5-Chloro-2-methylaniline → 5-Chloro-2-methylbenzenepropanal

HRID 1439914Notes

Reaction equation

HRID 1439914 reaction equation
N[C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[CH3:9].N([O-])=O.[Na+].[CH:14]([CH:16]=[CH2:17])=[O:15]>Cl.O.CN(C=O)C>[Cl:8][C:6]1[CH:5]=[CH:4][C:3]([CH3:9])=[C:2]([CH2:17][CH2:16][CH:14]=[O:15])[CH:7]=1

Participants

7

Reactant 3

HCID 72605-Chloro-2-methylanilineHCID 7847AcroleinHCID 23668193Sodium Nitrite

Product 1

HCID 189847215-Chloro-2-methylbenzenepropanalYield 60.8%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a suspension of 2-amino-4-chlorotoluene (1.41 g, 10 mmol) in 24% aq. HCl (5 mL) Was added dropwise NaNO2 (710 mg, 1.03 mmol) in H2O (3 mL) over 30 min at 0° C. The resulting solution was added dropwise to a solution of acrolein (1 mL, 15 mmol) in a mixture of DMF (15 mL) and 20% aq. TiCl3 (20 mL, 26 mmol). After the addition was completed, the mixture was stirred for 30 min at room temperature and extracted with diethyl ether. The extracts was dried over MgSO4 and concentrated. The residue was purified by silica gel column chromatography with 5:1 hexane/AcOEt to give 1.11 g of the title compound (60%): 1H NMR (CDCl3) δ9.83 (s, 1H), 7.06~7.12 (m, 3H), 2.90 (t, 2H, J=7.2 Hz), 2.74 (t, 2H, J=7.2 Hz), 2.27 (s, 3H).

Workup

  1. additionAfter the addition
  2. extractionextracted with diethyl ether
  3. dry with materialThe extracts was dried over MgSO4
  4. concentrationconcentrated
  5. customThe residue was purified by silica gel column chromatography with 5:1 hexane/AcOEt

Sources & evidence

ORD record
ord-0f266ed03b3742b5aeb36ddb48d42cf8
Source dataset
uspto-grants-1996_03
Patent number
US05496843

Reaction notes

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