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

HRID 1437893Notes

Reaction equation

HRID 1437893 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]=[C:33]([Cl:38])[CH:32]=1)=[O:28])([CH3:25])([CH3:24])[CH3:23].O>ClCCl>[C:22]([O:26][C:27]([NH:29][N:30]([C:31]1[CH:32]=[C:33]([Cl:38])[CH:34]=[C:35]([Cl:37])[CH:36]=1)[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

6

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 57941306(1R,4R)-4,7,7-trimethyl-3-oxo-bicyclo[2.2.1]heptane-2-carbonyl chloride2×HCID 57941314N'-(3,5-dichloro-phenyl)-hydrazinecarboxylic acid tert-butyl ester2×

Product 1

HCID 57941408N'-(3,5-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 6344DichloromethaneSolvent2×

Procedure

Triethylamine (10.75 mL, 77 mmol) was added in two portions 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; 5.5 g, 25.6 mmol) in dichloromethane (55 mL), giving a thick precipitate. N′-(3,5-dichloro-phenyl)-hydrazinecarboxylic acid tert-butyl ester (Intermediate 35; 5.5 g, 19.8 mmol) was added, along with dichloromethane (25-30 mL). The reaction mixture was placed in an oil-bath at 50° C., heated at this temperature overnight and then allowed to cool to room temperature and stir for 20 min. The reaction mixture was poured into water (100 mL) and two layers were separated. The organic layer was washed with water (100 mL) and brine (100 mL), dried (magnesium sulfate), filtered, evaporated, and then dried under high vacuum to give N′-(3,5-dichloro-phenyl)-N′-((1R,4R)-4,7,7-trimethyl-3-oxo-bicyclo[2.2.1]heptane-2-carbonyl)-hydrazinecarboxylic acid tert-butyl ester (10 g, 111% of the expected amount) as an orange foam, which was used directly in the next step without further purification.

Workup

  1. customgiving a thick precipitate
  2. customThe reaction mixture was placed in an oil-bath at 50° C.
  3. temperatureheated at this temperature overnight
  4. customwere separated
  5. washThe organic layer was washed with water (100 mL) and brine (100 mL)
  6. dry with materialdried (magnesium sulfate)
  7. filtrationfiltered
  8. customevaporated
  9. customdried under high vacuum

Sources & evidence

ORD record
ord-a7461b99398d46539dba427e70c97174
Source dataset
uspto-grants-2009_11
Patent number
US07622492B2

Reaction notes

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