Triphenylphosphine → HCID 118103540, compound

HRID 1057016Notes

Reaction equation

HRID 1057016 reaction equation
[Br:1][C:2]1[C:3]([O:21][C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=[C:4]([NH:9][C:10](=[O:20])[CH2:11][NH:12][C:13](=[O:19])[O:14][C:15]([CH3:18])([CH3:17])[CH3:16])[C:5](O)=[CH:6][CH:7]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>O1CCCC1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]2[O:20][C:10]([CH2:11][NH:12][C:13](=[O:19])[O:14][C:15]([CH3:16])([CH3:18])[CH3:17])=[N:9][C:4]=2[C:3]=1[O:21][C:22]1[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 118103539HCID 118103539, compound

Product 1

HCID 118103540HCID 118103540, compoundYield 72.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of tert-butyl {2-[(3-bromo-6-hydroxy-2-phenoxyphenyl)amino]-2-oxoethyl}carbamate (0.298 g, 0.681 mmol), triphenylphosphine (0.393 g, 1.50 mmol), and freshly activated 4 A molecular sieves (2.72 g, 4 g/mmol) at 0° C. was treated with tetrahydrofuran (10.2 mL) and stirred at 0° C. for 1 h, followed by dropwise addition of diisopropyl azodicarboxylate (0.295 mL, 1.50 mmol) at this temperature. The resultant reaction mixture was warmed to RT and stirred at RT for 16 h, after which time the reaction mixture was filtered through a pad of Celite and washed with ethyl acetate. The filtrate was concentrated in vacuo to yield a crude residue that was purified by flash column chromatography (100% hexanes to 40% EtOAc/hexanes) to give the desired product (207 mg, 72%) as a tan solid. LCMS calculated for C19H19BrN2O4Na (M+Na)+: m/z=441.0, 443.0. found: 441.0, 443.0.

Workup

  1. customat 0° C.
  2. customThe resultant reaction mixture
  3. temperaturewas warmed to RT
  4. stirringstirred at RT for 16 h
  5. filtrationafter which time the reaction mixture was filtered through a pad of Celite
  6. washwashed with ethyl acetate
  7. concentrationThe filtrate was concentrated in vacuo
  8. customto yield a crude residue that
  9. customwas purified by flash column chromatography (100% hexanes to 40% EtOAc/hexanes)

Sources & evidence

ORD record
ord-6f507b9c957548e8a9cf31520c90694e
Source dataset
uspto-grants-2016_07
Patent number
US09399640B2

Reaction notes

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