2,4,6-Trimethylpyridine → 1-(2-Nitrophenyl)-1,2,3,4-tetrahydroquinoline

HRID 35132

Reaction equation

HRID 35132 reaction equation
F[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9].[NH:11]1[C:20]2[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=2)[CH2:14][CH2:13][CH2:12]1.N1C(C)=CC(C)=CC=1C>CC1C=CC=C(C)C=1C>[N+:8]([C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[N:11]1[C:20]2[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=2)[CH2:14][CH2:13][CH2:12]1)([O-:10])=[O:9]

Participants

5

Reactant 3

HCID 79532,4,6-TrimethylpyridineHCID 694601,2,3,4-TetrahydroquinolineHCID 738951-Fluoro-2-nitrobenzene

Product 1

HCID 138129261-(2-Nitrophenyl)-1,2,3,4-tetrahydroquinolineYield 22.2%

Reagents, catalysts & solvents 1

HCID 106861,2,3-TrimethylbenzeneSolvent

Procedure

A stirred mixture, under nitrogen, of 70.6 g (0.50 mole) of 1-fluoro-2-nitrobenzene, 133.2 g (1.00 mole) of 1,2,3,4-tetra hydroquinoline and 121.2 g (1.00 mole) of symmetrical collidine in 500 ml of 1,2,3-trimethylbenzene was refluxed (bp 178°) for 5 days. The mixture was concentrated in vacuo. The residue was taken up in 1000 ml of chloroform and extracted with 500 ml of 2N-hydrochloric acid. The aqueous phase was back extracted with 250 ml of chloroform. The combined organic layers were washed 3 times with 2N-hydrochloric acid, once with 2N-sodium hydroxide solution, twice with water and dried over anhydrous sodium sulfate. The solvent was removed in vacuo. The residual oil was dissolved in 300 ml of 1:1 hexane:toluene and adsorbed on a chromatography column containing 2 kg of silica gel packed in hexane. Elution with 1:1 hexane:toluene gave fractions containing product. The fractions were combined and concentrated to afford 28.2 g (22%) of product. Recrystallization from hot isopropyl ether afforded the analytical sample, mp 69°-71° C.

Workup

  1. concentrationThe mixture was concentrated in vacuo
  2. extractionextracted with 500 ml of 2N-hydrochloric acid
  3. extractionThe aqueous phase was back extracted with 250 ml of chloroform
  4. washThe combined organic layers were washed 3 times with 2N-hydrochloric acid
  5. dry with materialonce with 2N-sodium hydroxide solution, twice with water and dried over anhydrous sodium sulfate
  6. customThe solvent was removed in vacuo
  7. dissolutionThe residual oil was dissolved in 300 ml of 1:1 hexane
  8. additioncontaining 2 kg of silica gel
  9. washElution with 1:1 hexane
  10. customtoluene gave fractions
  11. additioncontaining product
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-7da007d1d37b414984023c3a5aff68e2
Source dataset
uspto-grants-1988_08
Patent number
US04764616

Linked notes

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