Tetrahydrofuran → HCID 13370662, compound

HRID 2412970Notes

Reaction equation

HRID 2412970 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][CH:3]=1.O1CCCC1.C([Li])CCC.[CH3:19][O:20][C:21]1[CH:26]=[CH:25][C:24]([C:27]2[CH:32]([C:33]3[CH:38]=[CH:37][C:36]([O:39][CH3:40])=[CH:35][CH:34]=3)[CH2:31][CH2:30][C:29](=O)[CH:28]=2)=[CH:23][CH:22]=1>CCCCCC.C(OCC)C.O>[CH3:40][O:39][C:36]1[CH:35]=[CH:34][C:33]([CH:32]2[C:27]([C:24]3[CH:23]=[CH:22][C:21]([O:20][CH3:19])=[CH:26][CH:25]=3)=[CH:28][C:29]([C:2]3[CH:7]=[CH:6][C:5]([F:8])=[CH:4][CH:3]=3)=[CH:30][CH2:31]2)=[CH:38][CH:37]=1

Participants

8

Reactant 4

HCID 8028Tetrahydrofuran2×HCID 99931-Bromo-4-fluorobenzeneHCID 13370661HCID 13370661, compoundHCID 178418339Butyllithium

Product 1

HCID 13370662HCID 13370662, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 6.11 ml. of 4-bromofluorobenzene in 200 ml. of tetrahydrofuran was cooled to -60° C. by means of an external cooling bath. Under a nitrogen atmosphere, 33.75 ml. of a 1.6M solution of n-butyllithium in hexane were added at such a rate as to maintain the temperature between -65° to -55° C. After the addition was complete, the reaction was stirred for about 20 minutes. A solution of 15.11 g. of 3,4-bis(4-methoxyphenyl)-2-cyclohexen-1-one in 200 ml. of tetrahydrofuran was added over a period of about one hour. The reaction was then allowed to warm to 0° C. during the next three hours. Sixty milliliters of water were then added in a dropwise fashion. The solution was added to three liters of diethyl ether and the organic solution was washed several times with water. The organic solution was dried over sodium sulfate and evaporated in vacuo to dryness. The residue was dissolved in 400 ml. of toluene and treated with 2.5 g. of p-toluenesulfonic acid. The solution was allowed to reflux overnight. The solvent was then removed by evaporation and the residue was purified by chromatography to afford 13.98 g. of the title diene intermediate.

Workup

  1. temperatureto maintain the temperature between -65° to -55° C
  2. additionAfter the addition
  3. washthe organic solution was washed several times with water
  4. dry with materialThe organic solution was dried over sodium sulfate
  5. customevaporated in vacuo to dryness
  6. dissolutionThe residue was dissolved in 400 ml
  7. additionof toluene and treated with 2.5 g
  8. temperatureto reflux overnight
  9. customThe solvent was then removed by evaporation
  10. customthe residue was purified by chromatography
  11. customto afford 13.98 g

Sources & evidence

ORD record
ord-356ee43f415c4cba889eeaa949dd4aa7
Source dataset
uspto-grants-1985_01
Patent number
US04495202

Reaction notes

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