Ammonia → HCID 11637442, compound

HRID 908365Notes

Reaction equation

HRID 908365 reaction equation
[CH3:1][C:2]1[CH:19]=[CH:18][C:5]([CH2:6][CH:7]2[C:16]3[CH2:15][CH2:14][CH2:13][CH2:12][C:11]=3[CH2:10][CH2:9][N:8]2[CH3:17])=[CH:4][CH:3]=1.P(=O)(O)(O)O.N>O>[CH3:1][C:2]1[CH:19]=[CH:18][C:5]2[CH2:6][C@H:7]3[N:8]([CH3:17])[CH2:9][CH2:10][C@@:11]4([C:4]=2[CH:3]=1)[C@H:16]3[CH2:15][CH2:14][CH2:13][CH2:12]4

Participants

5

Reactant 3

HCID 222AmmoniaHCID 1004Phosphoric AcidHCID 132078072-Methyl-1-[(4-methylphenyl)methyl]-1,2,3,4,5,6,7,8-octahydroisoquinoline

Product 1

HCID 11637442HCID 11637442, compoundYield 27.5%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
135 °C

Procedure

(+)-1-p-methylbenzyl-2-methyl-1,2,3,4,5,6,7,8-octahydroisoquinoline (26.5 g) was added to 85% phosphoric acid (130 ml) and the mixture was heated to 130-140° C. for 72 h. After the reaction was complete, the reaction mixture was poured into ice-water and the solution was made strongly alkaline by the addition of conc. ammonia solution (about 300 ml) and diluted with water (500 ml). The solution was then extracted with ether (500 ml×2). The ether layers were combined and washed with water (200 ml), and dried (K2CO3), filtered and evaporated to yield an oil. The oil was immediately vacuum-distilled to produce a faint yellow oil (10 g; bp 130-136° C./0.3 mm Hg) which was crystallized on standing. Recrystallization from acetone (˜10 ml) provided white prisms ((7.3 g) of (+)-3-methyl-17-methyl-morphinan; MS (ESI+): m/z 256 (M+1). This procedure is similar to the procedure in U.S. Pat. No. 3,786,054, incorporated by reference herein in its entirety.

Workup

  1. extractionThe solution was then extracted with ether (500 ml×2)
  2. washwashed with water (200 ml)
  3. dry with materialdried (K2CO3)
  4. filtrationfiltered
  5. customevaporated
  6. customto yield an oil
  7. distillationThe oil was immediately vacuum-distilled
  8. customto produce a faint yellow oil (10 g; bp 130-136° C./0.3 mm Hg) which
  9. customwas crystallized
  10. customRecrystallization from acetone (˜10 ml)

Sources & evidence

ORD record
ord-327396721c4545a8a5e5fc759d1e825a
Source dataset
uspto-grants-2011_09
Patent number
US08017622B2

Reaction notes

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