Tri-o-tolylphosphine → HCID 173175774, compound

HRID 1836696Notes

Reaction equation

HRID 1836696 reaction equation
I[C:2]1[CH:7]=C[C:5]([C:8]2[C:9]3[NH:13][C:12]([C:14]([C:45]4C=[CH:49][C:48](C)=[CH:47][CH:46]=4)=[C:15]4[N:44]=[C:18]([C:19](C5C=CC=CC=5)=[C:20]5[NH:37][C:23](=[C:24]([C:30]6C=[CH:34][C:33](C)=[CH:32][CH:31]=6)[C:25]6[CH:26]=[CH:27][C:28]=2[N:29]=6)[CH:22]=[CH:21]5)[CH:17]=[CH:16]4)=[CH:11][CH:10]=3)=[CH:4][CH:3]=1.I[C:53]1[CH:58]=[CH:57][C:56](SC(=O)C)=[CH:55][CH:54]=1.[CH3:63][C:64]1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:63]([C:53]1[CH:54]=[CH:55][C:56]([C:19]2[C:20]3[NH:37][C:23]([C:24]([CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])=[C:25]4[N:29]=[C:28]([C:8]([CH2:5][CH2:4][CH2:3][CH2:2][CH3:7])=[C:9]5[NH:13][C:12](=[C:14]([CH2:45][CH2:46][CH2:47][CH2:48][CH3:49])[C:15]6[CH:16]=[CH:17][C:18]=2[N:44]=6)[CH:11]=[CH:10]5)[CH:27]=[CH:26]4)=[CH:22][CH:21]=3)=[CH:57][CH:58]=1)#[CH:64]

Participants

5

Reactant 3

HCID 80271Tri-o-tolylphosphineHCID 110331771-Iodo-4(S-acetylthio)benzeneHCID 135485770HCID 135485770, compound

Product 1

HCID 173175774HCID 173175774, compound

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Procedure

S-Acetylthio-derivatized triple decker (15). Samples of (Pc)Eu(Pc)Eu(E′B-Por) (28) (15 mg, 7.0 μmol), 4-iodo-1-(S-acetylthio)benzene (2.0 mg, 7.0 μmol), Pd2(dba)3 (1.0 mg, 1.1 μmol) and P(o-tolyl)3 (2.5 mg, 8.3 μmol) were added to a Schlenk flask. The flask was evacuated and purged with argon three times. Then deaerated toluene (3 mL) and deaerated N,N-diisopropylethylamine (0.6 mL) were added by syringe. The flask was immersed in an oil bath at 35° C. and stirred under argon. The reaction was monitored by TLC (silica, toluene) and LD-MS. After 24 h, the solvent was removed under vacuum, the residue dissolved in toluene/ether (60:1), and loaded onto a silica gel column packed with the same solvent. Elution with toluene/ether (60:1) afforded the desired product together with trace of unreacted starting material as the first band. The product thus obtained was further purified by a second column chromatography procedure (silica gel, toluene), affording a black solid (15) (3.1 mg, 19%) after removal of the solvent and washing with CH3OH. 1H NMR (CDCl3) δ 1.91 (m, 27H), 2.62 (s, 3H), 3.28 (m, 8H), 4.70-4.80 (m, 3H), 4.98 (d, J=6.6 Hz, 1H), 6.68 (m, 4H), 6.94 (d, J=6.6 Hz, 1H), 7.54 (m, 1H), 7.71 (m, 1H), 8.03 (m, 1H), 8.71 (brs, 8H), 9.05-9.12 (m, 3H), 9.42 (m, 1H), 10.10 (brs, 8H), 11.11 (brs, 8H), 11.56 (m, 2H), 11.72 (m, 1H), 12.02 (m, 1H), 12.98 (brs, 8H); LD-MS obsd 2291.4 (M+), 2250.2 (M+-CH3CO), 1181.0 (M+-(Por)Eu), 1111.6 (M+-(Pc)Eu(Pc)), 1067.8 (M+-(Pc)Eu(Pc)-CH3CO); FAB-MS obsd 2284.59, calcd exact mass 2284.58 (C130H90OSN20Eu2); λabs 341, 419, 523, 618, 721 nm.

Workup

  1. customThe flask was evacuated
  2. custompurged with argon three times
  3. additionThen deaerated toluene (3 mL) and deaerated N,N-diisopropylethylamine (0.6 mL) were added by syringe
  4. customThe flask was immersed in an oil bath at 35° C.
  5. customthe solvent was removed under vacuum
  6. dissolutionthe residue dissolved in toluene/ether (60:1)
  7. washElution with toluene/ether (60:1)

Sources & evidence

ORD record
ord-d818314facb54fe298f55163fd655df3
Source dataset
uspto-grants-2004_08
Patent number
US06777516B2

Reaction notes

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