Diisopropylethylamine → HCID 86632309, compound

HRID 551825Notes

Reaction equation

HRID 551825 reaction equation
[O:1]1[C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][C:5]=2[NH:4][CH2:3][CH2:2]1.C(N(C(C)C)CC)(C)C.Cl[C:21](Cl)([O:23]C(=O)OC(Cl)(Cl)Cl)Cl.[NH:32]1[CH2:36][CH:35]=[C:34]([O:37][S:38]([C:41]([F:44])([F:43])[F:42])(=[O:40])=[O:39])[CH2:33]1>ClCCl>[O:1]1[C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][C:5]=2[N:4]([C:21]([N:32]2[CH2:36][CH:35]=[C:34]([O:37][S:38]([C:41]([F:42])([F:43])[F:44])(=[O:39])=[O:40])[CH2:33]2)=[O:23])[CH2:3][CH2:2]1

Participants

6

Reactant 4

HCID 81531Diisopropylethylamine2×HCID 94429TriphosgeneHCID 5850963,4-Dihydro-2H-1,4-benzoxazineHCID 86632307HCID 86632307, compound

Product 1

HCID 86632309HCID 86632309, compoundYield 116.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

2.7 g of 3,4-dihydro-2H-benzo[1,4]oxazine and 50 ml of dichloromethane are introduced into a 250 ml three-necked flask equipped with a magnetic stirrer and placed under an inert atmosphere. After cooling to +4° C., 9.92 ml of diisopropylethylamine and 2.97 g of triphosgene are successively added. The reaction medium is stirred at ambient temperature for 3 h. 4.52 ml of diisopropylethylamine and 3.04 g of trifluoromethanesulfonic acid 2,5-dihydro-1H-pyrrol-3-yl ester are then introduced and the mixture is stirred at ambient temperature for 18 h. The reaction medium is washed with a saturated aqueous sodium hydrogencarbonate solution; the aqueous phase is extracted twice with ethyl acetate. The organic phases are combined, dried over sodium sulfate and concentrated under reduced pressure. The residue is chromatographed on silica gel eluted with a gradient of ethyl acetate from 0% to 10% in dichloromethane. 4.4 g of trifluoromethanesulfonic acid 1-(2,3-dihydrobenzo[1,4]oxazine-4-carbonyl)-2,5-dihydro-1H-pyrrol-3-yl ester are obtained.

Workup

  1. customequipped with a magnetic stirrer
  2. temperatureAfter cooling to +4° C.
  3. stirringthe mixture is stirred at ambient temperature for 18 h
  4. washThe reaction medium is washed with a saturated aqueous sodium hydrogencarbonate solution
  5. extractionthe aqueous phase is extracted twice with ethyl acetate
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe residue is chromatographed on silica gel
  9. washeluted with a gradient of ethyl acetate from 0% to 10% in dichloromethane

Sources & evidence

ORD record
ord-bf5c398e8a23457abd6ecc25610a4093
Source dataset
uspto-grants-2011_05
Patent number
US07947834B2

Reaction notes

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