1,4-Dibromobenzene → HCID 70162635, compound

HRID 2306506Notes

Reaction equation

HRID 2306506 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][CH:3]=1.C([Li])CCC.[CH2:14]([N:17]([CH3:31])[CH2:18][CH2:19][CH2:20]/[C:21](/[CH3:30])=[CH:22]/[CH2:23][CH2:24]/[C:25](/[CH3:29])=[CH:26]/[CH:27]=[O:28])[CH:15]=[CH2:16]>C1COCC1.CCCCCC>[CH2:14]([N:17]([CH3:31])[CH2:18][CH2:19][CH2:20]/[C:21](/[CH3:30])=[CH:22]/[CH2:23][CH2:24]/[C:25](/[CH3:29])=[CH:26]/[CH:27]([C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][CH:3]=1)[OH:28])[CH:15]=[CH2:16]

Participants

6

Reactant 3

HCID 78041,4-DibromobenzeneHCID 86755216HCID 86755216, compoundHCID 178418339Butyllithium

Product 1

HCID 70162635HCID 70162635, compoundYield 23.3%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

A solution of 6.4 g of 1,4-dibromobenzene in 50 ml of absolute THF is cooled −78° C. and treated within 30 min. with 15.3 ml of 1.6M butyllithium in hexane. After 1 hr. 3.0 g of (2E,6E)-10-(allyl-methyl-amino)-3,7-dimethyl-deca-2,6-dienal (Ex. 57.1.A) in 12 ml of THF are added dropwise. After 1½ hr. at −78° C. the bath is removed until the suspension has dissolved. Subsequently, 4.5 ml of acetic acid in 6 ml of ether are added dropwise at −78° C. Then, the mixture is poured into saturated ammonium chloride solution/ethyl acetate. The organic phase is washed with saturated sodium bicarbonate solution and 10% sodium chloride solution, dried and evaporated. After silica gel chromatography with methylene chloride/methanol (95:5) there are obtained 1.14 g of (2E,6E)-(RS)-10-(allyl-methyl-amino)-1-(4-bromo-phenyl)-3,7-dimethyl-deca-2,6-dien-1-ol. This is dissolved in ethanol with 0.29 g of fumaric acid, evaporated and converted with ethyl acetate/ether into 0.91 g of (2E,6E)-(RS)-10-(allyl-methyl-amino)-1-(4-brom-phenyl)-3,7-dimethyl-deca-2,6-dien-1-ol•fumarate (1:1), MS: m/e 406 (M+H+, 1Br).

Workup

  1. waitAfter 1½ hr
  2. customat −78° C. the bath is removed until the suspension
  3. dissolutionhas dissolved
  4. additionSubsequently, 4.5 ml of acetic acid in 6 ml of ether are added dropwise at −78° C
  5. additionThen, the mixture is poured into saturated ammonium chloride solution/ethyl acetate
  6. washThe organic phase is washed with saturated sodium bicarbonate solution and 10% sodium chloride solution
  7. customdried
  8. customevaporated

Sources & evidence

ORD record
ord-2d55804902aa4742857f298d4d637036
Source dataset
uspto-grants-2002_08
Patent number
US06441177B1

Reaction notes

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