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

HRID 393909Notes

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.C(N([CH2:25][CH3:26])CC)C.[C:27]([O:36][CH3:37])(=[O:35])[C:28]1[C:29](=[CH:31][CH:32]=[CH:33][CH:34]=1)[OH:30].[C]=[O:39]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CN(C=O)C>[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:26]=1[C:25]([O:30][C:29]1[CH:31]=[CH:32][CH:33]=[CH:34][C:28]=1[C:27]([O:36][CH3:37])=[O:35])=[O:39])[O:13][CH2:12][CH2:11][O:10]3

Participants

Conditions

Temperature: 80 °C

Procedure

A Fisher-Porter tube (defined in Example 3A) 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, 1.53 g (15 mmol) of triethylamine, 23 mg (0.1 mmol) of palladium acetate, 1.67 g (11 mmol) of methyl salicylate, and 20 mL of DMF. The mixture was heated for 3 hr at 80° C. followed by 17 hr at 50° C. in a carbon monoxide atmosphere at 70 psi (4.8×105 Pa). The mixture was poured into 150 mL of ice water and filtered. The solid was washed with 10 mL of water, 10 mL of acetonitrile, and 10 mL of diethyl ether to give the title product as 3.50 g of pink solid, m.p. 179-181° C. 1H NMR (CDCl3): δ 2.58 (s, 3), 2.60 (m, 2), 2.84 (s, 3), 3.52 (m, 2), 3.84 (s, 3), 4.19 (m, 2), 4.34 (m, 2), 7.20 (d, 1), 7.36 (t, 1), 7.61 (t, 1), 8.02 (s, 1), 8.08 (d, 1).

Workup

filtrationfiltered
washThe solid was washed with 10 mL of water, 10 mL of acetonitrile, and 10 mL of diethyl ether

Sources & evidence

ORD record: ord-442471aec4014ab985317d76aa5b6fbe
Source dataset: uspto-grants-2004_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06809206B2

Reaction notes

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