Synthesis of Donor-Acceptor Substituted Molecular Caltrops: Strategic Use of an AB₃ Synthon Based on a Tetraphenylmethane Core

Abstract

Using a tetraphenylmethane based AB₃ tecton, a facile synthetic route to donor-acceptor substituted unsymmetrical mole­cular caltrops is described. The former compound was readily prepared in two steps from the cheap commercial dye New Fuchsin.

molecular caltrops - dyad - tetraphenylmethane - Sonogashira coupling - Heck reaction

References

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5f

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9

Compound 5: mp 206-207 °C (MeOH). IR (KBr): 3400, 1605, 1500, 1460, 1370 cm^-1. ¹H NMR (300 MHz, CDCl₃/TMS): δ = 2.33 (s, 9 H), 6.65 (dd, J = 8.4, 2.1 Hz, 3 H), 6.70 (d, J = 6.6 Hz, 2 H), 6.99 (d, J = 6.6 Hz, 2 H), 7.02 (d, J = 2.1 Hz, 3 H), 7.65 (d, J = 8.4 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 28.2, 63.3, 98.7, 114.5, 130.1, 131.9, 138.0, 140.5, 146.5, 153.6.

10a Sonogashira K. In Comprehensive Organic Synthesis   Vol. 3:  Trost BM. Fleming I. Pergamon Press; Oxford: 1991.  p.551 

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11

Representative Procedure for Three-fold Sonogashira Couplings on 5: PdCl₂(PPh₃)₂ (5 mg) was added to a degassed solution of 5 (0.10 g, 0.13 mmol), phenyl acetylene (0.08 g, 0.8 mmol) and CuI (4 mg) in a mixture of DMF (3 mL) and Et₃N (2 mL). The reaction mixture was stirred at r.t. for 16 h. It was then concentratedd under reduced pressure, diluted with water and extracted with CH₂Cl₂. The organic layer was dried and the solvent removed under reduced pressure. The residue was purified by silica gel chromatography (10% EtOAc in light petroleum) to give 6 (0.057 g, 66%) as a white solid; mp 126-127 °C (CHCl₃-MeOH). IR (KBr): 3410, 1600, 1520, 1465, 1360 cm^-1. ¹H NMR (300 MHz, CDCl₃/TMS): δ = 2.43 (s, 9 H), 6.73 (d, J = 8.6 Hz, 2 H), 6.90-7.16 (m, 8 H), 7.29-7.48 (m, 12 H), 7.49-7.62 (m, 6 H). ¹³C NMR (75 MHz, CDCl₃): δ = 21.0, 64.5, 88.5, 93.8, 114.5, 121.2, 123.9, 125.6, 128.3, 128.7, 128.9, 130.1, 131.9, 132.2, 138.0, 139.5, 147.0, 156.5. 8: mp 105-106 °C (MeOH). IR (KBr): 3290, 3000, 2910, 2090, 1595, 1480 cm^-1. ¹H NMR (300 MHz, CDCl₃/TMS): δ = 2.35 (s, 9 H), 3.26 (s, 3 H), 6.71 (d, J = 8.7 Hz, 2 H), 6.93 (d, J = 8 Hz, 3 H), 7.00 (d, J = 8.7 Hz, 2 H), 7.01 (s, 3 H), 7.33 (d, J = 8 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 20.9, 64.0, 80.9, 82.3, 114.5, 119.6, 128.3, 131.7, 132.1, 138.0, 139.9, 147.0, 153.7.

12

Compound 9: mp 130-132 °C (MeOH). IR (KBr): 2916, 1596, 1521, 1500, 1442, 1344 cm^-1. ¹H NMR (300 MHz, CDCl₃/TMS): δ = 2.36 (s, 9 H), 5.08 (s, 2 H), 6.78 (d, J = 9 Hz, 2 H), 6.92 (dd, J = 8.1, 2 Hz, 3 H), 7.01 (d, J = 2 Hz, 3 H), 7.06 (d, J = 9 Hz, 2 H), 7.25-7.33 (m, 11 H), 7.42-7.46 (m, 6 H), 7.54 (d, J = 8.1 Hz, 3 H), 8.18 (d, J = 9 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 21.4, 64.5, 69.1, 88.5, 93.8, 114.2, 121.2, 123.9, 124.2, 128.0, 128.5, 128.7, 128.9, 131.3, 131.4, 131.9, 132.2, 132.6, 139.5, 139.8, 144.8, 147.0, 156.7.
Compound 10: mp 132-135 °C (MeOH). IR (KBr): 2900, 2100, 1590, 1518, 1487, 1350 cm^-1. ¹H NMR (300 MHz, CDCl₃/TMS): δ = 2.36 (s, 9 H), 3.24 (s, 3 H), 5.09 (s, 2 H), 6.73 (d, J = 9 Hz, 2 H), 6.91 (dd, J = 8, 1.8 Hz, 3 H), 7.00 (d, J = 1.8 Hz, 3 H), 7.06 (d, J = 9 Hz, 2 H), 7.30-7.36 (m, 5 H), 8.08 (d, J = 8.7 Hz, 2 H). Compound 13: mp 203-205 °C. IR (KBr): 2902, 1604, 1521, 1508, 1456, 1344, 1242 cm^-1. ¹H NMR (300 MHz, CDCl₃/TMS): δ = 1.33 (s, 27 H), 2.36 (s, 9 H), 5.16 (s, 2 H), 6.87 (d, J = 9 Hz, 2 H), 7.00 (d, J = 16.2 Hz, 3 H), 7.05-7.12 (m, 6 H), 7.24 (d, J = 9 Hz, 2 H), 7.28 (d, J = 16.2 Hz, 3 H), 7.35-7.53 (m, 14 H), 7.62 (d, J = 9 Hz, 3 H), 8.25 (d, J = 9 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 20.7, 31.7, 35.0, 64.1, 69.0, 114.0, 124.2, 124.4, 124.8, 125.8, 126.0, 126.6, 128.0, 129.5, 129.9, 130.3, 132.6, 133.1, 134.4, 135.1, 135.4, 140.5, 145.0, 146.4, 156.5.

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13c Beletskaya IP. Cheprakov AV. Chem. Rev.  2000,  100:  3009 

14

Compound 11: mp 201-202 °C. IR (KBr): 3290, 1595, 1500, 1445, 1260 cm^-1. ¹H NMR (300 MHz, CDCl₃/TMS): δ = 2.35 (s, 9 H), 6.73 (d, J = 8.7 Hz, 2 H), 7.00 (d, J = 16.2 Hz, 3 H), 7.05-7.11 (m, 6 H), 7.14 (d, J = 8.7 Hz, 2 H), 7.20-7.31 (m, 6 H), 7.34 (d, J = 5.4 Hz, 3 H), 7.35 (d, J = 16.2 Hz, 3 H), 7.45-7.54 (m, 9 H). ¹³C NMR (75 MHz, CDCl₃): δ = 20.2, 63.7, 114.3, 124.4, 126.1, 126.5, 127.4, 128.6, 129.1, 129.7, 132.2, 132.7, 133.7, 134.7, 137.8, 139.2, 146.3, 153.4. Compound 12: mp 220-224 °C (CHCl₃-MeOH). IR (KBr): 3300, 1600, 1510, 1440, 1280 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.33 (s, 27 H), 2.34 (s, 9 H), 4.67 (br s, 1 H), 6.72 (d, J = 8.5 Hz, 2 H), 6.98 (d, J = 16 Hz, 3 H), 7.04-7.11 (m, 6 H), 7.14 (d, J = 8.3 Hz, 2 H), 7.26 (d, J = 16 Hz, 3 H), 7.37 (d, J = 8.2 Hz, 6 H), 7.45 (d, J = 8.8 Hz, 6 H), 7.48 (d, J = 9.2 Hz, 3 H).

15 Meier H. Angew. Chem., Int. Ed. Engl.  1992,  31:  1399