Sodium Iodide → Ethyl methoxycinnamate

HRID 1194571Notes

Reaction equation

HRID 1194571 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][CH:3]=1.[Na+].[I-].CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[C:34]([O:38][CH2:39][CH3:40])(=[O:37])[CH:35]=[CH2:36].CCN(CC)CC>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].CCOCC.CCCCCC>[CH3:40][CH2:39][O:38][C:34](/[CH:35]=[CH:36]/[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][CH:3]=1)=[O:37]

Participants

9

Reactant 5

HCID 5238Sodium IodideHCID 8471TriethylamineHCID 8821Ethyl AcrylateHCID 121674-ChloroanisoleHCID 80271Tri-o-tolylphosphine

Product 1

HCID 5281783Ethyl methoxycinnamateYield 73.7%

Reagents, catalysts & solvents 3

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 3283Diethyl EtherSolvent2×HCID 8058HexaneSolvent2×

Procedure

4-Chloroanisole (1430 mg, 10 mmoles, 1229 ml), NiBr2 (438 mg, 2 mmoles), NaI (1650 mg, 11 mmoles) and P(o-tol)3 (1216 mg, 4 mmoles) were combined according to Method B and treated with ethyl acrylate (1100 mg, 11 mmoles, 1.130 ml), Et3N (1111 mg, 11 mmoles, 1.530 ml), and Pd(dba)2 (29 mg, 0.05 mmoles). Isolation by radial chromatography as described in Example 2 (Si gel, 5:1 volume mixture of hexane and Et2O for the first fraction, 1:1 volume mixture of hexane and Et2O for the second) gave 1519 mg (74 mole % yield) of 4-methoxy ethyl cinnamate as a brown oil. The results of NMR (CDCl3) analysis were: δ1.35 (t, 3H,--COOCH2CH3), 3.84 (s, 3H, OCH3), 4.26 (q, 2H, COOCH2CH3), 6.33 (d, 1H, PhCH=CH--), 6.90 (d, 2H, aromatic), 7.49 (d, 2H, aromatic), 7.65 (d, 1H, PhCH=CH--R), indicating the desired product.

Sources & evidence

ORD record
ord-e7b996d2d16d44039ca544799918496e
Source dataset
uspto-grants-1989_03
Patent number
US04814489

Reaction notes

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