Aluminum(III) Chloride → 2-Benzyl-5,6-dibromo-2,3,3a,7a-tetrahydro-1H-4-thia-2-aza-cyclopenta[alpha]pentalen-7-one

HRID 30248Notes

Reaction equation

[Al+3].[Cl-].[Cl-].[Cl-].Cl.[CH2:6]([N:13]1[CH2:17][CH:16]([C:18]2[S:19][C:20]([Br:24])=[C:21]([Br:23])[CH:22]=2)[CH:15]([C:25](Cl)=[O:26])[CH2:14]1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1>C(Cl)Cl>[CH2:6]([N:13]1[CH2:17][CH:16]2[CH:15]([C:25](=[O:26])[C:22]3[C:21]([Br:23])=[C:20]([Br:24])[S:19][C:18]=32)[CH2:14]1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Participants

Conditions

Temperature: 0 °C

Procedure

A slurry of AlCl3 (2.38 g, 18 mmol) in CH2Cl2 (21 ml) was cooled to 0° C. under N2. Next, a solution of the product from step d) (3.0 g, 6 mmol) in CH2Cl2 (9 ml) was added dropwise over 5 minutes and the reaction mixture was stirred for an additional 45 minutes at 0° C. The reaction was poured into ice cold 2M NaOH (100 ml) and extracted with CH2Cl2 (2×100 ml). The organic layer was dried (MgSO4), evaporated, and purified by silica-gel chromatography using a gradient of 0-50% ethyl acetate in hexane to give the subtitle product (696 mg, 27%). 1H NMR (300 MHz, CDCl3, ppm) 2.39-2.49 (m, 2H); 2.92 (br d, J=9 Hz, 1H); 3.24 (br d, J=9 Hz, 1H); 3.34-3.40 (m, 1H); 3.54 (d, J=13 Hz, 1H); 3.60 (d, 13 Hz, 1H); 3.76-3.81 (m, 1H); 7.13-7.32 (m, 5H); MS calculated for C16H13Br2NOS+H 428, observed 426, 428, 430.

Workup

extractionextracted with CH2Cl2 (2×100 ml)
dry with materialThe organic layer was dried (MgSO4)
customevaporated
custompurified by silica-gel chromatography

Sources & evidence

ORD record: ord-4cdd9278c52e4bcbbc76f1f0f8d165a7
Source dataset: uspto-grants-2008_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07423056B2

Reaction notes

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