JРН 440.9), 7.16–7.76 m (14H, Naph). 13С NMR spectrum (CDCl3), δС, ppm: 29.02 (CH2Naph), 31.75 d (CH2P, 1JPC 50.3 Hz), 125.67, 163.32, 126.68, 127.57, 127.70, 128.46, 128.54, 132.29, 133.53, 137.16, 137.48, 137.65 (Naph). 31Р NMR spectrum (CDCl3), δР, ppm: 20.22. Found, %: С 76.85; Н 6.14; Р 8.35; S 8.61. С24Н23РS. Calculated, %: С 76.98; Н 6.19; Р 8.27; S 8.56. Bis[2-(2-naphthyl)ethyl]phosphine selenide (V). Yield 3.58 g (87%), yellow-brown oil. IR spectrum, cm–1: 3051, 3021, 2925, 2858, 2334, 1952, 1804, 1631, 1599, 1508, 1445, 1367, 1271, 1124, 1018, 996, 950, 892, 858, 819, 796, 746, 476. 1Н NMR spectrum (CDCl3), δ, ppm (J, Hz): 2.28–2.35 m (2H, CH2Р),

2.38–2.49 m (2H, CH2Р), 2.99–3.28 m (4H, CH2Naph), 6.00 d (1Н, РН, 1JРН 433.8), 7.13–7.82 m (14H, Naph). 13С NMR spectrum (CDCl3), δС, ppm: 29.86 d (CH2Naph, 2JPC 2.9 Hz), 30.62 d (CH2P, 1JPC 43.5 Hz), 125.79, 126.35, 126.68, 126.80, 127.59, 127.71, 128.58, 132.32, 133.53, 136.84, 136.92, 137.04 (Naph). 31Р NMR spectrum (CDCl3), δР, ppm: 2.27 (1JPSe 710 Hz). 77Se NMR spectrum (CDCl3), δSe, ppm: –414.07 d (1JPSe 710 Hz). Found, %: С 68.35; Н 5.61; Р 7.40; Se 18.96. С24Н23РSe. Calculated, %: С 68.41; Н 5.50; Р 7.35; Se 18.74. Synthesis of phosphine chalcogenides (VII, VIII). To suspension of 20 g KOH in 50 ml DMSO and 6 ml H2O flushed with argon and saturated with phosphine– hydrogen mixture the solution of 10.0 g of 5-vinyl-2methylpyridine in 10 ml DMSO was added dropwise at 45–50°С in the course of 2 h upon continuous bubbling of phosphine. The supply of phosphine was stopped, the mixture was stirred at this temperature for 30 min, then cooled, diluted with water (100 ml), extracted with diethyl ether (70 ml×3), the extract were washed with water (30 ml×3), dried over potassium carbonate, 1.35 g of elemental sulfur or 3.31 g of selenium was added. The suspension was stirred at room temperature for 30 min, filtered, the solvent was removed under a reduced pressure, the residue was washed with hexane (5 ml×2). Bis[2-(2-methylpyrid-5-yl)ethyl]phosphine sulfide (VII). Yield 11.00 g (86%), white crystalline powder, mp 103–105ºС. IR spectrum (KBr), cm–1: 3444. 3096, 3029, 3006, 2919, 2855, 2354, 1639, 1601, 1568, 1491, 1445, 1402, 1334, 1300, 1247, 1213, 1197, 1147, 1029, 1017, 969, 952, 930, 910, 865, 836, 789, 764, 755, 739, 729, 714, 646, 616, 562, 542, 489, 411. 1 Н NMR spectrum (CDCl3), δ, ppm (J, Hz): 2.07–2.40 m (4H, CH2Р), 2.52 s (6H, Me), 2.90–3.26 m (4H, CH2Py), 6.51 d (1Н, РН, 1JРН 441.8), 7.10 d (2Н, CH=С–Me, 3JHН 8.1), 7.46-7.48 m (2Н, CH=С), 8.39 d (2Н, CH=N, 4JHН 1.8). 13С NMR spectrum (CDCl3), δС, ppm: 23.91 (Ме), 25.74 (CH2Py), 31.47 d (CH2P, 1 JPC 50.4 Hz), 123.33 (HС=CMe), 132.13 d (CCH2CH2P, 3JPC 12.6 Hz), 136.60 (CH=С), 148.70 (HС=N), 156.77 (CMe). 31Р NMR spectrum (CDCl3), δР, ppm: 20.17. Found, %: C 63.20; H 7.10; P 10.20; S 10.46. C16H21N2PS. Calculated, %: C 63.13; H 6.95; P 10.18; S 10.53. Bis[2-(2-methylpyrid-5-yl)ethyl]phosphine selenide (VIII). Yield 11.94 g (81%), yellowish-grey powder, mp 91–92ºС (hexane). IR spectrum (KBr), cm–1: 3432, 3098, 3028, 3004, 2919, 2854, 2354, 2344,

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1601, 1567, 1491, 1443, 1400, 1368, 1332, 1300, 1247, 1212, 1195, 1147, 1122, 1030, 1014, 971, 949, 929, 890, 847, 833, 783, 763, 750, 729, 645, 542, 501, 489, 466, 410. 1Н NMR spectrum (CDCl3), δ, ppm (J, Hz): 2.17–2.33 m (2H, CH2Р), 2.40–2.49 m (2H, CH2Р), 2.52 s (6H, Ме), 2.91-3.27 m (4H, CH2Py) 6.05 d (1Н, РН, 1JРН 432.7), 7.11 d (2Н, CH=С–Me, 3 JHН 7.75), 7.48–7.51 m (2Н, CH=С), 8.41 d (2Н, CH=N, 4JHН 1.9). 13С NMR spectrum (CDCl3), δС, ppm: 23.84 (Me), 26.54 (CH2Py), 30.19 d (CH2P, 1JPC 43.8 Hz), 123.39 (HС=CMe), 131.98 d (CCH2CH2P, 3 JPC 12.8 Hz), 136.77 s (CH=С), 148.62 (HС=N), 156.72 (CMe). 31Р NMR spectrum (CDCl3), δР, ppm: 2.24 (1JPSe 718 Hz). 77Se NMR spectrum (CDCl3), δSe, ppm: –216.63 d (1JPSe 718 Hz). Found, %: C 54.74; H 6.12; P 8.91; Se 22.50. C16H21N2PSe. Calculated, %: C 54.71; H 6.03; P 8.82; Se 22.48. ACKNOWLEDGMENTS This work was performed with a financial support from the Russian Foundation for Basic Research (grant nos. 7-03-00562 and 08-03-00251). REFERENCES 1. Walther, B., Coord. Chem. Rev., 1984, vol. 60, p. 67. 2. Aplleby, T. and Woolkins, J.D., Ibid., 2002, vol. 235, p. 121. 3. Li, G.Y., J. Organomet. Chem., 2002, vol. 653, p. 63. 4. Khanapure, S.P. and Garvey, D.S., Tetrahedron Lett., 2004, vol. 45, p. 5283. 5. Wolf, C. and Lerebours, R., J. Org. Chem., 2003, vol. 68, p. 7077. 6. Wolf, C. and Lerebours, R., Org. Biomol. Chem., 2004, vol. 2, p. 2161. 7. Li, G.Y., J. Org. Chem., 2002, vol. 67, no. 11, p. 3643. 8. Li, G.Y. and Marshall, W.J., Organometallics, 2002, vol. 21, no. 4, p. 590. 9. Trofimov, B.A., Brandsma, L., Arbuzova, S.N., Malysheva, S.F., and Gusarova, N.K., Tetrahedron Lett., 1994, vol. 35, p. 7647. 10. Sukhov, B.G., Gusarova, N.K., Ivanova, N.I., Bogdanova, M.V., Kazheva, O.N., Alexandrov, G.G., Dтyachenko, O.A., Sinegovskaya, L.M., Malysheva, S.F.,

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and Trofimov, B.A., J. Struct. Chem., 2005, vol. 46, no. 6, p. 1066. 11. Gusarova, N.K., Bogdanova, M.V., Ivanova, N.I., Сhernysheva, N.А., Sukhov, B.G., Sinegovskaya, L.M., Kazheva, O.N., Alexandrov, G.G., D’yachenko, O.A., and Trofimov, B.A., Synthesis, 2005, no. 18, p. 3103. 12. Trofimov, B.A., Sukhov, B.G., Malysheva, S.F., and Gusarova, N.K., Kataliz v Promyshlennosti, 2006, no. 4, p. 18. 13. Gusarova, N.K., Malysheva, S.F., Kuimov, V.A., Belogorlova, N.A., Mikhailenko, V.L., and Trofimov, B.A., Mendeleev Commun., 2008, vol. 18, no. 5, p. 260. 14. Gusarova, N.K., Malysheva, S.F., Arbuzova, S.N., Brandsma, L., and Trofimov, B.A., Zh. Obshch. Khim., 1994, vol. 64, no. 12, p. 2062. 15. Kabachnik, M.I., Khimiya i primenenie fosfororganicheskikh soedinenii (Chemistry and Application of Organophosphorus Compounds), Мoscow: Akad. Nauk SSSR, 1957, p. 18. 16. Aladzheva, I.M., Odinets, I.L., Petrovskii, P.V., Mastryukova, T.A., and Kabachnik, M.I., Zh. Obshch. Khim., 1993, vol. 63, no. 3, p. 611. 17. Arbuzova, S.N., Gusarova, N.K., and Trofimov, B.A., Arkivoc, 2006, no. 5, p. 12. 18. Gusarova, N.K., Malysheva, S.F., Belogorlova, N.A., Sukhov, B.G., and Trofimov, B.А., Synthesis, 2007, no. 18, p. 2849. 19. Gusarova, N.K., Chernysheva, N.A., Yas’ko, S.V., Kazantseva, T.I., Ushakov, I.A., and Trofimov, B.A., Synthesis, 2008, no. 17, p. 2743. 20. Trofimov, B.A., Gusarova, N.K., Arbuzova, S.N., Ivanova, N.I., Artem’ev, A.V., Volkov, P.A., Ushakov, I.A., Malysheva, S.F., and Kuimov, V.A., J. Organomet. Chem., 2009, vol. 694, no. 5, p. 677. 21. Arbuzova, S.N., Gusarova, N.K., Malysheva, S.F., Brandsma, L., Albanov, A.I., and Trofimov, B.A., Russ. J. Gen. Chem., 1996, vol. 66, no. 1, p. 56. 22. Gusarova, N.K., Shaikhudinova, S.I., Kazantseva, T.I., Malysheva, S.F., Sukhov, B.G., Belogorlova, N.A., Dmitriev, V.I., and Trofimov, B.A., Russ. J. Gen. Chem., 2002, vol. 72, no. 3, p. 371. 23. Gusarova, N.K., Trofimov, B.A., Malysheva, S.F., Shaikhudinova, S.I., Belogorlova, N.A., Arbuzova, S.N., Nepomnyashchikh, K.V., Dmitriev, V.I., Russ. J. Gen. Chem., 1997, vol. 67, no. 1, p. 65.

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