tert-Butanol → HCID 59363634, compound

HRID 2219469Notes

Reaction equation

HRID 2219469 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:10](C(O)=O)=[CH:9][CH:8]=[C:7]([CH3:14])[N:6]=1)=[O:4].C[N:16]1[CH2:21]COCC1.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:29])C=CC=CC=1.[C:39]([OH:43])([CH3:42])([CH3:41])[CH3:40]>C(Cl)Cl.[Cu]Cl>[CH3:1][O:2][C:3]([C:5]1[C:10]([NH:16][C:21]([O:43][C:39]([CH3:42])([CH3:41])[CH3:40])=[O:29])=[CH:9][CH:8]=[C:7]([CH3:14])[N:6]=1)=[O:4]

Participants

7

Reactant 4

HCID 6386tert-ButanolHCID 79724-MethylmorpholineHCID 199401P,P-Diphenylphosphinic azideHCID 15679401HCID 15679401, compound

Product 1

HCID 59363634HCID 59363634, compoundYield 76%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of 6-Methyl-pyridine-2,3-dicarboxylic acid 2-methyl ester (CAS:[135338-27-1]) (4.93 g, 25 mmol) and N-methylmorpholine (3.05 ml, 2.81 g, 28 mmol, 1.1 equiv.) in methylene chloride (100.0 ml) was added diphenylphosphoryl-azide (DPPA, 6.14 ml, 7.88 g, 28 mmol, 1.1 equiv.) dropwise at room temperature. The mixture was stirred for 30 min at r.t. and then heated to 70° C. for 2 h whereby nitrogen evolution is observed. Then tert-Butanol (3.56 ml, 2.81 g, 38 mmol, 1.5 equiv.) and copper(I) chloride (25 mg, 0.25 mmol, 0.01 equiv.) were added and the mixture was heated at 70° C. for another 4 h. The reaction mixture was allowed to cool to r.t., stirred overnight, and concentrated in vaccuo. The resulting dark brown oil (16.9 g) was purified by flash chromatography (heptane/ethyl acetate 3:2) to yield the title compound as a white solid (total 5.06 g, 75%), MS (ISP): m/e=267.2 (M+H+).

Workup

  1. temperatureheated to 70° C. for 2 h whereby nitrogen evolution
  2. temperaturethe mixture was heated at 70° C. for another 4 h
  3. temperatureto cool to r.t.
  4. stirringstirred overnight
  5. concentrationconcentrated in vaccuo
  6. customThe resulting dark brown oil (16.9 g) was purified by flash chromatography (heptane/ethyl acetate 3:2)

Sources & evidence

ORD record
ord-e88b618e6e254f64a42d850fa5cab20a
Source dataset
uspto-grants-2008_08
Patent number
US07414060B2

Reaction notes

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