Hydrochloric Acid → HCID 57179735, compound

HRID 485713Notes

Reaction equation

HRID 485713 reaction equation
[CH3:1][C:2]1([CH3:14])[C@@H:4]([C:5]#[CH:6])[C@H:3]1[C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8].C=O.[CH:17](NC(C)C)(C)C.Cl>O.[Cu](Br)Br.O1CCOCC1>[CH3:1][C:2]1([CH3:14])[C@@H:4]([CH:5]=[C:6]=[CH2:17])[C@H:3]1[C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 712FormaldehydeHCID 7912DiisopropylamineHCID 57310583HCID 57310583, compound

Product 1

HCID 57179735HCID 57179735, compound

Reagents, catalysts & solvents 3

HCID 24611Copper bromide (CuBr2)CatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 131 g of tert.-butyl (1R,cis) 2,2-dimethyl-3-ethynyl-cyclopropane-carboxylate, 32 g of paraformaldehyde, 111 ml of diisopropylamine, 31 g of copper bromide and 1,300 ml of dioxane was heated at 80° C. for 161/2 hours and was cooled to 20° C. and diluted with water. The mixture was adjusted to a pH of 1 with aqueous N hydrochloric acid and was extracted with methylene chloride. The organic phase was evaporated to dryness under reduced pressure and the residue was chromatographed over silica gel. Elution with a 1-1 hexane-methylene chloride mixture yielded 44 g of tert.-butyl (1R,cis) 2,2-dimethyl-3-(1,2-propadienyl)-cyclopropane-carboxylate.

Workup

  1. temperaturewas cooled to 20° C.
  2. extractionwas extracted with methylene chloride
  3. customThe organic phase was evaporated to dryness under reduced pressure
  4. customthe residue was chromatographed over silica gel
  5. washElution with a 1-1 hexane-methylene chloride mixture

Sources & evidence

ORD record
ord-0168c8cbb40148aea10cd36b32223720
Source dataset
uspto-grants-1985_08
Patent number
US04537897

Reaction notes

Loading…