Sodium Azide → HCID 117600285, compound

HRID 931658Notes

Reaction equation

HRID 931658 reaction equation
[N-:1]=[N+:2]=[N-:3].[Na+].O[C@H]([C@@H]1C([O-])=C(O)C(=O)O1)CO.[Na+].Br[C:19]1[CH:32]=[C:31]2[C:22]([O:23][C:24]3[C:25]([F:41])=[CH:26][C:27]([O:39][CH3:40])=[CH:28][C:29]=3[C@@:30]32[CH2:37][CH2:36][O:35][C:34]([NH2:38])=[N:33]3)=[CH:21][CH:20]=1.CN[C@@H]1CCCC[C@H]1NC>CCOC(C)=O.[Cu]I.O>[N:1]([C:19]1[CH:32]=[C:31]2[C:22]([O:23][C:24]3[C:25]([F:41])=[CH:26][C:27]([O:39][CH3:40])=[CH:28][C:29]=3[C@@:30]32[CH2:37][CH2:36][O:35][C:34]([NH2:38])=[N:33]3)=[CH:21][CH:20]=1)=[N+:2]=[N-:3]

Participants

8

Reactant 4

HCID 33557Sodium AzideHCID 2733821trans-N,N'-dimethyl-1,2-cyclohexanediamineHCID 23667548Sodium AscorbateHCID 58465963(S)-7'-bromo-4'-fluoro-2'-methoxy-5,6-dihydrospiro[[1,3]oxazine-4,9'-xanthen]-2-amine

Product 1

HCID 117600285HCID 117600285, compound

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

A resealable vessel was flushed with argon and loaded with copper(I) iodide (0.138 g, 0.726 mmol), sodium azide (0.708 g, 10.90 mmol), and sodium (R)-2-((S)-1,2-dihydroxyethyl)-4-hydroxy-5-oxo-2,5-dihydrofuran-3-olate (0.072 g, 0.363 mmol). A solution of (S)-7′-bromo-4′-fluoro-2′-methoxy-5,6-dihydrospiro[[1,3]oxazine-4,9′-xanthen]-2-amine (1.428 g, 3.63 mmol) in dmso (20 mL) was degassed and transferred via cannula into the resealable vessel. Water (4 mL) was added. The vessel was flushed with argon, and (1R,2R)—N1,N2-dimethylcyclohexane-1,2-diamine (0.163 mL, 1.090 mmol) was added. The vessel was sealed and heated in a 90° C. oil bath. After 4 h, the reaction mixture was taken up in EtOAc (600 mL) and the organic layer was extracted with quarter-saturated brine (2×70 mL), half-saturated brine (70 mL), and saturated brine (70 mL), dried over MgSO4 and concentrated to afford crude (S)-7′-azido-4′-fluoro-2′-methoxy-5,6-dihydrospiro[[1,3]oxazine-4,9′-xanthen]-2-amine, which was used without purification in the next step. MS m/z=356 [M+H]+.

Workup

  1. customA resealable vessel was flushed with argon
  2. additionwas added
  3. customThe vessel was sealed
  4. extractionthe organic layer was extracted with quarter-saturated brine (2×70 mL), half-saturated brine (70 mL), and saturated brine (70 mL)
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-3a0c3673492f4296ae4662389475cc08
Source dataset
uspto-grants-2016_03
Patent number
US09296759B2

Reaction notes

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