HCID 68649267, compound → HCID 68649353, compound

HRID 570901Notes

Reaction equation

HRID 570901 reaction equation
[N:1]1[CH:6]=[CH:5][C:4]([C:7]2[C:12]([C:13]3[CH:25]=[CH:24][C:23]4[C:22]5[C:17](=[CH:18][C:19](I)=[CH:20][CH:21]=5)[C:16]([CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH3:42])([CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])[C:15]=4[CH:14]=3)=[CH:11][CH:10]=[CH:9][CH:8]=2)=[CH:3][CH:2]=1>C1(C)C=CC=CC=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>[N:1]1[CH:6]=[CH:5][C:4]([C:7]2[C:12]([C:13]3[CH:25]=[CH:24][C:23]4[C:22]5[C:17](=[CH:18][C:19]([C:18]6[C:17]7[C:16]([CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH3:40])([CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32])[C:15]8[C:23](=[CH:24][CH:25]=[CH:13][CH:14]=8)[C:22]=7[CH:21]=[CH:20][CH:19]=6)=[CH:20][CH:21]=5)[C:16]([CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH3:42])([CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])[C:15]=4[CH:14]=3)=[CH:11][CH:10]=[CH:9][CH:8]=2)=[CH:3][CH:2]=1

Participants

5

Reactant 1

HCID 68649267HCID 68649267, compound

Product 1

HCID 68649353HCID 68649353, compound

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

To a solution of 400 mg (0.60 mmol) of 2-(6-p-pyridyl-phenyl)-7-iodo-9,9-dioctylfluorene, 362 mg (0.60 mmol) of 2-(4,4,5,5 tetramethyl-1,3,2-dioxaborolane)-9,9-dihexylfluorene in 10 mL of toluene was added: 4 mg (0.004 mmol) Pd(PPh3)4 and 2.5 ml of an 20% (3.1 mmol) Et4NOH solution in water. This two-phase reaction mixture was stirred for 48 h at 110° C. after which it was extracted using dichloromethane/water. The organic layer was dried on MgSO4 and the solvents were removed under reduced pressure. The crude product was purified using flash chromatography. Yield 450 mg (86%). 1H NMR (400 MHz, CDCl3): δ=8.74 (d, 3J=4.9 Hz, 1H; CH—N), 8.13 (d, 3J=4.6 Hz, 2H; CH—C—C(CH)—N), 7.84-7.77 (mp, 6H, ArH), 7.74 (d, 3J=6.0 Hz, 2H, CH—CH—CH—N), 7.69-7.63 (mp, 6H; ArH), 7.39-7.30 (mp, 3H; ArH), 7.27-7.24 (mp, 1H (obscured by CDCl3 peak; ArH), 2.11-2.02 (mp, 8H, C—CH2), 1.18-1.09 (mp, 32H, CH2), 0.81-0.74 (mp, 20H, CH2—CH3). 13C{1H} NMR (500 MHz, CDCl3): δ=157.1 (CN), 151.8, 151.4, 151.0 (C—C—CH2), 149.8 (CH—N), 142.2, 140.8, 140.6, 140.42; 140.39, 140.3, 139.9, 139.3, 138.1 (ArC), 136.8 (CH—CH—CH—N), 127.5, 127.3, 126.9, 126.8, 126.1, 126.0, 122.1, 122.0, 121.44, 121.38, 120.4, 120.0, 119.8, 119.7 (CH), 55.3, 55.1 (C—CH2), 40.4 (C—CH2), 31.7, 31.5, 30.0, 29.7, 29.18, 29.16 (CH2), 23.8, 23.7 (C—CH2—CH2), 22.6, 22.5 (CH3—CH2), 14.03, 13.99 (CH3). Exact Mass (IE): 875.6367 [M]+(calcd 875.6369) fractions m/z: 762.3 (m; [M-(C8H17)]+, 650.4 (m; [M-(C8H17)2]+. C65H81N: calcd. C, 89.09; H, 9.32; N, 1.60. found: C, 88.60; H, 9.25; N, 1.52.

Workup

  1. customThis two-phase reaction mixture
  2. extractionwas extracted
  3. customThe organic layer was dried on MgSO4
  4. customthe solvents were removed under reduced pressure
  5. customThe crude product was purified

Sources & evidence

ORD record
ord-a796c68ee04a4705895ec6dbd41e6977
Source dataset
uspto-grants-2015_05
Patent number
US09023978B2

Reaction notes

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