Toluene → HCID 67304246, compound

HRID 1009880Notes

Reaction equation

HRID 1009880 reaction equation
[CH2:1]([O:8][C@@H:9]1[C@@H:14]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@H:13]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C@@H:12]([CH2:31][O:32][CH2:33][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[O:11][C@H:10]1[C:40]1[CH:45]=[C:44]([CH2:46][C:47]2[CH:52]=[CH:51][C:50]([CH2:53][CH2:54]O)=[CH:49][CH:48]=2)[C:43]([Cl:56])=[CH:42][C:41]=1[O:57][CH2:58][C:59]1[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(=O)[NH:88]C(=O)C2=CC=CC=C12.N(C(OC(C)C)=O)=NC(OC(C)C)=O.C1(C)C=CC=CC=1.O.NN.[OH-].[Na+]>CO.O1CCCC1>[NH2:88][CH2:54][CH2:53][C:50]1[CH:51]=[CH:52][C:47]([CH2:46][C:44]2[C:43]([Cl:56])=[CH:42][C:41]([O:57][CH2:58][C:59]3[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=3)=[C:40]([C@@H:10]3[O:11][C@H:12]([CH2:31][O:32][CH2:33][C:34]4[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=4)[C@@H:13]([O:23][CH2:24][C:25]4[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=4)[C@H:14]([O:15][CH2:16][C:17]4[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=4)[C@H:9]3[O:8][CH2:1][C:2]3[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=3)[CH:45]=2)=[CH:48][CH:49]=1

Participants

10

Reactant 7

HCID 1140TolueneHCID 6809PhthalimideHCID 11776TriphenylphosphineHCID 14798Sodium HydroxideHCID 24654Hydrazine hydrate (1:1)HCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 67304488HCID 67304488, compound

Product 1

HCID 67304246HCID 67304246, compoundYield 50%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a tetrahydrofuran solution (2.0 mL) of (1S)-1,5-anhydro-2,3,4,6-tetra-O-benzyl-1-[2-(benzyloxy)-4-chloro-5-[4-(2-hydroxyethyl)benzyl]phenyl]-D-glucitol (79.0 mg, 0.090 mmol), triphenyl phosphine (53.1 mg, 0.203 mmol), and phthalimide (23.9 mg, 0.162 mmol) cooled in ice was added a 40% diisopropyl azodicarboxylate solution in toluene (386 μL, 0.203 mmol) under nitrogen atmosphere. After the reaction solution was stirred at room temperature for 1.5 hours, methanol (1 mL) was added thereto. Then hydrazine monohydrate (43.7 μL, 0.90 mmol) was added, and the reaction mixture was stirred at 60° C. for 3 hours. After the mixture was cooled to room temperature, a 2 M sodium hydroxide aqueous solution was added thereto, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with brine, and dried with anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure. Thus obtained residue was purified with silica gel column chromatography (chloroform:methanol=9:1) to obtain the title compound (39.2 mg, 50%) as a colorless oily compound.

Workup

  1. stirringthe reaction mixture was stirred at 60° C. for 3 hours
  2. temperatureAfter the mixture was cooled to room temperature
  3. extractionthe resulting mixture was extracted with ethyl acetate
  4. washThe organic layer was washed with brine
  5. dry with materialdried with anhydrous magnesium sulfate
  6. customThe solvent was evaporated under reduced pressure
  7. customThus obtained residue was purified with silica gel column chromatography (chloroform:methanol=9:1)

Sources & evidence

ORD record
ord-a0228687c75a4ef5bfa582232311295a
Source dataset
uspto-grants-2011_07
Patent number
US07973012B2

Reaction notes

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