Benzo(B)Thiophene-2-Boronic Acid → HCID 89456132, compound

HRID 1050696Notes

Reaction equation

HRID 1050696 reaction equation
Br[C:2]1[C:7]2=[N:8][N:9]([C:11]3[CH:16]=[CH:15][N:14]=[CH:13][CH:12]=3)[N:10]=[C:6]2[C:5]([C:17]2[CH:29]=[CH:28][C:27]3[C:26]4[C:21](=[CH:22][C:23]([C:30]5[C:38]6[C:34](=[N:35][N:36]([C:39]7[CH:44]=[CH:43][N:42]=[CH:41][CH:40]=7)[N:37]=6)[C:33](Br)=[CH:32][CH:31]=5)=[CH:24][CH:25]=4)[C:20]([CH2:52][CH2:53][CH2:54][CH2:55][CH2:56][CH3:57])([CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH3:51])[C:19]=3[CH:18]=2)=[CH:4][CH:3]=1.[S:58]1[C:62](B(O)O)=[CH:61][C:60]2[CH:66]=[CH:67][CH:68]=[CH:69][C:59]1=2.C(=O)([O-])[O-].[Na+].[Na+].[OH-].[Na+]>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.C1(C)C=CC=CC=1.C(O)CCC>[S:58]1[C:62]([C:33]2[C:34]3=[N:35][N:36]([C:39]4[CH:44]=[CH:43][N:42]=[CH:41][CH:40]=4)[N:37]=[C:38]3[C:30]([C:23]3[CH:24]=[CH:25][C:26]4[C:27]5[C:19](=[CH:18][C:17]([C:5]6[C:6]7[C:7](=[N:8][N:9]([C:11]8[CH:12]=[CH:13][N:14]=[CH:15][CH:16]=8)[N:10]=7)[C:2]([C:62]7[S:58][C:59]8[CH:69]=[CH:68][CH:67]=[CH:66][C:60]=8[CH:61]=7)=[CH:3][CH:4]=6)=[CH:29][CH:28]=5)[C:20]([CH2:52][CH2:53][CH2:54][CH2:55][CH2:56][CH3:57])([CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH3:51])[C:21]=4[CH:22]=3)=[CH:31][CH:32]=2)=[CH:61][C:60]2[CH:66]=[CH:67][CH:68]=[CH:69][C:59]1=2

Participants

9

Reactant 4

HCID 2359Benzo(B)Thiophene-2-Boronic AcidHCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 89456211HCID 89456211, compound

Product 1

HCID 89456132HCID 89456132, compound

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 2631-ButanolSolventHCID 962WaterSolvent2×HCID 1140TolueneSolvent

Procedure

A mixture of Intermediate E (90%, 488 mg, 0.50 mmol),), benzo[b]thiophen-2-ylboronic acid (356 mg, 2.00 mmol), sodium carbonate (530 mg, 5 mmol) in water (4 mL), tetrakis(triphenylphosphine)palladium (0) (240 mg, 0.20 mmol), n-butanol (15 mL), and toluene (15 mL) was heated under argon at 110° C. for 24 hours. The reaction mixture was poured into water (200 mL), treated with 5N NaOH (25 mL), stirred for 1 hour, and extracted with dichloromethane (3×200 mL). The volatiles were removed under reduced pressure, and the residue was chromatographed (silica gel, dichloromethane/tetrahydrofuran 9:1). The obtained product was washed with ethyl acetate and dried in a vacuum oven to give 2,7-bis(7-(benzo[b]thiophen-2-yl)-2-(pyridin-4-yl)-2H-benzo[d][1,2,3]triazol-4-yl)-9,9-dihexyl-9H-fluorene (Example 24), orange crystals, 430 mg (87%). 1H NMR (400 MHz, CDCl3): δ 8.89 (m, 4H, pyridine), 8.56 (s, 2H, benzothiophene), 8.44 (m, 4H, pyridine), 8.21 (s, 2H, fluorene), 8.14 (d, 2H, J=8.8 Hz, fluorene), 7.88-7.98 (m, 8H, benzothiophene, fluorene and benzotriazole), 7.79 (d, J=7.3 Hz, 2H, benzotriazole), 7.41 (m, 4H, benzothiophene), 2.20 (m, 4H, hexyl), 1.20 (m, 4H, hexyl), 1.14 (m, 8H, hexyl), 0.95 (m, 4H, hexyl), 0.74 (t, J=6.5 Hz, 6H, hexyl). UV-vis spectrum (dichloromethane): λmax=440 nm. Fluorimetry (dichloromethane): λmax=515 nm.

Workup

  1. extractionextracted with dichloromethane (3×200 mL)
  2. customThe volatiles were removed under reduced pressure
  3. customthe residue was chromatographed (silica gel, dichloromethane/tetrahydrofuran 9:1)
  4. washThe obtained product was washed with ethyl acetate
  5. customdried in a vacuum oven

Sources & evidence

ORD record
ord-19cc4ed8b6d04028b328276db0e77469
Source dataset
uspto-grants-2016_07
Patent number
US09382424B2

Reaction notes

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