1-chloropent-2-yne

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

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

Procedure: (4-Pent-2-ynyloxy-phenylsulfanyl)-acetic acid ethyl ester was prepared according to the general method as outlined in Example 1 (Step 2). Starting from (4-hydroxy-phenylsulfanyl)-acetic acid ethyl ester (5 g, 30 mmol) and 2-pentynyl chloride (3.7 g, 36.6 mmol) 7.15 g of the product isolated. Yield 7.15 g (86%); brown oil; MS: 278 EI (M+H)+. isolated

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

Procedure: (4-Pent-2-ynyloxy-phenylsulfanyl)-acetic acid ethyl ester was prepared according to the general method as outlined in Example 1 (Step 2). Starting from (4-hydroxy-phenylsulfanyl)-acetic acid ethyl ester (5 g, 30 mmol) and 2-pentynyl chloride (3.7 g, 36.6 mmol) 7.15 g of the product isolated. Yield 7.15 g (86%); brown oil; MS: 278 EI (M+H)+ isolated

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

Procedure: (4-Pent-2-ynyloxy-phenylsulfanyl)-acetic acid ethyl ester was prepared according to the general method as outlined in Example 1 (Step 2). Starting from (4-hydroxy-phenylsulfanyl)-acetic acid ethyl ester (5 g, 30 mmol) and 2-pentynyl chloride (3.7 g, 36.6 mmol) 7.15 g of the product isolated. Yield 7.15 g (86%); brown oil; MS: 278 EI (M+H)+ isolated

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

Procedure: (4-Pent-2-ynyloxy-phenylsulfanyl)-acetic acid ethyl ester was prepared according to the general method as outlined in Example 1 (Step 2). Starting from (4-hydroxy-phenylsulfanyl)-acetic acid ethyl ester (5 g, 30 mmol) and 2-pentynyl chloride (3.7 g, 36.6 mmol) 7.15 g of the product isolated. Yield 7.15 g (86%); brown oil; MS: 278 EI (M+H)+. isolated

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

Procedure: (4-Pent-2-ynyloxy-phenylsulfanyl)-acetic acid ethyl ester was prepared according to the general method as outlined in Example 1 (Step 2). Starting from (4-hydroxy-phenylsulfanyl)-acetic acid ethyl ester (5 g, 30 mmol) and 2-pentynyl chloride (3.7 g, 36.6 mmol) 7.15 g of the product isolated. Yield 7.15 g (86%); brown oil; MS: 278 EI (M+H)+. isolated

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

Procedure: (4-Pent-2-ynyloxy-phenylsulfanyl)-acetic acid ethyl ester was prepared according to the general method as outlined in Example 1 (Step 2). Starting from (4-hydroxy-phenylsulfanyl)-acetic acid ethyl ester (5 g, 30 mmol) and 2-pentynyl chloride (3.7 g, 36.6 mmol) 7.15 g of the product isolated. Yield 7.15 g (86%); brown oil; MS: 278 EI (M+H)+ isolated

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

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

Procedure: The title compound was prepared in a manner similar to Preparation 3 from 1-chloro-pent-2-yne and (2S,3R,6S)-4-(4-Hydroxy-benzenesulfonyl)-2,6-dimethyl-morpholine-3-carboxylic acid methyl ester. 1HNMR (400 MHz, CDCl3): δ=7.70 (d, J=8.9 Hz, 2H), 7.0 (d, J=8.9 Hz, 2H), 4.71 (bs, 2H), 4.52 (q, J=7.0 Hz, 1H), 4.27 (s, 1H), 3.97 (m, 1H), 3.54 (s, 3H), 2.98 (dd, J=12.1 and 10.8, 1H), 2.21 (m, 2H), 1.44 (d, J=6.9 Hz, 3H), 1.11 (t, J=7.5 Hz, 3H), 1.05 (d, J=6.0 Hz, 3H).

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

Procedure: The 0.4 g of 3-(4-chlorophenyl)-1,2,4-triazin-6-one (1.9 mmol) was placed in 10 mL of DMF and cooled in an ice bath. Sodium hydride (NaH) (0.8 g of 60% dispersion, 2 mmol) was added, and the reaction mixture was held for 15 minutes. Excess 1-chloro-2-pentyne was added, the bath was removed, and the reaction mixture was allowed to warm to room temperature. Water and ethyl acetate were added. The organic phase was washed with water and brine, dried over magnesium sulfate, filtered and stripped. The crude product was chromatographed on silica gel to give 0.05 g of 1-(2-pentynyl)-3-(4-chlorophenyl)-1,2,4-triazin-6-one. cooled in an ice bath the bath was removed Water and ethyl acetate were added The organic phase was washed with water and brine dried over magnesium sulfate filtered The crude product was chromatographed on silica gel

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

Procedure: A solution of 1.3 g (3.1 mmol) 2-(4-chloro-phenyl)-N-(4′-hydroxy-3′-methoxy-biphenyl-2-yl)-2-prop-2-ynyloxy-acetamide, 6.0 ml (6.0 mmol) of a 1 M solution of sodium methoxide in methanol and 0.5 g (4.7 mmol) 2-pentynyl chloride in 50 ml of methanol is heated to reflux for 3 hours. After cooling, the reaction mixture is poured into ethyl acetate. The organic layer is washed with brine, dried over sodium sulfate and evaporated. The remaining product is subjected to flash-chromatography (ethyl acetate/hexane 4:6) to yield 2-(4-chlorophenyl)-N-(3′-methoxy-4′-pent-2-ynyloxy-biphenyl-2-yl)-2-prop-2-ynyloxy-acetamide as yellow oil. to reflux for 3 hours After cooling The organic layer is washed with brine dried over sodium sulfate evaporated

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of LDA (146 ml, 291 mmol, 2M in THF) at −78° C. under nitrogen was added a solution of ethyl isobutyrate (33.9 g, 291 mmol) in dry THF (100 ml) and the mixture was stirred at −78° C. for 2 hours. To the mixture was added 2-pentynyl chloride (25 g, 243 mmol) slowly over a period of 20 min. The reaction mixture was slowly warmed to RT over a period of 12 hours. Water (200 ml) was added and the product was extracted with Et2O (2×200 ml). The combined organic layers were washed with water, brine and dried (MgSO4). The solvent was removed under vacuum and the residue was purified by flash chromatography on silica (pet. ether/EtOAc 9/1) to afford the titled compound as a colorless liquid (29 g, 66%). TLC: Pet ether/EtOAc (8/2): Rf=0.75. 1H-NMR (CDCl3:300 MHz) δ 1.11 (3H, t), 1.24 (6H, s), 2.15 (2H, m), 2.38 (2H, s), 4.14 (2H, m). The reaction mixture was slowly warmed to RT over a period of 12 hours the product was extracted with Et2O (2×200 ml) The combined organic layers were washed with water, brine dried (MgSO4) The solvent was removed under vacuum the residue was purified by flash chromatography on silica (pet. ether/EtOAc 9/1)