Methacrylic Acid → HCID 20745888, compound

HRID 2308133Notes

Reaction equation

HRID 2308133 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][CH:20]2[CH2:25][CH: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])[CH2:23][CH:22]([O:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48]Cl)[CH2:21]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][CH:20]1[CH2:25][CH: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])[CH2:23][CH:22]([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])[CH2:21]1

Participants

6

Reactant 2

HCID 4093Methacrylic AcidHCID 20745897HCID 20745897, compound

Product 1

HCID 20745888HCID 20745888, compoundYield 94.1%

Reagents, catalysts & solvents 3

HCID 7108PhenothiazineCatalystHCID 67553Tetrabutylammonium IodideCatalystHCID 6228DimethylformamideSolvent3×

Conditions

Temperature
80 °C

Procedure

786 mg (5.16 mmol) 1,8-diazabicyclo[5.4.0]undec-7-ene(1,5-5) (DBU) in 5 ml N,N-dimethylformamide were added dropwise to a solution of 413 mg (4.8 mmol) 2-methylacrylic acid in 5 ml N,N-dimethylformamide over a period of 30 minutes. After addition of 4 mg phenothiazine, 146 mg tetrabutylammonium iodide and 2.6 g (3.9 mmol) (E)-3-[4-[[3-[(6-chlorohexyl)oxy]-5-[[2-methoxy-4-[(E)-2-(methoxycarbonyl)vinyl]phenoxy]methyl]cyclohexyl]methoxy]-3-methoxyphenyl]acrylic acid methyl ester dissolved in 10 ml N,N-dimethylformamide the resulting mixture was stirred at 80° C. for 20 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 270 g silica gel using toluene/ethanol (9:1) as eluent yielded 2.6 g (92%) of 2-methylacrylic acid 6-[3,5-bis[[2-methoxy-4-[(E)-2-(methoxycarbonyl)vinyl]phenoxy]methyl]cyclohexyloxy]hexyl ester as 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 270 g silica gel

Sources & evidence

ORD record
ord-efd84a1dbfba4a1a80ada19f79d5afec
Source dataset
uspto-grants-2004_12
Patent number
US06833421B1

Reaction notes

Loading…