Triphenylphosphine → Tert-butyl [2-(6-acetyl-4-chloro-3-cyano-2-iodophenoxy)ethyl]carbamate

HRID 626835Notes

Reaction equation

HRID 626835 reaction equation
N(C(OCC)=O)=NC(OCC)=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[OH:32][CH2:33][CH2:34][NH:35][C:36](=[O:42])[O:37][C:38]([CH3:41])([CH3:40])[CH3:39].[C:43]([C:46]1[CH:53]=[C:52]([Cl:54])[C:49]([C:50]#[N:51])=[C:48]([I:55])[C:47]=1O)(=[O:45])[CH3:44]>O1CCCC1.C(OCC)(=O)C>[C:43]([C:46]1[C:47]([O:32][CH2:33][CH2:34][NH:35][C:36](=[O:42])[O:37][C:38]([CH3:39])([CH3:41])[CH3:40])=[C:48]([I:55])[C:49]([C:50]#[N:51])=[C:52]([Cl:54])[CH:53]=1)(=[O:45])[CH3:44]

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 2733206tert-butyl N-(2-hydroxyethyl)carbamateHCID 866975264-Acetyl-6-chloro-3-hydroxy-2-iodobenzonitrile

Product 1

HCID 86697527Tert-butyl [2-(6-acetyl-4-chloro-3-cyano-2-iodophenoxy)ethyl]carbamateYield 71.7%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

Diethyl azodicarboxylate (2.3 mL, 14 mmol) was added slowly to a solution of triphenylphosphine (3.79 g, 14.5 mmol) and tert-butyl (2-hydroxyethyl)carbamate (2.3 g, 14 mmol) in tetrahydrofuran (93 mL) and cooled in an ice bath. After stirring for 15 minutes, the 4-acetyl-6-chloro-3-hydroxy-2-iodobenzonitrile (3.1 g, 9.6 mmol) was added. The reaction was allowed to warm to room temperature and stirred overnight. The reaction was diluted with ethyl acetate and washed with water, 1 N HCl, and brine, then dried over magnesium sulfate and concentrated to give a dark oil. The product was purified by FCC on silica gel eluting hexane:ethyl acetate gradient to give tert-butyl [2-(6-acetyl-4-chloro-3-cyano-2-iodophenoxy)ethyl]carbamate as a tan solid (3.2 g, 71%). LCMS calculated for C16H18ClIN2O4Na (M+Na)+: m/z=487.1; found: 486.9.

Workup

  1. temperaturecooled in an ice bath
  2. stirringstirred overnight
  3. washwashed with water, 1 N HCl, and brine
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated
  6. customto give a dark oil
  7. customThe product was purified by FCC on silica gel
  8. washeluting hexane

Sources & evidence

ORD record
ord-49eb59589419450397700506904cc0f4
Source dataset
uspto-grants-2016_04
Patent number
US09309251B2

Reaction notes

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