Cornforth reagent → HCID 22905214, compound

HRID 1655702Notes

Reaction equation

HRID 1655702 reaction equation
[OH:1][CH2:2][CH2:3][CH2:4][N:5]1[CH2:11][CH:10]([CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[O:9][C:8]2[CH:19]=[CH:20][C:21]([I:23])=[CH:22][C:7]=2[C:6]1=[O:24].[Cr](O[Cr]([O-])(=O)=O)([O-])(=O)=[O:26].[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1>CN(C)C=O.O>[C:2]([CH2:3][CH2:4][N:5]1[CH2:11][CH:10]([CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[O:9][C:8]2[CH:19]=[CH:20][C:21]([I:23])=[CH:22][C:7]=2[C:6]1=[O:24])([OH:26])=[O:1]

Participants

5

Reactant 2

HCID 2724130Cornforth reagentHCID 22905385HCID 22905385, compound

Product 1

HCID 22905214HCID 22905214, compoundYield 73%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×

Procedure

To a magnetically stirred solution of 2-(3-hydroxypropyl)-4-benzyl-8-iodo-2,3,4,5-tetrahydro-1H-5-oxa-2-benzazepin-1-one (0.75 grams, 1.7 mmol) in 5 mL dimethylformamide at room temperature was added a solution of pyridinium dichromate (2.58 grams, 6.86 mmol) in 5 mL dimethylformamide. The reaction mixture was stirred overnight, diluted with 75 mL water, washed 3×75 mL diethyl ether, made acidic to a pH of 2 with conc. HCl and extracted 3×75 mL diethyl ether. The combined organics were extracted 3×40 mL 1N sodium hydroxide. The combined aqueous layers were acidified to a pH of 2 with canc HCl and extracted 3×50 mL diethyl ether. These ether layers were combined and dried over magnesium sulfate, filtered, and concentrated in vacuo to yield 0.557 grams (73%) of 2-(2-carboxyethyl)-4-benzyl-8-iodo-2,3,4,5-tetrahydro-1H-5-oxa-2-benzazepin-1-one. 1H NMR (CDCl3, dTMS) 8.07 (1H, d, 4JHH =2 Hz, C9-H), 7.69 (1H, dd, 4JHH =2 Hz, 3JHH =8 Hz, C7-H), 7.4-7.2 (5H, m, C6H5), 6.75 (1H, d, 3JHH =8 Hz, C6-H), 4.75 (1H, m, ArOCH), 3.89 (1H, dt, 2JHH =14 Hz, 3JHH =6 Hz, NCHHCH2CO2), 3.69 (1H, dt, 2JHH =14 Hz, 3JHH =6 Hz, NCHHCH2CO2), 3.44 (2H, d, 3JHH =3 Hz, CH2Ph), 3.07 (1H, dd, 2JHH =14 Hz, 3JHH =7 Hz, C3-H), 2.8-2.7 (3H, m, C3-H, CH2CO2). 13C NMR (CDCl3) 176.1, 167.6, 164.4, 152.8, 141.7, 139.5, 136.4, 129.4, 129.1, 128.9, 128.8, 127.0, 124.7, 86.7, 84.7, 51.4, 45.0, 38.8, 33.0.

Workup

  1. washwashed 3×75 mL diethyl ether
  2. extractionextracted 3×75 mL diethyl ether
  3. extractionThe combined organics were extracted 3×40 mL 1N sodium hydroxide
  4. extractionextracted 3×50 mL diethyl ether
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-fbb2777a2d8a4c8ab0d83a88b6469858
Source dataset
uspto-grants-1993_10
Patent number
US05250679

Reaction notes

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