tert-Butanol → Methyl 1-((tert-butoxycarbonyl)amino)cyclopropanecarboxylate

HRID 132574Notes

Reaction equation

HRID 132574 reaction equation
[CH3:1][O:2][C:3]([C:5]1(C(O)=O)[CH2:7][CH2:6]1)=[O:4].C([N:13]([CH2:16]C)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:25])C=CC=CC=1.[C:35]([OH:39])([CH3:38])([CH3:37])[CH3:36]>C1(C)C=CC=CC=1>[C:35]([O:39][C:16]([NH:13][C:5]1([C:3]([O:2][CH3:1])=[O:4])[CH2:6][CH2:7]1)=[O:25])([CH3:38])([CH3:37])[CH3:36]

Participants

6

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 138618231-(Methoxycarbonyl)cyclopropane-1-carboxylic acid

Product 1

HCID 546046Methyl 1-((tert-butoxycarbonyl)amino)cyclopropanecarboxylate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

A solution of 80 g of 1-(methoxycarbonyl)cyclopropanecarboxylic acid and 78 ml of triethylamine in 550 ml of toluene, to which 152 g of diphenylphosphoryl azide is added, is heated to 80° C. When the evolution of gas has ceased, the temperature is brought to 50° C. and 61 g of tert-butanol are added. After 7 hours' reaction at 80° C., the mixture is concentrated. The residue is taken up in ether, washed with saturated Na2CO3 solution, then with 1N hydrochloric acid solution, and then with NaHCO3 solution. After drying and evaporation of the organic phase, the residue is taken up in 300 ml of cyclohexane and then concentrated to dryness. The residue obtained is triturated in pentane, filtered and then dried, allowing the expected product to be isolated.

Workup

  1. customis brought to 50° C.
  2. customAfter 7 hours' reaction at 80° C.
  3. concentrationthe mixture is concentrated
  4. washwashed with saturated Na2CO3 solution
  5. customAfter drying
  6. customevaporation of the organic phase
  7. concentrationconcentrated to dryness
  8. customThe residue obtained
  9. customis triturated in pentane
  10. filtrationfiltered
  11. customdried
  12. customto be isolated

Sources & evidence

ORD record
ord-6993acfdf6804cb4a653e29ea1cd6232
Source dataset
uspto-grants-2008_06
Patent number
US07388022B2

Reaction notes

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