Hydrochloric Acid → 1-(6-Benzyloxy-5-tert-butyl-4'-methyl-3-biphenylyl)ethanone

HRID 2377201Notes

Reaction equation

HRID 2377201 reaction equation
[CH2:1]([O:8][C:9]1[C:14]([C:15]2[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=2)=[CH:13][C:12]([C:22]([O:24]C)=O)=[CH:11][C:10]=1[C:26]([CH3:29])([CH3:28])[CH3:27])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.O.[OH-].[Li+].Cl.C[Li].[CH3:36][Si](Cl)(C)C.[Cl-].[NH4+]>C1COCC1.C(OCC)C.O.CO>[CH2:1]([O:8][C:9]1[C:14]([C:15]2[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=2)=[CH:13][C:12]([C:22](=[O:24])[CH3:36])=[CH:11][C:10]=1[C:26]([CH3:28])([CH3:27])[CH3:29])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

11

Reactant 6

HCID 313Hydrochloric AcidHCID 6397ChlorotrimethylsilaneHCID 25517Ammonium ChlorideHCID 168937Lithium hydroxide, monohydrateHCID 12084817Methyl 6-benzyloxy-5-tert-butyl-4'-methyl-3-biphenylcarboxylateHCID 178418348HCID 178418348, compound

Product 1

HCID 120848201-(6-Benzyloxy-5-tert-butyl-4'-methyl-3-biphenylyl)ethanoneYield 60%

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

2 g (5.1 mmol) of methyl 6-benzyloxy-5-tert-butyl-4′-methyl-3-biphenylcarboxylate (Example 1,d) are dissolved in 30 mL of THF, 15 mL of methanol and 2 mL of water. 320 mg (7.7 mmol) of lithium hydroxide hydrate are added and the reaction medium is refluxed for 5 hours and then cooled. The medium is neutralized with a 1 N hydrochloric acid solution and the medium is then extracted with ethyl ether. A white powder is obtained (m.p.=196° C.), which is dissolved in 10 mL of ethyl ether and 5 mL of THF. The medium is cooled to −78° C., and 11 mL (11 mmol) of 1 N methyllithium solution are then added dropwise. The medium is stirred at this temperature for 3 hours and is then treated with 5 mL of trimethylsilyl chloride. The medium is hydrolysed with a saturated ammonium chloride solution and then extracted with ethyl ether. The residue obtained is purified by chromatography (eluent: 9 heptane/1 ethyl acetate). A yellow crystalline solid is obtained (m=1.1 g; yield=60%; m.p.=104° C.).

Workup

  1. temperaturethe reaction medium is refluxed for 5 hours
  2. temperaturecooled
  3. extractionthe medium is then extracted with ethyl ether
  4. customA white powder is obtained (m.p.=196° C.), which
  5. extractionextracted with ethyl ether
  6. customThe residue obtained
  7. customis purified by chromatography (eluent: 9 heptane/1 ethyl acetate)
  8. customA yellow crystalline solid is obtained (m=1.1 g; yield=60%; m.p.=104° C.)

Sources & evidence

ORD record
ord-715e4e027d7849789b079f2301e11a1b
Source dataset
uspto-grants-2008_12
Patent number
US07468457B2

Reaction notes

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