Methacrylic Acid → HCID 20745896, compound

HRID 2308131Notes

Reaction equation

HRID 2308131 reaction equation
[CH3:1][C:2](=[CH2:6])[C:3]([OH:5])=[O:4].[CH3:7][O:8][C:9](=[O:54])/[C:10](/[C:52]#[N:53])=[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]=[C:10](\[C:52]#[N:53])/[C:9]([O:8][CH3:7])=[O:54])[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 20745898HCID 20745898, compound

Product 1

HCID 20745896HCID 20745896, compoundYield 30.1%

Reagents, catalysts & solvents 3

HCID 7108PhenothiazineCatalystHCID 67553Tetrabutylammonium IodideCatalystHCID 6228DimethylformamideSolvent3×

Conditions

Temperature
80 °C

Procedure

0.32 ml (2 mmol) 1,8-diazabicyclo[5.4.0]undec-7-ene(1,5-5) (DBU) in 2 ml N,N-dimethylformamide (DMF) were added dropwise to a solution of 0.2 ml (1.9 mmol) 2-methylacrylic acid in 2 ml DMF. After addition of 2 mg phenothiazine, 60 mg tetrabutylammonium iodide and 1.1 g (1.6 mmol) (E)-3-[4-[[3-[(6-chlorohexyl)oxy]-5-[[2-methoxy-4[(E)-2-(methoxycarbonyl)vinyl]phenoxy]methyl]benzyl]oxy]-3-methoxyphenyl]-2-cyanoacrylic acid methyl ester in 7 ml DMF the resulting mixture was stirred at 80° C. for 20 hours. The reaction mixture was poured into an ice cold 1 M HCl solution. The aqueous phase was extracted three times with ethyl acetate. The organic phase was washed with a saturated sodium bicarbonate solution and repeatedly with water, dried over magnesium sulfate, filtered and concentrated by vacuum evaporation. The crude product was filtered through a thin silica gel layer. (eluent: ethyl acetate). The filtrate was evaporated to dryness and recrystallized from ethanol to yield 0.35 g (30%) of 2-methylacrylic acid 6-[3-[2-methoxy-4-[2-cyano-(E)-2-(methoxycarbonyl)vinyl]phenoxymethyl]-5-[2-methoxy-4-[(E)-2-(methoxycarbonyl)vinyl]phenoxymethyl]phenoxy]hexyl ester as slightly yellow crystals.

Workup

  1. extractionThe aqueous phase was extracted three times with ethyl acetate
  2. washThe organic phase was washed with a saturated sodium bicarbonate solution and repeatedly with water
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated by vacuum evaporation
  6. filtrationThe crude product was filtered through a thin silica gel layer
  7. customThe filtrate was evaporated to dryness
  8. customrecrystallized from ethanol

Sources & evidence

ORD record
ord-cb0a0c939ab3472fbc420303497ca731
Source dataset
uspto-grants-2004_12
Patent number
US06833421B1

Reaction notes

Loading…