1,4-Dioxane → (E)-methyl-2-(2-((4-(2-methoxyethoxy)phenoxy)methyl)-4-chlorophenyl)-3-methoxyacrylate

HRID 1516142Notes

Reaction equation

HRID 1516142 reaction equation
[CH3:1][O:2][CH2:3][CH2:4][O:5][C:6]1[CH:23]=[CH:22][C:9]([O:10][CH2:11][C:12]2[CH:17]=[C:16]([Cl:18])[CH:15]=[CH:14][C:13]=2B(O)O)=[CH:8][CH:7]=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].O1CCOCC1.[CH3:38][O:39][C:40](=[O:46])/[C:41](/I)=[CH:42]\[O:43][CH3:44]>[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(OCC)(=O)C.O>[CH3:38][O:39][C:40](=[O:46])/[C:41](/[C:13]1[CH:14]=[CH:15][C:16]([Cl:18])=[CH:17][C:12]=1[CH2:11][O:10][C:9]1[CH:22]=[CH:23][C:6]([O:5][CH2:4][CH2:3][O:2][CH3:1])=[CH:7][CH:8]=1)=[CH:42]/[O:43][CH3:44]

Participants

8

Reactant 4

HCID 312751,4-DioxaneHCID 62657Potassium Phosphate, TribasicHCID 669702642-((4-(2-Methoxyethoxy)phenoxy)methyl)-4-chlorophenylboronic acidHCID 86624615(E)-methyl-2-iodo-3-methoxy-2-propenoate

Product 1

HCID 11611173(E)-methyl-2-(2-((4-(2-methoxyethoxy)phenoxy)methyl)-4-chlorophenyl)-3-methoxyacrylateYield 71.3%

Reagents, catalysts & solvents 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

1.1 g (3.3 mmol) of the compound obtained in Step 3, 0.17 g (0.15 mmol) of tetrakis(triphenylphosphine) palladium and 1.96 g (9.0 mmol) of K3PO4 were placed in a flask, and 5 ml of dioxane and 1 ml of water were added thereto. After adding 0.73 g (3.0 mmol) of (E)-methyl-2-iodo-3-methoxy-2-propenoate thereto, the resulting mixture was stirred at 90° C. for 22 hours. The mixture was cooled to room temperature, and 10 ml of ethyl acetate was added thereto. The water layer was separated and extracted twice with 10 ml of ethyl acetate, and the organic layers were combined, washed with 20 ml of water and then with 20 ml of a brine solution, dried over anhydrous MgSO4 and concentrated under a reduced pressure. The resulting residue was subjected to column chromatography using 20% ethyl acetate/hexane as an eluent to obtain 0.87 g (yield 71%) of (E)-methyl-2-(2-((4-(2-methoxyethoxy)phenoxy)methyl)-4-chlorophenyl)-3-methoxyacrylate.

Workup

  1. temperatureThe mixture was cooled to room temperature
  2. customThe water layer was separated
  3. extractionextracted twice with 10 ml of ethyl acetate
  4. washwashed with 20 ml of water
  5. dry with materialwith 20 ml of a brine solution, dried over anhydrous MgSO4
  6. concentrationconcentrated under a reduced pressure

Sources & evidence

ORD record
ord-9a7a82dd9a9145ada8a907e3038be509
Source dataset
uspto-grants-2012_07
Patent number
US08227456B2

Reaction notes

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