Dichloromethane → HCID 12211311, compound

HRID 1439360Notes

Reaction equation

HRID 1439360 reaction equation
C(Cl)Cl.[CH3:4][O:5][C:6]1[CH:15]=[CH:14][CH:13]=[C:12]2[C:7]=1[CH2:8][CH2:9][N:10]([CH3:16])[CH2:11]2.[CH3:17][O:18]C(Cl)Cl.[OH-].[Na+]>[Ti](Cl)(Cl)(Cl)Cl.O>[CH3:4][O:5][C:6]1[CH:15]=[CH:14][C:13]([CH:17]=[O:18])=[C:12]2[C:7]=1[CH2:8][CH2:9][N:10]([CH3:16])[CH2:11]2

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 14798Sodium HydroxideHCID 21004Methane, dichloromethoxy-HCID 12211310HCID 12211310, compound

Product 1

HCID 12211311HCID 12211311, compoundYield 74.5%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

Into a flask equipped with a mechanical stirrer, an equilibrium addition funnel, and a condenser fitted with a calcium chloride drying tube, were placed methylene chloride (150 ml) and 5-methoxy-2-methyl-1,2,3,4-tetrahydroisoquinoline (15.0 g, 0.085 mole). The solution was cooled to 0° C and stirred. Titanium tetrachloride (51.6 g, 0.272 mole) was added gradually, followed by the rapid dropwise addition of α,α-dichloromethyl methyl ether (9.8 g, 0.085 mole). After the reaction mixture was allowed to warm to room temperature, it was refluxed for 7 hours. The titanium chloride complex of the product was decomposed with water and ice, and the resulting solution kept cool as it was made basic with excess sodium hydroxide (20%). The resulting suspension was extracted with chloroform. The extract was dried over sodium sulfate and the solvent removed, affording the crude product which was vacuum distilled (b.p. 122° C/0.1 mm) to yield 13.0 g (74%) of 5-methoxy-2-methyl-1,2,3,4-tetrahydroisoquinoline-8-carboxaldehyde. The hydrochloride salt melted at 244°-245° C after recrystallization from absolute ethanol. Anal. Calcd. for C12H13NO2Cl; C, 59.6; H, 6.7; N, 5.8; Cl, 14.7. Found: C, 59.8; H, 6.8; N, 5.8; Cl, 14.4.

Workup

  1. customInto a flask equipped with a mechanical stirrer, an equilibrium addition funnel, and a condenser
  2. customfitted with a calcium chloride drying tube
  3. temperatureto warm to room temperature
  4. temperatureit was refluxed for 7 hours
  5. temperaturethe resulting solution kept cool as it
  6. extractionThe resulting suspension was extracted with chloroform
  7. dry with materialThe extract was dried over sodium sulfate
  8. customthe solvent removed
  9. customaffording the crude product which
  10. distillationdistilled (b.p. 122° C/0.1 mm)

Sources & evidence

ORD record
ord-fa74e77f1aa14dc9987bebcc7304964a
Source dataset
uspto-grants-1977_11
Patent number
US04059586

Reaction notes

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