Ammonium Chloride → HCID 117640745, compound

HRID 1773116Notes

Reaction equation

HRID 1773116 reaction equation
C[Mg]Cl.[Cl:4][CH2:5][CH2:6][CH2:7][CH2:8][C:9]#[CH:10].[CH:11](OCC)([O:15][CH2:16][CH3:17])[O:12][CH2:13][CH3:14].[Cl-].[NH4+]>O1CCCC1.C1(C)C=CC=CC=1.O.C(O)(=O)C>[Cl:4][CH2:5][CH2:6][CH2:7][CH2:8][C:9]#[C:10][CH:11]([O:15][CH2:16][CH3:17])[O:12][CH2:13][CH3:14]

Participants

9

Reactant 4

HCID 25517Ammonium ChlorideHCID 31214Ethyl orthoformateHCID 2720016-Chloro-1-hexyneHCID 178418332HCID 178418332, compound

Product 1

HCID 117640745HCID 117640745, compoundYield 61%

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
47.5 °C

Procedure

In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer was placed a solution of methyl magnesium chloride (89.7 g:1.2 mol) in tetrahydrofuran (370.0 g), and stirred at a solution temperature of from 45 to 50° C. The 6-chloro-1-hexyne (116.6 g:1.0 mol) was dropwise added thereto at a reaction mixture temperature of from 50 to 60° C. over one hour, and then stirred at from 60 to 65° C. for 5 hours. A solution of triethyl orthoformate (177.8 g:1.2 mol) in toluene (120.0 g) was dropwise added thereto at a reaction mixture temperature of from 80 to 85° C. over 30 minutes, and then stirred at from 90 to 95° C. for 6 hours. After completion of the reaction was confirmed by gas chromatography, acetic acid (57.0 g), ammonium chloride (35.0 g) and water (400.0 g) were added to the reaction mixture. The organic phase separated from the aqueous phase was washed with an aqueous 1.0% sodium hydroxide solution (170.0 g). The organic phase was subjected to removal of the solvent under reduced pressure, and then the residue was distilled under reduced pressure to obtain 7-chloro-1,1-diethoxy-2-heptyne [bp: 100-104° C./0.13 KPa, 133.4 g, 0.61 mol]. [Yield: 61.0%]

Workup

  1. customIn a reactor equipped with a stirrer, a cooling condenser, a dropping funnel
  2. stirringstirred at from 60 to 65° C. for 5 hours
  3. waitat a reaction mixture temperature of from 80 to 85° C. over 30 minutes
  4. stirringstirred at from 90 to 95° C. for 6 hours
  5. additionwere added to the reaction mixture
  6. customThe organic phase separated from the aqueous phase
  7. washwas washed with an aqueous 1.0% sodium hydroxide solution (170.0 g)
  8. customThe organic phase was subjected to removal of the solvent under reduced pressure
  9. distillationthe residue was distilled under reduced pressure

Sources & evidence

ORD record
ord-af594b4d3b714034a867bf1d192b0445
Source dataset
uspto-grants-2016_02
Patent number
US09255056B2

Reaction notes

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