Hydrochloric Acid → Ethyl 9,10-dihydrophenanthrene-1-carboxylate

HRID 2164825Notes

Reaction equation

HRID 2164825 reaction equation
N[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH:8]=[CH:9][C:10]1[CH:20]=[CH:19][CH:18]=[CH:17][C:11]=1[C:12]([O:14][CH2:15][CH3:16])=[O:13].Cl.N([O-])=O.[Na+]>C(O)(=O)C.O.S([O-])([O-])(=O)=O.[Cu+2]>[C:11]1([C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:10]2[CH2:9][CH2:8][C:3]3[C:4](=[CH:5][CH:6]=[CH:7][CH:2]=3)[C:20]=2[CH:19]=[CH:18][CH:17]=1

Participants

7

Reactant 3

HCID 313Hydrochloric AcidHCID 23668193Sodium NitriteHCID 53977807Ethyl 2-[2-(2-aminophenyl)ethenyl]benzoate

Product 1

HCID 13281335Ethyl 9,10-dihydrophenanthrene-1-carboxylateYield 43.6%

Reagents, catalysts & solvents 3

HCID 24462Copper SulfateCatalystHCID 176Acetic AcidSolvent2×HCID 962WaterSolvent3×

Procedure

To a stirred solution of ethyl 2-[2-(2-aminophenyl)ethenyl]benzoate (13.5 grams, 0.05 mole) in warm glacial acetic acid (75 ml) was added a solution of concentrated hydrochloric acid (12 ml) in water (10 ml). The mixture was cooled to 0°, and during a 20 minute period a solution of sodium nitrite (3.7 grams, 0.054 mole) in water (30 ml) was added. The resultant mixture was stirred at 0°-5° for three hours. During a 90 minute period the mixture was added to a refluxing solution of copper sulfate (35 grams, 0.14 mole) in water (500 ml). After complete addition, glacial acetic acid (40 ml) was added and the mixture refluxed for one hour. The mixture was cooled to room temperature and extracted with three 200 ml portions of methylene chloride. The extracts were combined, washed with water, and evaporated under reduced pressure to give a brown oil. Distillation of the oil under reduced pressure gave ethyl 9,10-dihydrophenanthrene-1-carboxylate (5.5 grams, bp 145°-165°/0.25 mm) as a yellow oil.

Workup

  1. temperatureThe mixture was cooled to 0°
  2. additionwas added
  3. temperaturethe mixture refluxed for one hour
  4. extractionextracted with three 200 ml portions of methylene chloride
  5. washwashed with water
  6. customevaporated under reduced pressure
  7. customto give a brown oil
  8. distillationDistillation of the oil under reduced pressure

Sources & evidence

ORD record
ord-1430811983894bc19d2aa613a18d5e6f
Source dataset
uspto-grants-1985_03
Patent number
US04507317

Reaction notes

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