Hydrofluoric Acid → 5-Amino-2-fluorobenzonitrile

HRID 614511Notes

Reaction equation

HRID 614511 reaction equation
C1CCC(=C(F)CNCC2C=CC([F:15])=CC=2)CC1.[C:19]([C:21]1[CH:22]=[C:23]([N:27]=[N+]=[N-])[CH:24]=[CH:25][CH:26]=1)#[N:20].F>CCCCCC.CCOCC>[C:19]([C:21]1[CH:22]=[C:23]([CH:24]=[CH:25][C:26]=1[F:15])[NH2:27])#[N:20]

Participants

6

Reactant 3

HCID 14917Hydrofluoric AcidHCID 1180488331656-78-7HCID 23646094HCID 23646094, compound

Product 1

HCID 27376735-Amino-2-fluorobenzonitrile

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 8058HexaneSolvent3×

Conditions

Temperature
0 °C

Procedure

A 50 ml. ether and hexane solution of 9.8g. of 3-cyanophenylazide prepared in Step A above was charged to a rocker bomb and the ether and hexane were blown down under nitrogen. Then, 100 ml. of hexane was introduced, followed by 20 ml. of concentrated hydrogen fluoride, after which the bomb was shaken at room temperature for 10 hours. The reaction mixture was cooled, vented, and poured from the bomb, and the bomb rinsed with 40 ml. of water and 40 ml. of dichloromethane. The combined hexane, dichloromethane, and hydrogen fluoride were blown down under nitrogen. The resulting residue was combined with the aqueous rinse, cooled to 0° C., and rendered alkaline with KHCO3. The residue was then extracted three times with 75 ml. of dichloromethane per extraction, and the combined extracts dried over MgSO4 and then concentrated under reduced pressure to yield 6.5g. of a brown solid. This product was then recrystallized from boiling cyclohexane to yield 5.8g. (53%) of product with a m.p. of 88°-89° C. whose structure was confirmed by IR.

Workup

  1. temperatureThe reaction mixture was cooled
  2. additionpoured from the bomb
  3. washthe bomb rinsed with 40 ml
  4. extractionThe residue was then extracted three times with 75 ml
  5. extractionof dichloromethane per extraction
  6. dry with materialthe combined extracts dried over MgSO4
  7. concentrationconcentrated under reduced pressure
  8. customto yield 6.5g
  9. customThis product was then recrystallized
  10. customto yield 5.8g

Sources & evidence

ORD record
ord-e11a634119bc4bb69afd766913a1a56b
Source dataset
uspto-grants-1979_03
Patent number
US04145364

Reaction notes

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