Methacrylic Acid → HCID 20745891, compound

HRID 2308124Notes

Reaction equation

HRID 2308124 reaction equation
[CH3:1][C:2](=[CH2:6])[C:3]([OH:5])=[O:4].[CH3:7][O:8][C:9](=[O:52])/[CH:10]=[CH:11]/[C:12]1[CH:17]=[CH:16][C:15]([O:18][CH2:19][C:20]2[CH:25]=[C:24]([CH2:26][O:27][C:28]3[CH:33]=[CH:32][C:31](/[CH:34]=[CH:35]/[C:36]([O:38][CH3:39])=[O:37])=[CH:30][C:29]=3[O:40][CH3:41])[CH:23]=[C:22]([O:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48]Cl)[CH:21]=2)=[C:14]([O:50][CH3:51])[CH:13]=1>CN(C)C=O.[I-].C([N+](CCCC)(CCCC)CCCC)CCC.C1C2NC3C(=CC=CC=3)SC=2C=CC=1>[CH3:51][O:50][C:14]1[CH:13]=[C:12](/[CH:11]=[CH:10]/[C:9]([O:8][CH3:7])=[O:52])[CH:17]=[CH:16][C:15]=1[O:18][CH2:19][C:20]1[CH:21]=[C:22]([CH:23]=[C:24]([CH2:26][O:27][C:28]2[CH:33]=[CH:32][C:31](/[CH:34]=[CH:35]/[C:36]([O:38][CH3:39])=[O:37])=[CH:30][C:29]=2[O:40][CH3:41])[CH:25]=1)[O:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][O:4][C:3](=[O:5])[C:2]([CH3:1])=[CH2:6]

Participants

6

Reactant 2

HCID 4093Methacrylic AcidHCID 20745899HCID 20745899, compound

Product 1

HCID 20745891HCID 20745891, compoundYield 90.3%

Reagents, catalysts & solvents 3

HCID 7108PhenothiazineCatalystHCID 67553Tetrabutylammonium IodideCatalystHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
80 °C

Procedure

382 mg (2.5 mmol) 1,8-diazabicyclo[5.4.0]undec-7-ene(1,5-5) (DBU) in 4 ml N,N-dimethylformamide were added dropwise to a solution of 200 mg (2.3 mmol) 2-methylacrylic acid in 8 ml N,N-dimethylformamide over a period of 35 minutes. After addition of 4 mg phenothiazine, 1.5 g (2.3 mmol) (E)-3-[4-[[3-[(6-chlorohexyl)oxy]-5-[[2-methoxy-4-[(E)-2-(methoxycarbonyl)vinyl]phenoxy]methyl]benzyl]oxy]-3-methoxyphenyl]acrylic acid methyl ester and 84 mg tetrabutylammonium iodide the resulting mixture was stirred at 80° C. for 25 hours. The reaction mixture was poured into 50 ml of an ice cold 1 M HCl solution. The aqueous phase was extracted three times with 50 ml ethyl acetate. The organic phase was washed with 50 ml of a saturated sodium bicarbonate solution and repeatedly with water, dried over magnesium sulfate, filtered and concentrated by vacuum evaporation. Purification of the residue by column chromatography on 275 g silica gel using hexane:ethyl acetate (1:1) as eluent yielded 1.46 g (90%) of 2-methylacrylic acid 6-[3,5-bis[[2-methoxy-4-[(E)-2-(methoxycarbonyl)vinyl]phenoxy]methyl]phenoxy]hexyl ester as a yellowish oil.

Workup

  1. extractionThe aqueous phase was extracted three times with 50 ml ethyl acetate
  2. washThe organic phase was washed with 50 ml of a saturated sodium bicarbonate solution and repeatedly with water
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated by vacuum evaporation
  6. customPurification of the residue by column chromatography on 275 g silica gel

Sources & evidence

ORD record
ord-25fa4a686fb44796acecea59ac78e727
Source dataset
uspto-grants-2004_12
Patent number
US06833421B1

Reaction notes

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