Ammonium Chloride → HCID 54011856, compound

HRID 1085714Notes

Reaction equation

HRID 1085714 reaction equation
C([Li])CCC.Br[C:7]1[C:20]([F:21])=[C:19]([F:22])[C:10]([CH2:11][O:12][CH:13]2[CH2:18][CH2:17][CH2:16][CH2:15][O:14]2)=[C:9]([F:23])[C:8]=1[F:24].[Cl:25]/[CH:26]=[CH:27]\[CH2:28]I.[Cl-].[NH4+]>O1CCCC1.[Cu]Br>[Cl:25][CH:26]=[CH:27][CH2:28][C:7]1[C:20]([F:21])=[C:19]([F:22])[C:10]([CH2:11][O:12][CH:13]2[CH2:18][CH2:17][CH2:16][CH2:15][O:14]2)=[C:9]([F:23])[C:8]=1[F:24]

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 11333156HCID 11333156, compoundHCID 136705722-[(4-Bromo-2,3,5,6-tetrafluorophenyl)methoxy]tetrahydro-2H-pyranHCID 178418339Butyllithium

Product 1

HCID 54011856HCID 54011856, compound

Reagents, catalysts & solvents 2

HCID 24593copper(I) bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-70 °C

Procedure

n-Butyl lithium (2.5M in hexane, 3 cm3) was added portionwise to a solution of 2-[4-bromo-2,3,5,6-tetrafluorobenzyloxy]-tetrahydropyran (1.7 g) in dry tetrahydrofuran (10 cm3) under an atmosphere of dry nitrogen, whilst the reaction temperature was maintained at -70° C. After 30 minutes, copper (I) bromide--dimethyl sulphide complex (1.54 g) was added in one portion and the reaction temperature allowed to warm to 0° C., for a period of 15 minutes. After cooling to -70° C., a solution of Z-1-chloro-3-iodoprop-1-ene (2.03 g) in dry tetrahydrofuran (3 cm3) was added portionwise, and the reaction mixture stirred for a further hour at -70° C. After warming to the ambient temperature, (ca. 25° C.), aqueous ammonium chloride was added to the reaction mixture, which was then extracted with ethyl acetate. After drying, the solvent was evaporated under reduced pressure to give an orange oil. The residue was then subjected to medium pressure column chromaatography on a silica gel column using a Gilson apparatus, eluting with petroleum ether (boiling range 40°-60° C.) containing diethyl ether (5% by volume) to give 2-[4-(3-chloroprop-2-en-1-yl)-2,3,5,6-tetrafluorobenzyloxy]-tetrahydropyran, as a mixture consisting predominantly of the Z isomer.

Workup

  1. temperatureto warm to 0° C., for a period of 15 minutes
  2. temperatureAfter cooling to -70° C.
  3. additionwas added to the reaction mixture, which
  4. extractionwas then extracted with ethyl acetate
  5. customAfter drying
  6. customthe solvent was evaporated under reduced pressure
  7. customto give an orange oil
  8. washeluting with petroleum ether (boiling range 40°-60° C.)
  9. additioncontaining diethyl ether (5% by volume)

Sources & evidence

ORD record
ord-0a80ef750a594b68b9724826bf42e68d
Source dataset
uspto-grants-1991_04
Patent number
US05010200

Reaction notes

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