methyl 3-iodobenzoate

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1H-Indazol-4-amine (81 mg, 0.61 mmol) and methyl 3-iodobenzoate (160 mg, 0.61 mmol) were dissolved in DMF (1 mL) in a microwave tube. Copper (I) iodide (23 mg, 0.12 mmol), trans-N,N′-dimethyl-1,2-cyclohexanediamine (34 mg, 0.24 mmol) and potassium carbonate (169 mg, 1.22 mmol) were added and the mixture heated by microwave (250 W) at 100° C. for 20 minutes. The mixture was filtered through a cartridge, washing with DCM (5 mL) and the filtrate was evaporated to dryness and purified by mass-directed autopreparation. The appropriate fractions were evaporated, dissolved in DCM (10 mL), washed with aqueous sodium bicarbonate, and evaporated to give the title compound (32.7 mg). The mixture was filtered through a cartridge washing with DCM (5 mL) the filtrate was evaporated to dryness purified by mass-directed autopreparation The appropriate fractions were evaporated dissolved in DCM (10 mL) washed with aqueous sodium bicarbonate evaporated

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

Procedure: A suspension of 1-tri(n-butyl)stannyl-2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)benzene (5 g), methyl 3-iodobenzoate (2.17 g) and tetrakis(triphenylphosphine) palladium(0) (0.29 g) in dioxane was refluxed for 18 hours. After being cooled to room temperature, 25% potassium fluoride aqueous solution (11 ml) was added to the reaction mixture and the mixture was stirred for 15 minutes. Insoluble material was filtered by using celite The filtrate was extracted with ethyl acetate (50 ml), washed with brine, dried over magnesium sulfate, filtered and evaporated in vacuo. The residue was purified by column chromatography on silica gel (200 g) with benzene-ethyl acetate (20:1) as an eluent. The fractions containing the object compound were combined and evaporated in vacuo. The residue was recrystallized from methanol to afford methyl 3-[2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenyl]benzoate (370 mg). was refluxed for 18 hours Insoluble material was filtered was extracted with ethyl acetate (50 ml) washed with brine dried over magnesium sulfate filtered evaporated in vacuo The residue was purified by column chromatography on silica gel (200 g) with benzene-ethyl acetate (20:1) as an eluent The fractions containing the object compound evaporated in vacuo The residue was recrystallized from methanol

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4-(3-cyclopentyloxy-4-methoxyphenyl)-1,1-(ethylenedioxy)-4-ethynylcyclohexane (0.150 g, 0.421 mmol) and methyl 3-iodobenzoate (0.110 g, 0.421 mmol) in piperidine (2.1 mL, dry) under an argon atmosphere was treated with a mixture of tetrakis(triphenylphosphine)palladium(0) (0.020 g, 0.017 mmol), cuprous iodide (0.010 g, 0.053 mmol) and triphenylphosphine (crystal) and the mixture was heated at 80° C. for 40 min. The reaction mixture was chilled to 0° C., was poured into ice-water, was acidified with 3N hydrochloric acid and was extracted five times with methylene chloride. The organic phase was washed with dilute hydrochloric acid, water, saturated brine, was dried over magnesium sulfate, was filtered and concentrated in vacuo. The residue was preadsorbed and chromatographed on silica gel, eluting the with 15 to 20% ethyl acetate in hexanes, to afford a light yellow oil. 1H-NMR (250 MHz, CDCl3) δ 8.11 (t, J=1.4 Hz, 1H), 7.97 (d-d, J=1.3 Hz;J=7.9 Hz, 1H), 7.63 (d-d, J=7.8 Hz;J=1.3 Hz, 1H), 7.39 (t, J=7.8 Hz, 1H), 7.23 (d, J=2.2, 1H), 7.15 (d-d, J=8.4 Hz;J=2.3 Hz, 1H), 6.89 (d, J=8.4 Hz, 1H), 4.80 (m, 1H), 4.00 (s, br, 4H), 3.92 (s, 3H), 3.84 (s, 3H), 2.4 to 1.75 (m, 18H). The reaction mixture was chilled to 0° C. was extracted five times with methylene chloride The organic phase was washed with dilute hydrochloric acid, water, saturated brine was dried over magnesium sulfate was filtered concentrated in vacuo chromatographed on silica gel eluting the with 15 to 20% ethyl acetate in hexanes to afford a light yellow oil

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: 52.5 g (0.2 mol) of methyl 3-iodobenzoate were heated to reflux for 18 hours with 81 g (0.2 mol) of Lawesson reagent in 330 ml of xylene. By working-up in an analogous manner to that described in Example 1(B) there were obtained 47 g (84.4%) of O-methyl 3-iodothiobenzoate as a yellow evil-smelling oil which was used without further purification.

Conditions: temp:205.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of methyl 3-iodobenzoate (26.1 g) in 4-iodotoluene (21.9 g) was added copper powder (31.8 g) gradually at 180°-190° C. The mixture was then stirred for 6 hours at 200-210° C. The reaction mixture was cooled to room temperature, to which was added toluene. Insoluble materials were filtered off, and the filtrate was concentrated to dryness. The residue was purified by column chromatography on silica gel to afford the title compound as a colorless oil (6.61 g, 29%). The reaction mixture was cooled to room temperature, to which Insoluble materials were filtered off the filtrate was concentrated to dryness The residue was purified by column chromatography on silica gel

Conditions: temp:205.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of methyl 3-iodobenzoate (26.1 g) in 4-iodotoluene (21.9 g) was added copper powder (31.8 g) gradually at 180°-190° C. The mixture was then stirred for 6 hours at 200-210° C. The reaction mixture was cooled to room temperature, to which was added toluene. Insoluble materials were filtered off, and the filtrate was concentrated to dryness. The residue was purified by column chromatography on silica gel to afford the title compound as a colorless oil (6.61 g, 29%). The reaction mixture was cooled to room temperature, to which Insoluble materials were filtered off the filtrate was concentrated to dryness The residue was purified by column chromatography on silica gel

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

Procedure: A solution of 5.0 g methyl-m-iodobenzoate in 70 ml chloroform was cooled to 0°-10° and treated with gaseous chlorine for 1 hour. The resulting yellow solution was evaporated to afford 6.2 g methyl-m-iodobenzoate dichloride as yellow needles, mp=108°-110°. IR: 5.83, 7.80, 8.00, 8.90, 9.18, 10.52, 11.12, 12.39, and 13.48. The resulting yellow solution was evaporated

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

Procedure: To a stirred solution of 25.2 g of methyl 3-iodobenzoate and 21.0 g of 4-iodotoluene at 180°-190° under nitrogen was added 30.3 g of copper powder portionwise over 1 hour. When approximately one-third of the copper had been added, the reaction initiated and the temperature increased spontaneously to 240°. The mixture was allowed to cool to 210°, then was held at 210° during the addition of the remaining copper and for an additional hour. The mixture was allowed to cool to room temperature and was filtered employing benzene as solvent; the resulting filtrate was concentrated in vacuum to provide the crude product. Column chromatography on silica gel (elution=50-100% benzene/hexane) followed by distillation furnished 7.60 g of methyl 4'-methylbiphenyl-3-carboxylate [bp: 114°-115° C. (0.025 torr)] as a colorless oil; NMR (200 MHz, CDCl3): δ 8.27 (br S, 1H); 7.99 (d, 1H); 7.77 (d, 1H); 7.50 (t, 1H); 7.39 (A2B2, 4H); 3.94 (s, 3H); 2.41 (s, 3H). the temperature increased spontaneously to 240° to cool to 210° was filtered the resulting filtrate was concentrated in vacuum to provide the crude product Column chromatography on silica gel (elution=50-100% benzene/hexane) followed by distillation