Bis(4-bromophenyl)acetylene → 1,2-Bis(4-bromophenyl)-3,6-bis(biphenyl-3-yl)-4,5-diphenylbenzene

HRID 57309Notes

Reaction equation

HRID 57309 reaction equation
[C:1]1([C:39]2[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=2)[CH:6]=[CH:5][CH:4]=[C:3]([C:7]2C(=O)[C:9]([C:26]3[CH:27]=[C:28]([C:32]4[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=4)[CH:29]=[CH:30][CH:31]=3)=[C:10]([C:19]3[CH:24]=[CH:23][C:22](Br)=[CH:21][CH:20]=3)[C:11]=2[C:12]2[CH:17]=[CH:16][C:15](Br)=[CH:14][CH:13]=2)[CH:2]=1.[Br:45][C:46]1[CH:51]=[CH:50][C:49]([C:52]#[C:53][C:54]2[CH:59]=[CH:58][C:57]([Br:60])=[CH:56][CH:55]=2)=[CH:48][CH:47]=1>C1(OC2C=CC=CC=2)C=CC=CC=1.CCCCCC>[Br:45][C:46]1[CH:47]=[CH:48][C:49]([C:52]2[C:7]([C:3]3[CH:2]=[C:1]([C:39]4[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=4)[CH:6]=[CH:5][CH:4]=3)=[C:11]([C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)[C:10]([C:19]3[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=3)=[C:9]([C:26]3[CH:27]=[C:28]([C:32]4[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=4)[CH:29]=[CH:30][CH:31]=3)[C:53]=2[C:54]2[CH:55]=[CH:56][C:57]([Br:60])=[CH:58][CH:59]=2)=[CH:50][CH:51]=1

Participants

5

Reactant 2

HCID 3464242Bis(4-bromophenyl)acetyleneHCID 895341902,5-Di([1,1'-biphenyl]-3-yl)-3,4-bis(4-bromophenyl)cyclopenta-2,4-dienone

Product 1

HCID 895341931,2-Bis(4-bromophenyl)-3,6-bis(biphenyl-3-yl)-4,5-diphenylbenzene

Reagents, catalysts & solvents 2

HCID 7583Diphenyl EtherSolventHCID 8058HexaneSolvent

Procedure

A degassed solution of 300 mg of 2,5-di([1,1′-biphenyl]-3-yl)-3,4-bis(4-bromophenyl)cyclopenta-2,4-dienone (8a, 0.432 mmol) and 77.0 mg of 4,4′-dibromotolane (0.432 mmol) in 3 ml of diphenyl ether was heated to 230° C. in a microwave reactor at power 300 watts and a maximum pressure of 7 bar for 3×12 h. After cooling to room temperature, the reaction solution was diluted with hexane and purified by column chromatography (silica, hexane with 6% ethyl acetate). After purification by means of recycling GPC and drying under high vacuum, 145 mg of monomer 6a were obtained in the form of colorless crystals (40%, 0.172 mmol). Elemental analysis measured: C 76.7; H 3.1% (calculated for C54H36Br2: C, 76.8; H, 4.3%); 1H NMR (700 MHz, d8-THF) δ=7.30-7.25 (m, 4H, CH), 7.23-7.17 (m, 6H, CH), 7.13 (d, J=1.5 Hz, 1H, CH), 7.12-7.11 (m, 1H, CH), 7.11-7.09 (m, 4H, CH), 7.09-7.06 (m, 2H, CH), 6.95 (s, 1H, CH), 6.94 (br s, 2H, CH), 6.93 (s, 1H, CH), 6.91 (t, J=4.1 Hz, 2H, CH), 6.89 (d, J=8.0 Hz, 2H, CH), 6.85 (d, J=7.0 Hz, 4H, CH), 6.83 (d, J=2.0 Hz, 2H, CH), 6.81 (d, J=1.4 Hz, 1H, CH), 6.79 (d, J=8.3 Hz, 2H, CH), 6.78 (s, 1H, CH); 13C NMR (125 MHz, d2-TCE) δ=141.05, 140.74, 140.20, 140.00, 139.44, 139.03, 138.52, 133.03, 132.92, 131.30, 131.15, 130.26, 129.92, 129.85, 128.42, 127.17, 126.87, 126.62, 126.52, 125.20, 124.15, 120.18, 119.51; MS (MALDI-TOF): m/z (%): 845.1 (100) [M+] (calculated for C54H36Br2: 844.1); Rf (hexane with 6% ethyl acetate)=0.40; m.p. (° C.): decomposition at >400° C.

Workup

  1. customfor 3×12 h
  2. custompurified by column chromatography (silica, hexane with 6% ethyl acetate)
  3. customAfter purification by means of recycling GPC
  4. customdrying under high vacuum

Sources & evidence

ORD record
ord-c5363609b7834b56828aeca34c86645d
Source dataset
uspto-grants-2016_09
Patent number
US09434619B2

Reaction notes

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