Hexane → N1-(3,4-bis-octadec-9-enyloxy-benzyl)-octane-1,8-diamine

HRID 604763Notes

Reaction equation

HRID 604763 reaction equation
[CH2:1]([CH2:7][CH2:8][CH2:9][NH2:10])[CH2:2][CH2:3][CH2:4][CH2:5][NH2:6].[CH2:11]([O:29][C:30]1[CH:31]=[C:32]([CH:35]=[CH:36][C:37]=1[O:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH:47]=[CH:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH2:55][CH3:56])[CH:33]=O)[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH:19]=[CH:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28].[BH4-].[Na+].CCCCCC>C(Cl)Cl.CO>[CH2:11]([O:29][C:30]1[CH:31]=[C:32]([CH:35]=[CH:36][C:37]=1[O:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH:47]=[CH:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH2:55][CH3:56])[CH2:33][NH:6][CH2:5][CH2:4][CH2:3][CH2:2][CH2:1][CH2:7][CH2:8][CH2:9][NH2:10])[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH:19]=[CH:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28]

Participants

6

Reactant 4

HCID 8058HexaneHCID 242501,8-OctanediamineHCID 4311764Sodium borohydrideHCID 862608213,4-Bis-octadec-9-enyloxy-benzaldehyde

Product 1

HCID 123142334N1-(3,4-bis-octadec-9-enyloxy-benzyl)-octane-1,8-diamineYield 63%

Reagents, catalysts & solvents 1

HCID 21226129Dichloromethane methanolSolvent2×

Procedure

To a vigorously stirred solution of diaminooctane (0.23 g, 1.56 mmol, 5 equiv) in CH2Cl2/MeOH (3:1, 5 mL) was added a solution of the aldehyde 8a (0.20 g, 0.33 mmol) in CH2Cl2/MeOH (3:1, 5 mL), dropwise over 1 hour. The resulting mixture was stirred at RT under an atmosphere of nitrogen overnight. NMR showed the reaction to be complete when there was no aldehyde peak present in the NMR spectrum. The solvent was removed in vacuo and the crude imine dissolved in CH2Cl2/MeOH (1:1, 10 mL). The solution was cooled to 0° C. and sodium borohydride (60 mg, 1.58 mmol) was added in 15 mg portions over 30 minutes. TLC (10% EtAc/hexane) showed the reaction to be complete after stirring overnight. The solvent was removed in vacuo and the crude solid dissolved in CH2Cl2 (50 mL) and washed with sodium carbonate (10% aq, 3×40 mL). The CH2Cl2 layer was dried over sodium sulfate, filtered, the solvent removed in vacuo and the solid residue purified by flash column chromatography (1:10:89 NH4OH:MeOH:CHCl3) to give the product 16 as a white solid (0.15 g, 63%), Rf=0.5 (1:10:89 NH4OH:MeOH:CHCl3). 1H NMR (CDCl3) d 6.85 (s, 1H, aryl), 6.80 (m, 2H, aryl), 5.34 (t, 4H, olefinic), 3.97 (q, 4H, OCH2), 3.69 (s, 2H, benzylic), 2.67 (t, 2H, CH2NH2), 2.60 (t, 2H, CH2NH2), 2.01 (m, 8H, CH2C═C), 1.80 (m, 4H, CH2CH2O), 1.54-1.18 (m, 56H, 28×CH2), 0.88 (t, 6H, CH3); 13C NMR (CDCl3) d 149.31, 148.20, 133.55, 130.11, 130.00, 120.59, 114.14, 114.07, 69.70, 69.50, 54.24, 49.83, 42.60, 34.20, 32.28, 30.46, 30.16, 29.92, 29.81, 29.71, 29.67, 27.73, 27.60, 27.22, 26.44, 23.08, 14.53; HRMS (FAB): theory for C51H95N2O2 (M+1), 767.7394; found (M+1), 767.7377. Anal. (C51H94N2O2.0.3H2O): C, H, N.

Workup

  1. customthe reaction
  2. customThe solvent was removed in vacuo
  3. dissolutionthe crude imine dissolved in CH2Cl2/MeOH (1:1, 10 mL)
  4. temperatureThe solution was cooled to 0° C.
  5. customthe reaction
  6. stirringafter stirring overnight
  7. customThe solvent was removed in vacuo
  8. dissolutionthe crude solid dissolved in CH2Cl2 (50 mL)
  9. washwashed with sodium carbonate (10% aq, 3×40 mL)
  10. dry with materialThe CH2Cl2 layer was dried over sodium sulfate
  11. filtrationfiltered
  12. customthe solvent removed in vacuo
  13. customthe solid residue purified by flash column chromatography (1:10:89 NH4OH:MeOH:CHCl3)

Sources & evidence

ORD record
ord-1ca51704cc7f4017b68e2b2e553c35bd
Source dataset
uspto-grants-2011_03
Patent number
US07910363B1

Reaction notes

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