Sodium Sulfite → 2,3,4,5-tetrahydro-1-benzothiepine 1,1-dioxide

HRID 1604506Notes

Reaction equation

[S:1]1(=[O:12])[C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][C:6]=2[CH2:5][CH2:4][CH2:3][CH2:2]1.ClC1C=C(C=CC=1)C(OO)=[O:18].[O-]S([O-])=O.[Na+].[Na+].C([O-])(O)=O.[Na+]>C(Cl)Cl>[S:1]1(=[O:18])(=[O:12])[C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][C:6]=2[CH2:5][CH2:4][CH2:3][CH2:2]1

Participants

Conditions

Temperature: 0 °C

Procedure

To a stirred solution of 13.44 g (31.07 mmol) of enantiomerically-enriched tetrahydrobenzothiepine-1-oxide (obtained from Step 7) in 150 mL of methylene chloride was added 9.46 g of 68% m-chloroperoxybenzoic acid (37.28 mmol, Sigma) at 0° C. After stirring at 0° C. for 2 hours, the mixture was allowed to warm up to room temperature and stirred for 4 hours. 50 mL of saturated Na2SO3 was added into the mixture and stirred for 30 minutes. The solution was then neutralized with 50 mL of saturated NaHCO3 solution. The methylene chloride layer was separated, dried over MgSO4, and concentrated in vacuo to give 13.00 g (97.5%) of the enantiomerically-enriched tetrahydrobenzothiepine-1,1-dioxide (4R,5R) as a light yellow solid: 1H NMR (CDCl3) δ 0.89-0.95 (m, 6H), 1.09-1.42 (m, 12H), 2.16-2.26 (m, 1H), 3.14 (q, J=15.6 Hz, 1H), 3.87 (s, 3H), 4.18 (s, 1H), 5.48 (s, 1H), 6.54 (dd, J 10.2 Hz, 2.4 Hz, 1H), 6.96-7.07 (m, 3H), 7.40 (d, J 8.1 Hz, 2H), 8.11 (dd, J=8.6 Hz, 5.9 Hz, 1H).

Workup

temperatureto warm up to room temperature
stirringstirred for 4 hours
stirringstirred for 30 minutes
customThe methylene chloride layer was separated
dry with materialdried over MgSO4
concentrationconcentrated in vacuo

Sources & evidence

ORD record: ord-402ddbe6c6e943709f72fd8a1fd375cd
Source dataset: uspto-grants-1999_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05994391

Reaction notes

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