Hydrochloric Acid → 7-Chloro-1,2,3,4-tetrahydronaphthalen-1-one

HRID 1033392Notes

Reaction equation

HRID 1033392 reaction equation
N[C:2]1[CH:11]=[C:10]2[C:5]([CH2:6][CH2:7][CH2:8][C:9]2=[O:12])=[CH:4][CH:3]=1.N([O-])=O.[Na+].[ClH:17]>O.Cl[Cu]>[Cl:17][C:2]1[CH:11]=[C:10]2[C:5]([CH2:6][CH2:7][CH2:8][C:9]2=[O:12])=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 313Hydrochloric Acid2×HCID 3271777-Amino-1,2,3,4-tetrahydronaphthalen-1-oneHCID 23668193Sodium Nitrite

Product 1

HCID 2566777-Chloro-1,2,3,4-tetrahydronaphthalen-1-oneYield 98%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 962WaterSolvent2×

Procedure

7-Amino-1-tetralone (500 mg, 3.1 mmol) was suspended in 3 mL of water and treated with 3 mL of concentrated hydrochloric acid with stirring. The mixture was cooled in an ice bath and treated dropwise with vigorous stirring with a solution of 241 mg of sodium nitrite in 1.5 mL of water (3.5 mmol, 1.1eq). The mixture was stirred at 0°-5° for 15 minutes then added dropwise to a cold solution of 366 mg of CuCl (3.7 mmol, 1.2 eq) in 6 mL of concentrated hydrochloric acid. The mixture was stirred for 5 minutes at 0° and 1 hour at room temperature. The mixture was extracted with methylene chloride (3×15 mL); the combined extracts were washed with brine, dried over magnesium sulfate, filtered and evaporated to dryness under vacuum at room temperature to give 550 mg (3.05 mmol, 98%) of the product, 1H NMR (300MHz, CDCl3): 2.16 (m,2H), 2.67 (t,6Hz,2H), 2.95 (t,6Hz,2H), 7.22 (d,8Hz,1H), 7.44 (dd;2,8Hz;1H), 8.01 (d,2Hz,1H). FAB-MS: calculated for C10H9C10 180; found 181 (M+H,10%).

Workup

  1. temperatureThe mixture was cooled in an ice bath
  2. additiontreated dropwise
  3. stirringThe mixture was stirred at 0°-5° for 15 minutes
  4. stirringThe mixture was stirred for 5 minutes at 0° and 1 hour at room temperature
  5. extractionThe mixture was extracted with methylene chloride (3×15 mL)
  6. washthe combined extracts were washed with brine
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. customevaporated to dryness under vacuum at room temperature

Sources & evidence

ORD record
ord-d26979eae1b54ae1bbffd0a0aba61c15
Source dataset
uspto-grants-1994_05
Patent number
US05310737

Reaction notes

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