4-Chlorophenol → 2-(4-Chlorophenoxy)benzonitrile

HRID 1612793Notes

Reaction equation

HRID 1612793 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][CH:3]=1.[H-].[Na+].C1OCCOCCOCCOCCOCCOC1.Br[C:30]1[CH:37]=[CH:36][CH:35]=[CH:34][C:31]=1[C:32]#[N:33]>CN(C)C=O>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][C:30]2[CH:37]=[CH:36][CH:35]=[CH:34][C:31]=2[C:32]#[N:33])=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 46844-ChlorophenolHCID 162722-BromobenzonitrileHCID 24758Sodium hydrideHCID 2855718-Crown-6

Product 1

HCID 141307012-(4-Chlorophenoxy)benzonitrileYield 60%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Conditions

Temperature
100 °C

Procedure

A solution of 51.4 g of 4-chlorophenol in 500 ml of dry N,N-dimethylformamide (DMF) was added to a suspension of 20 g of 60% sodium hydride in 800 ml of dry DMF under nitrogen. After 30 min at 25° C., 1 g of 18-crown-6 was added. After the addition of 73 g of 2-bromobenzonitrile in 500 ml of dry DMF, the mixture was heated at 100° C. for 16 h. After concentration in vacuo, 2 N sodium hydroxide and ethyl acetate were added. The organic layer was separated, washed with 2 N sodium hydroxide and water, dried over magnesium sulfate, and evaporated to dryness. The residue was recrystallized from methanol to give in 60% yield 2-(4-chlorophenoxy)benzonitrile. To a suspension of 6 g of lithium aluminum hydride in 100 ml of dry tetrahydrofuran (THF) were added under nitrogen 20 of 2-(4-chlorophenoxy)benzonitrile. The mixture was heated at reflux for 3 h, cooled, and 25 ml of 1 N sodium hydroxide were added dropwise. The precipitate formed was filtered off and washed with diethyl ether. The filtrate was evaporated to dryness, dissolved in ethyl acetate and acidified with a saturated solution of hydrochloric acid in ethanol. The precipitate was collected and recrystallized from ethanol to give in 95% yield 2-(4-chlorophenoxy)benzenemethanamine hydrochloride. mp 253° C.

Workup

  1. concentrationAfter concentration in vacuo, 2 N sodium hydroxide and ethyl acetate
  2. additionwere added
  3. customThe organic layer was separated
  4. washwashed with 2 N sodium hydroxide and water
  5. dry with materialdried over magnesium sulfate
  6. customevaporated to dryness
  7. customThe residue was recrystallized from methanol

Sources & evidence

ORD record
ord-933ce2b9f03f4deea1942d134beac8a1
Source dataset
uspto-grants-1993_03
Patent number
US05190965

Reaction notes

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