Acetonitrile → HCID 12518841, compound

To a stirred solution containing 4.36 mL (38.0 mmol) of dimethyl malonate and 2.00 mL (38.0 mmol) of acetonitrile in 20 mL of 1,2-dichloroethane were added 8.90 mL (76.0 mmol) of SnCl4. The reaction mixture was stirred at reflux for 2 h. The reaction mixture was then concentrated under diminished pressure and the residue was dissolved into 100 mL of acetone. Then, 70 mL of satd. aq. sodium carbonate were added and the mixture was stirred for 20 minutes. The mixture was poured into 200 mL of satd. aq. sodium bicarbonate and extracted with two 200-mL portions of DCM. The combined organic solution was washed with a 200-mL portion of brine, dried (MgSO4) and concentrated under diminished pressure. The residue was recrystallized in ethyl acetate/hexanes to afford the expected product as colorless crystals: yield 3.96 g (60%); mp: 81-82° C.; silica gel TLC Rf 0.5 (1:1 ethyl acetate-hexanes); 1H NMR (CDCl3) δ 2.10 (s, 3H), 3.66 (s, 3H), 3.69 (s, 3H), 5.29 (br s, 1H) and 8.94 (br s, 1H); 13C NMR (CDCl3) δ 22.0, 51.0, 51.6, 92.4, 164.0, 168.7 and 168.9; mass spectrum (APCI), m/z 174.0760 (M+H)+ (C7H12NO4 requires 174.0766).

1. temperatureat reflux for 2 h
2. concentrationThe reaction mixture was then concentrated under diminished pressure
3. dissolutionthe residue was dissolved into 100 mL of acetone
4. additionaq. sodium carbonate were added
5. stirringthe mixture was stirred for 20 minutes
6. additionThe mixture was poured into 200 mL of satd
7. extractionaq. sodium bicarbonate and extracted with two 200-mL portions of DCM
8. washThe combined organic solution was washed with a 200-mL portion of brine
9. dry with materialdried (MgSO4)
10. concentrationconcentrated under diminished pressure
11. customThe residue was recrystallized in ethyl acetate/hexanes

ORD record

ord-a0d0b14d418a4450a744e7cb5b55643d

Source dataset

uspto-grants-2015_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08952025B2