Formaldehyde → tert-Butyl buta-2,3-dien-1-ylcarbamate

HRID 1291725Notes

Reaction equation

HRID 1291725 reaction equation
[C:1]([O:5][C:6]([NH:8][CH2:9][C:10]#[CH:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].C=O.[CH:14](NC(C)C)(C)C.O1CCOCC1>CCOCC>[C:1]([O:5][C:6]([NH:8][CH2:9][CH:10]=[C:11]=[CH2:14])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 712FormaldehydeHCID 7912DiisopropylamineHCID 312751,4-DioxaneHCID 11073648tert-butyl N-(prop-2-yn-1-yl)carbamate

Product 1

HCID 14585915tert-Butyl buta-2,3-dien-1-ylcarbamate

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

Reflux a mixture containing N-(t-butoxycarbonyl)-propargylamine (70 gm), 93.5 ml of 32% formaldehyde, 76.4 ml of diisopropylamine, 19.66 gm of cuprous bromide and 860 ml of p-dioxane for 12 hours. Cool and dilute the resulting mixture with 3000 ml of Et2O, wash with 500 ml of water, 1000 ml acetic acid, 500 ml of water (2×), 200 ml sat'd. sodium chloride, dry (MgSO4) and evaporate in vacuo. Flash chromatograph the residue eluting from silica gel with 10% Et2O/hexane to yield 40.8 g of the desired compound. Rf is 0.31 (eluted from silica gel with 10% EtOAc/hexane).

Workup

  1. temperatureReflux a mixture
  2. temperatureCool
  3. washwash with 500 ml of water, 1000 ml acetic acid, 500 ml of water (2×), 200 ml
  4. dry with materialsodium chloride, dry (MgSO4)
  5. customevaporate in vacuo
  6. washFlash chromatograph the residue eluting from silica gel with 10% Et2O/hexane

Sources & evidence

ORD record
ord-07d83ee07563443182230429860fa0df
Source dataset
uspto-grants-1998_05
Patent number
US05753714

Reaction notes

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