2-Aminopyridine → HCID 20605592, compound

HRID 497422Notes

Reaction equation

HRID 497422 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1.C[Al](C)C.C[O:13][C:14]([C:16]1[C:25]2[C:24]3[N:26]=[CH:27][CH:28]=[CH:29][C:23]=3[CH2:22][N:21]([CH2:30][C:31]3[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=3)[CH2:20][C:19]=2[NH:18][CH:17]=1)=O>C(Cl)Cl>[N:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[NH:1][C:14]([C:16]1[C:25]2[C:24]3[N:26]=[CH:27][CH:28]=[CH:29][C:23]=3[CH2:22][N:21]([CH2:30][C:31]3[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=3)[CH2:20][C:19]=2[NH:18][CH:17]=1)=[O:13]

Participants

5

Reactant 3

HCID 104392-AminopyridineHCID 16682925TrimethylaluminumHCID 20605629HCID 20605629, compound

Product 1

HCID 20605592HCID 20605592, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of 110 mg (1.2 mmol) of 2-aminopyridine in 2 mL of methylene chloride is added dropwise 0.5 mL (1.0 mmol) of trimethyl aluminum (2M solution in toluene). This mixture is stirred at room temperature for ½ hour. The resulting solution is then added dropwise to a 68 mg (0.2 mmol) solution of 5-Benzyl-3,4,5,6-tetrahydro-3,5,10-triaza-benzo[e]azulene-1-carboxylic acid methyl ester dissolved in 8 mL of methylene chloride and the mixture heated to 40° C. for 4 hours. The reaction mixture is quenched with the dropwise addition of 0.75 mL of 1N NaOH and then dried with anhydrous Na2SO4. The reaction mixture is filtered, and the filtrate evaporated. The residue is chromatographed on 9 grams of silica gel using 50/1 chloroform/methanol as the eluant. Appropriate fractions are combined and evaporated to yield 65 mg of 5-benzyl-3,4,5,6-tetrahydro-3,5,10-triaza-benzo[e]azulene-1-carboxylic acid pyridin-2-ylamide. 1H NMR (CDCl3) δ 14.1 (s, 1H), 11.0 (s, 1H), 8.8 (m, 1H), 8.4 (m, 2H), 7.7 (s, 1H), 7.6 (m, 2H), 7.4 (m, 6H), 6.95 (m, 1H), 3.7 (s, 2H), 3.55 (s, 2H), 3.50 (s, 2H). Mass spectrum: m/e=396.3 (p+1). TLC (10/1 chloroform/methanol) Rf=0.6

Workup

  1. temperaturethe mixture heated to 40° C. for 4 hours
  2. customThe reaction mixture is quenched with the dropwise addition of 0.75 mL of 1N NaOH
  3. dry with materialdried with anhydrous Na2SO4
  4. filtrationThe reaction mixture is filtered
  5. customthe filtrate evaporated
  6. customThe residue is chromatographed on 9 grams of silica gel using 50/1 chloroform/methanol as the eluant
  7. customevaporated

Sources & evidence

ORD record
ord-1bc40403e487463aa6717d7b42114338
Source dataset
uspto-grants-2005_09
Patent number
US06949562B2

Reaction notes

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