Water → HCID 59841562, compound

HRID 547959Notes

Reaction equation

HRID 547959 reaction equation
[C:1]([O:5][C:6]([N:8]1[C:22]2[C:23]3[C:10]([CH2:11][C@@H:12]4[C@@H:17]([C:18]=3[CH:19]=[CH:20][CH:21]=2)[CH2:16][C@@H:15]([CH2:24][OH:25])[CH2:14][N:13]4[C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])=[CH:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].O.CC1(C)N([O])C(C)(C)CCC1.C(O)(=[O:47])C.C(O)(=O)C.IC1C=CC=CC=1>ClCCl>[C:1]([O:5][C:6]([N:8]1[C:22]2[C:23]3[C:10]([CH2:11][C@@H:12]4[C@@H:17]([C:18]=3[CH:19]=[CH:20][CH:21]=2)[CH2:16][C@@H:15]([C:24]([OH:47])=[O:25])[CH2:14][N:13]4[C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])=[CH:9]1)=[O:7])([CH3:3])([CH3:4])[CH3:2]

Participants

6

Reactant 4

HCID 962WaterHCID 2724126TempoHCID 12217721Iodo benzene diacetateHCID 59841550HCID 59841550, compound

Product 1

HCID 59841562HCID 59841562, compoundYield 98.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 1,6-di-(tert-butoxycarbonyl)-8β-hydroxymethyl-ergoline (328 g) in dichloromethane (1.97 L) and water (13.5 g) is added TEMPO (22.2 g). The solution is cooled using a ice-bath and iodobenzene diacetate (597 g) is added in portions. The mixture is stirred at room temperature for 12-16 h and the reaction is monitored by TLC. The reaction is quenched with the addition of sodium thiosulfate solution (184 g in 1315 mL of water), and the organic layer is separated. The aqueous is extracted with dichloromethane (656 mL) and the combined dichloromethane layers are washed with water and then evaporated to remove the solvent. The product is crystallized from cold methanol to furnish 1,6-di-(tert-butoxycarbonyl)-ergoline-8β-carboxylic acid (334 g) in 88.5% yield.

Workup

  1. temperatureThe solution is cooled
  2. customThe reaction is quenched with the addition of sodium thiosulfate solution (184 g in 1315 mL of water)
  3. customthe organic layer is separated
  4. extractionThe aqueous is extracted with dichloromethane (656 mL)
  5. washthe combined dichloromethane layers are washed with water
  6. customevaporated
  7. customto remove the solvent
  8. customThe product is crystallized from cold methanol

Sources & evidence

ORD record
ord-c3679bd87c294957b37745745fbf4f4e
Source dataset
uspto-grants-2011_05
Patent number
US07939665B2

Reaction notes

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