1-Butanol → 4,7-Bis(4-isobutoxyphenyl)-2-(4-aminophenyl)-2H-benzo[d][1,2,3]triazole

HRID 1050700Notes

Reaction equation

HRID 1050700 reaction equation
Br[C:2]1[C:10]2[C:6](=[N:7][N:8]([C:11]3[CH:16]=[CH:15][C:14]([N+:17]([O-])=O)=[CH:13][CH:12]=3)[N:9]=2)[C:5](Br)=[CH:4][CH:3]=1.[CH2:21]([O:25][C:26]1[CH:31]=[CH:30][C:29](B(O)O)=[CH:28][CH:27]=1)[CH:22]([CH3:24])[CH3:23].[C:35](=[O:38])([O-])[O-].[Na+].[Na+].[CH2:41](O)[CH2:42][CH2:43]C.[C:46]1(C)[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1>O.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>[CH2:21]([O:25][C:26]1[CH:31]=[CH:30][C:29]([C:2]2[C:10]3[C:6](=[N:7][N:8]([C:11]4[CH:16]=[CH:15][C:14]([NH2:17])=[CH:13][CH:12]=4)[N:9]=3)[C:5]([C:46]3[CH:47]=[CH:48][C:49]([O:38][CH2:35][CH:42]([CH3:43])[CH3:41])=[CH:50][CH:51]=3)=[CH:4][CH:3]=2)=[CH:28][CH:27]=1)[CH:22]([CH3:24])[CH3:23]

Participants

8

Reactant 5

HCID 2631-ButanolHCID 1140TolueneHCID 10340Sodium CarbonateHCID 162177734-Isobutoxyphenylboronic acidHCID 866799034,7-dibromo-2-(4-nitrophenyl)-2H-benzo[d][1,2,3]triazole

Product 1

HCID 866799184,7-Bis(4-isobutoxyphenyl)-2-(4-aminophenyl)-2H-benzo[d][1,2,3]triazoleYield 75%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent2×

Conditions

Temperature
100 °C

Procedure

A mixture of Intermediate H (3.98 g, 10.0 mmol), 4-isobutoxyphenylboronic acid (5.00 g, 25.7 mmol), sodium carbonate (5.30 g, 50 mmol) in water (40 mL), tetrakis(triphenylphosphine)palladium(0) (2.00 g), n-butanol (60 mL), and toluene (30 mL) was stirred under argon and heated at 100° C. for 4 hours. The reaction mixture was poured into water (200 mL), stirred for 30 minutes and extracted with toluene (500 mL). The extract was washed with water (200 mL), concentrated to a volume of 100 mL and diluted with dichloromethane (200 mL) and methanol (200 mL). The obtained solution was hydrogenated for 20 minutes at 50 psi over 10% Pd/C (2 g), filtered through a layer of Celite, and the solvent was removed under reduced pressure. The residue was chromatographed (silica gel, hexane/dichloromethane/ethyl acetate, 35:50:5) to give 4,7-Bis(4-isobutoxyphenyl)-2-(4-aminophenyl)-2H-benzo[d][1,2,3]triazole (Intermediate I) (3.80 g, 75%). 1H NMR (400 MHz, CDCl3): δ 8.22 (d, J=8.4 Hz, 2H, 4-aminophenyl), 8.09 (d, J=8.7 Hz, 4H, 4-i-BuOC6H4), 7.57 (s, 2H, benzotriazole), 7.06 (d, J=8.7 Hz, 4H, 4-i-BuOC6H4), 6.79 (d, J=8.5 Hz, 2H, 4-aminophenyl), 3.90 (bs, 2H, NH2), 3.81 (d, J=6.6 Hz, 4H, i-BuO), 2.14 (m, 2H, i-BuO), 1.06 (d, J=7.0 Hz, 12H, i-BuO).

Workup

  1. stirringstirred for 30 minutes
  2. extractionextracted with toluene (500 mL)
  3. washThe extract was washed with water (200 mL)
  4. concentrationconcentrated to a volume of 100 mL
  5. additiondiluted with dichloromethane (200 mL) and methanol (200 mL)
  6. filtrationfiltered through a layer of Celite
  7. customthe solvent was removed under reduced pressure
  8. customThe residue was chromatographed (silica gel, hexane/dichloromethane/ethyl acetate, 35:50:5)

Sources & evidence

ORD record
ord-00a77bd5d4d345229ec260a6dce96144
Source dataset
uspto-grants-2016_07
Patent number
US09382424B2

Reaction notes

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