Diphenylamine → 9,9-Didecyl-7-iodo-N,N-diphenyl-9H-fluoren-2-amine

HRID 1816866Notes

Reaction equation

HRID 1816866 reaction equation
[CH2:1]([C:11]1([CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH3:35])[C:23]2[CH:22]=[C:21]([I:24])[CH:20]=[CH:19][C:18]=2C2C1=CC(I)=CC=2)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH3:10].[C:36]1([NH:42][C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1>>[CH2:26]([C:11]1([CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH3:10])[C:45]2[CH:44]=[C:43]([N:42]([C:18]3[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=3)[C:36]3[CH:37]=[CH:38][CH:39]=[CH:40][CH:41]=3)[CH:48]=[CH:47][C:46]=2[C:18]2[C:23]1=[CH:22][C:21]([I:24])=[CH:20][CH:19]=2)[CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH3:35]

Participants

3

Reactant 2

HCID 11487DiphenylamineHCID 3849039HCID 3849039, compound

Product 1

HCID 222425489,9-Didecyl-7-iodo-N,N-diphenyl-9H-fluoren-2-amine

Procedure

9,9-Didecyl-7-iodofluoren-2-yl)diphenylamine (15) (0.49 g, 0.66 mmol) was subjected to similar Ullmann condensation reaction with 9,9-didecyl-2,7-bis(phenylamino)fluorene (0.17 g, 0.27 mmol) to yield the desired product. (9,9-Didecyl-7-iodofluoren-2-yl)diphenylamine (15) was prepared by reaction of 9,9-didecyl-2,7-diiodofluorene (reported in Example 7) with one equivalent of diphenylamine. TLC analysis (60:40 hexanes/CH2Cl2) indicated condensation was complete after 4 days. The orange-brown oil was further purified by column chromatography on silica gel using first (70:30) hexanes/CH2Cl2 followed by (80:20) hexanes/CH2Cl2 resulting in 0.42 g of yellow solid (85% yd). Anal. Calcd for C135H174N4: C, 87.51%, H, 9.46%, N, 3.02%. Found: C, 87.37; H, 9.53%, N, 3.02%. 1H NMR (300 MHz. C6D) δ: 7.09 (d, 2H), 7.04 (s, 1H), 7.0 (dd, 5H), 6.93 (s, 1H), 6.85 (t, 6H), 6.73 (t, 6H), 6.53 (m, 3H), 1.33 (m, 4H), 0.87 (bd, 28H), 0.52 (bt, 10H). 13C NMR (300 MHz, C6D6) δ: 152.4, 148.5. 147.0, 136.6, 129.4, 124.2, 123.9, 120.2, 119.6, 119.1, 55.2, 40.3, 32.2, 30.4, 30.0, 29.8, 29.7, 29.6, 24.4, 22.9, 14.2. FT-IR (KBr, cm1): 3036 (vArCH), 2926; 2854 (valCH), 1593 (vArC═C).

Workup

  1. customcondensation
  2. customThe orange-brown oil was further purified by column chromatography on silica gel using first (70:30) hexanes/CH2Cl2

Sources & evidence

ORD record
ord-753efd25dd3541cf899823ea7f7ca1c1
Source dataset
uspto-grants-2009_10
Patent number
US07598018B1

Reaction notes

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