Carbamic acid, ethyl ester → HCID 86690137, compound

HRID 1184345Notes

Reaction equation

HRID 1184345 reaction equation
C(=O)(O)[O-].[Na+].[NH2:6][C:7]1[C:22]([F:23])=[CH:21][C:10]2[O:11][C:12]([F:20])([F:19])[C:13](=[O:18])[N:14]([CH2:15][C:16]#[CH:17])[C:9]=2[CH:8]=1.[C:24](Cl)(Cl)=[S:25].C(=O)(OCC)N>C(O)C>[F:20][C:12]1([F:19])[O:11][C:10]2[CH:21]=[C:22]([F:23])[C:7]([N:6]=[C:24]=[S:25])=[CH:8][C:9]=2[N:14]([CH2:15][C:16]#[CH:17])[C:13]1=[O:18]

Participants

6

Reactant 4

HCID 5641Carbamic acid, ethyl esterHCID 10040ThiophosgeneHCID 516892Sodium BicarbonateHCID 866695376-amino-2,2,7-trifluoro-4-(prop-2-ynyl)-2H-benzo[b][1,4]oxazin-3(4H)-one

Product 1

HCID 86690137HCID 86690137, compoundYield 90%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Sodium bicarbonate (4.10 g, 48.8 mmol) was added to a stirred solution of 6-amino-2,2,7-trifluoro-4-(prop-2-ynyl)-2H-benzo[b][1,4]oxazin-3(4H)-one (the product of Step 1.6 above, 5.0 g, 19.52 mmol) in absolute ethanol (100 ml) at 0° C. under nitrogen. Thereafter thiophosgene (1.795 ml, 23.42 mmol) was added dropwise under ice-bath cooling, keeping the temperature of the reaction mixture below 10° C. After the addition was complete, the reaction mixture was stirred for 1 h at room temperature, by which time, according to TLC analysis, the reaction was complete. The salts were removed by filtration and washed with ethyl acetate. The filtrate was concentrated in vacuo to yield 6.55 g of crude product, containing ca. 30% ethyl carbamate. Recrystallisation from dichloromethane afforded 3.84 g of the desired product (>90% purity), which was used without further purification.

Workup

  1. temperaturecooling
  2. customthe temperature of the reaction mixture below 10° C
  3. additionAfter the addition
  4. customThe salts were removed by filtration
  5. washwashed with ethyl acetate
  6. concentrationThe filtrate was concentrated in vacuo
  7. customto yield 6.55 g of crude product
  8. customRecrystallisation from dichloromethane

Sources & evidence

ORD record
ord-ef8f05c3cbbb4c6991df861781fae432
Source dataset
uspto-grants-2014_03
Patent number
US08669208B2

Reaction notes

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