Methyl chloroformate → HCID 6918099, compound

HRID 2399262Notes

Reaction equation

HRID 2399262 reaction equation
FC(F)(F)C(O)=O.[NH2:8][C:9]1[N:10]=[C:11]2[CH:16]=[CH:15][C:14]([O:17][CH2:18][C:19]3[CH:24]=[C:23]([O:25][CH3:26])[C:22]([O:27][CH3:28])=[C:21]([O:29][CH3:30])[CH:20]=3)=[N:13][N:12]2[CH:31]=1.[OH-].[Na+].C(N(CC)CC)C.Cl[C:42]([O:44][CH3:45])=[O:43]>ClCCl.CN(C)C1C=CN=CC=1>[CH3:26][O:25][C:23]1[CH:24]=[C:19]([CH:20]=[C:21]([O:29][CH3:30])[C:22]=1[O:27][CH3:28])[CH2:18][O:17][C:14]1[CH:15]=[CH:16][C:11]2[N:12]([CH:31]=[C:9]([NH:8][C:42](=[O:43])[O:44][CH3:45])[N:10]=2)[N:13]=1

Participants

7

Reactant 4

HCID 6586Methyl chloroformateHCID 8471TriethylamineHCID 14798Sodium HydroxideHCID 19434251HCID 19434251, compound

Product 1

HCID 6918099HCID 6918099, compoundYield 22.9%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Procedure

The product of stage (a) (1.0 g, 3.03 mmol) was suspended in dichloromethane and shaken with dilute sodium hydroxide solution. The organic phase was dried (Na2SO4) and evaporated to give a brown oil which was dissolved in dichloromethane and treated, with stirring, with triethylamine (0.42 ml, 3.03 mmol), methyl chloroformate (0.23 ml, 3.03 mmol) and 4-dimethylaminopyridine (18 mg, 0.3 mmol). The mixture was stirred at ambient temperature for 17 h then heated under reflux for 2 h and evaporated in vacuo. The resulting solid was partioned between chloroform and water, the organic phase was separated, dried (Na2SO4) and evaporated to give a solid which was chromatographed on SiO2 eluting with 2% methanol-chloroform. The product was recrystallised from DMF-H2O to give the title compound (0.27 g), mp. 210°-212°, NMR identical to the product of Example 1.

Workup

  1. dry with materialThe organic phase was dried (Na2SO4)
  2. customevaporated
  3. customto give a brown oil which
  4. additiontreated
  5. temperaturethen heated
  6. temperatureunder reflux for 2 h
  7. customevaporated in vacuo
  8. customthe organic phase was separated
  9. dry with materialdried (Na2SO4)
  10. customevaporated
  11. customto give a solid which
  12. customwas chromatographed on SiO2 eluting with 2% methanol-chloroform
  13. customThe product was recrystallised from DMF-H2O

Sources & evidence

ORD record
ord-91e2aed0158d4e59a440c36d1b7a9666
Source dataset
uspto-grants-1995_09
Patent number
US05447956

Reaction notes

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