Ethyl chloroacetate → Ethyl 3-amino-5-(tert-butyl)selenophene-2-carboxylate
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]([O:17][CH2:18][CH3:19])=[O:16].C[O-].[Na+]>CN(C=O)C.CO>[NH2:8][C:7]1[CH:6]=[C:5]([C:9]([CH3:12])([CH3:11])[CH3:10])[Se:1][C:14]=1[C:15]([O:17][CH2:18][CH3:19])=[O:16]Participants
Reactant 4
Product 1
Reagents, catalysts & solvents 2
Conditions
- Temperature
- 65 °C
Procedure
To a suspension of sodium selenide (4.4 g, 34.84 mmol, prepared from 2.78 g of selenium as described above) in DMF (35 mL) was added a solution of 3-chloro-4,4-dimethylpent-2-enenitrile (5 g, 34.84 mmol) in DMF (10 mL) at rt for 5 min and stirred the mixture at 60-70° C. for 2 h. Then ethyl chloroacetate (3.71 mL, 34.84 mmol) was added dropwise to the reaction mixture and again stirred at 60-70° C. for 2 h. Then, a solution of sodium methoxide (1.88 g, 34.84 mmol) in methanol (25 mL) was added dropwise and stirring was continued for 1 h at the same temperature. The mixture was allowed to rt and poured into ice cold water and stirred for 15 min. The precipitated solid was filtered, washed with water and dried to give the product as a yellow color solid (6.2 g, 65%), mp 66-68° C. 1H NMR (400 MHz, CDCl3): δ 6.59 (1H, s, H-4), 5.52 (2H, br s, —NH2), 4.24 (2H, q, J=7.1 Hz, —COOCH2CH3), 1.33 (9H, s, tert-butyl), 1.31 (3H, t, J=7.1 Hz, —COOCH2CH3).
Workup
- stirringagain stirred at 60-70° C. for 2 h
- stirringstirring
- waitwas continued for 1 h at the same temperature
- customwas allowed to rt
- additionpoured into ice cold water
- stirringstirred for 15 min
- filtrationThe precipitated solid was filtered
- washwashed with water
- customdried
Sources & evidence
- ORD record
- ord-6f6bf825072743a1aac70e67b775ec86
- Source dataset
- uspto-grants-2012_03
- Patent number
- US08143237B2
Reaction notes
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