HCID 131711077, compound → HCID 252593, compound

HRID 2083565Notes

Reaction equation

HRID 2083565 reaction equation
[CH3:1][CH:2]([C:4]1([NH:26][C:27]([CH:29]2[CH:44]=[C:43]3[CH:32]([CH2:33][C:34]4[C:42]5[C:37](=[CH:38][CH:39]=[CH:40][C:41]=53)[NH:36][CH:35]=4)[N:31]([CH3:45])[CH2:30]2)=[O:28])[O:17][C:16]2([OH:18])[N:7]([CH:8]([CH2:19][C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[C:9]([N:11]3[CH:15]2[CH2:14][CH2:13][CH2:12]3)=[O:10])[C:5]1=[O:6])[CH3:3].[CH3:46][CH:47]([C:49]1([NH:71][C:72]([CH:74]2[CH:89]=[C:88]3[CH:77]([CH2:78][C:79]4[C:87]5[C:82](=[CH:83][CH:84]=[CH:85][C:86]=53)[NH:81][CH:80]=4)[N:76]([CH3:90])[CH2:75]2)=[O:73])[O:62][C:61]2([OH:63])[N:52]([CH:53]([CH2:64][C:65]3[CH:70]=[CH:69][CH:68]=[CH:67][CH:66]=3)[C:54]([N:56]3[CH:60]2[CH2:59][CH2:58][CH2:57]3)=[O:55])[C:50]1=[O:51])[CH3:48].C1C=CC=CC=1.[H][H]>O1CCOCC1.[Ni]>[CH3:3][CH:2]([C:4]1([NH:26][C:27]([CH:29]2[CH:44]=[C:43]3[CH:32]([CH2:33][C:34]4[C:42]5[C:37](=[CH:38][CH:39]=[CH:40][C:41]=53)[NH:36][CH:35]=4)[N:31]([CH3:45])[CH2:30]2)=[O:28])[O:17][C:16]2([OH:18])[N:7]([CH:8]([CH2:19][C:20]3[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=3)[C:9]([N:11]3[CH:15]2[CH2:14][CH2:13][CH2:12]3)=[O:10])[C:5]1=[O:6])[CH3:1].[CH3:48][CH:47]([C:49]1([NH:71][C:72]([CH:74]2[CH:89]=[C:88]3[CH:77]([CH2:78][C:79]4[C:87]5[C:82](=[CH:83][CH:84]=[CH:85][C:86]=53)[NH:81][CH:80]=4)[N:76]([CH3:90])[CH2:75]2)=[O:73])[O:62][C:61]2([OH:63])[N:52]([CH:53]([CH2:64][C:65]3[CH:66]=[CH:67][CH:68]=[CH:69][CH:70]=3)[C:54]([N:56]3[CH:60]2[CH2:59][CH2:58][CH2:57]3)=[O:55])[C:50]1=[O:51])[CH3:46]

Participants

5

Reactant 2

HCID 131711077HCID 131711077, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 252593HCID 252593, compound

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 312751,4-DioxaneSolvent

Procedure

The ergotoxine-benzene adduct formed in accordance with Example 7 in an amount of 50.0 g was hydrogenated in 0.7 liter of dioxane at 60° C at a hydrogen pressure of 50 atmospheres above atmospheric in a shaking or stirring autoclave provided with heating means in the presence of Raney nickel within a time of 2 hours. The solution of the formed 9,10-dihydroergotoxine was filtered off the catalyst and concentrated by evaporation to dryness in a vacuum. The hydrogenated base was then caused to crystallize out in ethylacetate at 4° C. The crystallizate was removed by suction and dried at 60° C. There were obtained 47.5 g (equal to 90% of the theoretical) tlc-pure white crystalline product in the form of the ergotoxine base with a degree of purity of 90%. The specific rotation was (α)D20 = -45.6° (c = 2 in pyridine).

Workup

  1. filtrationThe solution of the formed 9,10-dihydroergotoxine was filtered off the catalyst
  2. concentrationconcentrated by evaporation to dryness in a vacuum
  3. customto crystallize out in ethylacetate at 4° C
  4. customThe crystallizate was removed by suction
  5. customdried at 60° C

Sources & evidence

ORD record
ord-d0185f06abd54b3aa7d59dce202d96df
Source dataset
uspto-grants-1978_04
Patent number
US04086141

Reaction notes

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