P-Phenylenediamine → HCID 86663467, compound

HRID 446575Notes

Reaction equation

HRID 446575 reaction equation
[F:1][C:2]([F:56])([F:55])[C:3]1[CH:4]=[C:5]([CH:48]=[C:49]([C:51]([F:54])([F:53])[F:52])[CH:50]=1)[C:6]([N:8]1[CH2:12][C@@:11]([CH2:20][CH2:21][N:22]2[CH2:27][CH2:26][C:25]3([C:35]4[C:30](=[CH:31][CH:32]=[CH:33][CH:34]=4)[CH2:29][C@@H:28]3[O:36][CH2:37][C:38]([N:40]([CH3:47])[CH2:41][CH2:42][CH2:43][C:44](O)=[O:45])=[O:39])[CH2:24][CH2:23]2)([C:13]2[CH:18]=[CH:17][C:16]([F:19])=[CH:15][CH:14]=2)[O:10][CH2:9]1)=[O:7].[C:57]1([NH2:64])[CH:62]=[CH:61][C:60]([NH2:63])=[CH:59][CH:58]=1.Cl.C(N=C=NCCCN(C)C)C.C(N(CC)CC)C.C(=O)([O-])O.[Na+]>ClCCl.C(#N)C>[NH2:63][C:60]1[CH:61]=[CH:62][C:57]([NH:64][C:44](=[O:45])[CH2:43][CH2:42][CH2:41][N:40]([C:38](=[O:39])[CH2:37][O:36][C@@H:28]2[C:25]3([CH2:24][CH2:23][N:22]([CH2:21][CH2:20][C@:11]4([C:13]5[CH:14]=[CH:15][C:16]([F:19])=[CH:17][CH:18]=5)[O:10][CH2:9][N:8]([C:6](=[O:7])[C:5]5[CH:48]=[C:49]([C:51]([F:53])([F:54])[F:52])[CH:50]=[C:3]([C:2]([F:1])([F:55])[F:56])[CH:4]=5)[CH2:12]4)[CH2:27][CH2:26]3)[C:35]3[C:30](=[CH:31][CH:32]=[CH:33][CH:34]=3)[CH2:29]2)[CH3:47])=[CH:58][CH:59]=1

Participants

8

Reactant 5

HCID 7814P-PhenylenediamineHCID 8471TriethylamineHCID 516892Sodium BicarbonateHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochloride2×HCID 86663468HCID 86663468, compound

Product 1

HCID 86663467HCID 86663467, compoundYield 78%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent2×

Procedure

The compound (163 mg, 0.206 mmol) obtained in Example 63e and benzene-1,4-diamine (111 mg, 1.03 mmol) were suspended in a mixed solvent of dichloromethane (8 mL) and acetonitrile (8 mL), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (59.0 mg, 0.309 mmol) and triethylamine (0.057 mL, 0.41 mmol) were added, and the mixture was stirred at room temperature for 3 hours. 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (59.0 mg, 0.309 mmol) and 4-N,N-dimethylaminopyridine (0.5 mg, 0.004 mmol) were further added, and the mixture was stirred at room temperature for 13 hours. After the reaction was completed, a saturated aqueous sodium hydrogencarbonate solution was added to the reaction mixture, and dichloromethane was added (×2) to separate the layers. The resulting organic layer was dried with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by NH silica gel column chromatography (hexane:ethyl acetate=1:1→0:1, v/v) to give the title compound (141 mg; yield, 78%) as a light pink solid.

Workup

  1. additionwere added
  2. stirringthe mixture was stirred at room temperature for 13 hours
  3. additionwas added (×2)
  4. customto separate the layers
  5. dry with materialThe resulting organic layer was dried with anhydrous sodium sulfate
  6. customthe solvent was evaporated under reduced pressure
  7. customThe residue was purified by NH silica gel column chromatography (hexane:ethyl acetate=1:1→0:1, v/v)

Sources & evidence

ORD record
ord-c43738a8cede4317b9a050eaadca8f30
Source dataset
uspto-grants-2013_07
Patent number
US08476253B2

Reaction notes

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