Sodium Iodide → Ethyl 2-cyano-4,4-diethoxybutyrate

HRID 1520349Notes

Reaction equation

Br[CH2:2][CH:3]([O:7][CH2:8][CH3:9])[O:4][CH2:5][CH3:6].[C:10]([CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14])#[N:11].C([O-])([O-])=O.[K+].[K+].[Na+].[I-]>>[C:10]([CH:12]([CH2:2][CH:3]([O:7][CH2:8][CH3:9])[O:4][CH2:5][CH3:6])[C:13]([O:15][CH2:16][CH3:17])=[O:14])#[N:11]

Participants

Reactant 4

HCID 5238Sodium Iodide

HCID 7764Ethyl cyanoacetate

HCID 11430Potassium Carbonate

HCID 74852Ethane, 2-bromo-1,1-diethoxy-

Product 1

HCID 4151505Ethyl 2-cyano-4,4-diethoxybutyrateYield 78%

Conditions

Temperature: 145 °C

Procedure

2-Bromo-1,1-diethoxyethane (4 g, 20 mmol, 1.0 eq.) was added to a mixture of ethyl 2 cyanoacetate (11.4 g, 101 mmol, 5.0 eq.), K2CO3 (2.8 g, 20 mmol, 1.0 eq.) and NaI (200 mg, 1.3 mmol, 0.06 eq.), as described in J. Chem. Soc., 1960, 131-138. The reaction mixture was refluxed for 4 h at 145° C. After cooling, the reaction mixture was purified by chromatography on silica gel (eluted with petroleum ether/ethyl acetate (80:1→40:1→10:1) to give 3.57 g of xlii-a as a colorless oil (78%). 1H NMR (400 MHz, CDCl3): δ 4.70 (t, J=5.6 Hz, 1H), 4.26 (q, J=7.2 Hz, 2H), 3.78-3.64 (m, 3H), 3.62-3.45 (m, 2H), 2.35-2.14 (m, 2H), 1.34 (q, J=7.2 Hz, 3H), 1.25-1.16 (m, 6H).

Workup

temperatureAfter cooling
customthe reaction mixture was purified by chromatography on silica gel (
washeluted with petroleum ether/ethyl acetate (80:1→40:1→10:1)

Sources & evidence

ORD record: ord-43dfdc3444214467b0c6f5a1a3acde19
Source dataset: uspto-grants-2015_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09073890B2

Reaction notes

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