[(vinyloxy)methyl]oxirane synthesis

Yield:3678-15-7 63%

Reaction Conditions:

with 1,10-Phenanthroline;palladium diacetate in dichloromethane at 60; for 48 h;

Steps:

3.1 4.3.1. Vinyloxy-2-methyloxiranne (GcEV)

Palladium acetate (34.42 mg, 1.52 mmol) and 1,10 phenantroline (41.2 mg, 2.29 mmol) were dissolved separately in 10 mL of dichloromethane and mixed together at 20 °C for 15 min. 20.00 g (269.99 mmol) of glycidol and 263.00 g (2.29 mol) of vinyloxyethane were placed along with the catalyst solution into a pressure reactor. The reactor was closed and the reaction mixture was heated under stirring at 60 °C for 48 h. The volatiles were removed using a rotary evaporator. Diethyl ether was added to the residue, and the precipitated catalyst was filtered off. 17.03 g (170.09 mmol) of GcEV was then isolated by distillation under reduced pressure and obtained as a transparent colourless liquid. ¹H NMR (Acetone-d₆) δ (ppm): 0.89 (s, C-CH₃, 6H), 2.15 (s, -CH₂-N, 2H), 2.23 (s, N-CH₃, 6H), 3.44 (s, -CH₂-O, 2H), 3.91 (dd, CHH-CH=(E), ²J_gem = 1.77 Hz, ³J_cis = 6.82 Hz, 1H), 4.16 (dd, CHH-CH=(Z), ²J_gem = 1.64 Hz, ³J_trans = 14.27 Hz, 1H), 6.51 (ddt, CH₂-CH=, ³J_cis = 6.82 Hz, ³J_trans = 14.27 Hz, ⁴J = 0.51 Hz, 1H). ¹³C NMR (Acetone-d₆) δ (ppm): 23.5 (CH₃-C, 2C), 37.1 ((CH₃)₂-C<, 1C), 48.8 (CH₃-N, 2C), 67.2 (CH₂-N, 1C), 74.7 (CH₂-O, 1C), 86.2 (H₂C=CH, 1C), 153.1 (H₂C=CH, 1C). ¹H NMR (Acetone-d₆) δ (ppm): 2.61 (dd, -CHH-O- epoxy, ²J_gem = 5.05 Hz, ³J_trans = 2.53, 1H), 2.77 (dd, -CHH-O- epoxy, ²J_gem = 5.05 Hz, ³J_cis = 4.17 Hz, 1H), 3.17 (m, -CH₂-CH<, 1H), 3.56 (dd, -O-CHH-, ²J_gem = 11.62 Hz, ³J_cis = 6.32 Hz, 1H), 3.99 (dd, CHH-CH = (E), ²J_gem = 2.02 Hz, ³J_cis = 6.82 Hz, 1H), 4.01 (dd, -O-CHH-, ²J_gem = 11.62 Hz, ³J_trans = 2.78 Hz, 1H), 4.22 (dd, CHH-CH = (Z), ²J_gem = 2.02 Hz, ³J_trans = 14.27 Hz, 1H), 6.50 (ddt, CH₂-CH=, ³J_cis = 6.82 Hz, ³J_trans = 14.27 Hz, ⁴J = 0.51 Hz, 1H). ¹³C NMR (Acetone-d₆) δ (ppm): 44.2 (CH-CH₂-O-, 1C), 50.3 (-CH₂-CH<, 1C), 70.1 (>HC-CH₂-O-, 1C), 87.4 (H₂C=CHO-, 1C), 152.6 (>C=CH₂, 1C).

References:

Couture, Guillaume;Ladmiral, Vincent;Améduri, Bruno [Journal of Fluorine Chemistry,2015,vol. 171,p. 124 - 132]