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 30263Notes

Reaction equation

HRID 30263 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-755cd3588a794bef95d7a77e2fe8a570
Source dataset
uspto-grants-2008_09
Patent number
US07423056B2

Reaction notes

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