Ammonium Chloride → HCID 21763808, compound

HRID 904218Notes

Reaction equation

HRID 904218 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, compoundYield 74%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 241BenzeneSolventHCID 3283Diethyl EtherSolvent2×

Procedure

To a solution of lithium dimethyl cuprate in ether (500 ml), prepared from copper iodide (23.81 g, 125 mmol) and methyl lithium (250 mmol, 136 ml of a 1.8 M solution in ether containing lithium bromide), 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 mmol) in benzene (500 ml). The resulting suspension was stirred for 1 hr. in the cold, then poured into saturated NH4Cl solution (600 ml) and the mixture stirred for 15 min. The organic layer was separated, and the aqueous phase adjusted to pH 13-14 by use of 50% NaOH. The aqueous phase was then extracted with two portions of chloroform, the combined organic phases washed with dilute NH4OH and dried. Evaporation gave a foam which crystallized from chloroform with the addition of hexane to give 33.20 g (74%) of 2 as the mono-chloroform 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), H5α; 5.47, d(1), H8, J7,8 =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, J7H,7CH3 =7 Hz; exchangeable, 4--OH at ~6.20.

Workup

  1. stirringThe resulting suspension was stirred for 1 hr
  2. stirringthe mixture stirred for 15 min
  3. customThe organic layer was separated
  4. extractionThe aqueous phase was then extracted with two portions of chloroform
  5. washthe combined organic phases washed with dilute NH4OH
  6. customdried
  7. customEvaporation
  8. customgave a foam which
  9. customcrystallized from chloroform with the addition of hexane

Sources & evidence

ORD record
ord-13756947e2ba419987594a2c4553b1b3
Source dataset
uspto-grants-1980_10
Patent number
US04230712

Reaction notes

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