1-(3-bromoprop-1-en-2-yl)-4-chlorobenzene

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

Procedure: A mixture of 19.2 g (0.083 mol) of the product from Step A, 10.0 g (0.064 mol) of 4-chlorosalicylaldehyde, 17.6 g (0.13 mol) of potassium carbonate and 64 mL of DMF was stirred at RT for 72 h. Resulting mixture treated with 125 mL of H2O and filtered. Solids were washed with several portions of H2O and dried in a vacuum oven at 40° C. to give 21.0 g of a brown solid. 1H NMR (CDCl3, 200 MHz) δ4.99 (s, 2H), 5.51 (s, 1H), 5.65 (s, 1H), 7.04-7.07 (m, 2H), 7.25-7.45 (m, 4H), 7.77 (d, 1H), 10.28 (s, 1H). Resulting mixture filtered Solids were washed with several portions of H2O dried in a vacuum oven at 40° C.

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

Procedure: A mixture of 31.0 g (0.20 mol) of 4-chloro-α-methylstyrene, 38.0 g (0.21 mol) of N-bromosuccinimide, 3.9 g (0.02 mol) of p-toluenesulfonic acid monohydrate and 610 mL of THF was heated at reflux for 3 h and then concentrated at room temperature. The residue was partitioned between 400 mL of hexanes and 200 mL of H2O, the organic phase was washed twice with 100 mL H2O and dried (MgSO4). Removal of solvent gave 47.8 g of a yellow oil that was used without further purification. 1H NMR (CDCl3, 200 MHz) δ4.33 (s, 2H), 5.50 (d, 2H), 7.2-7.5 (m, 5H). was heated at reflux for 3 h concentrated at room temperature The residue was partitioned between 400 mL of hexanes and 200 mL of H2O the organic phase was washed twice with 100 mL H2O dried (MgSO4) Removal of solvent

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

Procedure: A mixture of 31.0 g (0.20 mol) of 4-chloro-α-methylstyrene, 38.0 g (0.21 mol) of N-bromosuccinimide, 3.9 g (0.02 mol) of p-toluenesulfonic acid monohydrate and 610 mL of THF was heated at reflux for 3 h and then concentrated at room temperature. The residue was partitioned between 400 mL of hexanes and 200 mL of H2O, the organic phase was washed twice with 100 mL H2O and dried (MgSO4). Removal of solvent gave 47.8 g of a yellow oil that was used without further purification. 1H NMR (CDCl3, 200 MHz) δ4.33 (s, 2H), 5.50 (d, 2H), 7.2-7.5 (m, 5H). was heated at reflux for 3 h concentrated at room temperature The residue was partitioned between 400 mL of hexanes and 200 mL of H2O the organic phase was washed twice with 100 mL H2O dried (MgSO4) Removal of solvent

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

Procedure: A mixture of 31.0 g (0.20 mol) of 4-chloro-α-methylstyrene, 38.0 g (0.21 mol) of N-bromosuccinimide, 3.9 g (0.02 mol) of p-toluenesulfonic acid monohydrate and 610 mL of THF was heated at reflux for 3 h and then concentrated at room temperature. The residue was partitioned between 400 mL of hexanes and 200 mL of H2O, the organic phase was washed twice with 100 mL H2O and dried (MgSO4). Removal of solvent gave 47.8 g of a yellow oil that was used without further purification. 1H NMR (CDCl3, 200 MHz) δ4.33 (s, 2H), 5.50 (d, 2H), 7.2-7.5 (m, 5H). was heated at reflux for 3 h concentrated at room temperature The residue was partitioned between 400 mL of hexanes and 200 mL of H2O the organic phase was washed twice with 100 mL H2O dried (MgSO4) Removal of solvent

Conditions: temp:0.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suspension of sodium hydride/oil (28 g, 0.7 mol @ 60%) in 800 ml of DMF, add in portions 1,2,4-triazole (50 g, 0.72 mol) at -10° to 0° C. Stir at 0.5° C. for 1 hour until soultion is clear brown. Add rapidly at -5° to 5° C. p-chloro-α-bromomethyl styrene (200 g, 0.86 mol total bromide, 0.56 mol allyl @ 65%). Stir and warm to room temperature over 2 hours. Evaporate off the DMF. Add saturated NaCl and extract the product with 2×300 ml of ethyl acetate. Dry the combined extracts over MgSO4 and filter. Evaporate the ethyl acetate and chromatograph the resultant oil on 2 Waters prep. 500 cartridges using ethyl acetate:hexane (1:1) as the eluent to obtain p-chloro-α-1H-1,2,4-triazolylmethyl styrene: 'HNMR (90 mHz, CDCl3) 8.06 (1 H, S), 7.93 (1H, S), 7.3 (H H, S), 5.59 (1H, S), 5.16 (3H, br S). Stir warm to room temperature over 2 hours Evaporate off the DMF Add saturated NaCl and extract the product with 2×300 ml of ethyl acetate Dry the combined extracts over MgSO4 filter Evaporate the ethyl acetate and chromatograph the resultant oil on 2 Waters prep