Chloroacetonitrile → 3-Amino-5-phenylthiophene-2-carbonitrile

HRID 2380811Notes

Reaction equation

[S-2:1].[Na+].[Na+].Cl[C:5]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=[CH:6][C:7]#[N:8].Cl[CH2:16][C:17]#[N:18].C[O-].[Na+]>CN(C=O)C.CO.O>[NH2:8][C:7]1[CH:6]=[C:5]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[S:1][C:16]=1[C:17]#[N:18]

Participants

Conditions

Temperature: 65 °C

Procedure

To a suspension of sodium sulfide (0.95 g, 12.23 mmol) in DMF (12.5 mL) was added a solution of 3-chloro-3-phenylprop-2-enenitrile (2 g, 12.23 mmol) in DMF (5 mL) at rt for 5 min and stirred the mixture at 60-70° C. for 2 h. Then chloroacetonitrile (0.77 mL, 12.23 mmol) was added dropwise to the reaction mixture and again stirred at 60-70° C. for 2 h. Then, a solution of sodium methoxide (0.66 g, 12.23 mmol) in methanol (5 mL) was added dropwise and stirring was continued for 1 h at the same temperature. The mixture was allowed to rt and poured into cold water and stirred for 15 min. The solid separated was filtered, washed with water and dried. The solid was recrystallized from hexane-chloroform to give the product as a pale brown color solid (150 mg, 8%), nip 158-160° C. 1H NMR (400 MHz, CDCl3): δ 7.52-7.54 (2H, m), 7.37-7.41 (3H, m), 6.75 (1H, s), 4.48 (2H, s); LC-MS (negative ion mode): m/z 199 (M−H)−.

Workup

stirringagain stirred at 60-70° C. for 2 h
stirringstirring
waitwas continued for 1 h at the same temperature
customwas allowed to rt
stirringstirred for 15 min
customThe solid separated
filtrationwas filtered
washwashed with water
customdried
customThe solid was recrystallized from hexane-chloroform

Sources & evidence

ORD record: ord-e303b211dd224814817efa9246fc399b
Source dataset: uspto-grants-2012_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08258119B2

Reaction notes

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