4-Nitro-1,2-phenylenediamine → HCID 69320502, compound

HRID 2114609Notes

Reaction equation

HRID 2114609 reaction equation
[NH2:1][C:2]1[C:3]2[C:10]([C:11](O)=O)=[CH:9][N:8]([CH:14]3[CH2:18][CH2:17][CH2:16][CH2:15]3)[C:4]=2[N:5]=[CH:6][N:7]=1.[NH2:19][C:20]1[CH:25]=[CH:24][C:23]([N+:26]([O-:28])=[O:27])=[CH:22][C:21]=1[NH2:29].CN(C(ON1N=NC2C=CC=NC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F>CN1C(=O)CCC1>[CH:14]1([N:8]2[C:4]3[N:5]=[CH:6][N:7]=[C:2]([NH2:1])[C:3]=3[C:10]([C:11]3[NH:29][C:21]4[CH:22]=[C:23]([N+:26]([O-:28])=[O:27])[CH:24]=[CH:25][C:20]=4[N:19]=3)=[CH:9]2)[CH2:18][CH2:17][CH2:16][CH2:15]1

Participants

5

Reactant 3

HCID 51117914-Nitro-1,2-phenylenediamineHCID 9886157Methanaminium, N-((dimethylamino)(3H-1,2,3-triazolo(4,5-b)pyridin-3-yloxy)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 693198034-Amino-7-cyclopentyl-7H-pyrrolo[2,3-d]pyrimidine-5-carboxylic acid

Product 1

HCID 69320502HCID 69320502, compoundYield 28.8%

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

4-Amino-7-cyclopentyl-7H-pyrrolo[2,3-d]pyrimidine-5-carboxylic acid (ID, 12.0 g, 488 mmol), 1,2-diamino-4-nitrobenzene (11.2 g, 73.1 mmol), and HATU (26.0 g, 73.1 mmol) were combined and stirred in 242 mL of anhydrous NMP under N2 at 50° C. After 6 hrs, reaction was monitored by LCMS confirming the loss of the starting material and the formation of a new component. The reaction mixture was decant into ten 50 mL centrifuge tubes and concentrated overnight in the GeneVac. Dark brown oil was taken up in EtOAc (1.6 L) and extracted using 1.2 L H2O. The organic layer was washed with H2O (3×900 mL) and then concentrated. The residue (dark brown gum) was triturate in ˜900 mL CH2Cl2, 10.02 g of a reddish black solid was collected after filtration and vacuum drying. 1H NMR suggested it contained the coupling product plus 20-30% impurity. The solid was again taken up in 1.5 L EtOAc, washed with H2O (5×900 mL). The organic layer was concentrated and residue triturated in ˜900 mL CH2Cl2, filtered and dried to furnish 7.65 g of a yellow solid. 1H NMR and LCMS suggested the coupling product plus minor impurities (88% pure by LCMS at 210 nm, M/Z 381.5, retention time 2.3 min. with analytical HPLC method 1).

Workup

  1. customreaction
  2. customThe reaction mixture was decant into ten 50 mL centrifuge tubes
  3. concentrationconcentrated overnight in the GeneVac
  4. extractionextracted
  5. washThe organic layer was washed with H2O (3×900 mL)
  6. concentrationconcentrated
  7. customThe residue (dark brown gum) was triturate in ˜900 mL CH2Cl2
  8. custom10.02 g of a reddish black solid was collected
  9. filtrationafter filtration and vacuum
  10. customdrying
  11. washwashed with H2O (5×900 mL)
  12. concentrationThe organic layer was concentrated
  13. customresidue triturated in ˜900 mL CH2Cl2
  14. filtrationfiltered
  15. customdried

Sources & evidence

ORD record
ord-c1bbaa9d09de4a328bcb18197c14d33f
Source dataset
uspto-grants-2008_10
Patent number
US07435739B2

Reaction notes

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