1-chloro-3-isothiocyanatobenzene

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

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: The compound of example 266 was prepared analogous to compound of example 256 by reaction of compound of example 223 with 3-chlorophenyl isothiocyanate. The compound of example 266 was used directly without isolation for the preparation of compound of example 267.

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

Procedure: The compound of example 63 was prepared analogous to compound of example 51 by reaction of compound of example 6 with 3-chlorophenyl isothiocyanate. The compound of example 63 was used directly without isolation for the preparation of compound of example 64.

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

Procedure: Mercury (II) oxide yellow (6.38 g, 29.47 mmol) was suspended in ca. 100 mL of anhydrous methanol. 4-Hydroxybenzoic acid hydrazide (4.48 g, 29.47 mmol) was added to this bright-orange suspension, followed by 3-chlorophenylisothiocyanate (5.0 g, 29.47 mmol). The reaction mixture was brought to reflux and refluxed for 2 hours. The reaction mixture turned pitch-black in color and formed black precipitate. Then it was cooled down to ambient temperature and filtered through a short pad of Celite. Then it was purified by silica gel chromatography using 0% to 20% methanol gradient in EtOAc. Solvent was removed in vacuo and the resulting grey precipitate was re-crystallized from ca. 50 mL of EtOAc. The formed white crystalline solid was filtered, washed with a small amount of EtOAc, anhydrous Et2O and dried in vacuo to give the title product as a white powder (7.606 g). Yield 89.7%. to reflux refluxed for 2 hours formed black precipitate filtered through a short pad of Celite Then it was purified by silica gel chromatography Solvent was removed in vacuo the resulting grey precipitate was re-crystallized from ca. 50 mL of EtOAc The formed white crystalline solid was filtered washed with a small amount of EtOAc, anhydrous Et2O dried in vacuo

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

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

Procedure: Dissolved malononitrile (3.328 g) in DMF (35 mL), added TEA (1 eq., 6.983 mL), and stirred for 5 minutes before adding 3-chlorophenylisothiocyante (1 eq., 8.54 mL) dropwise, then stirred until complete by TLC (absence of 3-chlorophenylisothiocyanate, 3 hrs). Added methyl iodide (1 eq., 3.136 mL) dropwise, then stirred until intermediate was fully consumed (absent on TLC, 18 hrs); poured into 500 mL ice water, then filtered resulting solution to 2-(((3-chlorophenyl)amino)(methylthio)methylene)malononitrile as a white powder. before adding 3-chlorophenylisothiocyante (1 eq., 8.54 mL) dropwise was fully consumed (absent on TLC, 18 hrs) poured into 500 mL ice water filtered

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

Procedure: The suspension of monosodium cyanamide (1.9 g, 29.4 mmol) in absolute ethanol (50 mL) was slowly treated with 3-chlorophenylisothiocyanate (5.0 g, 29.4 mmol). The reaction was allowed to stir at room temperature for 1 hour and then heated at 75° C. for 4 hours. The reaction was cooled to room temperature and the colorless solid was filtered and washed with ethanol to give the title A compound (5.4 g), m.p. 258°-260° C. heated at 75° C. for 4 hours The reaction was cooled to room temperature the colorless solid was filtered washed with ethanol

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

Procedure: Mercury (II) oxide yellow (6.38 g, 29.47 mmol) was suspended in ca. 100 mL of anhydrous methanol. 4-Hydroxybenzoic acid hydrazide (4.48 g, 29.47 mmol) was added to this bright-orange suspension, followed by 3-chlorophenylisothiocyanate (5.0 g, 29.47 mmol). The reaction mixture was brought to reflux and refluxed for 2 hours. The reaction mixture turned pitch-black in color and formed black precipitate. Then it was cooled down to ambient temperature and filtered through a short pad of Celite. Then it was purified by silica gel chromatography using 0% to 20% methanol gradient in EtOAc. Solvent was removed in vacuo and the resulting grey precipitate was re-crystallized from ca. 50 mL of EtOAc. The formed white crystalline solid was filtered, washed with a small amount of EtOAc, anhydrous Et2O and dried in vacuo to give the title product as a white powder (7.606 g). Yield 89.7%. to reflux refluxed for 2 hours formed black precipitate filtered through a short pad of Celite Then it was purified by silica gel chromatography Solvent was removed in vacuo the resulting grey precipitate was re-crystallized from ca. 50 mL of EtOAc The formed white crystalline solid was filtered washed with a small amount of EtOAc, anhydrous Et2O dried in vacuo

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

Procedure: A mixture of 5,6-Dihydro-cyclopenta[b]thiophen-4-one (1.0 g, 7.4 mmol) and 1-Chloro-3-isothiocyanato-benzene (1.5 g, 7.2 mmol) in THF (2.0 mL) was added to lithium hexamethyl disilane (7.0 mL, 7.2 mmol) dropwise at room temperature. The reaction mixture was stirred for 8 hr. Hydrazine monohydrate (0.4 mL, 7.9 mmol) and glacial acetic acid (0.5 mL) were added to the reaction mixture, which was then heated at the reflux temperature for 24 hr. The resulting mixture was added to water (30 mL) and then extracted with ethyl acetate. The target product was purified by gravity column chromatography (50% EtOAc in hexane) to give (3-Chloro-phenyl)-(4,7-dihydro-1-thia-4,5-diaza-cyclopenta[a]pentalen-6-yl)-amine as brown solid in 30% yield. was then heated at the reflux temperature for 24 hr extracted with ethyl acetate The target product was purified by gravity column chromatography (50% EtOAc in hexane)

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

Procedure: Dissolved malononitrile (3.328 g) in DMF (35 mL), added TEA (1 eq., 6.983 mL), and stirred for 5 minutes before adding 3-chlorophenylisothiocyante (1 eq., 8.54 mL) dropwise, then stirred until complete by TLC (absence of 3-chlorophenylisothiocyanate, 3 hrs). Added methyl iodide (1 eq., 3.136 mL) dropwise, then stirred until intermediate was fully consumed (absent on TLC, 18 hrs); poured into 500 mL ice water, then filtered resulting solution to 2-(((3-chlorophenyl)amino)(methylthio)methylene)malononitrile as a white powder. before adding 3-chlorophenylisothiocyante (1 eq., 8.54 mL) dropwise was fully consumed (absent on TLC, 18 hrs) poured into 500 mL ice water filtered