N-(tert-butoxycarbonyl)glycine → N-t-butoxycarbonylglycine iodopropargyl ester

HRID 1656152Notes

Reaction equation

HRID 1656152 reaction equation
[C:1]([O:5][C:6]([NH:8][CH2:9][C:10]([OH:12])=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].[I:13][CH:14](O)[C:15]#[CH:16].Cl.CN(C)CCCN=C=NCC>ClCCl.CN(C)C1C=CN=CC=1>[I:13][CH:14]([O:11][C:10](=[O:12])[CH2:9][NH:8][C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:7])[C:15]#[CH:16]

Participants

6

Reactant 3

HCID 78288N-(tert-butoxycarbonyl)glycineHCID 602749Iodopropargyl alcoholHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochloride

Product 1

HCID 57210957N-t-butoxycarbonylglycine iodopropargyl esterYield 96.5%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a magnetically stirred solution of N-t-butoxycarbonylglycine (3.00 g., 17.12 mmole) and iodopropargyl alcohol (3.12 g., 17.15 mmole) in anhydrous dichloromethane (40 ml.) cooled to 0° C. with an ice-bath was added 4-dimethylaminopyridine (0.21 g., 1.72 mmole) followed by 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (3.61 g., 18.83 mmole). After stirring at 0° C. for 1/2 hour, the reaction mixture was stored in a refrigerator at 6° C. overnight. The reaction mixture was transferred to a separatory funnel and diluted to 100 ml. with dichloromethane, then washed successively with water, 10% aqueous potassium hydrogen sulfate, water, saturated aqueous sodium bicarbonate, water and a final wash with saturated aqueous sodium chloride. The organic layer was dried with magnesium sulfate, filtered and concentrated in vacuo with a rotary evaporator to a clear colorless oil which crystallized on standing as N-t-butoxycarbonylglycine iodopropargyl ester (5.60 g., 96.4% yield). m.p.=65°-68° C. 1H-NMR (200 MHz, DMSOd6)δ=1.40 ppm, s, 9H; 3.73, d, 2H; 4.86, s, 2H; 7.28, t, 1H. IR (CDCl3) 1165, 1505, 1715, 1760, 2205, 3460 cm-1.

Workup

  1. waitthe reaction mixture was stored in a refrigerator at 6° C. overnight
  2. customThe reaction mixture was transferred to a separatory funnel
  3. additiondiluted to 100 ml
  4. washwith dichloromethane, then washed successively with water, 10% aqueous potassium hydrogen sulfate, water, saturated aqueous sodium bicarbonate, water
  5. washa final wash with saturated aqueous sodium chloride
  6. dry with materialThe organic layer was dried with magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo with a rotary evaporator to a clear colorless oil which
  9. customcrystallized

Sources & evidence

ORD record
ord-0dd4bb56d432497db0f4e8ebf38d345b
Source dataset
uspto-grants-1993_10
Patent number
US05252745

Reaction notes

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