tert-butyl N-(4-aminobutyl)carbamate → [4-(3,4-Bis-octadec-9-enyloxy-benzylamino)-butyl]-carbamic acid tert-butyl ester

HRID 604762Notes

Reaction equation

HRID 604762 reaction equation
[C:1]([O:5][C:6](=[O:13])[NH:7][CH2:8][CH2:9][CH2:10][CH2:11][NH2:12])([CH3:4])([CH3:3])[CH3:2].[CH2:14]([O:32][C:33]1[CH:34]=[C:35]([CH:38]=[CH:39][C:40]=1[O:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH2:49][CH:50]=[CH:51][CH2:52][CH2:53][CH2:54][CH2:55][CH2:56][CH2:57][CH2:58][CH3:59])[CH:36]=O)[CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH:22]=[CH:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31].[BH4-].[Na+].CCCCCC>C(Cl)Cl.CO>[C:1]([O:5][C:6](=[O:13])[NH:7][CH2:8][CH2:9][CH2:10][CH2:11][NH:12][CH2:36][C:35]1[CH:38]=[CH:39][C:40]([O:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH2:49][CH:50]=[CH:51][CH2:52][CH2:53][CH2:54][CH2:55][CH2:56][CH2:57][CH2:58][CH3:59])=[C:33]([O:32][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH:22]=[CH:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])[CH:34]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 4

HCID 4351tert-butyl N-(4-aminobutyl)carbamateHCID 8058HexaneHCID 4311764Sodium borohydrideHCID 862608213,4-Bis-octadec-9-enyloxy-benzaldehyde

Product 1

HCID 86761293[4-(3,4-Bis-octadec-9-enyloxy-benzylamino)-butyl]-carbamic acid tert-butyl esterYield 78%

Reagents, catalysts & solvents 1

HCID 21226129Dichloromethane methanolSolvent2×

Conditions

Temperature
0 °C

Procedure

To a vigorously stirred solution of the amine 9 (0.071 g, 0.38 mmol, 1.2 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 20 minutes. The resulting mixture was stirred at it under an atmosphere of nitrogen overnight. 1H NMR showed the reaction to be complete when there was no aldehyde peak present. 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 NaBH4 (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 oil dissolved in CH2Cl2 (50 mL) and washed with sodium carbonate (10% aq, 3×40 mL). The CH2Cl2 layer was dried over Na2CO3, filtered, the solvent removed in vacuo and the oily residue purified by flash column chromatography (4% MeOH/CHCl3) to give the product 15 as a clear oil (0.18 g, 78%), Rf=0.2 (3% MeOH/CHCl3). 1H NMR (500 MHz, CDCl3) d 6.85 (s, 1H, aryl), 6.80 (m, 2H, aryl), 5.34 (t, 4H, olefinic), 4.78 (br s, 1H, NHCO), 3.97 (q, 4H, OCH2), 3.69 (s, 2H, benzylic), 3.13 (m, 2H, CH2) 2.63 (t, 2H, CH2NH), 2.01 (m, 8H, CH2C═C), 1.80 (m, 4H, CH2CH2O), 1.55 (m, 4H), 1.49-1.12 (m, 57H, 24×CH2, 3×CH3), 0.89 (t, 6H, CH3); 13C NMR (CDCl3) d 156.17, 149.34, 148.29, 133.15, 130.11, 130.00, 120.67, 114.18, 114.08, 79.23, 69.69, 69.52, 54.12, 49.22, 40.80, 32.28, 30.16, 29.92, 29.82, 29.71, 29.67, 28.81, 28.27, 27.68, 27.60, 26.44, 23.09, 14.54; Anal. (C52H94N2O4): 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. customthe reaction
  5. stirringafter stirring overnight
  6. customThe solvent was removed in vacuo
  7. dissolutionthe crude oil dissolved in CH2Cl2 (50 mL)
  8. washwashed with sodium carbonate (10% aq, 3×40 mL)
  9. dry with materialThe CH2Cl2 layer was dried over Na2CO3
  10. filtrationfiltered
  11. customthe solvent removed in vacuo
  12. customthe oily residue purified by flash column chromatography (4% MeOH/CHCl3)

Sources & evidence

ORD record
ord-d2f4399e98ed49cc8d4117ed7bfc2ba3
Source dataset
uspto-grants-2011_03
Patent number
US07910363B1

Reaction notes

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