Triethylamine → N'-(2,5-dichloro-phenyl)-N'-((1R,4R)-4,7,7-trimethyl-3-oxo-bicyclo[2.2.1]heptane-2-carbonyl)-hydrazinecarboxylic acid tert-butyl ester

HRID 1437891Notes

Reaction equation

HRID 1437891 reaction equation
C(N(CC)CC)C.[CH3:8][C@:9]12[C:15]([CH3:17])([CH3:16])[C@H:12]([CH2:13][CH2:14]1)[CH:11]([C:18](Cl)=[O:19])[C:10]2=[O:21].[C:22]([O:26][C:27]([NH:29][NH:30][C:31]1[CH:36]=[C:35]([Cl:37])[CH:34]=[CH:33][C:32]=1[Cl:38])=[O:28])([CH3:25])([CH3:24])[CH3:23]>ClCCl>[C:22]([O:26][C:27]([NH:29][N:30]([C:31]1[CH:36]=[C:35]([Cl:37])[CH:34]=[CH:33][C:32]=1[Cl:38])[C:18]([CH:11]1[C:10](=[O:21])[C@@:9]2([CH3:8])[C:15]([CH3:17])([CH3:16])[C@@H:12]1[CH2:13][CH2:14]2)=[O:19])=[O:28])([CH3:25])([CH3:23])[CH3:24]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 57941306(1R,4R)-4,7,7-trimethyl-3-oxo-bicyclo[2.2.1]heptane-2-carbonyl chloride2×HCID 57941328N'-(2,5-dichloro-phenyl)-hydrazinecarboxylic acid tert-butyl ester2×

Product 1

HCID 57941412N'-(2,5-dichloro-phenyl)-N'-((1R,4R)-4,7,7-trimethyl-3-oxo-bicyclo[2.2.1]heptane-2-carbonyl)-hydrazinecarboxylic acid tert-butyl ester

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Triethylamine (26 mL, 186.5 mmol) was added dropwise to a cooled (0° C.) solution of (1R,4R)-4,7,7-trimethyl-3-oxo-bicyclo[2.2.1]heptane-2-carbonyl chloride (Intermediate 20; 13.33 g, 62.1 mmol) in dichloromethane (150 mL), yielding a thick suspension. This was stirred for 3 min and then N′-(2,5-dichloro-phenyl)-hydrazinecarboxylic acid tert-butyl ester (Intermediate 34; 13.00 g, 46.9 mmol) was added in one portion. The cooling bath was removed and the reaction mixture was stirred at room temperature for 10 min, then in an oil-bath at 50° C. for 4 h. The reaction mixture was cooled to room temperature, then added to water (200 mL) and extracted with dichloromethane (3×150 mL). The combined organic layers were washed with brine (200 mL), dried (magnesium sulfate), filtered, and evaporated to give N′-(2,5-dichloro-phenyl)-N′-((1R,4R)-4,7,7-trimethyl-3-oxo-bicyclo[2.2.1]heptane-2-carbonyl)-hydrazinecarboxylic acid tert-butyl ester (29.55 g, 138% of the expected amount) as a brown oil. This was used directly in the next step without further purification.

Workup

  1. customyielding a thick suspension
  2. customThe cooling bath was removed
  3. stirringthe reaction mixture was stirred at room temperature for 10 min
  4. waitin an oil-bath at 50° C. for 4 h
  5. additionadded to water (200 mL)
  6. extractionextracted with dichloromethane (3×150 mL)
  7. washThe combined organic layers were washed with brine (200 mL)
  8. dry with materialdried (magnesium sulfate)
  9. filtrationfiltered
  10. customevaporated

Sources & evidence

ORD record
ord-5a2e3c0eb48b43ab84bbfe1688e8ae43
Source dataset
uspto-grants-2009_11
Patent number
US07622492B2

Reaction notes

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