Benzyl Alcohol → Benzyl 2-(4-(chlorosulfonyl)-3,5-dimethylphenoxy)acetate

HRID 628155Notes

Reaction equation

[Cl:1][S:2]([C:5]1[C:15]([CH3:16])=[CH:14][C:8]([O:9][CH2:10][C:11](Cl)=[O:12])=[CH:7][C:6]=1[CH3:17])(=[O:4])=[O:3].[CH2:18]([OH:25])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.CCN(CC)CC.Cl>C1COCC1.CN(C1C=CN=CC=1)C>[Cl:1][S:2]([C:5]1[C:15]([CH3:16])=[CH:14][C:8]([O:9][CH2:10][C:11]([O:25][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[O:12])=[CH:7][C:6]=1[CH3:17])(=[O:4])=[O:3]

Participants

Conditions

Temperature: -78 °C

Procedure

Referring to FIG. 37, to a solution of 2-(4-(chlorosulfonyl)-3,5-dimethylphenoxy)acetyl chloride (6 g, 20.3 mmol) in THF (60 mL) were added dropwise a solution of BnOH (2.2 g, 20.3 mmol), Et3N (3.44 mL, 24.3 mmol) and DMAP (25 mg, 0.2 mmol) in THF (30 mL) at −78° C. The reaction mixture was stirred for 5 h at −78° C. and then poured into HCl solution (1 N, 100 mL). The resulting mixture was extracted with ethyl acetate (100 mL×2). The combined extracts were washed with brine, dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified by flash column chromatography (petroleum ether/EtOAc=60:1) to give product as a white powder (1.2 g, 16% yield). 2-(4-(Chlorosulfonyl)-3,5-dimethylphenoxy)acetyl chloride (2.0 g) was recovered. 1H NMR (CDCl3, 300 MHz): δ 7.42-7.32 (m, 5H), 6.67 (s, 2H), 5.32 (s, 2H), 4.74 (s, 2H) 2.72 (s, 6H).

Workup

extractionThe resulting mixture was extracted with ethyl acetate (100 mL×2)
washThe combined extracts were washed with brine
dry with materialdried over anhydrous Na2SO4
concentrationconcentrated under reduced pressure
customThe residue was purified by flash column chromatography (petroleum ether/EtOAc=60:1)

Sources & evidence

ORD record: ord-95711834b24a4d4491157c98ce5ce2f4
Source dataset: uspto-grants-2016_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09309283B2

Reaction notes

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