ETHYL1-CYANOCYCLOPROPANECARBOXYLATE

A suspension of cyano-acetic acid ethyl ester (11.3 g, 0.1 mol), 1, 2-Dibromo-ethane, Na(1) Description 85Ethyl 1-cyanocyclopropanecarboxylate (P85)NTo the mixture of ethyl 2-cyanoacetate (5 g) and potassium carbonate (18.33 g) in acetone (20 mL)was added 1 , 2-dibromoethane (9.96 g) over a period of 10 mm. The reaction mixture was heated toreflux overnight. More 1 , 2-dibromoethane (9.96 g) was added and the reaction mixture was refluxed for another 2 hours. The reaction mixture was filtered through a pad of Celite and the cake was rinsed with aetone (20 mL). The combined filtrate was concentrated under reduced pressure to give the title compound (5 g) as orange oil. MS (ESI): C7H9N02 requires 139; found 140 [M+H].To a stirred mixture of compound CXI-5 (30 g, 0.265 mol), l-bromo-2- chloroethane (75 g, 0.528 mol) in DMF (200 mL) was added KTo concentrated sulfuric acid (102 mL) was added A suspension of cyano-acetic acid ethyl ester (11.3 g, 0.1 mol), 1, 2-Dibromo-ethane, Na4(n-Bu)4Br and K2CO3 in DMF (100 mL) was heated to 80 C. overnight. The mixture was poured into water (600 mL) and extracted with EtOAc (3×50 mL). The combined organic layer was washed with brine, dried over Na2SO4, concentrated under reduced pressure to give the crude product, which was purified by column chromatography on silica gel (petroleum ether: EtOAc=10:15:1) to give Ethyl cyanoacetate (15 mL, 141 mmol) was added to a mixture of potassium carbonate (48.7 g, 353 mmol) and acetone (200 mL). 1, 2-Dibromoethane (13.4 mL, 155 mmol) was added dropwise over a period of 8 minutes. The reaction mixture was refluxed overnight. More 1, 2-dibromoethane (1.8 mL) was added and the reaction mixture was refluxed for 4 hours. The reaction mixture was filtered through a layer of CELITE filter aid. The filter cake was rinsed with acetone (200 mL). The filtrate was concentrated under reduced pressure to provide ethyl 1-cyanocyclopropionate as a pale orange oilEthylcyanoacetate (15.0 mL, 141 mmol) was added to a mixture of potassium carbonate (48.7 g, 353 mmol) and acetone (200 mL), and 1, 2-dibromoethane (13.4 mL, 155 mmol) was added dropwise to the resulting mixture over a period of eight minutes. The reaction was heated at reflux overnight. An analysis by TLC indicated the presence of ethylcyanoacetate, and additional 1, 2-dibromoethane (1.8 mL, 0.15 equivalent) was added. The reaction mixture was heated at reflux for an additional four hours and filtered through a layer of CELITE filter agent. The filter cake was washed with acetone (200 mL), and the combined filtrates were concentrated under reduced pressure to provide ethyl 1-cyanocyclopropanecarboxylate as an orange oil containing about 10 mole % 1, 2-dibromoethane.Example 87: ethyl 1-cyanocyclopropanecarboxylate100%Ethyl 2-cyanoacetate (0.85 g, 7.5 mmol, 1 equiv), 1, 2-dibromoethane (1.3 mL, 15 mmol, 2 equiv) and K2CO3 (3.18 g, 22.5 mmol, 3 equiv) was dissolved in acetone (6 mL), and the mixture was stirred for 16 h at 80 0C. The reaction mixture was filtred, concentrated to give the crude product as a yellow oil (1.84 g, 100%). 1U NMR (400 MHz, DMSO-d6) delta: 4.18 (t, 2H), 1.75 (t, 2H), 1.60 (m, 2H), 1.20 (t, 3H).(1) Synthesis of ethyl 1-cyanocyclopropanecarboxylate To a solution of ethyl cyanoacetate (11.8 g) in acetone (83.0 mL), potassium carbonate (43.1 g) and 1, 2-dibromoethane (39.2 g) were added and the mixture was refluxed for 12 hours. After being cooled to room temperature, the reaction mixture was filtered through Celite (registered trademark). The filtrate was concentrated under reduced pressure and further dried under reduced pressure with heating to give ethyl 1-cyanocyclopropanecarboxylate as a red oil (14.2 g). 1H NMR (300 MHz, DMSO-d6) delta ppm 1.23 (t, J=7.1 Hz, 3 H) 1.57 - 1.62 (m, 2 H) 1.73 - 1.79 (m, 2 H) 4.19 (q, J=7.1 Hz, 2 H).Description 85Ethyl 1-cyanocyclopropanecarboxylate (P85)NTo the mixture of ethyl 2-cyanoacetate (5 g) and potassium carbonate (18.33 g) in acetone (20 mL)was added 1 , 2-dibromoethane (9.96 g) over a period of 10 mm. The reaction mixture was heated toreflux overnight. More 1 , 2-dibromoethane (9.96 g) was added and the reaction mixture was refluxed for another 2 hours. The reaction mixture was filtered through a pad of Celite and the cake was rinsed with aetone (20 mL). The combined filtrate was concentrated under reduced pressure to give the title compound (5 g) as orange oil. MS (ESI): C7H9N02 requires 139; found 140 [M+H].

Molecular Weight:139.15
XLogP3:0.7
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:3
Exact Mass:139.063328530
Monoisotopic Mass:139.063328530
Topological Polar Surface Area:50.1
Heavy Atom Count:10
Complexity:197
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes