Nitric Acid → HCID 86586352, compound

HRID 1359063Notes

Reaction equation

[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([O:11][CH2:12][C@@H:13]2[O:18][C:17]3[CH:19]=[CH:20][C:21]([O:23][CH3:24])=[CH:22][C:16]=3[O:15][CH2:14]2)(=[O:10])=[O:9])=[CH:4][CH:3]=1.[N+:25]([O-])([OH:27])=[O:26]>ClCCCl>[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([O:11][CH2:12][CH:13]2[O:18][C:17]3[CH:19]=[C:20]([N+:25]([O-:27])=[O:26])[C:21]([O:23][CH3:24])=[CH:22][C:16]=3[O:15][CH2:14]2)(=[O:10])=[O:9])=[CH:4][CH:3]=1

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of 5.91 g (16.9 mmole) of {(2R)-6-methoxy-2,3-dihydro-1,4-benzodioxin-2-yl}methyl 4-methylbenzenesulfonate in 200 mL of 1,2-dichloroethane in an ice/water bath was added dropwise a solution of 2.50 mL (59.1 mmole) of fuming nitric acid (d 1.49) in 75 mL of 1,2-dichloroethane and the mixture was stirred for 2 hours at 0° C. After the reaction was complete, it was quenched with ice and diluted with 500 mL of methylene chloride. After the ice had melted, the organic layer was separated and washed with equal volumes of saturated aqueous sodium bicarbonate and saturated brine, dried over magnesium sulfate, filtered and concentrated in vacuum to give 6.19 g of the (R)-enantiomer of the title compound as a light yellow solid. 1H-NMR (CDCl3): doublet 7.8 δ(2 H); multiplet 7.4 δ(3 H); singlet 6.5 δ(1 H); multiplet 4.10-4.5 δ(5 H); singlet 3.85 δ(3 H); singlet 2.5 δ(3 H).

Workup

customit was quenched with ice
additiondiluted with 500 mL of methylene chloride
customthe organic layer was separated
washwashed with equal volumes of saturated aqueous sodium bicarbonate and saturated brine
dry with materialdried over magnesium sulfate
filtrationfiltered
concentrationconcentrated in vacuum

Sources & evidence

ORD record: ord-81ebdab5161c4e4f95bff23f2795fa21
Source dataset: uspto-grants-2003_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06599915B2

Reaction notes

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