Ammonia → HCID 86743463, compound

HRID 2352071Notes

Reaction equation

HRID 2352071 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[CH2:7]([N:9]([CH2:33][CH3:34])[C:10]([NH:12][C@H:13]1[CH2:27][C@H:26]2[C@@H:16]([CH2:17][C:18]3[C:28]4[C:21](=[CH:22][CH:23]=[CH:24][C:25]2=4)[N:20]([CH3:29])[C:19]=3[CH:30]=[O:31])[N:15]([CH3:32])[CH2:14]1)=[O:11])[CH3:8].Cl.C(O)(=O)C(C(C(O)=O)O)O.N>C(OCC)(=O)C.O1CCCC1>[CH2:33]([N:9]([CH2:7][CH3:8])[C:10]([NH:12][C@H:13]1[CH2:27][C@H:26]2[C@@H:16]([CH2:17][C:18]3[C:28]4[C:21](=[CH:22][CH:23]=[CH:24][C:25]2=4)[N:20]([CH3:29])[C:19]=3[CH2:30][OH:31])[N:15]([CH3:32])[CH2:14]1)=[O:11])[CH3:34]

Participants

8

Reactant 5

HCID 222AmmoniaHCID 313Hydrochloric AcidHCID 8752,3-Dihydroxybutanedioic AcidHCID 21226445Aluminium lithium hydrideHCID 86743464HCID 86743464, compound

Product 1

HCID 86743463HCID 86743463, compoundYield 47%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

Under argon, 320 mg (8 mmol) of lithium aluminum hydride is suspended in 20 ml of absolute, freshly distilled tetrahydrofuran. At room temperature, a solution of 1.53 g (4 mmol) of 1,1-diethyl-3(1,6-dimethyl-2-formyl-8α-ergolinyl)urea in 40 ml of freshly distilled, absolute tetrahydrofuran is added dropwise. Subsequently the mixture is stirred for 1 1/4 hours at room temperature. The batch is then cooled in an ice bath and combined with 20 ml of 1N hydrochloric acid. To this is added 20 ml of 2N tartaric acid and the batch is layered over with ethyl acetate. For neutralizing, 80 ml of 2N ammonia solution is added dropwise. The ethyl acetate phase is separated and the aqueous phase additionally extracted with ethyl acetate. The combined ethyl acetate phases are dried over sodium sulfate. The concentrated crude product is chromatographed under pressure on silica gel with methylene chloride/methanol 95:5. The crude product (1.0 g) is crystallized from ethyl acetate, thus obtaining 0.72 g of 1,1-diethyl-3-(1,6-dimethyl-2-hydroxymethyl-8α-ergolinyl)urea (47% yield).

Workup

  1. temperatureThe batch is then cooled in an ice bath
  2. customThe ethyl acetate phase is separated
  3. extractionthe aqueous phase additionally extracted with ethyl acetate
  4. dry with materialThe combined ethyl acetate phases are dried over sodium sulfate
  5. concentrationThe concentrated crude product
  6. customis chromatographed under pressure on silica gel with methylene chloride/methanol 95:5
  7. customThe crude product (1.0 g) is crystallized from ethyl acetate

Sources & evidence

ORD record
ord-57a0941464a14c698756470bf24e9b1a
Source dataset
uspto-grants-1989_10
Patent number
US04874768

Reaction notes

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