Triphenylphosphine → HCID 86617349, compound

HRID 1692529Notes

Reaction equation

HRID 1692529 reaction equation
[C:1]1([P:7]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[I:20][C:21]1[CH:22]=[C:23]([CH:25]=[CH:26][CH:27]=1)[NH2:24]>CC([O-])=O.CC([O-])=O.[Pd+2].C1(C)C(C)=CC=CC=1>[I-:20].[NH2:24][C:23]1[CH:22]=[C:21]([P+:7]([C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=2)([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)[CH:27]=[CH:26][CH:25]=1

Participants

5

Reactant 2

HCID 11776Triphenylphosphine2×HCID 122713-Iodoaniline

Product 1

HCID 86617349HCID 86617349, compoundYield 97.2%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 7237O-XyleneSolvent

Procedure

To a 3000 mL 3-necked round-bottomed flask fitted with a condenser, mechanical stirrer and gas inlet, about 329.33 g (1.25 mol) of triphenylphosphine (PPh3), Pd(acetate)2 (2.82 g, 0.0126 mol) and 1600 mL of de-gassed xylene was added. The mixture was stirred under argon until the PPh3 is dissolved. m-Iodoaniline (about 275.00 g; 1.25 mol) was added and the yellow-orange solution was refluxed for around 80 minutes. The product phosphonium compound ((3-aminophenyl)triphenylphosphonium Iodide) separated from solution as a yellow-orange solid. Excessive refluxing was avoided to prevent discoloration of the product phosphonium compound. The progress of the reaction was monitored using thin layer chromatography (TLC) with a 50/50 hexane/ethyl acetate developing solution. After the reflux, the product was filtered. The product 15 was reslurried with hot toluene, and stirred for 15 minutes. The solution was then filtered and rinsed with additional toluene/xylene. After drying in a 150° C. vacuum oven for 20 hours, 585.01 g of off-white product was obtained in a 96% yield. The melting point and NMR data are consistent with the structure of product (15). MP: 316.0° C. 1H NMR (δ, D6-DMSO): 8-6.6 (m, 19H, aromatics), 5.88 (s, 2H).

Workup

  1. customTo a 3000 mL 3-necked round-bottomed flask fitted with a condenser, mechanical stirrer and gas inlet
  2. dissolutionis dissolved
  3. temperaturethe yellow-orange solution was refluxed for around 80 minutes
  4. customThe product phosphonium compound ((3-aminophenyl)triphenylphosphonium Iodide) separated from solution as a yellow-orange solid
  5. temperatureExcessive refluxing
  6. filtrationAfter the reflux, the product was filtered
  7. filtrationThe solution was then filtered
  8. washrinsed with additional toluene/xylene
  9. customAfter drying in a 150° C. vacuum oven for 20 hours

Sources & evidence

ORD record
ord-3aa3860c6d2c4b9a990f791bfde7a19c
Source dataset
uspto-grants-2012_04
Patent number
US08158243B2

Reaction notes

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