Water → tert-Butyl (4-chlorobut-2-yn-1-yl)carbamate

HRID 1698878Notes

Reaction equation

HRID 1698878 reaction equation
Cl.[NH2:2][CH2:3][C:4]#[C:5][CH2:6][Cl:7].O.[OH-].[Na+].[C:11]([O:15][C:16](=O)[O:17]C(C)(C)C)([CH3:14])([CH3:13])[CH3:12]>O1CCOCC1>[C:11]([O:15][C:16]([NH:2][CH2:3][C:4]#[C:5][CH2:6][Cl:7])=[O:17])([CH3:14])([CH3:13])[CH3:12]

Participants

6

Reactant 4

HCID 962WaterHCID 14798Sodium HydroxideHCID 27951244-chlorobut-2-yn-1-amine HydrochlorideHCID 10219638Carbonic acid, bis(1,1-dimethylethyl) ester

Product 1

HCID 14561224tert-Butyl (4-chlorobut-2-yn-1-yl)carbamateYield 43.9%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

Ex-8c) 14.1 g of 1-Amino-4-chloro-2-butyne hydrochloride was taken up in 70 mL of dioxane and :35 mL water. 4 g NaOH was added and the reaction mixture was stirred for 30 minutes followed by the addition of 21.8 g di-t-butylcarbonate at 20° C. The reaction mixture was stirred at 20° C. to 25° C. for 8 h and then the lower organic layer was separated. The upper aqueous layer was extracted with 100 mL of dichloromethane. Organic layers were combined and washed with 50% aqueous NaHCO3, dried over anhydrous MgSO4, treated with Darco, filtered over celite and concentrated to give a brown oil. This oil was chromatographed to give 9 g of 1-t-Butyloxycarbonylamino-4-chloro-2-butyne as a white solid.

Workup

  1. stirringThe reaction mixture was stirred at 20° C. to 25° C. for 8 h
  2. customthe lower organic layer was separated
  3. extractionThe upper aqueous layer was extracted with 100 mL of dichloromethane
  4. washwashed with 50% aqueous NaHCO3
  5. dry with materialdried over anhydrous MgSO4
  6. additiontreated with Darco
  7. filtrationfiltered over celite and
  8. concentrationconcentrated
  9. customto give a brown oil
  10. customThis oil was chromatographed

Sources & evidence

ORD record
ord-53a5d4e8a9d6444dad0f7283ad111b8c
Source dataset
uspto-grants-2002_02
Patent number
US06344483B1

Reaction notes

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