1-Chloro-4-nitrobenzene → HCID 3055537, compound

HRID 1447651Notes

Reaction equation

HRID 1447651 reaction equation
[H-].[Na+].[CH3:3][N:4]([CH3:17])[C@H:5]1[CH2:11][CH2:10][C:9]2[CH:12]=[CH:13][CH:14]=[CH:15][C:8]=2[C@H:7]([OH:16])[CH2:6]1.Cl[C:19]1[CH:24]=[CH:23][C:22]([N+:25]([O-:27])=[O:26])=[CH:21][CH:20]=1>CS(C)=O>[CH3:3][N:4]([CH3:17])[C@H:5]1[CH2:11][CH2:10][C:9]2[CH:12]=[CH:13][CH:14]=[CH:15][C:8]=2[C@H:7]([O:16][C:19]2[CH:24]=[CH:23][C:22]([N+:25]([O-:27])=[O:26])=[CH:21][CH:20]=2)[CH2:6]1

Participants

5

Reactant 3

HCID 74741-Chloro-4-nitrobenzeneHCID 24758Sodium hydrideHCID 53682307HCID 53682307, compound

Product 1

HCID 3055537HCID 3055537, compoundYield 104.2%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
55 °C

Procedure

14.4 ml of anhydrous dimethylsulfoxide were added at room temperature to 1.44 g of sodium hydride as a 50% dispersion in oil and the mixture was heated in a bath at 55° C. for one hour and was then cooled to 20° C. 5.13 g of trans 7-dimethylamino-6,7,8,9-tetrahydro-5H-benzocycloheptene-5-ol were added thereto and the mixture was stirred at room temperature for 10 minutes. Then, 4.73 g of p-chloro-nitrobenzene were added thereto all at once and the mixture was stirred at room temperature for 3 hours. The mixture was extracted with methylene chloride and the organic phase was washed with water, dried over magnesium sulfate and evaporated to dryness under reduced pressure to obtain 9.5 g of raw product. The latter was extracted with 0.5 N hydrochloric acid and the neutral fraction was extracted twice with 100 ml of ether. The combined aqueous phases were made alkaline with a strong excess of ammonium hydroxide and were extracted with methylene chloride. The organic phase was dried over magnesium sulfate and filtered and the filtrate was evaporated to dryness under reduced pressure to obtain 8.5 g of trans N,N-dimethyl-5-[4-nitrophenoxy]-6,7,8,9-tetrahydro-5H-benzocycloheptene-7-amine. The said product was dissolved in 20 ml of ethyl acetate and an excess of a solution of gaseous hydrogen chloride in ethyl acetate was added thereto. Crystallization was induced and the mixture was held in the refrigerator for 12 hours and was then vacuum filtered. The recovered precipitate was washed with methyl ethyl ketone and was dried at 100° C. under reduced pressure to obtain 5.5 g of the hydrochloride of the trans compound in the form of colorless crystals melting at 192°-196° C.

Workup

  1. temperaturewas then cooled to 20° C
  2. stirringall at once and the mixture was stirred at room temperature for 3 hours
  3. extractionThe mixture was extracted with methylene chloride
  4. washthe organic phase was washed with water
  5. dry with materialdried over magnesium sulfate
  6. customevaporated to dryness under reduced pressure
  7. customto obtain 9.5 g of raw product
  8. extractionThe latter was extracted with 0.5 N hydrochloric acid
  9. extractionthe neutral fraction was extracted twice with 100 ml of ether
  10. extractionwere extracted with methylene chloride
  11. dry with materialThe organic phase was dried over magnesium sulfate
  12. filtrationfiltered
  13. customthe filtrate was evaporated to dryness under reduced pressure

Sources & evidence

ORD record
ord-6280b2dcaa6147d49281bc9130d8e1c2
Source dataset
uspto-grants-1979_12
Patent number
US04177292

Reaction notes

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