Potassium Carbonate → HCID 69036841, compound

HRID 369003Notes

Reaction equation

HRID 369003 reaction equation
Cl.[O:2]1[C@:14]2([CH3:20])[C@@:15]34[CH2:17][CH2:18][NH:19][C@@H:9]([C@:10]3([O:22][CH2:23][CH2:24][CH3:25])[CH2:11][CH2:12][C:13]2=[O:21])[CH2:8][C:7]2=[C:16]4[C:3]1=[C:4]([O:26][CH3:27])[CH:5]=[CH:6]2.C(=O)([O-])[O-].[K+].[K+].[CH:34]1([CH2:37][Cl:38])[CH2:36][CH2:35]1>CN(C)C=O>[ClH:38].[CH:34]1([CH2:37][N:19]2[CH2:18][CH2:17][C@:15]34[C:16]5[C:3]6[O:2][C@@:14]3([CH3:20])[C:13](=[O:21])[CH2:12][CH2:11][C@@:10]4([O:22][CH2:23][CH2:24][CH3:25])[C@H:9]2[CH2:8][C:7]=5[CH:6]=[CH:5][C:4]=6[O:26][CH3:27])[CH2:36][CH2:35]1

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 80013(Chloromethyl)cyclopropaneHCID 69039241HCID 69039241, compound2×

Product 1

HCID 69036841HCID 69036841, compoundYield 55.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
85 °C

Procedure

A mixture of 4,5α-epoxy-3-methoxy-5-methyl-14-n-propyloxymorphinan-6-one hydrochloride (compound 12 of Example 7) (1.46 g, 3.71 mmol), potassium carbonate (2.24 g, 16.24 mmol), cyclopropylmethyl chloride (0.43 ml, 4.44 mmol), and 15 ml of anhydrous N,N-dimethyl formamide was stirred at 85° C. (bath temperature) for 36 h. The inorganic solid was filtered off and the filtrate evaporated. A solution of the residue in 30 ml of CH2Cl2 was washed with H2O (3×30 ml), dried over Na2SO4 and evaporated. The residue (1,69 g orange-yellow oil) was dissolved in diethyl ether and treated with ethereal HCl to give 920 mg (55%) of 17-(cydopropylmethyl)-4,5α-epoxy-3-methoxy-5-methyl-14-n-propyloxymorphinan-6-one hydrochloride (compound 16) as colorless powder. M.p. 156-158° C. IR (KBr): 3400 (+NH), 1723 (CO) cm-1. CI-MS: m/z 412 (M+ +1). 1H-MR (DMSO-d6): δ 8.57 (s, +NH), 6,85 (d, J=8.2 Hz, 1 arom. H), 6.75 (d, J=8.2 Hz, 1 rom. H), 3.79 (s, OCH3), 1.51 (s, CH3 --C(5)), 0.97 (t, J=7.4 Hz, CH3). Analysis calculated for C25H33NO4HCl. 0.6 H2O(458.81): C 65.45, H 7.73, N 3.05, Cl 7.73; found: C 65.45, H 7.85, N 3.08, Cl 7.84.

Workup

  1. filtrationThe inorganic solid was filtered off
  2. customthe filtrate evaporated
  3. washA solution of the residue in 30 ml of CH2Cl2 was washed with H2O (3×30 ml)
  4. dry with materialdried over Na2SO4
  5. customevaporated
  6. dissolutionThe residue (1,69 g orange-yellow oil) was dissolved in diethyl ether
  7. additiontreated with ethereal HCl

Sources & evidence

ORD record
ord-a5e42aac27b7492480558d1306b5e923
Source dataset
uspto-grants-2000_10
Patent number
US06136817

Reaction notes

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