Water → HCID 178440463, compound

HRID 1931581Notes

Reaction equation

HRID 1931581 reaction equation
C([BH3-])#N.[Na+].[C:5]([O:9][C:10]([NH:12][N:13]=[C:14]1[CH2:19][CH2:18][CH:17]([C:20]2[O:24][N:23]=[C:22]([CH:25]([CH3:27])[CH3:26])[N:21]=2)[CH2:16][CH2:15]1)=[O:11])([CH3:8])([CH3:7])[CH3:6].O.[OH-].[Na+]>C(O)(=O)C>[C:5]([O:9][C:10]([NH:12][NH:13][C@H:14]1[CH2:19][CH2:18][C@@H:17]([C:20]2[O:24][N:23]=[C:22]([CH:25]([CH3:27])[CH3:26])[N:21]=2)[CH2:16][CH2:15]1)=[O:11])([CH3:8])([CH3:7])[CH3:6].[C:5]([O:9][C:10]([NH:12][NH:13][C@H:14]1[CH2:19][CH2:18][C@H:17]([C:20]2[O:24][N:23]=[C:22]([CH:25]([CH3:27])[CH3:26])[N:21]=2)[CH2:16][CH2:15]1)=[O:11])([CH3:8])([CH3:7])[CH3:6]

Participants

7

Reactant 4

HCID 962WaterHCID 14798Sodium HydroxideHCID 5003444Sodium cyanoborohydrideHCID 66915389N'-[4-(3-isopropyl-[1,2,4]oxadiazol-5-yl)cyclohexylidene]-hydrazinecarboxylic acid tert-butyl ester

Product 2

HCID 178440462HCID 178440462, compoundHCID 178440463HCID 178440463, compoundYield 36%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

Sodium cyanoborohydride (389 mg, 6.2 mmol) was added in 8 portions to a solution of N′-[4-(3-isopropyl-[1,2,4]oxadiazol-5-yl)-cyclohexylidene]-hydrazinecarboxylic acid tert-butyl ester (from Step 1; 1.9 g, 5.9 mmol) in 50% aqueous acetic acid, and the mixture was stirred at room temperature for 2.5 h. The mixture was cooled slightly using cold water, and then 2 M aqueous sodium hydroxide solution was added to bring the pH to approximately 7. The mixture was extracted four times with dichloromethane, and the combined extracts were washed with water and brine, then dried (sodium sulfate), filtered, evaporated, and held under high vacuum to give a gum. This was purified on a Supelco 100 g column, eluting with 0-3% methanol/dichloromethane, to give N′-[4-(3-isopropyl-[1,2,4]oxadiazol-5-yl)-cis-cyclohexyl]-hydrazinecarboxylic acid tert-butyl ester (309 mg), N′-[4-(3-isopropyl-[1,2,4]oxadiazol-5-yl)-trans-cyclohexyl]-hydrazinecarboxylic acid tert-butyl ester (680 mg, 36%), and some mixed fractions. 1H NMR (300 MHz, DMSO-d6) δ 1.22 (d, 6H, J=7.0 Hz), 1.36 (s, 9H), 1.45-1.53 (m, 4H), 1.60-1.68 (m, 2H), 1.94-2.04 (m, 2H), 2.90-3.05 (m, 3H), 4.20-4.25 (m, 1H), 8.16 (br s, 1H).

Workup

  1. temperatureThe mixture was cooled slightly
  2. extractionThe mixture was extracted four times with dichloromethane
  3. washthe combined extracts were washed with water and brine
  4. dry with materialdried (sodium sulfate)
  5. filtrationfiltered
  6. customevaporated
  7. customto give a gum
  8. customThis was purified on a Supelco 100 g column
  9. washeluting with 0-3% methanol/dichloromethane

Sources & evidence

ORD record
ord-6a14c6fa956a4c428504991718028eb4
Source dataset
uspto-grants-2012_05
Patent number
US08188098B2

Reaction notes

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