1,2-Diaminocyclohexane, trans- → HCID 86722431, compound

HRID 718821Notes

Reaction equation

HRID 718821 reaction equation
[O:1]1[CH2:5][CH2:4][O:3][C:2]21[CH2:18][C:10]1[CH:11]=[C:12]3[C:16](=[CH:17][C:9]=1[CH2:8][CH2:7][CH2:6]2)[NH:15][N:14]=[CH:13]3.I[C:20]1[CH:25]=[CH:24][N:23]=[C:22]([CH3:26])[CH:21]=1.[C@@H]1(N)CCCC[C@H]1N.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>O1CCOCC1.[Cu]I>[CH3:26][C:22]1[CH:21]=[C:20]([N:15]2[C:16]3[C:12](=[CH:11][C:10]4[CH2:18][C:2]5([O:1][CH2:5][CH2:4][O:3]5)[CH2:6][CH2:7][CH2:8][C:9]=4[CH:17]=3)[CH:13]=[N:14]2)[CH:25]=[CH:24][N:23]=1

Participants

7

Reactant 4

HCID 438061,2-Diaminocyclohexane, trans-HCID 62657Potassium Phosphate, TribasicHCID 126913224-Iodo-2-methylpyridineHCID 86722428HCID 86722428, compound

Product 1

HCID 86722431HCID 86722431, compoundYield 79%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A 100 mL round-bottom flask equipped with an air cooled reflux container was charged with 5,7,8,9-tetrahydro-1H-spiro[cyclohepta[f]indazole-6,2′-[1,3]dioxolane] (81) (3.00 g, 12.3 mmol), 4-iodo-2-methylpyridine (3.84 g, 14.7 mmol), CuI (0.234 g, 1.23 mmol), (+/−)-trans-cyclohexane-1,2-diamine (0.295 mL, 2.46 mmol) and K3PO4 (5.21 g, 24.6 mmol) in 1,4-dioxane (31 mL). The reaction mixture was heated at about 100° C. for about 21 h. The reaction was allowed to cool and then it was filtered through a pad of Celite® and rinsed with EtOAc (3×10 mL). The filtrate was concentrated then the residue was purified on silica gel (120 g), using a gradient of 10-100% EtOAc in DCM). Collection and concentration of the appropriate fractions gave 1-(2-methylpyridin-4-yl)-5,7,8,9-tetrahydro-1H-spiro[cyclohepta[f]indazole-6,2′-[1,3]dioxolane] (82, R1=2-methylpyridin-4-yl) (3.26 g, 79%); LC/MS, method 3, Rt=1.86 min, MS m/z 336 (M+H)+.

Workup

  1. customA 100 mL round-bottom flask equipped with an air
  2. temperaturecooled
  3. temperaturereflux container
  4. temperatureto cool
  5. filtrationit was filtered through a pad of Celite®
  6. washrinsed with EtOAc (3×10 mL)
  7. concentrationThe filtrate was concentrated
  8. customthe residue was purified on silica gel (120 g)
  9. customCollection and concentration of the appropriate fractions

Sources & evidence

ORD record
ord-5b02ced2537f4ae1a2c68991eee933c4
Source dataset
uspto-grants-2015_11
Patent number
US09193744B2

Reaction notes

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