Hydroquinone → 6-Bromo-5,7-dimethyl-3,3a,7,7a-tetrahydro-1H-4-thia-2-aza-cyclopenta[alpha]pentalene-2-carboxylic acid ethyl ester

HRID 1013383Notes

Reaction equation

HRID 1013383 reaction equation
[CH2:1]([O:3][C:4]([N:6]1[CH2:13][CH:12]2[CH:8]([CH:9]([CH3:18])[C:10]3[CH:16]=[C:15]([CH3:17])[S:14][C:11]=32)[CH2:7]1)=[O:5])[CH3:2].C(Cl)(Cl)Cl.C1(C=CC(O)=CC=1)O.C1C(=O)N([Br:38])C(=O)C1>CC(O)=O>[CH2:1]([O:3][C:4]([N:6]1[CH2:13][CH:12]2[CH:8]([CH:9]([CH3:18])[C:10]3[C:16]([Br:38])=[C:15]([CH3:17])[S:14][C:11]=32)[CH2:7]1)=[O:5])[CH3:2]

Participants

6

Reactant 4

HCID 785HydroquinoneHCID 6212ChloroformHCID 67184N-bromobutanimideHCID 1317270365,7-Dimethyl-3,3a,7,7a-tetrahydro-1H-4-thia-2-aza-cyclopenta[alpha]pentalene-2-carboxylic acid ethyl ester

Product 1

HCID 1317270376-Bromo-5,7-dimethyl-3,3a,7,7a-tetrahydro-1H-4-thia-2-aza-cyclopenta[alpha]pentalene-2-carboxylic acid ethyl esterYield 17%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A solution of the product from step k) (110 mg, 0.42 mmol) in AcOH (1 ml) and CHCl3 (1 ml) was treated with hydroquinone (5 mg) and NBS (77.8 mg, 0.437 mmol) at 40° C. for 3 hours in the dark. Next, the reaction mixture was carefully quenched with sat. NaHCO3 (5 ml) and extracted with EtOAc (3×20 ml). The combined organic extracts were dried (MgSO4) and purified by preparative TLC hexanes:EtOAc (1:1) to give the subtitle compound (24.2 mg, 17%). MS calculated for C14H18BrNO2S+H 344, observed 344, 346.

Workup

  1. customNext, the reaction mixture was carefully quenched with sat. NaHCO3 (5 ml)
  2. extractionextracted with EtOAc (3×20 ml)
  3. dry with materialThe combined organic extracts were dried (MgSO4)
  4. custompurified by preparative TLC hexanes:EtOAc (1:1)

Sources & evidence

ORD record
ord-a613e61b1111423f8570a3d8585537a1
Source dataset
uspto-grants-2011_07
Patent number
US07981919B2

Reaction notes

Loading…