Triphenylphosphine → tert-Butyl [2-(6-acetyl-2-bromo-4-chloro-3-methylphenoxy)ethyl]carbamate

HRID 626813Notes

Reaction equation

HRID 626813 reaction equation
[Br:1][C:2]1[C:3]([OH:13])=[C:4]([C:10](=[O:12])[CH3:11])[CH:5]=[C:6]([Cl:9])[C:7]=1[CH3:8].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O[CH2:34][CH2:35][NH:36][C:37](=[O:43])[O:38][C:39]([CH3:42])([CH3:41])[CH3:40].N(C(OC(C)C)=O)=NC(OC(C)C)=O>C(Cl)Cl.O>[C:10]([C:4]1[C:3]([O:13][CH2:34][CH2:35][NH:36][C:37](=[O:43])[O:38][C:39]([CH3:42])([CH3:41])[CH3:40])=[C:2]([Br:1])[C:7]([CH3:8])=[C:6]([Cl:9])[CH:5]=1)(=[O:12])[CH3:11]

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 2733206tert-butyl N-(2-hydroxyethyl)carbamateHCID 120274791-(3-Bromo-5-chloro-2-hydroxy-4-methylphenyl)ethanone

Product 1

HCID 86697510tert-Butyl [2-(6-acetyl-2-bromo-4-chloro-3-methylphenoxy)ethyl]carbamateYield 59.8%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

A suspension of 1-(3-bromo-5-chloro-2-hydroxy-4-methylphenyl)ethanone (8.0 g, 30 mmol) in methylene chloride (304 mL) was heated with a heat gun to dissolve the solids and cooled to 0° C. To the mixture was added triphenylphosphine (11 g, 43 mmol) and tert-butyl (2-hydroxyethyl)carbamate (9.4 mL, 61 mmol). Diisopropyl azodicarboxylate (8.4 mL, 43 mmol) was added dropwise. The mixture was stirred for 23 hours at room temperature. The reaction mixture was poured into water and extracted with methylene chloride. The organic layer was separated, washed with brine, dried with sodium sulfate, filtered, and concentrated. The oil was dissolved in methylene chloride and was purified on silica using ethyl acetate in hexanes (0-25%) to give the desired compound (7.3 g, 59%). LCMS calculated for C16H21BrClNO4Na (M+Na)+: m/z=428.0, 430.0; found: 428.0, 430.0.

Workup

  1. temperaturewas heated with a heat gun
  2. dissolutionto dissolve the solids
  3. extractionextracted with methylene chloride
  4. customThe organic layer was separated
  5. washwashed with brine
  6. dry with materialdried with sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. dissolutionThe oil was dissolved in methylene chloride
  10. customwas purified on silica

Sources & evidence

ORD record
ord-31a60cafc84c48d59dddfa917fe02efa
Source dataset
uspto-grants-2016_04
Patent number
US09309251B2

Reaction notes

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