Dichloromethane → HCID 11532567, compound

HRID 641630Notes

Reaction equation

HRID 641630 reaction equation
[CH2:1]([CH:3]1[C:12]2[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=2[C:6]2[S:13][C:14]([C:16]3[CH:20]=[CH:19][S:18][CH:17]=3)=[CH:15][C:5]=2[N:4]1[S:21]([C:24]1[CH:29]=[CH:28][C:27]([O:30]C)=[CH:26][CH:25]=1)(=[O:23])=[O:22])[CH3:2].C(=O)(O)[O-].[Na+].B(Br)(Br)Br.C(Cl)Cl>C1CCCCC=1>[CH2:1]([CH:3]1[C:12]2[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=2[C:6]2[S:13][C:14]([C:16]3[CH:20]=[CH:19][S:18][CH:17]=3)=[CH:15][C:5]=2[N:4]1[S:21]([C:24]1[CH:25]=[CH:26][C:27]([OH:30])=[CH:28][CH:29]=1)(=[O:23])=[O:22])[CH3:2]

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 25134Boron tribromideHCID 516892Sodium BicarbonateHCID 68579599HCID 68579599, compound

Product 1

HCID 11532567HCID 11532567, compoundYield 289.4%

Reagents, catalysts & solvents 1

HCID 8079CyclohexeneSolvent

Conditions

Temperature
-78 °C

Procedure

A suspension of 5-ethyl-4-[(4-methoxyphenyl)sulfonyl]-2-thien-3-yl-4,5-dihydrothieno[3,2-c]isoquinoline (0.73 g, 1.6 mmol) in cyclohexene (11 mL) was treated with sodium bicarbonate (4.0 g, 48 mmol) and the mixture was cooled to −78° C. A solution of boron tribromide in methylene chloride (1.0 M, 6.4 mL, 6.4 mmol) was added dropwise during ca. 10 min. At this time the cooling bath was removed and the reaction mixture was warmed to 23° C. After 4 h the mixture was poured into saturated aqueous sodium bicarbonate (75 mL) and extracted with ethyl acetate (50 mL). The extract was washed with brine (75 mL), dried (Na2SO4), and concentrated in vacuo to give a dark oil (2.1 g) which was taken up in methylene chloride (ca. 5 mL) and pre-adsorbed on silica gel (5 g). Flash chromatography on silica (50 g) eluting 1.25-, and then 2.5% ethyl acetate-benzene gave the product (0.26 g) as a yellow solid. Recrystallization from hot ethyl acetate-hexane gave the title compound (0.15 g, 21%, m.p. 195-96° C.) as shiny tan needles.

Workup

  1. customAt this time the cooling bath was removed
  2. temperaturethe reaction mixture was warmed to 23° C
  3. additionAfter 4 h the mixture was poured into saturated aqueous sodium bicarbonate (75 mL)
  4. extractionextracted with ethyl acetate (50 mL)
  5. washThe extract was washed with brine (75 mL)
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-29c0206044e345a19af961e96b3ab14b
Source dataset
uspto-grants-2010_04
Patent number
US07696221B2

Reaction notes

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