Ammonium Chloride → HCID 21763808, compound

HRID 1733558Notes

Reaction equation

HRID 1733558 reaction equation
[CH3:1][Li].[Br-].[Li+].[CH3:5][N:6]1[C@@H:22]2[CH2:23][C:11]3[CH:12]=[CH:13][C:14]([O:26][CH3:27])=[C:15]4[O:16][C@H:17]5[C:18]([O:24][CH3:25])=[CH:19][CH:20]=[C:21]2[C@:9]5([C:10]=34)[CH2:8][CH2:7]1.[NH4+].[Cl-]>CCOCC.C1C=CC=CC=1.[Cu](I)I>[CH3:27][O:26][C:14]1[CH:13]=[CH:12][C:11]2[CH2:23][C@H:22]3[N:6]([CH3:5])[CH2:7][CH2:8][C@@:9]4([C:10]=2[C:15]=1[OH:16])[C:21]3=[CH:20][C@@H:19]([CH3:1])[C:18]([O:24][CH3:25])=[CH:17]4

Participants

8

Reactant 4

HCID 25517Ammonium ChlorideHCID 82050Lithium BromideHCID 5324289ThebaineHCID 178418348HCID 178418348, compound

Product 1

HCID 21763808HCID 21763808, compound

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 241BenzeneSolventHCID 3283Diethyl EtherSolvent2×

Procedure

To a solution of lithium dimethyl cuprate, prepared from copper iodide (23.81 g, 125 mmole) and methyl lithium (250 mmole, 136 ml of a 1.8 M solution in ether containing lithium bromide), in ether (500 ml) stirred in an ice-salt bath under an argon atmosphere, was added rapidly in a thin stream a solution of thebaine (1, 31.14 g, 100 mmole) in benzene (500 ml). The resulting suspension was stirred for 1 hour in the cold, poured into saturated NH4Cl solution (600 ml) and stirred for 15 minutes. The organic layer was separated and the aqueous phase adjusted to pH 13-14 by use of 50% NaOH solution. The aqueous phase was extracted with two portions of chloroform, the combined organic phases were washed with dilute ammonium hydroxide and dried. Evaporation of the organic phase gave a foam which crystallized from chloroform with the addition of hexane to give 33.20 g (74% theory of (2)) as the monochloroform solvate, mp 97°- 100°. Recrystallization from the same solvent pair gave analytically pure (2.CHCl3), mp 98°-101.5°. IR (CDCl3): 3500 cm-1 (OH). NMR (CDCl3): δ7.30, s (1), CHCl3 ; 6.65, m (2), H1 and H2; 6.13, s (1), H5; 5.47, d (1), H8, J 7,8=3 Hz; 3.86, s (3), 3--OCH3 ; 3.63, s(3), 6---OCH3 ; 2.33, s(3), 17--NCH3 ; 1.17, d(3), 7--CH3, J 7H,7CH3 =7 Hz; exchangeable, 4--OH at ~6.20.

Workup

  1. stirringThe resulting suspension was stirred for 1 hour in the cold
  2. stirringstirred for 15 minutes
  3. customThe organic layer was separated
  4. extractionThe aqueous phase was extracted with two portions of chloroform
  5. washthe combined organic phases were washed with dilute ammonium hydroxide
  6. customdried
  7. customEvaporation of the organic phase
  8. customgave a foam which
  9. customcrystallized from chloroform with the addition of hexane

Sources & evidence

ORD record
ord-610eabdf60e54710b53ea1e3e93de36c
Source dataset
uspto-grants-1980_12
Patent number
US04242514

Reaction notes

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