Phosgene → Carbamate

HRID 1919589Notes

Reaction equation

HRID 1919589 reaction equation
[CH:1]([N:4]([CH:7]([CH3:9])[CH3:8])[CH2:5][CH3:6])([CH3:3])[CH3:2].C(Cl)(Cl)=O.[C:14](=[O:17])(O)[O-:15].[Na+]>ClCCl.CN(C1C=CN=CC=1)C.N1C=CC=CC=1.C(N(CC)CC)C>[CH:1]([N:4]([CH:7]([CH3:9])[CH3:8])[CH2:5][CH3:6])([CH3:3])[CH3:2].[C:14](=[O:17])([O-:15])[NH2:4]

Participants

9

Reactant 3

HCID 6371PhosgeneHCID 81531Diisopropylethylamine2×HCID 516892Sodium Bicarbonate

Product 2

HCID 276CarbamateHCID 81531Diisopropylethylamine

Reagents, catalysts & solvents 4

HCID 142844-(Dimethylamino)pyridineCatalyst2×HCID 1049PyridineSolvent2×HCID 6344DichloromethaneSolvent3×HCID 8471TriethylamineSolvent2×

Procedure

An alcohol was dissolved in dichloromethane or tetrahydrofunan under argon atmosphere, followed by addition of an appropriate amount of a base (triethylamine, diisopropyl ethyl amine, pyridine or 4-(N,N-dimethyl)aminopyridine). To the reaction mixture, a solution of solid phosgene in dichloromethane or tetrahydrofunan was added dropwisely under ice bath, then the reaction was allowed to react for half an hour under ice bath and then for a few hours at room temperature to obtain a chlorofomate. After the addition of an appropriate amount of the base (triethylamine, diisopropylethylamine, pyridine or 4-(N,N-dimethyl)aminopyridine) under ice bath, a solution of the compound B in dichloromethane or tetrahydrofunan was slowly added dropwisely. The reaction was allowed to react for half an hour under ice bath and then for three hours at room temperature. After the reaction was completed, saturated sodium bicarbonate solution was added therein and the reaction mixture was extracted with dichloromethane. Then the combined organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and then treated with an anhydride or an acyl chloride in the presence of a base (triethylamine, diisopropylethylamine, pyridine or 4-(N,N-dimethyl)aminopyridine) to give carbamate derivative F.

Workup

  1. customto react for half an hour under ice bath
  2. customfor a few hours at room temperature to obtain a chlorofomate
  3. customto react for half an hour under ice bath
  4. extractionthe reaction mixture was extracted with dichloromethane
  5. dry with materialThen the combined organic phase was dried over anhydrous sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. additiontreated with an anhydride

Sources & evidence

ORD record
ord-b099b7c6e9b14e1db4bb5cde6c0ebc7e
Source dataset
uspto-grants-2012_05
Patent number
US08168647B2

Reaction notes

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