Toluene → (-)-10,11-Dimethoxyaporphine

HRID 1105665Notes

Reaction equation

HRID 1105665 reaction equation
OC1C(O)=C2C(C[CH:7]3[C:19]4[C:11](=[CH:12][CH:13]=[CH:14][C:15]2=4)[CH2:10][CH2:9][N:8]3[CH3:20])=CC=1.CN(C)[CH:23]=[O:24].[OH-:26].[C:27]1([N+](C)(C)C)C=CC=CC=1.[C:37]1([CH3:43])[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1>>[CH3:27][O:26][C:40]1[C:41]([O:24][CH3:23])=[C:42]2[C:37]([CH2:43][CH:7]3[C:19]4[C:11](=[CH:12][CH:13]=[CH:14][C:15]2=4)[CH2:10][CH2:9][N:8]3[CH3:20])=[CH:38][CH:39]=1

Participants

5

Reactant 4

HCID 1140TolueneHCID 2215(+-)-ApomorphineHCID 6228DimethylformamideHCID 15913Trimethylphenylammonium hydroxide

Product 1

HCID 626368(-)-10,11-Dimethoxyaporphine

Conditions

Temperature
130 °C

Procedure

1.7 g. (-)-10,11-Dihydroxyaporphine are dissolved in 15 ml. dimethyl formamide. After the addition of 130 ml. toluene, the mixture is heated to 110° C. (bath temperature) and, within the course of 30 minutes, 25.6 ml. of a 1N methanolic solution of phenyl trimethyl ammonium hydroxide added thereto dropwise, with vigorous stirring and the simultaneous distilling off of the toluene/alcohol azeotrope. After completion of the addition, the bath temperature is gradually increased to 130° C. As soon as the temperature of the distillate passing over has reached 110°-111° C., a further 12.5 ml. of the above-described methylation solution are added thereto. The reaction mixture is subsequently heated under reflux for 1 hour and then worked up in a manner analogous to that described in Example 1, Variant A, to give (-)-10,11-dimethoxyaporphine in the form of a yellowish syrup which is purified chromatographically on basic aluminium oxide (activity stage III) using methylene chloride/petroleum ether (1:1 v/v) as elution agent, the yield being 1.555 g. (83% of theory); NMR spectrum (CDCl3) δ 2.5 (3H, s, N--CH3), 3.65 (3H,s, O--CH3), 3.83 (3H, s, O--CH3), 6.63-7.27 (4H, m), 8.1 (1H,dd, C--1--H) ppm.

Workup

  1. additionAfter the addition of 130 ml
  2. customwithin the course of 30 minutes, 25.6 ml
  3. distillationthe simultaneous distilling off of the toluene/alcohol
  4. additionAfter completion of the addition
  5. customover has reached 110°-111° C.
  6. additionof the above-described methylation solution are added
  7. temperatureThe reaction mixture is subsequently heated
  8. temperatureunder reflux for 1 hour

Sources & evidence

ORD record
ord-774b40b82654499788459d81b25e95a4
Source dataset
uspto-grants-1982_01
Patent number
US04309542

Reaction notes

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