Dimethylacetamide → Corypalline

HRID 597390Notes

Reaction equation

HRID 597390 reaction equation
CN(C)C(=O)C.[I-].[CH3:8][N+:9]1[CH2:18][CH2:17][C:16]2[C:11](=[CH:12][C:13]([OH:21])=[C:14]([O:19][CH3:20])[CH:15]=2)[CH:10]=1.CC(C)([O-])C.[K+]>O>[CH3:8][N:9]1[CH2:18][CH2:17][C:16]2[C:11](=[CH:12][C:13]([OH:21])=[C:14]([O:19][CH3:20])[CH:15]=2)[CH2:10]1

Participants

5

Reactant 3

HCID 31374DimethylacetamideHCID 21447046HCID 21447046, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 280225Corypalline

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

2,3',4'-Trimethoxy-5-methyl-4-nitrodiphenyl ether (2e) (6.38 g) was added to N,N-dimethyl acetamide (125 ml) under nitrogen, stirred for 5 min., and treated with 2 -methyl-6-methoxy-7-hydroxy-3,4-dihydroisoquinolinium iodide (1) (7.65 g). Potassium t-butoxide (4.39 g) was then added in small portions over 15 min. The reaction mixture was stirred under nitrogen at room temperature for 7 hours, diluted with cold water (600 ml), stirred for 10-15 min. and refrigerated overnight. The supernatant aqueous layer was decanted from the solid which was collected and washed with 1:1 methanol-ether (20 ml) followed by ether (100 ml) and sucked dry (9.40 g, 92%), to yield 1-[2'-nitro-4'-methoxy-5'-(3", 4"-dimethoxy)phenoxybenzyl]-2-methyl-6-methoxy-7-hydroxy-1,2,3,4-tetrahydroisoquinoline (3e), mp 169°-171°. An analytical sample was crystallized from chloroform-methanol: mp 173°-174°; nmr δ 2.40 (3H, NCH3), 3.85, 3.88, 3.92, and 3.98 (each 3H, 4 OCH3), 6.37-7.60 (7H, ArH).

Workup

  1. stirringThe reaction mixture was stirred under nitrogen at room temperature for 7 hours
  2. stirringstirred for 10-15 min. and refrigerated overnight
  3. customThe supernatant aqueous layer was decanted from the solid which
  4. customwas collected
  5. washwashed with 1:1 methanol-ether (20 ml)
  6. customsucked dry (9.40 g, 92%)

Sources & evidence

ORD record
ord-92bf203be5e9460d998b5b3d802bc825
Source dataset
uspto-grants-1977_03
Patent number
US04013664

Reaction notes

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