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Tetrakis(diphenylphosphino)allene^†

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Prof. Dr. Hubert Schmidbaur

Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)

Anorganisch-chemisches Institut der Technischen Universität München Lichtenbergstrasse 4, D-8046 Garching (FRG)Search for more papers by this author

Dipl.-Chem. Thomas Pollok,

Dipl.-Chem. Thomas Pollok

Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)

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Prof. Dr. Hubert Schmidbaur,

Corresponding Author

Prof. Dr. Hubert Schmidbaur

Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)

Anorganisch-chemisches Institut der Technischen Universität München Lichtenbergstrasse 4, D-8046 Garching (FRG)Search for more papers by this author

Dipl.-Chem. Thomas Pollok,

Dipl.-Chem. Thomas Pollok

Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)

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First published: April 1986

https://doi.org/10.1002/anie.198603481

Citations: 19

^†

This work was supported by the Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie, Hoechst AG, Knapsack and Frankfurt, and SKW Trostberg.

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A one-pot reaction afforded the title compound 1, R  Ph, in 60% yield via lithiation of 1-diphenylphosphinopropyne with n BuLi followed by reaction with ClPPh₂. The colorless, crystalline allene 1 is very reactive: for example, it reacts with oxygen, sulfur, and selenium to give the corresponding chalcogenides 2a-c.

References

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H. Hopf in S. Patai (Ed.): The Chemistry of Ketenes, Allenes and Related Compounds, Wiley, New York, 1980, p. 848.
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10 Experimental Procedure: 1: A solution of 5 (1.99 g, 8.87 mmol) in 15 mL of THF was metalated at −70°C with the equivalent amount of nBuLi (in hexane). The reaction mixture was allowed to warm up to 20°C and then cooled again to 0°C after 2 h. After slow addition (1 h) of Ph₂PCl (1.96 g, 8.86 mmol) in 10 mL of THF, the mixture was stirred for ca. 15 h and the solvent was then removed; the oily residue was crystallized from ethanol and dried; yield: 1.3 g (56%). Correct elemental analyses were obtained for 1, 7a-c, 8, and 9.
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11 We thank SKW Trostberg for chemicals and advice.
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12 G. Reber, G. Müller, unpublished results.
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13 The reaction of 1(1.17 g, 1.51 mmol) with 2 mL (32.1 mmol) of iodomthane in 50 mL of benzene at 0°C affords, after 3 h, 1.20 g of 8 (87%), decomposition temperature: 203°C. IR: v(C = C = C) = 1880 cm⁻¹. ¹H-NMR (CDCl₃): δ = 2.25 (br. d, J = 12.4 Hz, 3H, CH₃), 6.9–7.9 (m, 40H, C₆H₅). ¹³ C-NMR (CDCl₃): δ = 10.1 (d, J = 55.7 Hz, CH₃), 99.0 (m, CP₂), 117.9 (d, J = 86.9 Hz, Cl), 207.3 (m, CC₂), signals of C2-C6 overlap.–³¹P-NMR (CDCl₃): AB₂X multiplet δ = −7 and + 22. MS (FD): m/z 792 ( M^⊕).
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14 A solution of 1 (1.34 g, 1.73 mmol) and 2 mL (32.1 mmol) of iodomethane in 50 mL of THF was refluxed for 30 min. Upon cooling, 9 separates out as a yellow precipitate (yield: 1.52 g, 99%, m.p. = 225°C (dec.)). IR: vC°C) = 2120 cm⁻¹. MS (FD): m/z 764 ( M^⊕-1,100%), 319 ( M^⊕-21, 40.5). ¹H-NMR (CDCl₃): δ = 2.5–2.9 (m, 9H), 7.4–8.2 (m, 30 H). ¹³C-NMR (CDCl₃): δ = 13.3 (t, ² J(PC) = 48.3 Hz, CH₃C), 18.2 (dt, ¹ J(PC) = 110.3, ³ J(PC) = 4.4 Hz, CP₂), 65.4 (dt, ¹ J(PC) = 191.4, ³ J(PC) = 6.3 Hz, P-C), 120.3 (d, ¹ J(PC) = 99.6, Cl of PPh₂), 120.7 (AXX', N = 91.8 Hz, Cl of PPh₂Me), signals of C2-C6 overlap; 125.6 (dt, ² J(PC) = 36.0, ² J(PC) = 2.4 Hz, C- CC). ³¹P-NMR (CDCl₃): δ = 1.1 (t, ⁴ J(PP) = 7.3 Hz, P^III, 22.7 (d, P^v).
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Volume25, Issue4

April 1986

Pages 348-349

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Tetrakis(diphenylphosphino)allene^†