Hydrochloric Acid → Hydrochloric Acid

HRID 1906319Notes

Reaction equation

HRID 1906319 reaction equation
[F:1][CH:2]=[C:3]([CH2:16]Br)[CH2:4][N:5]1C(=O)C2=CC=CC=C2C1=O.[H-].[Na+].O.NN.[ClH:23].[CH:24]([OH:27])([CH3:26])[CH3:25]>CN(C)C=O.[Cl-].[Na+].O.C(O)C.CCOCC>[ClH:23].[CH:24]([O:27][CH2:16]/[C:3](=[CH:2]\[F:1])/[CH2:4][NH2:5])([CH3:26])[CH3:25]

Participants

11

Reactant 5

HCID 313Hydrochloric AcidHCID 3776IsopropanolHCID 24654Hydrazine hydrate (1:1)HCID 24758Sodium hydrideHCID 54187565HCID 54187565, compound

Product 2

HCID 313Hydrochloric AcidHCID 14724219HCID 14724219, compound

Reagents, catalysts & solvents 4

HCID 702EthanolSolventHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

Solid 1-fluoro-2-bromomethyl-3-phthalimidopropene (0.60 g) is added to a previously prepared mixture of isopropanol (0.12 g) and sodium hydride dispersion (96 mg of 55-60% oil dispersion) in dimethylformamide (10 ml) at room temperature. Stirring is continued for 3 hours, then brine is added and the product is isolated by ether extraction. This product is treated with hydrazine hydrate (0.13 g) in ethanol (20 ml) under reflux for 3 hours. Dilute aqueous hydrochloric acid is added and the resulting mixture is washed with ethyl acetate, then the aqueous layer is concentrated to about 5 ml. The residual solution is treated with di-tert-butyl dicarbonate (0.44 g), sodium chloride (1 g) and chloroform (20 ml) then sufficient sodium bicarbonate is added to adjust the pH of the aqueous layer to about 8. The mixture is refluxed for 11/2 hours then the crude N-Boc derivative can be isolated by extractive work-up. Purification is achieved by silica chromatography using ether/petroleum ether as eluent. Cleavage of the Boc protecting group (anhydrous hydrogen chloride in ether) affords (Z)-2-isopropoxymethyl-3-fluoroallylamine as its hydrochloride salt.

Workup

  1. temperatureunder reflux for 3 hours
  2. washthe resulting mixture is washed with ethyl acetate
  3. concentrationthe aqueous layer is concentrated to about 5 ml
  4. additionThe residual solution is treated with di-tert-butyl dicarbonate (0.44 g), sodium chloride (1 g) and chloroform (20 ml)
  5. additionsufficient sodium bicarbonate is added
  6. temperatureThe mixture is refluxed for 11/2 hours
  7. customthe crude N-Boc derivative can be isolated by extractive work-up
  8. customPurification

Sources & evidence

ORD record
ord-82a17360ae04476cb2edde3cccb732bd
Source dataset
uspto-grants-1987_03
Patent number
US04650907

Reaction notes

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