Methyl iodide → 4-Chloro-2-methylbenzaldehyde

HRID 1078411Notes

Reaction equation

HRID 1078411 reaction equation
C([Li])CCC.CN(C)[CH2:8][CH2:9]NC.[Cl:13][C:14]1[CH:21]=C[C:17]([CH:18]=[O:19])=[CH:16][CH:15]=1.IC>CCCCCC.C1COCC1>[Cl:13][C:14]1[CH:15]=[CH:16][C:17]([CH:18]=[O:19])=[C:8]([CH3:9])[CH:21]=1

Participants

7

Reactant 4

HCID 6328Methyl iodideHCID 77264-ChlorobenzaldehydeHCID 673381,2-Ethanediamine, N1,N1,N2-trimethyl-HCID 178418339Butyllithium2×

Product 1

HCID 27576584-Chloro-2-methylbenzaldehyde

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent2×

Conditions

Temperature
-23 °C

Procedure

A solution of n-butyllithium in hexane (30.4 ml, 2.5M) was added dropwise with stirring under nitrogen to a solution of N,N,N'-trimethylethylenediamine (7.9 g) in dry THF (150 ml) at -15 to -20° C. After the addition the mixture was stirred at -23° C. for 15 minutes and then 4-chlorobenzaldehyde (10.0 g) was added dropwise at -15 to -20° C. After the addition the mixture was stirred at -23° C. for 15 minutes and then more n-butyllithium in hexane (85.4 ml, 2.5M) was added dropwise at -15° C. The mixture was stirred at -23° C. for 3 hours, cooled to -40° C. and iodomethane (60.6 g) added at -40° to -20° C. After the addition, the mixture was stirred at -40° C. for 5 minutes and then allowed to warm up to ambient temperature and then stirred at that temperature for 30 minutes. The mixture was carefully poured into ice cold 10% hydrochloric acid (2 1) and left standing for 64 hours. The mixture was extracted with diethyl ether to give an oil which was distilled twice under vacuum to give 4-chloro-2-methylbenzaldehyde, b.p. 105°-110° (15 mmHg) which was sufficiently pure for synthetic use in Example 40.

Workup

  1. additionAfter the addition the mixture
  2. additionAfter the addition the mixture
  3. stirringwas stirred at -23° C. for 15 minutes
  4. stirringThe mixture was stirred at -23° C. for 3 hours
  5. temperaturecooled to -40° C.
  6. additionAfter the addition
  7. stirringthe mixture was stirred at -40° C. for 5 minutes
  8. temperatureto warm up to ambient temperature
  9. stirringstirred at that temperature for 30 minutes
  10. waitleft
  11. waitstanding for 64 hours
  12. extractionThe mixture was extracted with diethyl ether
  13. customto give an oil which
  14. distillationwas distilled twice under vacuum

Sources & evidence

ORD record
ord-83ea29ca7afb4905beca121592fd74ca
Source dataset
uspto-grants-1996_08
Patent number
US05547972

Reaction notes

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