Water → HCID 118599653, compound

HRID 1054168Notes

Reaction equation

HRID 1054168 reaction equation
[Li+].C[Si]([N-][Si](C)(C)C)(C)C.C(OP([CH2:19][C:20]([O:22][CH2:23][CH3:24])=[O:21])(OCC)=O)C.[Cl:25][C:26]1[CH:43]=[CH:42][C:29]2[N:30]([C:35]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])=[O:36])[CH:31](O)[CH2:32][O:33][C:28]=2[CH:27]=1.O>C1COCC1>[Cl:25][C:26]1[CH:43]=[CH:42][C:29]2[N:30]([C:35]([O:37][C:38]([CH3:39])([CH3:40])[CH3:41])=[O:36])[CH:31]([CH2:19][C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH2:32][O:33][C:28]=2[CH:27]=1

Participants

6

Reactant 4

HCID 962WaterHCID 13345Triethyl phosphonoacetateHCID 2733832Lithium HexamethyldisilazideHCID 118599754HCID 118599754, compound2×

Product 1

HCID 118599653HCID 118599653, compoundYield 106.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A 1 M solution of LiHMDS (23.0 mL, 23.0 mmol) in THF was a added dropwise to a solution of ethyl 2-(diethoxyphosphoryl)acetate (4.57 mL, 23.0 mmol) in THF (30 mL) at 0° C. under nitrogen and the resulting mixture was stirred for 10 min where after tert-butyl 7-chloro-3-hydroxy-2,3-dihydro-4H-1,4-benzoxazine-4-carboxylate (Intermediate 17, 3.29 g, 11.5 mmol) dissolved in THF (30 mL) was added dropwise at 0° C. The reaction mixture was stirred under nitrogen at rt for 1 h where after water (100 mL) was added and the mixture was extracted with EtOAc (3×75 mL). The combined organic layers were washed with brine (100 mL), dried by passage through a phase separator and concentrated giving crude the title compound (4.36 g, 106%) as a brown oil.

Workup

  1. additionwas added dropwise at 0° C
  2. additionwas added
  3. extractionthe mixture was extracted with EtOAc (3×75 mL)
  4. washThe combined organic layers were washed with brine (100 mL)
  5. customdried by passage through a phase separator
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-22f2b97693ea48f5a6847ecf9a0df7c0
Source dataset
uspto-grants-2016_07
Patent number
US09394291B2

Reaction notes

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