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

HRID 1647213Notes

Reaction equation

HRID 1647213 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, 2N sodium hydroxide and ethyl acetate were added. The organic layer was separated, washed with 2N 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 g of 2-(4-chlorophenoxy)benzonitrile. The mixture was heated at reflux for 3 h, cooled, and 25 ml of 1N 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, 2N sodium hydroxide and ethyl acetate
  2. additionwere added
  3. customThe organic layer was separated
  4. washwashed with 2N 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-7ae5f19fb42d4439945d4bb95f6dbccd
Source dataset
uspto-grants-1995_07
Patent number
US05430063

Reaction notes

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