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Hydrochloric Acid → 9-Cyclopentyl-N-(5-(4-((dimethylamino)acetyl)-1-piperazinyl)-2-pyridinyl)-8-fluoro-9H-pyrido[4',3':4,5]pyrrolo[2,3-d]pyrimidin-2-amine

HRID 876010
Notes
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Reaction equation

HRID 876010 reaction equation
[CH:1]1([N:6]2[C:10]3[N:11]=[C:12]([NH2:15])[N:13]=[CH:14][C:9]=3[C:8]3[CH:16]=[CH:17][N:18]=[C:19]([F:20])[C:7]2=3)[CH2:5][CH2:4][CH2:3][CH2:2]1.Cl[C:22]1[N:27]=[CH:26][C:25]([N:28]2[CH2:33][CH2:32][N:31]([C:34](=[O:39])[CH2:35][N:36]([CH3:38])[CH3:37])[CH2:30][CH2:29]2)=[CH:24][CH:23]=1.C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1.CC(C)([O-])C.[Na+].Cl>C([O-])([O-])=O.[K+].[K+].CO.C(O)C.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].C(OCC)C.O1CCOCC1>[CH:1]1([N:6]2[C:10]3[N:11]=[C:12]([NH:15][C:22]4[CH:23]=[CH:24][C:25]([N:28]5[CH2:33][CH2:32][N:31]([C:34](=[O:39])[CH2:35][N:36]([CH3:37])[CH3:38])[CH2:30][CH2:29]5)=[CH:26][N:27]=4)[N:13]=[CH:14][C:9]=3[C:8]3[CH:16]=[CH:17][N:18]=[C:19]([F:20])[C:7]2=3)[CH2:2][CH2:3][CH2:4][CH2:5]1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

12

Reactant 5

HCID 313Hydrochloric AcidHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 23676156Sodium t-butoxideHCID 582996521-(4-(6-Chloropyridin-3-yl)piperazin-1-yl)-2-(dimethylamino)ethanoneHCID 582996889-Cyclopentyl-8-fluoro-9H-pyrido[4',3':4,5]pyrrolo[2,3-d]pyrimidin-2-amine

Product 1

HCID 58299625
9-Cyclopentyl-N-(5-(4-((dimethylamino)acetyl)-1-piperazinyl)-2-pyridinyl)-8-fluoro-9H-pyrido[4',3':4,5]pyrrolo[2,3-d]pyrimidin-2-amine
Yield 17%

Reagents, catalysts & solvents 6

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 702EthanolSolventHCID 887MethanolSolventHCID 3283Diethyl EtherSolventHCID 11430Potassium CarbonateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

A 10 mL reaction vessel was charged with compound 245 (100 mg, 369 μmol), compound 300 (109 mg, 387 μmol), tris(dibenzylideneacetone)dipalladium (0) (25.3 mg, 27.6 μmol), 4,5-bis(diphenylphosphino)-9,9-dimethyl-9H-xanthene (32.0 mg, 55.3 μmol), sodium t-butoxide (70.8 mg, 737 μmol), and dioxane (2.5 mL). The reaction was purged with argon and heated with microwave energy (300 W) for 2.5 hours at 120° C. The reaction was added to aqueous K2CO3 (10%, 30 mL) and extracted with dichloromethane+10% methanol (3×30 mL). The combined organics were dried (MgSO4) and evaporated to give an orange oil. Preparative reverse phase HPLC (gradient elution 0.1% TFA in water/10-70% acetonitrile) afforded. a yellow oil. This residue was taken up in aqueous K2CO3 (30 mL) and extracted with dichloromethane+10% methanol (3×30 mL). The combined organics were dried (MgSO4) and evaporated to give a yellow solid. This was taken up in methanol (2 mL) and 1M HCl in ethanol (0.5 mL) was added. Diethyl ether (10 mL) was added to precipitate the product, which was filtered and dried in vacuo to give compound 299 as a yellow solid (32 mg, 17%). 1H NMR (500 MHz, DMSO-d6) δ 9.43-9.61 (m, 1 H) 9.27-9.40 (m, 1 H) 8.01-8.12 (m, 1 H) 7.91-8.01 (m, 1 H) 7.75-7.91 (m, 3 H) 7.62-7.75 (m, 1 H) 5.27-5.42 (m, 1 H) 4.14-4.28 (m, 3 H) 3.10-3.18 (m, 3 H) 3.06 (none, 3 H) 2.68 (d, J=4.65 Hz, 8 H) 2.06-2.18 (m, 2 H) 1.93-2.06 (m, 2 H) 1.80-1.93 (m, 3 H) 1.48-1.69 (m, 3 H) ppm.

Workup

  1. customA 10 mL reaction vessel
  2. customThe reaction was purged with argon
  3. additionThe reaction was added to aqueous K2CO3 (10%, 30 mL)
  4. extractionextracted with dichloromethane+10% methanol (3×30 mL)
  5. dry with materialThe combined organics were dried (MgSO4)
  6. customevaporated
  7. customto give an orange oil
  8. washPreparative reverse phase HPLC (gradient elution 0.1% TFA in water/10-70% acetonitrile)
  9. customafforded
  10. extractionextracted with dichloromethane+10% methanol (3×30 mL)
  11. dry with materialThe combined organics were dried (MgSO4)
  12. customevaporated
  13. customto give a yellow solid
  14. customto precipitate the product, which
  15. filtrationwas filtered
  16. customdried in vacuo

Sources & evidence

ORD record
ord-75bc9fb48d2c41aa886017928bdafd61
Source dataset
uspto-grants-2015_03
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08980903B2

Reaction notes

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