1,2-Dichlorobenzene → Benzene, 1,2-bis(phenylmethyl)-

HRID 485957

Reaction equation

HRID 485957 reaction equation
Cl[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1Cl.CC[Mg+].[Br-].[C:13]1([CH2:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.ClC1C=CC=CC=1CC1C=CC=CC=1>CCOCC.C1COCC1>[CH2:14]([C:15]1[CH:16]=[CH:17][CH:18]=[CH:13][C:19]=1[CH2:20][C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 72391,2-Dichlorobenzene2×HCID 7647DibenzylHCID 123431Benzene, 1-chloro-2-(phenylmethyl)-HCID 178461630HCID 178461630, compound

Product 1

HCID 10934161Benzene, 1,2-bis(phenylmethyl)-Yield 38.4%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent3×HCID 8028TetrahydrofuranSolvent

Procedure

This Example illustrates the use of EtMgBr/[NitriphosCl]PF6 as an activator/catalyst to improve yield. To 2.00 g (13.61 mmoles) of o-dichlorobenzene, 0.050 g (0.065 mmoles) of [NitriphosCl]PF6 in 5 mL of ether at 0° C. was added 0.5 mL (1.5 mmoles) of 2.9M EtMgBr in ether. After stirring for 0.5 hrs, 30 mL of ether and 7.0 mL (14 mmoles) of 2M benzylMgCl in THF were added. The mixture was refluxed for 3 days and worked up as usual. After removing the solvent, the residue was distilled at 0.1 mm to initially remove 0.550 g (3.7 mmoles, 27%) of o-dichlorobenzene and then 1.482 g (bp: 68° to 83° C.) of a clear liquid was collected. 1H NMR spectrum in CDCl3 indicated a 10:1 ratio of 1-chloro-2-benzylbenzene to bibenzyl (representing 6.7 mmoles (67 % based on reacted o-dichlorobenzene) of 1-chloro-2-benzylbenzene and 0.67 mmoles of bibenzyl). The material that remained in the pot was chromatographed on silica gel eluted with 10% EtOAc/hexane to give 0.602 g (2.57 mmoles, 19%) of 1,2-dibenzylbenzene (mp: 61° to 67° C.).

Workup

  1. customto improve yield
  2. temperatureThe mixture was refluxed for 3 days
  3. customAfter removing the solvent
  4. custom1.482 g (bp: 68° to 83° C.) of a clear liquid was collected
  5. custompot was chromatographed on silica gel
  6. washeluted with 10% EtOAc/hexane

Sources & evidence

ORD record
ord-3aa0f4bbd4fe4f7aa0b802077bdc6964
Source dataset
uspto-grants-1985_08
Patent number
US04538003

Linked notes

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