Bis[2-(diphenylphosphino)phenyl] ether → HCID 57718221, compound

HRID 1366852Notes

Reaction equation

HRID 1366852 reaction equation
O(C1C=CC=CC=1P(C1C=CC=CC=1)C1C=CC=CC=1)C1C=CC=CC=1P(C1C=CC=CC=1)C1C=CC=CC=1.[N:40]1([S:46]([C:49]2[CH:54]=[CH:53][C:52]([SH:55])=[CH:51][CH:50]=2)(=[O:48])=[O:47])[CH2:45][CH2:44][CH2:43][CH2:42][CH2:41]1.[CH2:56]([O:61][C:62](=[O:82])[C:63]1[C:68](I)=[CH:67][N:66]=[C:65]([NH:70][S:71]([C:74]2[CH:79]=[CH:78][C:77]([Cl:80])=[CH:76][C:75]=2[Cl:81])(=[O:73])=[O:72])[CH:64]=1)[CH2:57][CH2:58][CH2:59][CH3:60].CC(C)([O-])C.[K+]>CN1CCCC1=O.[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1>[CH2:56]([O:61][C:62](=[O:82])[C:63]1[C:68]([S:55][C:52]2[CH:51]=[CH:50][C:49]([S:46]([N:40]3[CH2:41][CH2:42][CH2:43][CH2:44][CH2:45]3)(=[O:48])=[O:47])=[CH:54][CH:53]=2)=[CH:67][N:66]=[C:65]([NH:70][S:71]([C:74]2[CH:79]=[CH:78][C:77]([Cl:80])=[CH:76][C:75]=2[Cl:81])(=[O:72])=[O:73])[CH:64]=1)[CH2:57][CH2:58][CH2:59][CH3:60]

Participants

7

Reactant 4

HCID 4285986Bis[2-(diphenylphosphino)phenyl] etherHCID 23665647Potassium tert-butoxideHCID 57718178HCID 57718178, compoundHCID 577182904-(N-piperidinylsulfonyl)thiophenol

Product 1

HCID 57718221HCID 57718221, compoundYield 6%

Reagents, catalysts & solvents 2

HCID 9832798Tris(dibenzylideneacetone) dipalladiumCatalystHCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
100 °C

Procedure

A solution of (oxydi-2,1-phenylene)bis-(diphenylphosphine) (DPEphos) (43 mg, 0.08 mmol) and tris (dibenzylideneacetone) dipalladium (0) (18 mg, 0.02 mmol) in N-methylpyrrolidinone (10 ml) was stirred at room temperature for 5 minutes under nitrogen. 4-(Piperidine-1-sulfonyl)-benzenethiol (121 mg, 0.4 mmol), 2-(2,4-dichloro-benzenesulfonylamino)-5-iodo-isonicotinic acid pentyl ester (218 mg, 0.4 mmol) and potassium t-butoxide (90 mg, 0.8 mmol) were added and the reaction stirred overnight at 100° C. The solvent was removed under reduced pressure and the residue taken up in chloroform. The chloroform solution was washed with brine (25 ml), dried (MgSO4) and concentrated under reduced pressure. The residue was purified by flash column chromatography using ethyl acetate 2/3 hexane as eluent to afford 2-(2,4-dichloro -benzenesulfonylamino)-5-[4-(piperidine-1-sulfonyl)-phenylsulfanyl]-isonicotinic acid pentyl ester as a yellow foam (15 mg, 6%). 1H NMR (CDCl3): 10.82 (1 H, s, NH); 8.17 (1 H, s, Ar); 8.09 (1 H, d, Ar); 7.61 (2 H, m, Ar); 7.57 (1 H, s, Ar); 7.38 (4 H, m, py and Ar); 4.22 (2 H, t, OCH2); 2.90 (4 H, m, 2×CH2N pip); 1.66 (2 H, m, OCH2CH2); 1.54 (4 H, m, 2×CH2 pip); 1.33 (4 H, m, OCH2CH2CHCH2CH3); 1.19 (2 H, m, CH2 pip); 0.88 (3 H, t, CH2CH1). HPLC (Luna 2, Gradient 5): rt=7.82 minutes. LCMS rt=8.34 minutes, 673 (M+H)+.

Workup

  1. customThe solvent was removed under reduced pressure
  2. washThe chloroform solution was washed with brine (25 ml)
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was purified by flash column chromatography

Sources & evidence

ORD record
ord-996d4a43d3504109a5de60047534d38e
Source dataset
uspto-grants-2011_02
Patent number
US07893077B2

Reaction notes

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