2-phenylsulfanylacetyl chloride

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: As in the synthesis of N-(2-azidoethyl)tetradecanamide, 2-(phenylthio)acetyl chloride (0.222 g, 1.19 mmol) was reacted with 2-azidoethanamine (0.102 g, 1.19 mmol) and triethylamine (0.240 g, 2.37 mmol) in dichloromethane (5 mL) to give N-(2-azidoethyl)-2-(phenylthio)acetamide (0.179 g, 64%). 1H NMR (300 MHz, CDCl3) δ 7.29 (m, 4H), δ 7.18 (m, 2H), δ 3.60 (s, 2H), 3.34 (m, 4H) ppm; 13C NMR (75 MHz, CDCl3) δ 168.6, 134.8, 129.5, 128.6, 127.1, 50.8, 39.3, 37.7 ppm; HRMS (ESI) calcd for C10H12N4OS (M+) 236.0732, found 236.0729.

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

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

Procedure: To a stirred mixture of 5.89 g of 8-chloro-10,11-dihydrodibenz[b,f][1,4]oxazepine-10-carboxylic acid hydrazide (see U.S. Pat. No. 3,534,019) and 2.8 ml of triethylamine in 50 ml of cold (ca. 0° ) dichloromethane was slowly added 3.8 g of the title product of Example 1. The mixture was then stirred for twenty hours at room temperature. The solution was then washed three times with 50-ml portions of water, dried over sodium sulfate, filtered, and concentrated in vacuo to give the title compound, m.p. 172°-175°. The solution was then washed three times with 50-ml portions of water dried over sodium sulfate filtered concentrated in vacuo

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

Procedure: To a stirred mixture of 5.89 g of 8-chloro-10,11-dihydrodibenz[b,f][1,4]oxazepine-10-carboxylic acid hydrazide (see U.S. Pat. No. 3,534,019) and 2.8 ml of triethylamine in 50 ml of cold (ca. 0° ) dichloromethane was slowly added 3.8 g of the title product of Example 1. The mixture was then stirred for twenty hours at room temperature. The solution was then washed three times with 50-ml portions of water, dried over sodium sulfate, filtered, and concentrated in vacuo to give the title compound, m.p. 172°-175°. The solution was then washed three times with 50-ml portions of water dried over sodium sulfate filtered concentrated in vacuo

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

Procedure: To a solution of 5.0 g of (phenylthio)acetic acid in 20 ml of toluene under nitrogen was added 5.2 ml of oxalyl chloride in four portions. The solution was stirred at room temperature for about twenty hours and then concentrated in vacuo to the oily title compound, which was used in subsequent reactions without further purificaton or characterization. concentrated in vacuo to the oily title compound, which

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

Procedure: To a solution of 5.0 g of (phenylthio)acetic acid in 20 ml of toluene under nitrogen was added 5.2 ml of oxalyl chloride in four portions. The solution was stirred at room temperature for about twenty hours and then concentrated in vacuo to the oily title compound, which was used in subsequent reactions without further purificaton or characterization. concentrated in vacuo to the oily title compound, which

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

Procedure: 1,1-Dimethylethyl 2-acetyl-3-oxo-4-(phenylthio)butanoate Add tert-butyl acetoacetate (1.30 mL, 8.0 mmol) dropwise to a solution of sodium tert-butoxide (770 mg, 8.0 mmol) in diethyl ether (15 mL) at 0° C. under nitrogen. Stir the white precipitate at RT for 20 h and cool to 0° C. Add (phenylthio)acetyl chloride (1.2 mL, 8.0 mmol) dropwise and observe as the suspension turns yellow, then becomes a clear solution, and finally forms a white precipitate when all the reagent is added. Stir the reaction for 24 h at RT. Quench with 2 N HCl (15 mL), wash the aqueous layer with EtOAc (15 mL). Dry (MgSO4), concentrate and purify (silica gel chromatography, eluting with 100:0 to 90:10 2-methylpentane:EtOAc) to give the title compound as light yellow solid (1.11 g, 48%) cool to 0° C is added Stir the reaction for 24 h at RT Quench with 2 N HCl (15 mL) wash the aqueous layer with EtOAc (15 mL) Dry (MgSO4) concentrate purify (silica gel chromatography, eluting with 100:0 to 90:10 2-methylpentane:EtOAc)

Conditions: temp:105.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 10 g (0.046 mol) of 2-(1,3-dioxo-1,3-dihydro-isoindol-2-yl)-N-hydroxy-acetamidine dissolved in 500 mL of DMF, 1.84 g (0.046 mol, 1 eq) of magnesium oxide were added. After 15 min, 8.5 g (0.046 mol, 1 eq) of phenylsulfanyl-acetyl chloride were added, and the temperature was raised to 105° C. and the solution was stirred overnight. The reaction mixture was partitioned between aqueous NH4Cl and EtOAc, dried over Na2SO4. Column chromatography on silica gel with EtOAc/Heptane 1:1 yielded 8.7 g (55%) of 2-(5-phenylsulfanylmethyl-[1,2,4]oxadiazol-3-ylmethyl)-isoindole-1,3-dione as a light yellow solid, MS: 352 (MH+). The reaction mixture was partitioned between aqueous NH4Cl and EtOAc dried over Na2SO4

Conditions: temp:105.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 10 g (0.046 mol) of 2-(1,3-dioxo-1,3-dihydro-isoindol-2-yl)-N-hydroxy-acetamidine dissolved in 500 mL of DMF, 1.84 g (0.046 mol, 1 eq) of magnesium oxide were added. After 15 min, 8.5 g (0.046 mol, 1 eq) of phenylsulfanyl-acetyl chloride were added, and the temperature was raised to 105° C. and the solution was stirred overnight. The reaction mixture was partitioned between aqueous NH4Cl and EtOAc, dried over Na2SO4. Column chromatography on silica gel with EtOAc/Heptane 1:1 yielded 8.7 g (55%) of 2-(5-phenylsulfanylmethyl-[1,2,4]oxadiazol-3-ylmethyl)-isoindole-1,3-dione as a light yellow solid, MS: 352 (MH+). The reaction mixture was partitioned between aqueous NH4Cl and EtOAc dried over Na2SO4

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

Procedure: 300 mg (2.54 mmol) of amino-hydroxyimino-acetic acid methyl ester and 428 mg (2.29 mmol, 0.9 eq) of phenylsulfanyl-acetyl chloride were stirred in 10 mL of THF at RT for 1 hour. The solvent was evaporated, the residue dissolved in dioxane, and the reaction mixture was heated at reflux over night in the presence of molecular sieves. Filtration, concentration under vacuum and column chromatography over silica gel with EtOAc/heptane 1:1 yielded 310 mg (49%) of 5-phenylsulfanylmethyl-[1,2,4]oxadiazole-3-carboxylic acid methyl ester as light yellow oil, MS: 268 (MNH4+). The solvent was evaporated the residue dissolved in dioxane the reaction mixture was heated at reflux over night in the presence of molecular sieves Filtration, concentration under vacuum and column chromatography over silica gel with EtOAc/heptane 1:1