Chloroacetonitrile → 3-Amino-5-(tert-butyl)selenophene-2-carbonitrile

HRID 1529829Notes

Reaction equation

[Se-2:1].[Na+].[Na+].Cl[C:5]([C:9]([CH3:12])([CH3:11])[CH3:10])=[CH:6][C:7]#[N:8].Cl[CH2:14][C:15]#[N:16].C[O-].[Na+]>CN(C=O)C.CO.O>[NH2:8][C:7]1[CH:6]=[C:5]([C:9]([CH3:12])([CH3:11])[CH3:10])[Se:1][C:14]=1[C:15]#[N:16]

Participants

Conditions

Temperature: 65 °C

Procedure

To a suspension of sodium selenide (3.51 g, 27.87 mmol) in DMF (28 mL) was added a solution of 3-chloro-4,4-dimethylpent-2-enenitrile (4.0 g, 27.87 mmol; Ohta, H.; Ishizaka, T.; Tatsuzuki, M.; Yoshinaga, M.; Iida, I.; Yamaguchi, T.; Tomishima, Y.; Futaki, N.; Toda, Y.; Saito, S. Bioorg. Med. Chem., 2008, 16, 1111-1124) in DMF (10 mL) at rt for 5 min and stirred the mixture at 60-70° C. for 2 h. Then chloroacetonitrile (1.76 mL, 27.87 mmol) was added dropwise to the reaction mixture and again stirred at 60-70° C. for 2 h. Then, a solution of sodium methoxide (1.5 g, 27.87 mmol) in dry methanol (18 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 30 min. The precipitated solid was filtered and washed with water. The solid was recrystallized from chloroform-hexane to give the product as a brown color solid (3.8 g, 60%), mp 110-112° C. (Thomae, D.; Kirsch, G.; Seck, P. Synthesis, 2008, 1600-1606). 1H NMR (400 MHz, CDCl3): δ 6.59 (1H, s), 4.46 (2H, br s), 1.33 (9H, s); LC-MS (negative ion mode): m/z 225, 227 (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 30 min
filtrationThe precipitated solid was filtered
washwashed with water
customThe solid was recrystallized from chloroform-hexane
customto give the product

Sources & evidence

ORD record: ord-508ed43b2fbc487caee7ba480b39633b
Source dataset: uspto-grants-2015_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09090633B2

Reaction notes

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