Ethyl bromoacetate → 3-Amino-3-cyclopropyl-acrylic acid ethyl ester

Cyclopropanecarbonitrile (2.7 g, 40.5 mmol) was dissolved in dry THF (100 mL) and firstly zinc (13.2 g, 202.3 mmol) and then zinc oxide (1.6 g, 20.2 mmol) were added followed by dropwise addition of ethylbromoacetate (6.7 g, 40.5 mmol). The mixture was sonicated in a 35 kHz ultrasonic bath under N2 for 2 hours. After 30 minutes a green colour was observed. The mixture was filtered through celite to remove the zinc and zinc oxide. The filtrate was added to 20 ml of 50% K2CO3 (aq) solution. A thick precipitate formed which was filtered to remove the solid and the aqueous was extracted with 100 ml EtOAc. The extract was washed with 20 ml brine, dried over MgSO4 and concentrated in vacuo to give the crude product (3.8 g). The crude material was purified by column chromatography on silica gel eluting with 90:10 pentane:EtOAc to give the title compound (1.32 g) as a yellow oil.

1. customThe mixture was sonicated in a 35 kHz ultrasonic bath under N2 for 2 hours
2. filtrationThe mixture was filtered through celite
3. customto remove the zinc and zinc oxide
4. additionThe filtrate was added to 20 ml of 50% K2CO3 (aq) solution
5. customA thick precipitate formed which
6. filtrationwas filtered
7. customto remove the solid
8. extractionthe aqueous was extracted with 100 ml EtOAc
9. washThe extract was washed with 20 ml brine
10. dry with materialdried over MgSO4
11. concentrationconcentrated in vacuo
12. customto give the crude product (3.8 g)
13. customThe crude material was purified by column chromatography on silica gel eluting with 90:10 pentane

ORD record

ord-f1982537310243c6885ce38b406d4a86

Source dataset

uspto-grants-2010_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07691877B2