Triphenylphosphine → Methyl 4-benzyloxy-2-(1-o-tolylethoxy)benzoate

HRID 322926Notes

Reaction equation

HRID 322926 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O.[CH2:34]([O:41][C:42]1[CH:51]=[CH:50][C:45]([C:46]([O:48][CH3:49])=[O:47])=[C:44]([OH:52])[CH:43]=1)[C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1.[C:53]1([CH3:62])[CH:58]=[CH:57][CH:56]=[CH:55][C:54]=1[CH:59](O)[CH3:60]>C1COCC1>[CH2:34]([O:41][C:42]1[CH:51]=[CH:50][C:45]([C:46]([O:48][CH3:49])=[O:47])=[C:44]([O:52][CH:59]([C:54]2[CH:55]=[CH:56][CH:57]=[CH:58][C:53]=2[CH3:62])[CH3:60])[CH:43]=1)[C:35]1[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 1109531-(2-Methylphenyl)ethanolHCID 225489Methyl 4-(benzyloxy)-2-hydroxybenzoate

Product 1

HCID 22010393Methyl 4-benzyloxy-2-(1-o-tolylethoxy)benzoateYield 72.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of triphenylphosphine(5.48 g) in dry THF (35 mL) is treated with diisopropyl azodicarboxylate (4.23 g) at 0-5° C. and stirred for 15 minutes. The suspension is treated dropwise with a solution of methyl 4-benzyloxy-2-hydroxybenzoate (2.7 g) and 1-o-tolylethanol (1.42 g) in dry THF (35 mL) during 25 minutes at 0-5° C. and then stirred at 0-5° C. for 1 hour and at 25° C. for 24 hours. The mixture is evaporated and the residual gum purified by flash chromatography on silica, eluting with dichloromethane. Fractions homogeneous in the required product are combined and evaporated to yield methyl 4-benzyloxy-2-(1-o-tolyiethoxy)benzoate as a colourless oil (2.83 g, 72%). 1H NMR (CDCl3) 1.6(3H,d), 2.4(3H,s), 3.9(3H,s), 4.9(2H,s), 5.5(1H,q), 6.3(1H,s), 6.5(1H,d), 7.1-7.6(9H,m), 7.8(1H,d).

Workup

  1. stirringstirred at 0-5° C. for 1 hour and at 25° C. for 24 hours
  2. customThe mixture is evaporated
  3. customthe residual gum purified by flash chromatography on silica
  4. washeluting with dichloromethane
  5. customevaporated

Sources & evidence

ORD record
ord-d879e59eb5884b229a908d794015072d
Source dataset
uspto-grants-2001_04
Patent number
US06211234B1

Reaction notes

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