Carbon tetrabromide → 7-(3,3-dibromo-1-pentyl-allyl)-4,4-dimethyl-3,4-dihydro-2H-quinoline-1-carboxylic acid tert-butyl ester

HRID 899300Notes

Reaction equation

HRID 899300 reaction equation
[C:1]([Br:5])(Br)(Br)[Br:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:25]([O:29][C:30]([N:32]1[C:41]2[C:36](=[CH:37][CH:38]=[C:39]([CH:42]([CH:48]=O)[CH2:43][CH2:44][CH2:45][CH2:46][CH3:47])[CH:40]=2)[C:35]([CH3:51])([CH3:50])[CH2:34][CH2:33]1)=[O:31])([CH3:28])([CH3:27])[CH3:26]>ClCCl>[C:25]([O:29][C:30]([N:32]1[C:41]2[C:36](=[CH:37][CH:38]=[C:39]([CH:42]([CH2:43][CH2:44][CH2:45][CH2:46][CH3:47])[CH:48]=[C:1]([Br:5])[Br:2])[CH:40]=2)[C:35]([CH3:50])([CH3:51])[CH2:34][CH2:33]1)=[O:31])([CH3:28])([CH3:27])[CH3:26]

Participants

5

Reactant 3

HCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 865890267-(1-formyl-hexyl)-4,4-dimethyl-3,4-dihydro-2H-quinoline-1-carboxylic acid tert-butyl ester

Product 1

HCID 865890277-(3,3-dibromo-1-pentyl-allyl)-4,4-dimethyl-3,4-dihydro-2H-quinoline-1-carboxylic acid tert-butyl esterYield 31.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
0 °C

Procedure

To a solution of carbon tetrabromide (0.32 g, 0.96 mmole) in 5 mL of dichloromethane, at −20° C., was added triphenyl phosphine in 5 mL of dichloromethane. After stirring at 0° C. for 15 minutes reaction mixture was treated with a solution of 7-(1-formyl-hexyl)-4,4-dimethyl-3,4-dihydro-2H-quinoline-1-carboxylic acid tert-butyl ester (0.18 g, 0.48 mmole, from Example 5 step 8) in 2 mL of dichloromethane. The reaction mixture was stirred at room temperature for 4 hours, quenched by the successive addition of 5 mL of water and 1.5 mL of saturated sodium bicarbonate. The phases were separated and aqueous phase was extracted with two 25 mL portions of dichloromethane. Organic phase was dried over MgSO4, filtered and concentrated in vacuo affording a brownish thick oil. The product was purified by flash chromatography (SiO2, 20% ethyl acetate in hexanes) to yield 0.08 g of 7-(3,3-dibromo-1-pentyl-allyl)-4,4-dimethyl-3,4-dihydro-2H-quinoline-1-carboxylic acid tert-butyl ester as a colourless oil.

Workup

  1. customreaction mixture
  2. stirringThe reaction mixture was stirred at room temperature for 4 hours
  3. customquenched by the successive addition of 5 mL of water and 1.5 mL of saturated sodium bicarbonate
  4. customThe phases were separated
  5. extractionaqueous phase was extracted with two 25 mL portions of dichloromethane
  6. dry with materialOrganic phase was dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customaffording a brownish thick oil
  10. customThe product was purified by flash chromatography (SiO2, 20% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-c0281d92846c439e8cfac3d9b21fe11d
Source dataset
uspto-grants-2008_04
Patent number
US07354931B2

Reaction notes

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