1-Bromo-3-chloropropane → HCID 10868120, compound

HRID 568206Notes

Reaction equation

HRID 568206 reaction equation
[CH3:1][C:2]([O:6][CH:7]1[CH2:11][CH2:10][CH2:9][O:8]1)([C:4]#[CH:5])[CH3:3].C([Li])CCC.Br[CH2:18][CH2:19][CH2:20][Cl:21].[Cl-].[NH4+]>CN(C)P(=O)(N(C)C)N(C)C.O1CCCC1>[CH3:3][C:2]([O:6][CH:7]1[CH2:11][CH2:10][CH2:9][O:8]1)([C:4]#[C:5][CH2:18][CH2:19][CH2:20][Cl:21])[CH3:1]

Participants

7

Reactant 4

HCID 80061-Bromo-3-chloropropaneHCID 25517Ammonium ChlorideHCID 11073634HCID 11073634, compoundHCID 178418339Butyllithium

Product 1

HCID 10868120HCID 10868120, compoundYield 83.2%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
-70 °C

Procedure

To a dried flask (500 ml volume), the inside of which had been flushed with nitrogen, were charged 15.4 g (0.10 mol.) of 2-methyl-2-tetrahydrofuranoxy-3-butyne, 150 ml of tetrahydrofuran and 20 ml of hexamethylphosphoric triamide, and the resulting mixture was cooled to −70° C. Subsequently, 65 ml of n-butyllithium (1.55 mol./l n-hexane solution, 0.10 mol.) was added to the mixture and the resulting mixture was stirred at 70° C. for 30 minutes. After adding 15.8 g (0.10 mol.) of 1-bromo-3-chloropropane, the reaction solution was warmed to 0° C. over 2 hours and further stirred at 0° C. for 2 hours to complete the reaction. After the completion of the reaction, the reaction mixture was added to 500 ml of an aqueous saturated ammonium chloride solution, cooled by ice, and then subjected to extraction with two 200 ml portions of ethyl acetate. The extract was washed with an aqueous saturated sodium bicarbonate solution and a saturated saline solution, dried over anhydrous sodium sulfate and concentrated by distillation of the solvent through a rotary evaporator to give 22.8 g of a crude product. The crude product was purified by distillation under reduced pressure to give 2-methyl-2-tetrahydrofuranoxy-7-chloro-3-heptyne (19.2 g, purity 97.0%, yield 80.8%) having the following physical data:

Workup

  1. customTo a dried flask (500 ml volume), the inside of which had been flushed with nitrogen
  2. temperaturethe reaction solution was warmed to 0° C. over 2 hours
  3. stirringfurther stirred at 0° C. for 2 hours
  4. customthe reaction
  5. customAfter the completion of the reaction
  6. temperaturecooled by ice
  7. extractionsubjected to extraction with two 200 ml portions of ethyl acetate
  8. washThe extract was washed with an aqueous saturated sodium bicarbonate solution
  9. dry with materiala saturated saline solution, dried over anhydrous sodium sulfate
  10. concentrationconcentrated by distillation of the solvent through a rotary evaporator
  11. customto give 22.8 g of a crude product
  12. distillationThe crude product was purified by distillation under reduced pressure

Sources & evidence

ORD record
ord-2aa13a04432c4d7c8aae6c1eb130034a
Source dataset
uspto-grants-2001_01
Patent number
US06180835B2

Reaction notes

Loading…