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

HRID 1050703Notes

Reaction equation

HRID 1050703 reaction equation
Br[C:2]1[C:10]2[C:6](=[N:7][N:8]([CH2:11][CH:12]([CH3:14])[CH3:13])[N:9]=2)[C:5](Br)=[CH:4][CH:3]=1.[CH2:16]([O:20][C:21]1[CH:26]=[CH:25][C:24](B(O)O)=[CH:23][CH:22]=1)[CH:17]([CH3:19])[CH3:18].[C:30](=[O:33])([O-])[O-].[Na+].[Na+].[C:36]1(C)[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1.[CH2:43](O)[CH2:44][CH2:45]C>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>[CH2:16]([O:20][C:21]1[CH:26]=[CH:25][C:24]([C:2]2[C:10]3[C:6](=[N:7][N:8]([CH2:11][CH:12]([CH3:14])[CH3:13])[N:9]=3)[C:5]([C:36]3[CH:37]=[CH:38][C:39]([O:33][CH2:30][CH:44]([CH3:45])[CH3:43])=[CH:40][CH:41]=3)=[CH:4][CH:3]=2)=[CH:23][CH:22]=1)[CH:17]([CH3:19])[CH3:18]

Participants

8

Reactant 5

HCID 2631-ButanolHCID 1140TolueneHCID 10340Sodium CarbonateHCID 162177734-Isobutoxyphenylboronic acidHCID 866799204,7-Dibromo-2-isobutyl-2H-benzo[d][1,2,3]triazole

Product 1

HCID 866799194,7-bis(4-isobutoxyphenyl)-2-isobutyl-2H-benzo[d][1,2,3]triazole

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent2×

Conditions

Temperature
100 °C

Procedure

A mixture of Intermediate K (1.32 g, 4.0 mmol), 4-isobutoxyphenylboronic acid (1.94 g, 10.0 mmol), tetrakis(triphenylphosphine)palladium(0) (1.00 g, 0.86 mmol), solution of sodium carbonate (2.12 g, 20 mmol) in water (15 mL), butanol (50 mL), and toluene (30 mL) was vigorously stirred and heated under argon at 100° C. for 16 hours. The reaction mixture was poured into water (300 mL), stirred for 30 minutes and extracted with toluene/ethyl acetate/hexane (5:3:2, 500 mL). The volatiles were removed under reduced pressure, and the residue was chromatographed (silica gel, hexane/dichloromethane, 1:1). The separated product was recrystallized from ethanol to give pure 4,7-bis(4-isobutoxyphenyl)-2-isobutyl-2H-benzo[d][1,2,3]triazole, Compound 42 (1.57 g, 83% yield). 1H NMR (400 MHz, CDCl3): δ 7.99 (d, J=8.7 Hz, 4H, 4-i-BuOC6H4), 7.55 (s, 2H, benzotriazole), 7.04 (d, J=8.8 Hz, 4H, 4-i-BuOC6H4), 4.58 (d, J=7.3 Hz, 2H, i-Bu), 3.79 (d, J=6.6 Hz, 4H, 4-i-BuOC6H4), 2.59 (m, 1H, i-Bu), 2.13 (m, 2H, 4-i-BuOC6H4), 1.04 (d, J=6.6 Hz, 12H, 4-i-BuOC6H4), 1.00 (d, J=6.6 Hz, 6H, i-Bu). UV-vis spectrum (PVB): λmax=359 nm. Fluorimetry (PVB): λmax=434 nm.

Workup

  1. stirringstirred for 30 minutes
  2. extractionextracted with toluene/ethyl acetate/hexane (5:3:2, 500 mL)
  3. customThe volatiles were removed under reduced pressure
  4. customthe residue was chromatographed (silica gel, hexane/dichloromethane, 1:1)
  5. customThe separated product was recrystallized from ethanol

Sources & evidence

ORD record
ord-512fe2700cd9425fbc628b0747544a2d
Source dataset
uspto-grants-2016_07
Patent number
US09382424B2

Reaction notes

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