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

HRID 1050704Notes

Reaction equation

HRID 1050704 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.[CH:16]([O:19][C:20]1[CH:25]=[CH:24][C:23](B(O)O)=[CH:22][CH:21]=1)([CH3:18])[CH3:17].[C:29](=O)([O-])[O-].[Na+].[Na+].[C:35]1(C)[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1.[CH2:42]([OH:46])[CH2:43]CC>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>[CH:16]([O:19][C:20]1[CH:25]=[CH:24][C:23]([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:38]3[CH:37]=[CH:36][C:35]([O:46][CH:42]([CH3:43])[CH3:29])=[CH:40][CH:39]=3)=[CH:4][CH:3]=2)=[CH:22][CH:21]=1)([CH3:18])[CH3:17]

Participants

8

Reactant 5

HCID 2631-ButanolHCID 1140TolueneHCID 10340Sodium CarbonateHCID 36987264-Isopropoxybenzeneboronic acidHCID 866799204,7-Dibromo-2-isobutyl-2H-benzo[d][1,2,3]triazole

Product 1

HCID 866799214,7-bis(4-isopropoxyphenyl)-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 (666 mg, 2.0 mmol), 4-isopropoxyphenylboronic acid (1.00 g, 5.5 mmol), tetrakis(triphenylphosphine)palladium(0) (0.50 g, 0.43 mmol), solution of sodium carbonate (1.06 g, 10 mmol) in water (8 mL), butanol (30 mL), and toluene (20 mL) was vigorously stirred and heated under argon at 100° C. for 20 hours. The reaction mixture was poured into water (300 mL), stirred for 30 minutes and extracted with toluene/ethyl acetate (1:1, 300 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-isopropoxyphenyl)-2-isobutyl-2H-benzo[d][1,2,3]triazole, Compound 43 (655 mg, 74% yield). 1H NMR (400 MHz, CDCl3): δ 8.00 (d, J=8.7 Hz, 4H, 4-i-PrOC6H4), 7.55 (s, 2H, benzotriazole), 7.02 (d, J=8.8 Hz, 4H, 4-i-PrOC6H4), 4.64 (septet, J=6.2 Hz, 2H, 4-i-PrOC6H4), 4.59 (d, J=7.7 Hz, 2H, i-Bu), 2.61 (m, 1H, i-Bu), 1.38 (d, J=6.2 Hz, 12H, 4-i-PrOC6H4), 1.01 (d, J=6.6 Hz, 6H, i-Bu). UV-vis spectrum (PVB): λmax=360 nm. Fluorimetry (PVB): λmax=435 nm.

Workup

  1. stirringstirred for 30 minutes
  2. extractionextracted with toluene/ethyl acetate (1:1, 300 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-4ce6f8bb547949abb51a59ace1f2a139
Source dataset
uspto-grants-2016_07
Patent number
US09382424B2

Reaction notes

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