4-Toluenesulfonyl chloride → (7-Nitro-2,3-dihydrobenzo[b][1,4]dioxin-2-yl)methyl 4-methylbenzenesulfonate

HRID 1259455Notes

Reaction equation

[N+:1]([C:4]1[CH:5]=[CH:6][C:7]2[O:12][CH2:11][CH:10]([CH2:13][OH:14])[O:9][C:8]=2[CH:15]=1)([O-:3])=[O:2].[C:16]1([CH3:26])[CH:21]=[CH:20][C:19]([S:22](Cl)(=[O:24])=[O:23])=[CH:18][CH:17]=1>N1C=CC=CC=1>[CH3:26][C:16]1[CH:21]=[CH:20][C:19]([S:22]([O:14][CH2:13][CH:10]2[O:9][C:8]3[CH:15]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=[CH:6][C:7]=3[O:12][CH2:11]2)(=[O:24])=[O:23])=[CH:18][CH:17]=1

Participants

Conditions

Temperature: 5 °C

Procedure

A 500 mL round bottomed flask equipped with a magnetic stir bar is charged with [7-nitro-2,3-dihydro-1,4-benzodioxin-2-yl]methanol (37.3 g, 177 mmol) and anhydrous pyridine (150 mL). The solution is cooled to 5° C. and p-toluenesulfonyl chloride (42.1 g, 221 mmol) is added in one portion. After 1 h, the cooling bath is removed, and the solution is stirred for another 3 h. The reaction mixture is poured into a rapidly stirred flack containing water (750 mL). The precipitate is collected by vacuum filtration, and the filter cake is rinsed with water and suction dried to give the title compound (63.8 g, 99%) as yellow granules. LCMS (Standard Method): 2.81 min, 388 (M+Na)+. 1H NMR (300 MHz, DMSO-d6) δ7.79-7.72 (m, 3H), 7.49-7.42 (m, 3H), 7.06 (d, J=8.8 Hz, 1H), 4.59-4.55 (m, 1H), 4.41 (dd, J=2.6, 11.6 Hz, 2H), 4.22 (dd, J=6.3, 11.5 Hz, 1H), 4.12 (dd, J=6.8, 11.7 Hz, 1H), 2.38 (s, 3H).

Workup

customA 500 mL round bottomed flask equipped with a magnetic stir bar
customthe cooling bath is removed
additionThe reaction mixture is poured into a rapidly stirred flack
additioncontaining water (750 mL)
filtrationThe precipitate is collected by vacuum filtration
washthe filter cake is rinsed with water and suction
customdried

Sources & evidence

ORD record: ord-91a5f1bfa9fe4f70a9d73ed597dea3fc
Source dataset: uspto-grants-2013_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08466296B2

Reaction notes

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