Dichloromethane → 2,3,4,6-Tetra-O-benzyl-1-O-(1-amino-hex-6-yl)-mannopyranose

HRID 1265307Notes

Reaction equation

HRID 1265307 reaction equation
[CH2:1]([O:8][C@H:9]1[C@@H:15]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C@H:14]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C@@H:13]([CH2:32][O:33][CH2:34][C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[O:12][CH:10]1[OH:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH:41]1[CH2:46][CH2:45][CH2:44][CH2:43][CH2:42]1.Cl[CH2:48]Cl>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.[OH-].[K+]>[CH2:1]([O:8][C@H:9]1[C@@H:15]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C@H:14]([O:24][CH2:25][C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=2)[C@@H:13]([CH2:32][O:33][CH2:34][C:35]2[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=2)[O:12][CH:10]1[O:11][CH2:48][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][NH2:41])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 6344Dichloromethane2×HCID 8082PiperidineHCID 110169932,3,4,6-Tetra-O-benzyl-D-mannopyranose

Product 1

HCID 697131992,3,4,6-Tetra-O-benzyl-1-O-(1-amino-hex-6-yl)-mannopyranose

Reagents, catalysts & solvents 2

HCID 70681Tetrabutylammonium ChlorideCatalystHCID 14797Potassium HydroxideSolvent

Conditions

Temperature
0 °C

Procedure

A mixture that consists of 54.1 g (100 mmol) of 2,3,4,6-tetra-O-benzyl-mannopyranose, 1.39 g (5 mmol) of tetrabutylammonium chloride in 350 ml of dichloromethane and 200 ml of 60% aqueous potassium hydroxide solution is cooled to 0° C. At 0° C., 60.3 g (150 mmol) of 6-bromohexylamine-N-(9-fluorenylmethoxy-carbonyl) is added in drops over 30 minutes while being stirred vigorously. It is stirred for one hour at 0° C. 300 ml of dichloromethane is added, the organic phase is separated, and the aqueous phase is extracted twice with 200 ml of dichloromethane. The solvent of the combined organic phases is distilled off in a vacuum. The residue is taken up in 250 ml of ethanol, and 100 g (1.17 mol) of piperidine is added. It is stirred for five hours at 40° C. The solution is evaporated to the dry state, and the residue is chromatographed on silica gel (mobile solvent: dichloromethane/ethanol/triethylamine=20:2:0.1).

Workup

  1. stirringIt is stirred for one hour at 0° C
  2. customthe organic phase is separated
  3. extractionthe aqueous phase is extracted twice with 200 ml of dichloromethane
  4. distillationThe solvent of the combined organic phases is distilled off in a vacuum
  5. stirringIt is stirred for five hours at 40° C
  6. customThe solution is evaporated to the dry state
  7. customthe residue is chromatographed on silica gel (mobile solvent: dichloromethane/ethanol/triethylamine=20:2:0.1)

Sources & evidence

ORD record
ord-e924c31a16c749d7a049ce4b2304ed85
Source dataset
uspto-grants-2003_04
Patent number
US06545135B2

Reaction notes

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