Hydrochloric Acid → HCID 178526550, compound

HRID 1827210Notes

Reaction equation

HRID 1827210 reaction equation
N1C2C=CC=C(N)C=2N=[CH:2]1.[N+:11]([C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([NH2:20])[C:15]=1[NH2:21])([O-:13])=[O:12].O.C1(C)C=CC(S(O)(=O)=O)=CC=1.Cl.[OH-].[Na+]>C(OCC)(OCC)OCC>[N+:11]([C:14]1[C:15]2[NH:21][CH:2]=[N:20][C:16]=2[CH:17]=[CH:18][CH:19]=1)([O-:13])=[O:12]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 203297-Aminobenzimidazole2×HCID 521998p-Toluenesulfonic acid monohydrateHCID 43595253-Nitro-1,2-phenylenediamine

Product 1

HCID 178526550HCID 178526550, compound

Reagents, catalysts & solvents 1

HCID 31214Ethyl orthoformateSolvent

Procedure

EXAMPLE 105 was prepared from 1H-benzoimidazol-4-ylamine (The 1H-benzoimidazol-4-ylamine was prepared by heating 1.5 g of 3-nitro-benzene-1,2-diamine in 50 mL of triethyl orthoformate with 10 mg of p-toluenesulfonic acid monohydrate at reflux overnight, concentration to dryness under reduced pressure, hydrolysis with refluxing 3N HCl for 1 h and neutralization with NaOH. Then, cooling and collection yielded the 4-nitro-benzimidazole product by filtration. Catalytic reduction using Raney Nickel® in ethanol under 1 atm of hydrogen for 1 h gave 1H-benzoimidazol-4-ylamine as an air sensitive solid) and 4-formyl-piperidine-1-carboxylic acid benzyl ester (prepared from 4-(N-methoxy-N-methyl-carbamoyl)-piperidine-1-carboxylic acid benzyl ester, using the procedures described by S. Nahm and S. W. Weinreb, Tetrahedron Letters, 22:3815–3818(1981)) on a 1 mmol scale by reductive amination in 5 mL of 1,2-dichloromethane using sodium triacetoxyborohydride over 0.5 of Raney Nickel® under 1 atm of hydrogen for 1 h, followed by immediate conversion of the crude, air sensitive triaminopyridine into the imidazo[4,5b]pyridine by heating with 51 mL of 96% formic acid and 2 mL of 37% hydrochloric acid at reflux overnight. The free base was liberated with sodium hydroxide and purified by preparative chromatography, eluting with 90:10 chloroform:methanol: MS (m+1)=365.5.

Workup

  1. customwas prepared
  2. temperatureat reflux overnight
  3. concentrationconcentration to dryness
  4. customunder reduced pressure, hydrolysis
  5. temperatureThen, cooling
  6. customcollection

Sources & evidence

ORD record
ord-5c1def0454074d4db60277714c5c67f6
Source dataset
uspto-grants-2006_05
Patent number
US07053089B2

Reaction notes

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