Methylparaben → 4-(methoxycarbonyl)phenyl 2,3-dihydro-5,8-dimethylspiro[4H-1-benzothiopyran-4,2'-[1,3]dioxolane]-6-carboxylate 1,1-dioxide

HRID 393908Notes

Reaction equation

HRID 393908 reaction equation
I[C:2]1[CH:3]=[C:4]([CH3:19])[C:5]2[S:16](=[O:18])(=[O:17])[CH2:15][CH2:14][C:9]3([O:13][CH2:12][CH2:11][O:10]3)[C:6]=2[C:7]=1C.[OH:20][C:21]1[CH:30]=[CH:29][C:24]([C:25]([O:27][CH3:28])=[O:26])=[CH:23][CH:22]=1.C(N([CH2:36][CH3:37])CC)C.[C]=[O:39]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CN(C)C=O>[CH3:2][C:7]1[C:6]2[C:9]3([CH2:14][CH2:15][S:16](=[O:18])(=[O:17])[C:5]=2[C:4]([CH3:19])=[CH:3][C:37]=1[C:36]([O:20][C:21]1[CH:22]=[CH:23][C:24]([C:25]([O:27][CH3:28])=[O:26])=[CH:29][CH:30]=1)=[O:39])[O:13][CH2:12][CH2:11][O:10]3

Participants

7

Reactant 4

HCID 7456MethylparabenHCID 8471TriethylamineHCID 22648325HCID 22648325, compoundHCID 178418416HCID 178418416, compound

Product 1

HCID 226483234-(methoxycarbonyl)phenyl 2,3-dihydro-5,8-dimethylspiro[4H-1-benzothiopyran-4,2'-[1,3]dioxolane]-6-carboxylate 1,1-dioxide

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Procedure

A Fisher-Porter tube* was charged with 3.94 g (10 mmol) of 2,3-dihydro-6-iodo-5,8-dimethylspiro[4H-1-benzothiopyran-4,2′-[1,3]dioxolane] 1,1-dioxide, 1.67 g (11 mmol) of methyl 4-hydroxybenzoate, 2.28 g (22.5 mmol) of triethylamine, 23 mg (0.1 mmol) of palladium acetate, and 20 mL of dry N,N-dimethylformamide (DMF). The mixture was heated for 2.5 hr at 80° C. in a carbon monoxide atmosphere at 70 psi (4.8×105 Pa). The mixture was cooled to room temperature and filtered through Celite® diatomaceous earth filter aid into 150 mL of stirred ice water. The Celite® was rinsed with 10 mL of DMF, which was added to the ice water. The resulting precipitate was collected by filtration, washed with 25 mL of water, 15 mL of acetonitrile, 20 mL of diethyl ether and allowed to dry to give 4.20 g of the title product as a pale pink solid, m.p. 206-208° C. 1H NMR (CDCl3): δ 2.57 (s, 3), 2.58 (m, 2), 2.82 (s, 3), 3.52 (m, 2), 3.94 (s, 3), (s, 3), 4.20 (m, 2), 4.34 (m 2), 7.30 (m, 2), 7.79 (s, 1), 8.14 (m, 2).

Workup

  1. filtrationfiltered through Celite® diatomaceous earth
  2. filtrationfilter aid into 150 mL of stirred ice water
  3. washThe Celite® was rinsed with 10 mL of DMF, which
  4. additionwas added to the ice water
  5. filtrationThe resulting precipitate was collected by filtration
  6. washwashed with 25 mL of water, 15 mL of acetonitrile, 20 mL of diethyl ether
  7. customto dry

Sources & evidence

ORD record
ord-e603ba239cee4e36a98084c880ea0407
Source dataset
uspto-grants-2004_10
Patent number
US06809206B2

Reaction notes

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