Acetic Acid → HCID 178472457, compound

HRID 1893341Notes

Reaction equation

HRID 1893341 reaction equation
O=[C:2]1[CH2:7][CH2:6][CH:5]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:4][CH2:3]1.[NH:13]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[NH2:14].C(O)(=O)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCl>[CH2:11]([O:10][C:8]([C@H:5]1[CH2:6][CH2:7][C@@H:2]([NH:14][NH:13][C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:3][CH2:4]1)=[O:9])[CH3:12].[CH2:11]([O:10][C:8]([C@H:5]1[CH2:6][CH2:7][C@H:2]([NH:14][NH:13][C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:3][CH2:4]1)=[O:9])[CH3:12]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 70091tert-Butyl carbazateHCID 317638Ethyl 4-oxocyclohexanecarboxylateHCID 5049666Sodium triacetoxyborohydride

Product 2

HCID 178472457HCID 178472457, compoundYield 62%HCID 178472458HCID 178472458, compoundYield 37%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of ethyl 4-oxo-cyclohexanecarboxylate (1.00 g, 5.88 mmol), tert-butyl hydrazinecarboxylate (1.16 g, 8.81 mmol) and acetic acid (0.34 ml, 5.9 mmol) in dichloromethane (29 ml) was stirred for 1 h at room temperature and subsequently cooled to 0° C. on an ice-water bath. Sodium triacetoxyborohydride (2.49 g, 11.8 mmol) was added at 0-5° C. The cooling bath was removed after completed addition. Stirring at room temperature for 20 h was followed by quenching with ethanol (5 ml). The reaction mixture was washed with one 50-ml portion of water. The aqueous layer (pH 4) was extracted with two 50-ml portions of dichloromethane. The combined organic layers were washed with one 50 ml-portion of aqueous 2 M sodium carbonate solution, dried over anhydrous sodium sulfate and concentrated in vacuo. Flash-chromatography with n-heptane/ethyl acetate as eluent gave cis-4-(N′-tert-butoxycarbonyl-hydrazino)-cyclohexanecarboxylic acid ethyl ester (1.05 g, 62%) and trans-4-(N′-tert-butoxycarbonyl-hydrazino)-cyclohexanecarboxylic acid ethyl ester (0.63 g, 37%).

Workup

  1. customThe cooling bath was removed
  2. additionaddition
  3. customby quenching with ethanol (5 ml)
  4. washThe reaction mixture was washed with one 50-ml portion of water
  5. extractionThe aqueous layer (pH 4) was extracted with two 50-ml portions of dichloromethane
  6. washThe combined organic layers were washed with one 50 ml-portion of aqueous 2 M sodium carbonate solution
  7. dry with materialdried over anhydrous sodium sulfate
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-5466edab0b0f407e8d348a8602fd792f
Source dataset
uspto-grants-2013_08
Patent number
US08513238B2

Reaction notes

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