Aluminium lithium hydride → 1-N-methyl-4-N-[7-thia-9,11-diazatricyclo[6.4.0.0[2,6]]dodeca-1(12),2(6),8,10-tetraen-12-yl]cyclohexane-1,4-diamine

HRID 525099Notes

Reaction equation

HRID 525099 reaction equation
[C:1]12[C:12]([NH:13][CH:14]3[CH2:19][CH2:18][CH:17]([NH:20][C:21](=O)OC(C)(C)C)[CH2:16][CH2:15]3)=[N:11][CH:10]=[N:9][C:8]=1[S:7][C:6]1[CH2:5][CH2:4][CH2:3][C:2]2=1.[H-].[H-].[H-].[H-].[Al+3].[Li+]>O1CCCC1>[CH3:21][NH:20][CH:17]1[CH2:18][CH2:19][CH:14]([NH:13][C:12]2[C:1]3[C:2]4[CH2:3][CH2:4][CH2:5][C:6]=4[S:7][C:8]=3[N:9]=[CH:10][N:11]=2)[CH2:15][CH2:16]1

Participants

4

Reactant 2

HCID 21226445Aluminium lithium hydrideHCID 70957826tert-butyl N-[4-([7-thia-9,11-diazatricyclo[6.4.0.0^[2,6]]dodeca-1(8),2(6),9,11-tetraen-12-yl]amino)cyclohexyl]carbamate

Product 1

HCID 575202421-N-methyl-4-N-[7-thia-9,11-diazatricyclo[6.4.0.0[2,6]]dodeca-1(12),2(6),8,10-tetraen-12-yl]cyclohexane-1,4-diamineYield 100.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of tert-butyl N-[4-([7-thia-9,11-diazatricyclo[6.4.0.0^[2,6]]dodeca-1(8),2(6),9,11-tetraen-12-yl]amino)cyclohexyl]carbamate (1.1 g, 2.83 mmol, 1.00 equiv) in tetrahydrofuran (20 mL) was added into a solution of lithium aluminium tetrahydride (530 mg, 13.95 mmol, 5.00 equiv) in tetrahydrofuran (30 mL) dropwise with stirring at room temperature. The resulting solution was heated to reflux for 30 min in an oil bath. The reaction was then quenched by the addition of 20 mL of tetrahydrofuran/water. The solids were filtered out. The filtrate was extracted with 3×100 mL of dichloromethane and the organic layers combined and dried over anhydrous sodium sulfate and concentrated under vacuum to give 0.86 g (crude) of 1-N-methyl-4-N-[7-thia-9,11-diazatricyclo[6.4.0.0^[2,6]]dodeca-1(8), 2(6),9,11-tetraen-12-yl]cyclohexane-1,4-diamine as yellow oil. LC-MS: (ES, m/z): 303 [M+H]+

Workup

  1. temperatureThe resulting solution was heated
  2. temperatureto reflux for 30 min in an oil bath
  3. customThe reaction was then quenched by the addition of 20 mL of tetrahydrofuran/water
  4. filtrationThe solids were filtered out
  5. extractionThe filtrate was extracted with 3×100 mL of dichloromethane
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-afd3302190ed4b8f8ee6d8ba0e09fdc2
Source dataset
uspto-grants-2016_05
Patent number
US09340554B2

Reaction notes

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