(3-Iodophenyl)hydrazine

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred suspension of 61 (3.63 g, 8.57 mmol) in acetic acid (34 mL) was added 4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione (1.3 mL, 8.57 mmol). The resulting suspension was allowed to stir at 120° C. overnight turning clear upon heating. The mixture was then evaporated to dryness. The crude product was added to a silica gel column and eluted with 5% to 10% EtOAc/hexanes. The title product 62 (3.00 g, 87% yield) was isolated as a colorless oil that solidified upon standings. LRMS (ESI): calc. 404.1; found 405.2 (MH)+. upon heating The mixture was then evaporated to dryness The crude product was added to a silica gel column eluted with 5% to 10% EtOAc/hexanes

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

Procedure: To a stirred suspension of 3-iodoaniline (2 g, 9.13 mmol) in 37% hydrochloric acid (11 mL) at 0° C. was added a cold solution of sodium nitrite (0.66 g, 9.59 mmol) in water (3.2 mL). The resulting suspension was allowed to stir for 40 min. Then, a cold solution of tin(II) chloride dihydrate (6.18 g, 27.4 mmol) in 37% hydrochloric acid (4.3 mL) was added to the reaction mixture and stirred for another 40 min. The flask was then placed in the refrigerator for 12 h. The precipitate was isolated by filtration and washed with ice-cold brine (25 mL) followed by 2:1 petroleum ether/ether (25 mL) solution. The light pink solid was dried under vacuum for 2 h to give the title compound 61 (3.63 g, 94% yield) as the SnCl2 complex. LRMS (ESI): calc. 234.0; found 235.0 (MH)+ (compound 61 as the free hydrazine was previously reported in Recueil des Travaux Chimiques des Pays-Bas (1961), 80 1348-56). stirred for another 40 min The flask was then placed in the refrigerator for 12 h The precipitate was isolated by filtration washed with ice-cold brine (25 mL) The light pink solid was dried under vacuum for 2 h

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

Procedure: A solution of sodium nitrite (13.2 g, 186 mmol) in water (65 mL) was added over 90 minutes to a cooled (˜0 degrees) mixture of 3-iodo-aniline (40.71 g, 182 mmol) in concentrated hydrochloric acid (80 mL), taking care to ensure that the temperature remained below 0 degrees). The mixture was stirred for 30 min and then filtered. To the filtrate was added dropwise a solution of tin(II) chloride dihydrate (142 g, 0.63 mol) in water, and then the mixture was stirred for 30 minutes with the temperature maintained below 0 degrees. The reaction mixture was placed in the refrigerator overnight and then filtered. The residue was washed with brine, then 1:1 petroleum ether/ether (750 mL) and then with 2:1 petroleum ether/ether (375 mL) and the washings were discarded. The remaining residue was dissolved in 5 M NaOH and ether, and the aqueous layer was extracted with ether. The combined ether layers were washed with water and brine, dried (sodium sulfate), filtered, and evaporated to give 3-iodo-phenylhydrazine (25.3 g, 53%) as a dark red viscous oil. a cooled remained below 0 degrees filtered the mixture was stirred for 30 minutes with the temperature maintained below 0 degrees was placed in the refrigerator overnight filtered The residue was washed with brine The remaining residue was dissolved in 5 M NaOH ether, and the aqueous layer was extracted with ether The combined ether layers were washed with water and brine dried (sodium sulfate) filtered evaporated