Hydrochloric Acid → Methyl 4-((5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-YL)carbamoyl)benzoate

HRID 249567Notes

Reaction equation

HRID 249567 reaction equation
[CH3:1][C:2]1([CH3:18])[C:11]2[C:6](=[CH:7][C:8]([NH:12][C:13]([CH3:15])=[O:14])=[CH:9][CH:10]=2)[C:5]([CH3:17])([CH3:16])[CH2:4][CH2:3]1.CN(C)C1C=CC=CC=1.P(Cl)(Cl)(Cl)(Cl)Cl.C(Cl)(=O)C1[CH:43]=[CH:42][C:38]([C:39](Cl)=[O:40])=[CH:37][CH:36]=1.Cl.[CH3:47][OH:48]>C(Cl)Cl>[CH3:1][C:2]1([CH3:18])[CH2:3][CH2:4][C:5]([CH3:17])([CH3:16])[C:6]2[CH:7]=[C:8]([NH:12][C:13]([C:15]3[CH:36]=[CH:37][C:38]([C:39]([O:48][CH3:47])=[O:40])=[CH:42][CH:43]=3)=[O:14])[CH:9]=[CH:10][C:11]1=2

Participants

8

Reactant 6

HCID 313Hydrochloric AcidHCID 887MethanolHCID 949N,N-Dimethylaniline2×HCID 7488Terephthaloyl chlorideHCID 24819Phosphorus pentachlorideHCID 10399633N-(5,5,8,8-Tetramethyl-5,6,7,8-tetrahydronaphthalen-2-YL)acetamide

Product 1

HCID 13632689Methyl 4-((5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-YL)carbamoyl)benzoateYield 81%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-25 °C

Procedure

First, 125 g (0.51 mole) of 1,2,3,4-tetrahydro-1,1,4,4-tetramethyl-6-acetaminonaphthalene was dissolved in 625 ml of CH2Cl2. To this solution, 206 ml of dimethylaniline and 116.6 g (0.51×1.1 mole) of phosphorus pentachloride were added in this order at -25° C. under a nitrogen atmosphere, and the mixture was stirred at the same temperature for 1.5 hours. To this reaction mixture was added dropwise 2.06 l of methanol, after which the cooling bath was removed and the stirring of the mixture was continued for 2 hours (at -25° C. to room temperature). Furthermore, this reaction mixture was cooled to -25° C., and 306 ml of dimethylaniline and 101.1 g (1.01×0.51 mole) of terephthalic chloride were added thereto in this order. The mixture was stirred at -20° C. to -30° C. for 1 hour. After the reaction was completed, the reaction mixture was poured into 2.6 l of chilled 1N hydrochloric acid, and the mixture was extracted with 1.3 l of CH2Cl2. The CH2Cl2 layer was washed with 2.6 l of 1N hydrochloric acid, 4 l of water, 5% aqueous solution of sodium bicarbonate and 4 l of water in this order. After drying over MgSO4, the solution was evaporated to dryness. To this residue was added 740 ml methanol, and the mixture was allowed to stand overnight, resulting in 151 g (81%) of the above-described compound.

Workup

  1. customafter which the cooling bath was removed
  2. stirringthe stirring of the mixture
  3. waitwas continued for 2 hours
  4. custom(at -25° C. to room temperature)
  5. stirringThe mixture was stirred at -20° C. to -30° C. for 1 hour
  6. extractionthe mixture was extracted with 1.3 l of CH2Cl2
  7. washThe CH2Cl2 layer was washed with 2.6 l of 1N hydrochloric acid, 4 l of water, 5% aqueous solution of sodium bicarbonate and 4 l of water in this order
  8. dry with materialAfter drying over MgSO4
  9. customthe solution was evaporated to dryness
  10. additionTo this residue was added 740 ml methanol
  11. waitto stand overnight

Sources & evidence

ORD record
ord-531918cac7ac492f81666452911398ba
Source dataset
uspto-grants-1993_05
Patent number
US05214202

Reaction notes

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