Benzophenone imine → 8-chloro-N-(diphenylmethylene)-1,5-naphthyridin-3-amine

HRID 40372Notes

Reaction equation

HRID 40372 reaction equation
C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.CC(C)([O-])C.[Na+].Br[C:54]1[CH:55]=[N:56][C:57]2[C:62]([CH:63]=1)=[N:61][CH:60]=[CH:59][C:58]=2[Cl:64].[C:65]1([C:71]([C:73]2[CH:78]=[CH:77][CH:76]=[CH:75][CH:74]=2)=[NH:72])[CH:70]=[CH:69][CH:68]=[CH:67][CH:66]=1>ClCCl.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].C1(C)C=CC=CC=1>[Cl:64][C:58]1[CH:59]=[CH:60][N:61]=[C:62]2[C:57]=1[N:56]=[CH:55][C:54]([N:72]=[C:71]([C:65]1[CH:70]=[CH:69][CH:68]=[CH:67][CH:66]=1)[C:73]1[CH:78]=[CH:77][CH:76]=[CH:75][CH:74]=1)=[CH:63]2

Participants

8

Reactant 4

HCID 136809Benzophenone imineHCID 634876Binap, (A+-)-HCID 134591373-Bromo-8-chloro-1,5-naphthyridineHCID 23676156Sodium t-butoxide

Product 1

HCID 576910588-chloro-N-(diphenylmethylene)-1,5-naphthyridin-3-amineYield 50%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

A 25 ml round bottom flask set up under nitrogen was charged with Pd2(dba)3 (301 mg, 0.33 mmol), BINAP (614 mg, 0.99 mmol) and sodium tert-butoxide (237 mg, 2.46 mmol). System was purged with Argon and 3-bromo-8-chloro-1,5-naphthyridine (400 mg, 1.64 mmol), diphenylmethanimine (0.28 mL, 1.64 mmol), and toluene (1M, 1.64 mL) were added. This was placed in a preheated oil bath at 80° C. and stirred at this temperature for 16 hours. Reaction cooled to room temperature, diluted with dichloromethane, and passed over a celite cake. Filtrate collected was concentrated to afford brown oil. This was purified by ISCO silica gel chromatography (40 g, 1% MeOH/DCM over 50 mins) to afford clean 8-chloro-N-(diphenylmethylene)-1,5-naphthyridin-3-amine (280 mg, 50% yield). MS[M+H]=344.0. Calc'd for C21H14ClN3=343.8.

Workup

  1. customA 25 ml round bottom flask set up under nitrogen
  2. additionwere added
  3. customThis was placed in a preheated oil bath at 80° C.
  4. customReaction
  5. customFiltrate collected
  6. concentrationwas concentrated
  7. customto afford brown oil
  8. customThis was purified by ISCO silica gel chromatography (40 g, 1% MeOH/DCM over 50 mins)

Sources & evidence

ORD record
ord-0656311fd0534041882802a5c7ec95a5
Source dataset
uspto-grants-2013_09
Patent number
US08524900B2

Reaction notes

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