Phenylacetylene → Ammonia

HRID 2353198Notes

Reaction equation

HRID 2353198 reaction equation
Br[C:2]1[N:7]=[N:6][C:5]([N:8]2[CH2:13][C@@H:12]3[CH2:14][C@H:9]2[CH2:10][N:11]3[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])=[CH:4][CH:3]=1.[C:22]1([C:28]#[CH:29])[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.C(N(C(C)C)CC)(C)C.[OH-].[Na+]>[Cu]I.O1CCOCC1>[NH3:6].[C:18]([O:17][C:15]([N:11]1[CH2:10][C@@H:9]2[CH2:14][C@H:12]1[CH2:13][N:8]2[C:5]1[N:6]=[N:7][C:2]([C:29]#[C:28][C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=[CH:3][CH:4]=1)=[O:16])([CH3:21])([CH3:20])[CH3:19]

Participants

8

Reactant 4

HCID 10821PhenylacetyleneHCID 14798Sodium HydroxideHCID 81531DiisopropylethylamineHCID 86598713HCID 86598713, compound

Product 2

HCID 222AmmoniaHCID 68444255HCID 68444255, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 2-[6-bromo-3-pyridazinyl]-(1S,4S)-5-tert-butoxycarbonyl-2,5-diazabicyclo-[2.2.1]-heptane (2.0 g; 5.6 mmol), phenylacetylene (2.4 ml; 22.6 mmol), palladacycle (105 mg; 0.11 mmol), CuI (106 mg; 0.56 mmol), diisopropylethylamine (0.97 ml; 5.6 mmol) and dioxane (20 ml) was stirred at 100° C. for 40 hours. Aqueous sodium hydroxide (50 ml; 1 M) was added. The mixture was extracted with dichloromethane (3×50 ml). Chromatography on silica gel with dichloromethane, methanol and conc. ammonia (89:10:1) gave the title compound as free base. Yield 1.0 g (48%).

Workup

  1. extractionThe mixture was extracted with dichloromethane (3×50 ml)

Sources & evidence

ORD record
ord-f6a9fba2f7dc4711a9023cdad72f3859
Source dataset
uspto-grants-2010_07
Patent number
US07750011B2

Reaction notes

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