4-Chlorobenzoyl chloride → 4-Chlorobenzonitrile

HRID 963006Notes

Reaction equation

HRID 963006 reaction equation
[NH4+:1].[Cl-].[Cl:3][C:4]1[CH:12]=[CH:11][C:7]([C:8](Cl)=O)=[CH:6][CH:5]=1>>[CH:6]1[C:7]([C:8]#[N:1])=[CH:11][CH:12]=[C:4]([Cl:3])[CH:5]=1

Participants

3

Reactant 2

HCID 85014-Chlorobenzoyl chlorideHCID 25517Ammonium Chloride

Product 1

HCID 121634-Chlorobenzonitrile

Conditions

Temperature
220 °C

Procedure

A 2 L glass resin kettle was fitted with an overhead stirrer, glass thermocouple well, and a 15 cm (6 inch) 24/40 U-connector tube wrapped with an electrical heating tape and set at a 120° to 150° C. skin temperature. The U-connector tube was attached to a 1 L, 3-necked, round bottom flask fitted with an air condenser, which was used as a sublimate trap to a stop the easily sublimed product. To this was added either 1.1 eq. (first two runs) or 1.0 eq. (last three runs) NH4Cl, 7.50 g MgO (0.5 wt % based on the PCBTC) and 1500 g of 99 wt % PCBTC. The kettle was heated with a mantle to 220° C. The temperature was controlled using an Instruments for Research and Industry "Therm-O-Watch" model L11-1500 temperature controller with a K-type thermocouple. Samples were removed periodically and were analyzed by gas chromatograph (GC). Because p-chlorobenzoylchloride (PCBOC) has the same boiling point as PCBN but a slower reaction rate, the reaction was continued until all of the PCBOC had been consumed. In general, when less than 5 wt % of PCBTC remained (after 15 to 20 hours of reaction at 220° C.) the 1 L sublimate receiver was exchanged for a clean one and the product was up and over distilled. After cooling the reactor, it was recharged with the sublimate from the previous run, NH4Cl, and PCBTC, and the sequence was repeated. In this manner, 7 kg of PCBTC gave a 90.5 wt % isolated yield of PCBN with an average purity of 97 wt % by GC area%.

Workup

  1. customset at a 120° to 150° C.
  2. custom3-necked, round bottom flask fitted with an air condenser
  3. customwhich was used as a sublimate trap to a stop
  4. customSamples were removed periodically
  5. customa slower reaction rate
  6. customhad been consumed
  7. custom(after 15 to 20 hours of reaction at 220° C.) the 1 L sublimate receiver
  8. distillationover distilled
  9. temperatureAfter cooling the reactor, it
  10. customIn this manner, 7 kg of PCBTC gave a 90.5 wt %

Sources & evidence

ORD record
ord-09c94c65cb7e4df0a0be5a1e8979e2e8
Source dataset
uspto-grants-1998_06
Patent number
US05760274

Reaction notes

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