Sodium Carbonate → HCID 86679905, compound

HRID 1050682Notes

Reaction equation

HRID 1050682 reaction equation
Br[C:2]1[C:10]2[C:6](=[N:7][N:8]([C:11]3[CH:16]=[CH:15][N:14]=[CH:13][CH:12]=3)[N:9]=2)[C:5](Br)=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Na+].[Na+].[C:24]1([N:30]([C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)[C:31]2[CH:36]=[CH:35][C:34](B(O)O)=[CH:33][CH:32]=2)[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.[OH-].[Na+]>ClCCl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O.C1(C)C=CC=CC=1.O1CCOCC1>[C:24]1([N:30]([C:40]2[CH:45]=[CH:44][C:43]([C:2]3[C:10]4[C:6](=[N:7][N:8]([C:11]5[CH:16]=[CH:15][N:14]=[CH:13][CH:12]=5)[N:9]=4)[C:5]([C:43]4[CH:42]=[CH:41][C:40]([N:30]([C:31]5[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=5)[C:24]5[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=5)=[CH:45][CH:44]=4)=[CH:4][CH:3]=3)=[CH:42][CH:41]=2)[C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1

Participants

10

Reactant 4

HCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 121669344-(Diphenylamino)phenylboronic Acid (contains varying amounts of Anhydride)HCID 866799014,7-dibromo-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole

Product 1

HCID 86679905HCID 86679905, compound

Reagents, catalysts & solvents 5

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent2×HCID 1140TolueneSolventHCID 6344DichloromethaneSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

A mixture of Intermediate A (purity 90%, 1.95 g, 5 mmol), sodium carbonate (2.69 g, 25 mmol), 4-(diphenylamino)phenylboronic acid (3.47 g, 12 mmol), tetrakis(triphenylphosphine)palladium (0) (0.58 g, 0.5 mmol), water (20 mL), dioxane (80 mL), and toluene (10 mL) was heated under argon at 110° C. for 48 hours. The reaction mixture was poured into water (200 mL), diluted with dichloromethane (200 mL), treated with 2N NaOH (50 mL), stirred for 1 hour, and the dichloromethane layer was separated. The aqueous phase was washed with dichloromethane (200 mL). Both dichloromethane solutions were combined, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography and recrystallization from ethyl acetate/ethanol (1:1) to give 4,7-bis(4-(N,N-diphenylamino)phenyl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazole (Example 1), orange crystals, 1.71 g (50%). 1H NMR (400 MHz, CDCl3): δ 8.80 (m, 2H, pyridine), 8.34 (m, 2H, pyridine), 8.06 (d, J=8.7 Hz, 4H, p-phenylene), 7.67 (s, 2H, benzotriazole), 7.31 (m, 8H, Ph), 7.21 (m, 12H, p-phenylene and Ph), 7.08 (tt, J=7.3 and 2.2 Hz, 4H, Ph). UV-vis spectrum (dichloromethane): λmax=451 nm. Fluorimetry (dichloromethane): λmax=593 nm.

Workup

  1. customthe dichloromethane layer was separated
  2. washThe aqueous phase was washed with dichloromethane (200 mL)
  3. dry with materialdried over anhydrous sodium sulfate
  4. customthe solvent was removed under reduced pressure
  5. customThe crude product was purified by column chromatography and recrystallization from ethyl acetate/ethanol (1:1)

Sources & evidence

ORD record
ord-780ff2012c8442b7bc00fa0c433c8a48
Source dataset
uspto-grants-2016_07
Patent number
US09382424B2

Reaction notes

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