1,2-diiodobenzene

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The general procedure was used to convert diiodobenzene and n-butyl sulfide to the title product. Purification by flash chromatography (hexane as the eluent) gave the analytically pure product as a pale yellow oil (512 mg, 88% yield). 1H NMR (300 MHz, CDCl3) δ 7.58–7.55 (d, J=8.4, 2H; Ha, Ha′), 7.05–7.02 (d, J=8.2, 2H; Hb, Hb′), 2.91–2.86 (t, J=7.3, 2H; Hc), 1.67–1.49 (m, 2H; Hd), 1.42–1.30 (m, 2H; He), 0.94–0.89 (t, J=7.3, 3H; methyl protons). 13C NMR (75 MHz, CDCl3) δ 137.6 (C1, C1′), 137.2 (C4), 130.2 (C2, C2′), 90.0 (C3), 32.9 (C5), 30.9 (C6), 21.9 (C7), 13.6 (C8). High Resolution Mass. Spec. for C10H13S; Expected, 291.9783; Found, 291.9796

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a dry 3-neck, 25 mL round bottom flask equipped with a Teflon® resin coated stir bar, a balloon filled with carbon monoxide and a vacuum/argon inlet was placed o-diiodobenzene (320 mg, 0.97 mmol), aniline (90 mg, 0.97 mmol), palladium tetrakis(triphenylphosphine) (PdL4) (56 mg, 0.048 mmol=5%) and N,N-dimethylacetamide (DMAc, 2.9 mL). The mixture was stirred and degassed three times with argon, and then the argon atmosphere was replaced with carbon monoxide by three successive evacuations of the flask. The flask was then immersed in a 115° C. oil bath and heated until the reagents had dissolved. Then 1,8-diazobicyclo[5,4,0]undec-7-ene (DBU, 320 μl, 2.13 mmol) was added by syringe. After about 12 hours the product was produced in quantitative yield as determined by gas chromatography. The mixture was cooled, diluted with chloroform, extracted with water, dried over MgSO4, precipitated with methanol, collected by filtration, and dried in vacuo to give 40 mg product (19%). Much of the product remained in the filtrate. degassed three times with argon was then immersed in a 115° C. heated until the reagents had dissolved After about 12 hours the product was produced in quantitative yield The mixture was cooled extracted with water dried over MgSO4 precipitated with methanol collected by filtration dried in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Alternatively, 2-ethynylbenzonitrile (a3) may be prepared according to the procedures set forth in M. J. Wu et al. (1999), Organic Letters, 1 (5):767-768, which is incorporated herein by reference in its entirety. Specifically, palladium-catalyzed coupling reaction of trimethylsilylacetylene with 1,2-diiodobenzene produced 2-(2-trimethylsilylethynyl)iodobenzene in 58% yield; 2-(2-trimethylsilylethynyl)iodobenzene was then coupled with Zn(CN)2 using palladium(0) as a catalyst to give 2-(2-trimethylsilylethynyl)benzonitrile in 45% yield; and finally, 2-(2-trimethylsilylethynyl)benzonitrile was treated with tetrabutylammonium fluoride to give 2-ethynylbenzonitrile (a3) in 97% yield.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The title compound was synthesized as a yellow oil in 54% yield using 1,2-diiodobenzene and (trimethylsilyl)acetylene as the starting materials according to Method A of the above-described General Synthesis Procedures I. according to Method A of the above-described General Synthesis Procedures I

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 1,2-diiodobenzene (0.102 g, 3.08 mmol) in 60 mL of a mixture of THF and diethylether (Et2O) (1:1) was added dropwise at −78° C. isopropylmagnesium chloride (2 M in THF, 1.54 mL, 3.08 mmol). After the mixture was stirred for 2 h at that temperature, B(OiPr)3 (1.74 g 2.12 mL, 9.24 mmol) was added. The solution was warmed to room temperature overnight; then 40 mL of HCl (10%) was added, and the resulting mixture was stirred for 30 min at room temperature. The aqueous layer was extracted with Et2O (50 mL, 3 times). Drying over Na2SO4, evaporation and purification by flash chromatography gave 0.62 g of the pure product (82%). was added The aqueous layer was extracted with Et2O (50 mL, 3 times) Drying over Na2SO4, evaporation and purification by flash chromatography

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 1,2-diiodobenzene (6.6 g) and tetrakis(triphenylphosphine)palladium(0) (0.34 g) in AR toluene (100 ml) was stirred under a nitrogen atmosphere at ambient temperature. A solution of sodium carbonate (2 g) in water (15 ml) was added. The resulting orange mixture was stirred and heated under reflux while a solution of 4-methylbenzeneboronic acid (1.36 g) in industrial methylated spirit (40 ml) was added dropwise over a period of 40 minutes. The mixture obtained was heated under reflux for an additional 4 hours, then cooled to ambient temperature. Aqueous hydrogen peroxide (30%; 1 ml) was added and the resulting mixture was stirred for 1 hour at ambient temperature. Saturated aqueous sodium chloride solution (50 ml) was then added and the organic phase was separated. The aqueous phase was extracted with ethyl acetate (2×50 ml) and the combined organic phases were washed with saturated aqueous sodium chloride solution (1×70 ml), dried over magnesium sulphate and evaporated to give an orange oil. This oil was triturated with petroleum ether (b.p. 40°-60° C.) (200 ml) to give a gum which was partially purified by flash chromatography on silica gel (eluting with petroleum ether (b.p. 40°-60° C.): ethyl acetate (4:1)) then further purified by high performance liquid chromatography on a silica column (eluting with petroleum ether (b.p. 60°-80° C.) at 200 ml/minute), to give the intermediate compound 2'-iodo-4-methylbiphenyl as a colourless oil (1.3 g). The resulting orange mixture was stirred heated was added dropwise over a period of 40 minutes The mixture obtained was heated under reflux for an additional 4 hours cooled to ambient temperature the resulting mixture was stirred for 1 hour at ambient temperature the organic phase was separated The aqueous phase was extracted with ethyl acetate (2×50 ml) the combined organic phases were washed with saturated aqueous sodium chloride solution (1×70 ml) dried over magnesium sulphate evaporated to give an orange oil This oil was triturated with petroleum ether (b.p. 40°-60° C.) (200 ml) to give a gum which was partially purified by flash chromatography on silica gel (eluting with petroleum ether (b.p. 40°-60° C.): ethyl acetate (4:1)) then further purified by high performance liquid chromatography on a silica column (eluting with petroleum ether (b.p. 60°-80° C.) at 200 ml/minute)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution containing triethylamine (250 mL), copper (I) iodide (1.72 g, 9.09 mmol) and diiodobenzene (56) (20.00 g, 60.60 mmol) dissolved in anhydrous tetrahydrofuran (250 mL) was stirred at room temperature. The reaction flask was evacuated and then purged with nitrogen three times. The solution was treated with bis(triphenylphosphine) palladium(II) dichloride (4.20 g, 6.06 mmol) and continued to stir at room temperature for 30 min. A solution containing triethylamine (250 mL) and 2-but-3-ynylisoindole-1,3-dione (12.06 g, 60.06 mmol) dissolved in anhydrous tetrahydrofuran (250 mL) was added dropwise through an addition funnel over 12 hours. The reaction was allowed to stir at room temperature for 48 h. The solution was filtered and the filtrate was concentrated in vacuo. The resulting residue was purified by column chromatography eluting with 0-100% ethyl acetate in hexanes to afford the desired product 57 (12.5 g, 51%) as a brown solid: 1H NMR (500 MHz, CD2Cl2) δ 7.85 (dd, 2H), 7.74 (dd, 2H), 7.60 (d, 2H), 7.04 (d, 2H), 3.92 (t, 2H), 2.79 (t, 2H); m/z (ESI) 402 [C18H12INO2+H]+. The reaction flask was evacuated purged with nitrogen three times to stir at room temperature for 30 min was added dropwise through an addition funnel over 12 hours to stir at room temperature for 48 h The solution was filtered the filtrate was concentrated in vacuo The resulting residue was purified by column chromatography eluting with 0-100% ethyl acetate in hexanes