Nitrogen → HCID 86719383, compound

HRID 510339Notes

Reaction equation

HRID 510339 reaction equation
[Cl:1][C:2]1[N:11]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([N+:18]([O-:20])=[O:19])[CH:13]=2)[C:5]2[N:6]=[CH:7][N:8]=[C:9]([NH2:10])[C:4]=2[C:3]=1I.[Cl:22][C:23]1[CH:28]=[CH:27][C:26](B(O)O)=[CH:25][CH:24]=1.C([O-])([O-])=O.[Na+].[Na+].N#N>COCCOC.O.C(Cl)Cl.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].CO>[Cl:1][C:2]1[N:11]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([N+:18]([O-:20])=[O:19])[CH:13]=2)[C:5]2[N:6]=[CH:7][N:8]=[C:9]([NH2:10])[C:4]=2[C:3]=1[C:26]1[CH:27]=[CH:28][C:23]([Cl:22])=[CH:24][CH:25]=1

Participants

10

Reactant 4

HCID 947NitrogenHCID 10340Sodium CarbonateHCID 742994-Chlorophenylboronic acidHCID 86719382HCID 86719382, compound

Product 1

HCID 86719383HCID 86719383, compoundYield 95.5%

Reagents, catalysts & solvents 5

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 887MethanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent2×HCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of 6-chloro-5-iodo-7-(3-nitrophenyl)-7H-pyrrolo[2,3-d]pyrimidin-4-amine (18) (1.4 g, 3.4 mmol), 4-chlorophenylboronic acid (696 mg, 4.5 mmol), Pd(dppf)Cl2.DCM (140 mg, 0.17 mmol) and Na2CO3 (1.1 g, 10.3 mmol) in DME (30 mL) and H2O (15 mL) was purged with N2 before heated to 90° C. overnight. After cooled down to r.t., the reaction was quenched with H2O (50 mL). The resulting mixture was extracted with DCM contained 25% i-PrOH(50 mL×3). The combined organic phase were washed with brine, dried over Na2SO4 and concentrated. The crude product was purified by column chromatographic (silica gel, 0 to 50% EA in a mixture of PE & DCM (1:1) and then 0 to 5% MeOH in DCM) to afford 6-chloro-5-(4-chlorophenyl)-7-(3-nitrophenyl)-7H-pyrrolo[2,3-d]pyrimidin-4-amine (19) (1.3 g, 91% yield) as a yellow solid. LC-MS (ESI): m/z (M/M+2) 399.9/401.9.

Workup

  1. temperatureAfter cooled down to r.t.
  2. customthe reaction was quenched with H2O (50 mL)
  3. extractionThe resulting mixture was extracted with DCM
  4. washThe combined organic phase were washed with brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. customThe crude product was purified by column chromatographic (silica gel, 0 to 50% EA
  8. additionin a mixture of PE & DCM (1:1)

Sources & evidence

ORD record
ord-c95276dbebfb4347b19b242b80aebc41
Source dataset
uspto-grants-2015_08
Patent number
US09096604B2

Reaction notes

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