A new method for the synthesis of butatrienes

Regioisomeric allene dimer formation by the reaction of tetraarylbutatrienes with tetracyanoethene

“…Recrystallization from CH 2 Cl 2 -hexane gave red crystals 2c (0.11 g, 0.18 mmol, 84% yield), mp 160 °C (decomp). 1 H NMR δ: 3.90 (s, 6H, 2 × OMe), 7.02 (d, 2H, J = 8.6 Hz, PhOMe), 7.06 (d, 2H, J = 9.1 Hz, PhOMe), 7.25 (d, 2H, J = 9.1 Hz, PhOMe), 7.42 (d,2H,J = 8.6 Hz,PhOMe),7.44 (d,4H,J = 8.6 Hz,PhCl),7.54 (d,4H,J = 8.6 Hz,PhCl). 13 C NMR δ: 55.6,55.7,69.8,112.8,114.9,115.7,119.0,129.4,130.5,131.9,132.7,134.1,136.6,163.4,164.2,172.6 1,3-Bis(dichlorophenylvinylidene)-2,2,4,4-tetramethoxyphenylcyclobutane (3c).…”

“…Compound 2a (0.017 g, 0.029 mmol) was stirred in MeOH at room temperature for 4 h. The mixture was evaporated and the residue was recrystallized from CH 2 Cl 2 -hexane to give 6a (0.011 g, 0.019 mmol, 67% yield) as a pale yellow crystal, mp 164-166 °C. 1 H NMR (51 °C) δ: 3.84 (s, 3H, OMe), 3.85 (s, 3H, OMe), 3.86 (s, 3H, OMe), 3.89 (s, 3H, OMe), 4.64 (s, 1H, CH(CN) 2 ), 6.83 (s, 1H, ring C), 6.84 (d, 1H, J = 2.3 Hz, ring C), 6.92 (d,2H,J = 9.1 Hz,PhOMe),6H,PhOMe),7.13 (d,2H,J = 9.1 Hz,PhOMe),7.19 (d,2H,J = 8.6 Hz,PhOMe),7.39 (d,1H, J = 2.3 Hz, ring C). 13 C NMR (51 °C) δ: 27.6, 55.4, 55.5, 55.6, 55.8, 110.9, 112.9, 115.0, 115.4, 115.7, 118.0, 118.4, 126.6, 130.6, 130.7, 131.2, 132.6, 133.2, 134.1, 146.0, 152.6, 160.8, 161.8, 162.1, 163.3 4-( p-Methylphenyl)-2-bis( p-methoxyphenyl)methylene-1,1dicyano-3-dicyanomethyl-7-methyl-1,2-dihydronaphthalene (6b).…”

“…No further purification was achieved by recrystallization or by preparative layer chromatography. 1 H NMR (51 °C) δ: 2.40 (s,3H,Me),2.42 (s,3H,Me),3.84 (s,3H,OMe),3.89 (s,3H,OMe),4.64 (s,1H,CH(CN) 2 ), 6.84 (s, 1H, ring C), 6.85 (d,1H,J = 2.3 Hz,ring C),6.92 (d,2H,J = 9.1 Hz,PhMe),6H,PhOMe),7.12 (d,2H,J = 9.1 Hz,PhMe),7.19 (d,2H,J = 8.6 Hz,PhOMe),7.38 (d,1H, J = 2.3 Hz, ring C). 13 C NMR (51 °C) δ: 21.4, 21.6, 27.5, 55.4, 55.5, 110.8, 112.9, 115.0, 115.5, 115.8, 126.8, 129.6, 130.5, 132.6, 133.2, 134.2, 140.1, 141.3, 146.3, 162.2, 163.4 13 C NMR (51 °C) δ: 30.8, 55.…”

“…In addition, recrystallization of 6b by a vapor diffusion method with CH 2 Cl 2 -hexane mainly produced yellow crystals but also a few red crystals 9b, mp 244-246 °C. 1 H NMR δ: 2.38 (s, 6H, 2 × Me), 3.71 (s, 3H, OMe), 3.92 (s, 3H, OMe), 6.58 (d,1H,J = 1.8 Hz,ring D),6.81 (dd,1H,J = 1.8 and 8.8 Hz,ring D)…”

“…, 7.07(d, 4H, J = 8.2 Hz, PhMe), 7.11(d, 2H, J = 8.2 Hz, PhOMe), 7.20(d, 4H, J = 8.2 Hz, PhMe), 7.30(d, 1H, J = 8.8 Hz, ring D), 7.33 (d, 2H, J = 8.2 Hz, PhOMe). NALDI-TOF-MS m/z: calcd for: C 38 H 27 N 3 O 3 Na + 596.20.…”