Triphenylphosphine → 2-Chloro-5-(2-propenyl)-N-(tricyclo[3.3.1.13,7]dec-1-ylmethyl)-benzamide

HRID 1765531Notes

Reaction equation

HRID 1765531 reaction equation
[Cl:1][C:2]1[CH:21]=[CH:20][C:19](I)=[CH:18][C:3]=1[C:4]([NH:6][CH2:7][C:8]12[CH2:17][CH:12]3[CH2:13][CH:14]([CH2:16][CH:10]([CH2:11]3)[CH2:9]1)[CH2:15]2)=[O:5].[CH2:23]([CH:27]([Sn])C=C(CCCC)CCCC)[CH2:24]CC.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cl-].[Li+]>[Cl-].[Na+].O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CN(C)C=O>[Cl:1][C:2]1[CH:21]=[CH:20][C:19]([CH2:27][CH:23]=[CH2:24])=[CH:18][C:3]=1[C:4]([NH:6][CH2:7][C:8]12[CH2:17][CH:12]3[CH2:13][CH:14]([CH2:16][CH:10]([CH2:11]3)[CH2:9]1)[CH2:15]2)=[O:5]

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 433294Lithium ChlorideHCID 120853472-Chloro-5iodo-N-(tricyclo[3.3.1.13,7]dec-1-ylmethyl)-benzamideHCID 86589045Tributylallyltin

Product 1

HCID 211074042-Chloro-5-(2-propenyl)-N-(tricyclo[3.3.1.13,7]dec-1-ylmethyl)-benzamideYield 84.4%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

2-Chloro-5-iodo-N-(tricyclo[3.3.1.13,7]dec-1-ylmethyl)-benzamide (prepared as described in WO 99/29661) (7.74 g), tri-n-butylallyltin (5.99 g), dichlorobis(triphenylphosphine)palladium(II) (1.24 g), triphenylphosphine (1.86 g), lithium chloride (6.11 g) and N,N-dimethylformamide. (260 mL) were heated together under nitrogen from 110° C. to 130° C. over 20 minutes, and then at 130° C. for 25 minutes. The mixture was then cooled, poured into brine (500 mL), extracted into ethyl acetate (3×250 mL), dried over anhydrous magnesium sulfate, filtered and concentrated to give an oil. The crude mixture was purified by column chromatography eluting with 9:1 isohexane/ethyl acetate to give the sub-titled compound (5.23 g).

Workup

  1. temperature(260 mL) were heated together under nitrogen from 110° C. to 130° C. over 20 minutes
  2. temperatureThe mixture was then cooled
  3. extractionextracted into ethyl acetate (3×250 mL)
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto give an oil
  8. customThe crude mixture was purified by column chromatography
  9. washeluting with 9:1 isohexane/ethyl acetate

Sources & evidence

ORD record
ord-609ee50ed6cd4d9d81fd44b804743d4b
Source dataset
uspto-grants-2007_06
Patent number
US07227038B2

Reaction notes

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