Trifluoroacetic acid → (S)-2'-bromo-7'-iodo-2,6-dihydrospiro[[1,4]oxazine-3,9'-xanthen]-5-amine
Reaction equation
[Br:1][C:2]1[CH:15]=[CH:14][C:13]2[O:12][C:11]3[C:6](=[CH:7][C:8]([I:16])=[CH:9][CH:10]=3)[C@@:5]3([N:21]=[C:20]([NH:22]C(=O)OC(C)(C)C)[CH2:19][O:18][CH2:17]3)[C:4]=2[CH:3]=1.FC(F)(F)C(O)=O>>[Br:1][C:2]1[CH:15]=[CH:14][C:13]2[O:12][C:11]3[C:6](=[CH:7][C:8]([I:16])=[CH:9][CH:10]=3)[C@@:5]3([N:21]=[C:20]([NH2:22])[CH2:19][O:18][CH2:17]3)[C:4]=2[CH:3]=1Participants
Procedure
In a 150-mL resealable vessel, the (S)-tert-butyl 2′-bromo-7′-iodo-2,6-dihydrospiro[[1,4]oxazine-3,9′-xanthene]-5-ylcarbamate (1.475 g, 2.58 mmol) was dissolved in dcm (10 mL), and 2,2,2-trifluoroacetic acid (1.989 mL, 25.8 mmol) was added. The vessel was sealed and placed in a 50° C. oil bath. After 2 h, the reaction was concentrated and the mixture was neutralized with 0.5 M aqueous Na2CO3 (15 mL) and the aqueous phase was extracted with 5% MeOH-dcm (3×33 mL). The organics were combined, washed with dilute brine (10 mL), dried over sodium sulfate and concentrated. The residue was purified by chromatography (5.5% MeOH/DCM) to afford (S)-2′-bromo-7′-iodo-2,6-dihydrospiro[[1,4]oxazine-3,9′-xanthen]-5-amine (151 mg, 0.321 mmol). MS (m/z) 471/473 (M+H)+.
Workup
- additionwas added
- customThe vessel was sealed
- customplaced in a 50° C.
- concentrationthe reaction was concentrated
- extractionthe aqueous phase was extracted with 5% MeOH-dcm (3×33 mL)
- washwashed with dilute brine (10 mL)
- dry with materialdried over sodium sulfate
- concentrationconcentrated
- customThe residue was purified by chromatography (5.5% MeOH/DCM)
Sources & evidence
- ORD record
- ord-852cd5b7fdc540639bca24a9819a86dc
- Source dataset
- uspto-grants-2016_03
- Patent number
- US09296759B2
Reaction notes
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