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

HRID 1050705Notes

Reaction equation

HRID 1050705 reaction equation
Br[C:2]1[C:10]2[C:6](=[N:7][N:8]([CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])[N:9]=2)[C:5](Br)=[CH:4][CH:3]=1.[CH2:20]([O:24][C:25]1[CH:30]=[CH:29][C:28](B(O)O)=[CH:27][CH:26]=1)[CH:21]([CH3:23])[CH3:22].[C:34](=[O:37])([O-])[O-].[Na+].[Na+].[C:40]1(C)[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1.[CH2:47](O)[CH2:48][CH2:49]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>[CH2:20]([O:24][C:25]1[CH:30]=[CH:29][C:28]([C:2]2[C:10]3[C:6](=[N:7][N:8]([CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])[N:9]=3)[C:5]([C:40]3[CH:41]=[CH:42][C:43]([O:37][CH2:34][CH:48]([CH3:49])[CH3:47])=[CH:44][CH:45]=3)=[CH:4][CH:3]=2)=[CH:27][CH:26]=1)[CH:21]([CH3:23])[CH3:22]

Participants

8

Reactant 5

HCID 2631-ButanolHCID 1140TolueneHCID 10340Sodium CarbonateHCID 162177734-Isobutoxyphenylboronic acidHCID 717214984,7-Dibromo-2-octyl-2H-benzotriazole

Product 1

HCID 866799224,7-bis(4-isobutoxyphenyl)-2-octyl-2H-benzo[d][1,2,3]triazole

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent2×

Conditions

Temperature
105 °C

Procedure

A mixture of Intermediate L (778 mg, 2.0 mmol), 4-isobutoxyphenylboronic acid (970 mg, 5.0 mmol), tetrakis(triphenylphosphine)palladium(0) (500 mg, 0.43 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 105° C. for 16 hours. The reaction mixture was poured into water (200 mL), stirred for 30 minutes and extracted with toluene/ethyl acetate/hexane (2:1:1, 400 mL). The extract was dried over magnesium sulfate, the volatiles were removed under reduced pressure, and the residue was chromatographed (silica gel, hexane/dichloromethane, 1:1). The separated product was crystallized from acetonitrile to give pure 4,7-bis(4-isobutoxyphenyl)-2-octyl-2H-benzo[d][1,2,3]triazole, Compound 45 (1.57 g, 62% yield). 1H NMR (400 MHz, CDCl3): δ 7.99 (d, J=8.8 Hz, 4H, 4-i-BuOC6H4), 7.54 (s, 2H, benzotriazole), 7.04 (d, J=8.8 Hz, 4H, 4-i-BuOC6H4), 4.76 (t, J=7.0 Hz, 2H, octyl), 3.79 (d, J=6.2 Hz, 4H, 4-i-BuOC6H4), 2.13 (m, 4H, octyl), 1.28 (m, 2H, octyl), 1.25 (m, 6H, octyl), 1.04 (d, J=6.6 Hz, 12H, 4-i-BuOC6H4), 0.86 (t, J=6.6 Hz, 3H, octyl). UV-vis spectrum (PVB): λmax=359 nm. Fluorimetry (PVB): λmax=431 nm.

Workup

  1. stirringstirred for 30 minutes
  2. extractionextracted with toluene/ethyl acetate/hexane (2:1:1, 400 mL)
  3. dry with materialThe extract was dried over magnesium sulfate
  4. customthe volatiles were removed under reduced pressure
  5. customthe residue was chromatographed (silica gel, hexane/dichloromethane, 1:1)
  6. customThe separated product was crystallized from acetonitrile

Sources & evidence

ORD record
ord-617e33f6ca77489eb2e5b45ddd7668c6
Source dataset
uspto-grants-2016_07
Patent number
US09382424B2

Reaction notes

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