Nitrogen → 1-(Tetrahydro-2H-pyran-2-yl)-5-((trimethylsilyl)ethynyl)-1H-benzo[d][1,2,3]triazole

HRID 1057103Notes

Reaction equation

HRID 1057103 reaction equation
N#N.Br[C:4]1[CH:18]=[CH:17][C:7]2[N:8]([CH:11]3[CH2:16][CH2:15][CH2:14][CH2:13][O:12]3)[N:9]=[N:10][C:6]=2[CH:5]=1.[CH3:19][Si:20]([C:23]#[CH:24])([CH3:22])[CH3:21]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I.C(N(CC)CC)C>[O:12]1[CH2:13][CH2:14][CH2:15][CH2:16][CH:11]1[N:8]1[C:7]2[CH:17]=[CH:18][C:4]([C:24]#[C:23][Si:20]([CH3:22])([CH3:21])[CH3:19])=[CH:5][C:6]=2[N:10]=[N:9]1

Participants

7

Reactant 3

HCID 947NitrogenHCID 66111TrimethylsilylacetyleneHCID 668022905-Bromo-1-(tetrahydro-2H-pyran-2-yl)-1H-benzo[d][1,2,3]triazole

Product 1

HCID 668021201-(Tetrahydro-2H-pyran-2-yl)-5-((trimethylsilyl)ethynyl)-1H-benzo[d][1,2,3]triazoleYield 97%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
80 °C

Procedure

A 100-mL round-bottom flask equipped with a magnetic stir bar, a rubber septum and N2 inlet was charged with 5-bromo-1-(tetrahydro-2H-pyran-2-yl)-1H-benzo[d][1,2,3]triazole (3.5 g, 12.4 mmol), Pd(Ph3P)2Cl2 (0.87 g, 1.24 mmol), CuI (0.47 g, 0.48 mmol), and triethylamine (62 mL). This mixture was degassed with three vacuum/N2 cycles. Trimethylsilylacetylene (3.5 mL, 24.8 mmol) was added, and the mixture was heated at 80° C. for 4 h. The reaction was monitored by LCMS. Upon completion, the reaction mixture was cooled down to room temperature, filtered through Celite, washed with ethyl acetate (100 mL), and concentrated. The crude product was purified on a silica gel column eluting with 5% ethyl acetate in hexanes to afford the title compound as a pale yellow oil (3.6 g). LCMS: 216 [(M-THP+H)+H]+.

Workup

  1. customA 100-mL round-bottom flask equipped with a magnetic stir bar
  2. customThis mixture was degassed with three vacuum/N2 cycles
  3. temperatureUpon completion, the reaction mixture was cooled down to room temperature
  4. filtrationfiltered through Celite
  5. washwashed with ethyl acetate (100 mL)
  6. concentrationconcentrated
  7. customThe crude product was purified on a silica gel column
  8. washeluting with 5% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-8b3b25b1cc634ace850650a09c6bb8fe
Source dataset
uspto-grants-2016_07
Patent number
US09399646B2

Reaction notes

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