Synlett 2010(10): 1525-1527  
DOI: 10.1055/s-0029-1219950
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Regioselective Synthesis of Highly Functionalized Arylphosphonates by Cyclocondensation of 1,3-Bis(trimethylsilyloxy)buta-1,3-dienes with 3-Ethoxy-2-phosphonylalk-2-en-1-ones

Olumide Fatunsina, Mohanad Shkoora, Abdolmajid Riahia, Peter Langer*a,b
a Institut für Chemie, Universität Rostock, Albert Einstein Str. 3a, 18059 Rostock, Germany
b Leibniz-Institut für Katalyse an der Universität Rostock e.V., Albert Einstein Str. 29a, 18059 Rostock, Germany
Fax: +49(381)4986412; e-Mail: peter.langer@uni-rostock.de;
Further Information

Publication History

Received 12 February 2010
Publication Date:
25 May 2010 (online)

Abstract

Highly functionalized arylphosphonates were prepared by TiCl4-mediated cyclocondensation of 3-ethoxy-2-phosphonyl­alk-2-en-1-ones with 1,3-bis(trimethylsilyloxy)buta-1,3-dienes.

    References and Notes

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12

Diethyl (1-Ethoxy-3-oxobut-1-en-2-yl)phosphonate (2a)
A mixture of 1a (1.10 g, 1.0 mL, 5.55 mmol), triethyl orthoformiate (1.1 mL, 6.62 mmol) and Ac2O (1.5 mL, 16.0 mol) was stirred for 2 h at 120 ˚C and subsequently for 2 h at 140 ˚C. The resulting mixture was distilled to give 2a as a brownish oil (1.20 g, 86%). ¹H NMR (300 MHz, CDCl3): δ = 1.21-1.24 (m, 6 H, 2 × OCH2CH 3), 1.36 (t, ³ J = 6.9 Hz, 3 H, OCH2CH 3), 2.25 (s, 3 H, CH3), 4.04-4.08 (m, 4 H, 2 × OCH 2CH3), 4.23 (q, ³ J = 7.2 Hz, 2 H, OCH 2CH3), 7.70 (d, ³ J P,H = 11.4 Hz, 1 H, CH). ¹³C NMR (CDCl3, 75 MHz): δ = 15.0, 15.9, 16.0, 20.6 (CH3), 62.2, 62.4, 73.0 (OCH2), 107.3 (d, J C,P = 191 Hz,Cq), 169.9 (d, J CH,P = 25.5 Hz, CH), 195.0 (CO). ³¹P NMR (250 MHz, CDCl3): δ = 19.64. GC-MS (EI, 70 eV): m/z (%) = 250 (5) [M+], 235 (47), 221 (12), 207 (43), 205 (13), 179 (42), 177 (11), 151 (100), 123 (23), 121 (15), 105 (11), 81 (11), 53 (13), 43 (13), 29 (10). HRMS (EI): m/z calcd for C10H19O5P [M]+: 250.09646; found: 250.09666.

13

Diethyl (1-Ethoxy-3-oxo-3-phenylprop-1-en-2-yl)phosphonate (2b)
A mixture of 1b (1.50 g, 1.27 mL, 5.85 mmol), triethyl orthoformiate (1.70 mL, 10.24 mmol), and Ac2O (1.56 mL, 16.61 mmol) was stirred for 36 h at 140 ˚C. The mixture was cooled to 20 ˚C and purified by column chromatography to give 2b as a brownish oil (1.350 g, 74%). ¹H NMR (300 MHz, CDCl3): δ = 1.08 (t, ³ J = 7.1 Hz, 3 H, OCH2CH 3), 1.21 (t, ³ J = 7.0 Hz, 6 H, 2 × OCH2CH 3), 3.94 (q, ³ J = 7.1 Hz, 2 H, OCH 2CH3), 4.01-4.10 (m, 4 H, 2 × OCH 2CH3), 7.34-7.48 (m, 5 H, CHAr), 7.80-7.82 (m, 1 H, CH). ³¹P NMR (250 MHz, CDCl3): δ = 16.25 Hz. ¹³C NMR (75 MHz, CDCl3): δ = 15.1, 16.1, 16.2 (CH3), 62.3, 62.4, 71.4 (OCH2), 106.4 (d, J P,C = 189.3 Hz), 128.2 (2 × CHAr), 129.3 (2 × CHAr), 133.0 (CHAr), 137.6 (d, J P,C = 4.3 Hz), 163.5 (d, J P,C = 21.0 Hz, CH), 192.2 (d, J P,C = 4.8 Hz, CO). IR (neat): 3060 (w), 2982 (w), 2932 (w), 2905 (w), 1716 (w), 1660 (m), 1597 (m), 1448 (m), 1391 (m), 1305 (w), 1244 (s), 1204 (m), 1145 (m), 1050 (m), 1016 (s), 959 (s), 853 (m), 790 (s), 723 (m), 690 (m), 659 (m), 564 (m), 534 (m) cm. GC-MS (EI, 70 eV): m/z (%) = 312 (4) [M+], 297 (3), 283 (11), 267 (53), 239 (25), 211 (17), 183 (21), 159 (14), 151 (34), 129 (45), 105 (100), 77 (54). ESI-HRMS: m/z calcd for C15H22O5P [M + H]+: 313.1199; found: 313.1198.

17

General Procedure for the Synthesis of Arylphosphonates 4a-l To a CH2Cl2 solution (2 mL/1.0 mmol of 2a,b) of 2a,b was added 3a-k (1.1 mmol) and, subsequently, TiCl4 (1.1 mmol) at -78 ˚C. The temperature of the solution was allowed to warm to 20 ˚C over 12 h with stirring. To the solution was added HCl (10%, 20 mL), and the organic and the aqueous layer were separated. The latter was extracted with CH2Cl2 (3 × 20 mL). The combined organic layers were dried (Na2SO4), filtered, and the filtrate was concentrated in vacuo. The residue was purified by chromatography (silica gel, n-heptane-EtOAc) to give 4a-l.

18

Methyl 3-(Diethoxyphosphoryl)-6-hydroxy-2-methyl-benzoate (4a)
Starting with 2a (0.375 g, 1.5 mmol) and 3a (0.429 g, 1.65 mmol), 4a was isolated after chromatography (silica gel, heptanes-EtOAc) as a yellowish oil (0.217 g, 48%). ¹H NMR (300 MHz, CDCl3): δ = 1.24 (m, 6 H, 2 × OCH2CH 3), 2.65 (s, 3 H, CH3), 3.91 (s, 3 H, OCH3), 3.99-4.07 (m, 4 H, 2 × OCH 2CH3), 6.83 (dd, ³ J H,H = 8.6 Hz, 4 J P,H = 3.3 Hz, 1 H, CHAr), 7.90 (dd, ³ J H,H = 9.0 Hz, ³ J P,H = 14.0 Hz, 1 H, CHAr), 11.0 (s, 1 H, OH). ¹³C NMR (75 MHz, CDCl3): δ = 16.2, 16.2, 20.6 (CH3), 52.5 (OCH3), 62.0, 62.0 (OCH2), 114.9 (d, J P,CH = 15.2 Hz, CHAr), 115.9 (d, J P,C = 16.1 Hz), 119.0 (d, J P,C = 193.0 Hz), 139.3 (d, J P,CH = 11.0 Hz, CHAr), 145.8 (d, J P,C = 13.5 Hz), 164.0 (d, J P,C = 3.4 Hz, COH), 171.2 (d, J P,C = 2.4 Hz, CO). ³¹P NMR (250 MHz, CDCl3): δ = 19.56. IR (neat): 2920 (m), 2851 (m), 1733 (m), 1660 (w), 1636 (w), 1580 (m), 1456 (m), 1437 (m), 1376 (w), 1308 (m), 1285 (m), 1199 (m), 1161 (m), 1158 (m), 1016 (s), 961 (m), 906 (m), 844 (m), 793 (m), 741 (m), 678 (w), 614 (w), 535 (m) cm. GC-MS (EI, 70 eV): m/z (%) = 302 (65) [M]+, 287 (50), 274 (20), 270 (48), 259 (17), 242 (100), 229 (18), 227 (13), 214 (84), 197 (43), 186 (21), 167 (17), 161 (31), 158 (23), 134 (15), 105 (19), 77 (27), 65 (10), 51 (12), 29 (14). HRMS (EI): m/z calcd for C13H19O6P [M]+: 302.09138; found: 302.09139.