Toluene → 5'-(4-(Bis(4-methoxyphenyl)amino)phenyl)-3,4'-dihexyl-2,2'-bithiophen-5-yl(butyl)phosphinic acid

HRID 85408Notes

Reaction equation

HRID 85408 reaction equation
Br[C:2]1[S:6][C:5]([C:7]2[S:8][C:9]([C:18]3[CH:40]=[CH:39][C:21]([N:22]([C:31]4[CH:36]=[CH:35][C:34]([O:37][CH3:38])=[CH:33][CH:32]=4)[C:23]4[CH:28]=[CH:27][C:26]([O:29][CH3:30])=[CH:25][CH:24]=4)=[CH:20][CH:19]=3)=[C:10]([CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])[CH:11]=2)=[C:4]([CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH3:46])[CH:3]=1.C1(C)C=CC=CC=1.[CH2:54]([PH:58](=[O:62])[O:59]CC)[CH2:55][CH2:56][CH3:57].C(N(CC)CC)C>C(OCC)(=O)C>[CH3:30][O:29][C:26]1[CH:27]=[CH:28][C:23]([N:22]([C:31]2[CH:36]=[CH:35][C:34]([O:37][CH3:38])=[CH:33][CH:32]=2)[C:21]2[CH:39]=[CH:40][C:18]([C:9]3[S:8][C:7]([C:5]4[S:6][C:2]([P:58]([CH2:54][CH2:55][CH2:56][CH3:57])(=[O:59])[OH:62])=[CH:3][C:4]=4[CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH3:46])=[CH:11][C:10]=3[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])=[CH:19][CH:20]=2)=[CH:24][CH:25]=1

Participants

6

Reactant 4

HCID 1140TolueneHCID 8471TriethylamineHCID 67016569HCID 67016569, compoundHCID 178454912HCID 178454912, compound

Product 1

HCID 666713375'-(4-(Bis(4-methoxyphenyl)amino)phenyl)-3,4'-dihexyl-2,2'-bithiophen-5-yl(butyl)phosphinic acid

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
110 °C

Procedure

The 5′-(4-(bis(4-methoxyphenyl)amino)phenyl)-3,4′-dihexyl-2,2′-bithiophen-5-yl(butyl)phosphinic acid was prepared applying a modified procedure of Y. Xu et al., Synthesis, 1984, 778. 4-(5′-Bromo-3′,4-dihexyl-2,2′-bithiophen-5-yl)-N,N-bis(4-methoxyphenyl)aniline (216 mg, 0.8 mmol) was placed in a Schlenck tube, and toluene (0.2 ml), ethyl butylphosphinate (152 mg, 0.88 mmol), triethylamine (0.36 ml, 2.6 mmol), and tetrakis[triphenylphosphine]palladium (46.2 mg, 0.04 mmol) was added under a stream of argon, stoppered, and heated in an oil bath at 110° C. for 10 h. After the mixture has been cooled, ethyl acetate (5 ml) is added and the solid is removed by filtration. The filtrate is concentrated on a rotatory evaporator and the residue is purified by column chromatography on silica gel eluting with petroleum ether (bp. 60-90° C.)/ethyl acetate. The ester thus obtained was hydrolised with 12% aqueous HCl (2×2 mL) evaporating to dryness on a waterbath yielding 5′-(4-(bis(4-methoxyphenyl)amino)phenyl)-3,4′-dihexyl-2,2′-bithiophen-5-yl(butyl)phosphinic acid (190 mg, 82%).

Workup

  1. customXu et al., Synthesis, 1984, 778
  2. additionwas added under a stream of argon
  3. temperatureAfter the mixture has been cooled
  4. customthe solid is removed by filtration
  5. concentrationThe filtrate is concentrated on a rotatory evaporator
  6. customthe residue is purified by column chromatography on silica gel eluting with petroleum ether (bp. 60-90° C.)/ethyl acetate

Sources & evidence

ORD record
ord-73c3e084ae0d40398da220fab7b2b83c
Source dataset
uspto-grants-2014_09
Patent number
US08847065B2

Reaction notes

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