Sucrose → HCID 71752857, compound

HRID 374128Notes

Reaction equation

[CH2:1]([OH:23])[C@H:2]1[O:7][C@H:6]([O:8][C@:9]2([CH2:18][OH:19])[O:13][C@H:12]([CH2:14][OH:15])[C@@H:11]([OH:16])[C@@H:10]2[OH:17])[C@H:5]([OH:20])[C@@H:4]([OH:21])[C@@H:3]1[OH:22].C(N([CH2:29][CH3:30])CC)C.[C:31](Cl)([C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1)([C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1)[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1.C(Cl)Cl>CN(C)C=O>[CH:35]1[CH:36]=[CH:37][C:32]([C:31]([O:23][CH2:1][C@H:2]2[O:7][CH:6]([O:8][C@:9]3([CH2:18][O:19][C:31]([C:30]4[CH:29]=[CH:49][CH:44]=[CH:45][CH:46]=4)([C:32]4[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=4)[C:38]4[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=4)[O:13][C@H:12]([CH2:14][O:15][C:31]([C:38]4[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=4)([C:32]4[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=4)[C:44]4[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=4)[C@@H:11]([OH:16])[C@@H:10]3[OH:17])[C@H:5]([OH:20])[C@@H:4]([OH:21])[C@H:3]2[OH:22])([C:44]2[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=2)[C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)=[CH:33][CH:34]=1

Participants

Conditions

Temperature: 50 °C

Procedure

In a dry 5-L four-neck flask is dissolved 70 grams of sucrose (204.5 mmol) in 1 liter dry dimethylformamide (DMF) and dry triethylamine (200 ml, 145 grams, 1,423 mmol). The solution is allowed to attain a temperature of 25° to 30° C. and treated with a solution of trityl chloride (260 grams, 935.2 mmol, 4.5 equiv.) in dimethylformamide (600 ml), added dropwise over 1 hour. After the addition is complete, the reaction mixture is heated to a temperature of 50° C. and allowed to stir for 48 hours at that temperature. After 2 days, the reaction mixture is filtered through a short pad of silica gel to remove the precipitated triethylammonium hydrochloride and the residue is washed with methylene chloride:acetone (4:1). The effluent is then concentrated to a residue, which is reconstituted in methylene chloride and washed successively with 1N hydrochloric acid, saturated sodium bicarbonate solution, water, and brine and then dried over anhydrous sodium sulfate. The dry organic extract is then filtered and concentrated in vacuo to provide a yellow foamy solid. This material is then applied on a silica gel column (230 to 400 mesh, 10 cm×50 cm) packed with methylene chloride and successively eluted with methylene chloride, then 10% acetone in methylene chloride, followed by elution with 20% acetone in methylene chloride. The desired tri-O-tritylsucrose elutes with 20% acetone in methylene chloride and has an Rf of 0.21 in the same solvent. The amount of 1',6,6'-tri-O-tritylsucrose obtained by this method of synthesis and isolation is typically between 146 to 150 grams or 67% to 68.8%. On scales between 1 mmol and 50 mmol (314 mg to 15.7 grams) yields average about 76%.

Workup

customa temperature of 25° to 30° C.
additionadded dropwise over 1 hour
additionAfter the addition
waitAfter 2 days
filtrationthe reaction mixture is filtered through a short pad of silica gel
customto remove the precipitated triethylammonium hydrochloride
washthe residue is washed with methylene chloride:acetone (4:1)
concentrationThe effluent is then concentrated to a residue, which
washwashed successively with 1N hydrochloric acid, saturated sodium bicarbonate solution, water, and brine
dry with materialdried over anhydrous sodium sulfate
extractionThe dry organic extract
filtrationis then filtered
concentrationconcentrated in vacuo
customto provide a yellow foamy solid
washsuccessively eluted with methylene chloride
wash10% acetone in methylene chloride, followed by elution with 20% acetone in methylene chloride

Sources & evidence

ORD record: ord-f99c26e736384db59d2002e8b14234ee
Source dataset: uspto-grants-1992_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05166334

Reaction notes

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