1H-1,2,4-Triazole → HCID 24954098, compound

HRID 1801599Notes

Reaction equation

HRID 1801599 reaction equation
CN[C@@H]1CCCC[C@H]1NC.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[NH:19]1[CH:23]=[N:22][CH:21]=[N:20]1.[Cl:24][C:25]1[CH:40]=[CH:39][C:28]([CH2:29][NH:30][C@@H:31]([C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[CH3:32])=[CH:27][C:26]=1I>[Cu]I.CN(C=O)C>[Cl:24][C:25]1[CH:26]=[CH:27][C:28]([CH2:29][NH:30][C@@H:31]([C:33]2[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=2)[CH3:32])=[CH:39][C:40]=1[N:19]1[CH:23]=[N:22][CH:21]=[N:20]1

Participants

7

Reactant 4

HCID 92571H-1,2,4-TriazoleHCID 62657Potassium Phosphate, TribasicHCID 2733821trans-N,N'-dimethyl-1,2-cyclohexanediamineHCID 59803210HCID 59803210, compound

Product 1

HCID 24954098HCID 24954098, compoundYield 10.4%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
110 °C

Procedure

To a mixture of copper(I) iodide (0.022 g, 0.12 mmol), trans-N1,N2-dimethylcyclohexane-1,2-diamine (0.027 g, 0.19 mmol), potassium phosphate (0.420 g, 2.0 mmol), 1H-1,2,4-triazole (0.078 g, 1.1 mmol), and (R)—N-(4-chloro-3-iodobenzyl)-1-phenylethanamine 77 (0.352 g, 0.95 mmol) was added DMF (1 mL). The reaction mixture was degassed by a purge/nitrogen cycle (3×) and heated in a sealed tube to 110° C. After 24 h, the reaction mixture was diluted with EtOAc and the organic phase was washed with saturated NH4Cl/NH4OH (10:1) (1×), brine (1×), dried over MgSO4, filtered, and concentrated in vacuo. Purification by flash column chromatography on silica gel (eluted with 10% to 100% EtOAc in hexanes) gave (1R)—N-(4-chloro-3-(1H-1,2,4-triazol-1-yl)benzyl)-1-phenylethanamine 78 (0.031 g, 10% yield) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ 1.38 (d, J=6.5 Hz, 3H), 3.66 (s, 2H), 3.80 (q, J=6.5 Hz, 1H), 7.24-7.36 (m, 7H), 7.48 (d, J=8.2 Hz, 1H), 7.54 (s, 1H), 8.14 (s, 1H), 8.52 (s, 1H). Mass spectrum: calculated for C17H17ClN4 312.1. found 313.2 (M++1).

Workup

  1. customThe reaction mixture was degassed by
  2. customa purge/nitrogen cycle (3×)
  3. additionthe reaction mixture was diluted with EtOAc
  4. washthe organic phase was washed with saturated NH4Cl/NH4OH (10:1) (1×), brine (1×)
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customPurification by flash column chromatography on silica gel (eluted with 10% to 100% EtOAc in hexanes)

Sources & evidence

ORD record
ord-384fe80fe3534c83be2d0d15a543112e
Source dataset
uspto-grants-2013_01
Patent number
US08349831B2

Reaction notes

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