Methyl chloroformate → HCID 54561455, compound

HRID 1111490Notes

Reaction equation

HRID 1111490 reaction equation
[CH2:1]([C:5]1[CH:6]=[N:7][C:8]([C:11]2[CH:19]=[CH:18][C:14]([C:15](O)=[O:16])=[CH:13][CH:12]=2)=[N:9][CH:10]=1)[CH2:2][CH2:3][CH3:4].C(N(CC)CC)C.ClC(OC)=O.[N-:32]=[N+:33]=[N-:34].[Na+]>CC(C)=O.O>[CH2:1]([C:5]1[CH:6]=[N:7][C:8]([C:11]2[CH:19]=[CH:18][C:14]([C:15]([N:32]=[N+:33]=[N-:34])=[O:16])=[CH:13][CH:12]=2)=[N:9][CH:10]=1)[CH2:2][CH2:3][CH3:4]

Participants

7

Reactant 4

HCID 6586Methyl chloroformateHCID 8471TriethylamineHCID 33557Sodium AzideHCID 14495705HCID 14495705, compound

Product 1

HCID 54561455HCID 54561455, compound

Reagents, catalysts & solvents 2

HCID 180AcetoneSolvent3×HCID 962WaterSolvent

Conditions

Temperature
-4 °C

Procedure

A suspension of 12.62 g of p-(5-butyl-2-pyrimidinyl)-benzoic acid in 150 ml of acetone was treated dropwise with a solution of 8.1 ml of triethylamine in 25 ml of acetone while cooling with an ice/sodium chloride bath (internal temperature -4° C.) and thereafter dropwise within 15 minutes with a solution of 4.9 ml of methyl chloroformate in 25 ml of acetone. The suspension was stirred for a further 75 minutes and then treated dropwise within 10 minutes with a solution of 4.90 g of sodium azide in 17.5 ml of water. The mixture was stirred for another 1 hour while cooling with the ice/sodium chloride bath and then for 30 minutes without cooling. The mixture was poured on to 300 ml of ice-water and extracted once with 250 ml of diethyl ether and twice with 100 ml of diethyl ether each time. The extracts were washed with 100 ml of water, dried and concentrated in vacuo at a bath temperature of 35° C., whereby 13.32 g of solid, yellowish p-(5-butyl 2-pyrimidinyl)benzoic acid azide were obtained. The azide was dissolved in 100 ml of toluene and the solution was added dropwise slowly to a flask heated to 90° C., whereby a strong evolution of nitrogen took place. The solution was heated to 108° C. for a further 1.5 hours and then concentrated. There were obtained 11.59 g of crude, pale yellow p-(5-butyl-2-pyrimidinyl)phenyl isocyanate; m.p. 48° C.

Workup

  1. stirringThe mixture was stirred for another 1 hour
  2. temperaturefor 30 minutes without cooling
  3. extractionextracted once with 250 ml of diethyl ether and twice with 100 ml of diethyl ether each time
  4. washThe extracts were washed with 100 ml of water
  5. customdried
  6. concentrationconcentrated in vacuo at a bath temperature of 35° C., whereby 13.32 g of solid

Sources & evidence

ORD record
ord-dcc60800b3794ce8b4b75f59b9a88853
Source dataset
uspto-grants-1990_12
Patent number
US04980486

Reaction notes

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