4-Iodophenol → HCID 66956042, compound

HRID 2066647Notes

Reaction equation

HRID 2066647 reaction equation
CCOC(/N=N/C(OCC)=O)=O.[N+:13]([C:16]1[N:17]=[C:18]2[N:23]([CH:24]=1)[CH2:22][CH2:21][CH:20]([CH2:25][OH:26])[O:19]2)([O-:15])=[O:14].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[I:46][C:47]1[CH:52]=[CH:51][C:50](O)=[CH:49][CH:48]=1>C1COCC1>[I:46][C:47]1[CH:52]=[CH:51][C:50]([O:26][CH2:25][CH:20]2[O:19][C:18]3=[N:17][C:16]([N+:13]([O-:15])=[O:14])=[CH:24][N:23]3[CH2:22][CH2:21]2)=[CH:49][CH:48]=1

Participants

6

Reactant 4

HCID 108944-IodophenolHCID 11776TriphenylphosphineHCID 5462977Diethyl azodicarboxylateHCID 66956832HCID 66956832, compound

Product 1

HCID 66956042HCID 66956042, compoundYield 86%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Diethylazodicarboxylate (0.070 mL, 0.45 mmol) was added dropwise to a suspension of oxazine alcohol 134 (see Example 2BB above) (251 mg, 1.26 mmol), triphenylphosphine (448 mg, 1.71 mmol), and 4-iodophenol (377 mg, 1.71 mmol) in anhydrous THF (3.0 mL) at 0° C. under N2, and the resulting mixture was stirred at room temperature for 32 h. The solvent was removed and the residue was chromatographed on silica gel. Elution with CH2Cl2 firstly gave foreruns, and then further elution with 0-2% EtOAc/CH2Cl2 gave a crude solid, which was further chromatographed on silica gel. Elution with 0-50% EtOAc/petroleum ether firstly gave foreruns, and then further elution with 10% MeOH/CH2Cl2 gave 7-[(4-iodophenoxy)methyl]-2-nitro-6,7-dihydro-5H-imidazo[2,1-b][1,3]oxazine (135) (433 mg, 86%) as a cream solid: mp (MeOH/CH2Cl2/hexane) 224-227° C.; 1H NMR [(CD3)2SO] δ 8.08 (s, 1H), 7.62 (dt, J=9.0, 2.7 Hz, 2H), 6.86 (dt, J=9.0, 2.7 Hz, 2H), 4.89 (m, 1H), 4.31 (dd, J=11.1, 3.4 Hz, 1H), 4.25 (dd, J=11.1, 5.8 Hz, 1H), 4.18 (ddd, J=12.6, 5.8, 3.0 Hz, 1H), 4.09 (ddd, J=12.5, 10.8, 5.2 Hz, 1H), 2.35-2.26 (m, 1H), 2.25-2.12 (m, 1H). Anal. (C13H12IN3O4) C, H, N.

Workup

  1. customThe solvent was removed
  2. customthe residue was chromatographed on silica gel
  3. washElution with CH2Cl2 firstly gave foreruns
  4. washfurther elution with 0-2% EtOAc/CH2Cl2
  5. customgave a crude solid, which
  6. customwas further chromatographed on silica gel
  7. washElution with 0-50% EtOAc/petroleum ether firstly gave foreruns
  8. washfurther elution with 10% MeOH/CH2Cl2

Sources & evidence

ORD record
ord-013abd09e79444a190c638e00cf81e57
Source dataset
uspto-grants-2012_10
Patent number
US08293734B2

Reaction notes

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