N-(tert-butoxycarbonyl)-N-(2-cyanoethyl)-N',N'-dimethyl-1,4-diaminobutane → N-(3-aminopropyl)-N-(tert-butoxycarbonyl)-N',N'-dimethyl-1,4-diaminobutane

HRID 3088Notes

Reaction equation

HRID 3088 reaction equation
[H-].[H-].[H-].[H-].[Li+].[Al+3].[C:7]([O:11][C:12]([N:14]([CH2:22][CH2:23][C:24]#[N:25])[CH2:15][CH2:16][CH2:17][CH2:18][N:19]([CH3:21])[CH3:20])=[O:13])([CH3:10])([CH3:9])[CH3:8]>CCOCC>[NH2:25][CH2:24][CH2:23][CH2:22][N:14]([C:12]([O:11][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:13])[CH2:15][CH2:16][CH2:17][CH2:18][N:19]([CH3:20])[CH3:21]

Participants

4

Reactant 2

HCID 19695906N-(tert-butoxycarbonyl)-N-(2-cyanoethyl)-N',N'-dimethyl-1,4-diaminobutaneHCID 21226445Aluminium lithium hydride

Product 1

HCID 18934679N-(3-aminopropyl)-N-(tert-butoxycarbonyl)-N',N'-dimethyl-1,4-diaminobutaneYield 59%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of LAH (0.62 mg, 16.30 mmol) in anhydrous ether (100 ml) was added N-(tert-butoxycarbonyl)--N-(2-cyanoethyl)-N',N'-dimethyl-1,4-diaminobutane 324 (2.22 g, 8.10 mmol) in anhydrous ether (50 ml) at 0° C. The mixture was stirred at 0° C. for thirty minutes. The excess LAH was quenched with 1N NaOH at 0° C., and the resulting suspension was filtered through Celite and washed with ether. The combined ether layers were washed with brine, dried over MgSO4, and concentrated in vacuo to yield a crude product. The crude product was purified on a flash silica gel column and eluted with chloroform:methanol:isopropylamine (15:1:1) to give N-(3-aminopropyl)--N-(tert-butoxycarbonyl)-N',N'-dimethyl-1,4-diaminobutane 325 (1.30 g, 59% yield). 1H NMR (400 MHz, CDCl3) δ: 1.40 (9H, s, t-Bu), 2.15 (6H, s, --N(CH3)2), 2.22 (2H, m), 2.65 (2H, t), 3.20 (4H, m).

Workup

  1. customThe excess LAH was quenched with 1N NaOH at 0° C.
  2. filtrationthe resulting suspension was filtered through Celite
  3. washwashed with ether
  4. washThe combined ether layers were washed with brine
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated in vacuo
  7. customto yield a crude product
  8. customThe crude product was purified on a flash silica gel column
  9. washeluted with chloroform:methanol:isopropylamine (15:1:1)

Sources & evidence

ORD record
ord-9d5cb107bd0146788c6f94e9866436c0
Source dataset
uspto-grants-1998_03
Patent number
US05733899

Reaction notes

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