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Chemical Structure| 408332-88-7 Chemical Structure| 408332-88-7

Structure of 408332-88-7

Chemical Structure| 408332-88-7

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Product Details of [ 408332-88-7 ]

CAS No. :408332-88-7
Formula : C8H14O6
M.W : 206.19
SMILES Code : O=C(OCC)C(O)C(O)C(OCC)=O
MDL No. :MFCD00064873

Safety of [ 408332-88-7 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P264-P271-P280-P302+P352-P304+P340-P305+P351+P338-P312-P362-P403+P233-P501

Application In Synthesis of [ 408332-88-7 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 408332-88-7 ]

[ 408332-88-7 ] Synthesis Path-Downstream   1~4

  • 1
  • [ 408332-88-7 ]
  • [ 117977-21-6 ]
  • [ 117976-89-3 ]
YieldReaction ConditionsOperation in experiment
1.1 g (49%) With N-ethyl-N,N-diisopropylamine; isopropylbenzene hydroperoxide;titanium(IV) isopropylate; In water; toluene; Example 26 Asymmetric synthesis of (+)-2-[[[4-(3-methoxypropoxy)-3-methyl-2-pyridinyl]methyl]sulphinyl]-1H-benzimidazole, (+)-(If). 2.1 g (6.3 mmol) of 2-[[[4-(3-methoxypropoxy)-3-methyl-2-pyridinyl]methyl]thio]-1H-benzimidazole was dissolved in 50 ml of toluene. To the solution was added 40 mul (2.2 mmol) of water, 1.6 ml (9.4 mmol) of (+)-diethyl L-tartrate and 1.1 ml (3.8 mmol) of titanium(IV) isopropoxide. The mixture was stirred for 60 minutes at 50 C. and then cooled to room temperature. 0.44 ml (2.6 mmol) of N,N-diisopropylethylamine and 1.1 ml (6.0 mmol) of cumene hydroperoxide (80%) were added to the solution. After stirring for 2 h at room temperature the mixture consisted of 9% sulphide, 4% sulphone and 85% sulphoxide according to HPLC. To the mixture toluene (50 ml) was added and the resultant solution was extracted three times with an aqueous ammonia (12%) solution with a total volume of 150 ml. The combined aqueous layers were neutralized by the addition of concentrated acetic acid (30 ml). Thereafter, the workup procedure employed extraction, evaporation and flash chromatography yielding 1.63 g of the title compound with a purity of 99.9% (achiral analysis) and with an enantiomeric excess (e.e.) of 91% (chiral analysis). After treating the material with acetonitrile, there was a precipitate that could be removed by filtration. Concentrating the filtrate afforded 1.1 g (49%) of the title compound as an oil with an optical purity of 96.0% e.e.
  • 2
  • concentrated acetic acid [ No CAS ]
  • [ 408332-88-7 ]
  • [ 73590-85-9 ]
  • racemic omeprazole [ No CAS ]
  • [ 73590-58-6 ]
YieldReaction ConditionsOperation in experiment
With N-ethyl-N,N-diisopropylamine; isopropylbenzene hydroperoxide;titanium(IV) isopropylate; In 2,2,4-trimethylpentane; water; ethyl acetate; acetone; Example 9 Asymmetric synthesis followed by optical purification of (+)-5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridinyl)methyl]sulphinyl]-1H-benzimidazole, (+)-(Ia) 1.6 kg (5.0 mol) of 5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridinyl)-methyl]thio]-1H-benzimidazole was dissolved in 7.51 of ethyl acetate. To the solution was added 31 ml (1.7 mol) water. To the mixture was added 856 ml (5.0 mol) of (+)-diethyl L-tartrate, 744 ml (2.5 mol) of titanium(IV) isopropoxide and 436 ml (2.5 mol) diisopropylethylamine at room temperature. The addition of 830 ml (4.5 mol) cumene hydroperoxide was then performed at 30° C. After stirring for one hour at 30° C. the reaction was complete. Chiral and achiral chromatographic analyses showed that the mixture consited of 75percent sulphoxide with an enantiomeric excess (e.e.) of 80percent. The mixture was cooled to 10° C. and after addition of 1.5 l of isooctane and ethyl acetate (0.5 l), the product was extracted three times with an aqueous ammonia (12percent) solution with a total volume of 14 l. The combined aqueous phases were neutralised by addition of 1.5 l of concentrated acetic acid in the presence of ethyl acetate (4 l). The phases were separated and the aqueous phase was extracted with ethyl acetate (4 l). The solvent of the combined organic solutions was removed. Acetone (3.0 l) was added to precipitate the racemate of omeprazole which was filtered off. HPLC--analyses (achiral and chiral columns) of the filtrate showed that this solution consisted of 90percent sulphoxide with an optical purity of 95percent e.e. and thus the optical purity has been improved from 80percent e.e. to 95percent e.e. simply by one precipitation of racemic omeprazole. Further, a content analysis (HPLC) of the filtrate showed that the yield was 1.0 kg (58percent).
  • 3
  • [ 861359-74-2 ]
  • [ 408332-88-7 ]
  • [ 73590-85-9 ]
  • [ 73590-58-6 ]
YieldReaction ConditionsOperation in experiment
With isopropylbenzene hydroperoxide;titanium(IV) isopropylate; In water; toluene; Example 2 Asymmetric synthesis of (+)-5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridinyl)-methyl]sulphinyl]-1H-benzimidazole, (+)-(Ia) Titanium(IV) isopropoxide (1.3 ml, 4.5 mmol) and water (41 mul, 2.3 mmol) were added with stirring to a solution of (+)-diethyl L-tartrate (1.5 ml, 9.0 mmol) dissolved in toluene (10 ml). The mixture was stirred for 20 minutes at room temperature and then 5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridinyl)methyl]thio]-1H-benzimidazole (3.0 g, 9 mmol) and diisopropylethyl amine (0.45 ml, 2.6 mmol) were introduced. At 30 C. cumene hydroperoxide (tech, 80%, 1.8 ml, 9.9 mmol) was added. After 3 h at 30 C. the mixture consisted of 2.1% sulphide, 8.8% sulphone and 86.8% sulphoxide with an enantiomeric excess of 74%.
  • 4
  • [ 408332-88-7 ]
  • [ 73590-85-9 ]
  • [ 73590-58-6 ]
YieldReaction ConditionsOperation in experiment
With potassium hydrogencarbonate; isopropylbenzene hydroperoxide;titanium(IV) isopropylate; In water; ethyl acetate; Example 3 Asymmetric synthesis of (+)-5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridinyl)-methyl]sulphinyl]-1H-benzimidazole, (+)-(Ia). To a mixture of (+)-diethyl L-tartrate (4.2 g, 20 mmol), titanium(IV) isopropoxide (2.9 g, 10 mmol) and ethyl acetate was added water (0.18 ml, 10 mmol). The solution was stirred for 20 minutes whereupon 5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridinyl)-methyl]thio]-1H-benzimidazole (3,4 g, 10 mmol) was added together with KHCO3 (0.31 g, 3.1 mmol) and cumene hydroperoxide (1.8 ml, 10 mmol). The addition was performed at room temperature. HPLC analysis was performed after 1.5 hours which showed 63.3percent sulphoxide with an enantiomeric excess of 38.9percent.
With isopropylbenzene hydroperoxide;titanium(IV) isopropylate; In dichloromethane; water; Example 6 Asymmetric synthesis of (+)-5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridinyl)-methyl]sulphinyl]-1H-benzimidazole, (+)-(Ia). (+)-Diethyl L-tartrate (1.71 ml, 10 mmol) and titanium(IV) isopropoxide (1.5 ml, 5 mmol) were dissolved in methylene chloride (50 ml). Water (90 mul, 5 mmol) was added with stirring and the resultant mixture was heated to reflux for one hour. The mixture was cooled to room temperature. Thereafter, 5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridinyl)methyl]thio]-1H-benzimidazole (1.65 g, 5 mmol) and cumene hydroperoxide (80percent, 1.05 g, 5.5 mmol) were added at room temperature. The solution was stirred at room temperature for 90 minutes. The crude mixture was shown to consist of 42.8percent sulphide, 4.1percent sulphone and 48.3percent sulphoxide with an optical purity of 43percent e.e. The product was not isolated.
With isopropylbenzene hydroperoxide;titanium(IV) isopropylate; In dichloromethane; water; Example 7 Asymmetric synthesis of (+)-5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridinyl)-methyl]sulphinyl]-1H-benzimidazole, (+)-(Ia). 5-Methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridinyl)methyl]thio]-1H-benzimidazole (1.65 g, 5 mmol) was dissolved in methylene chloride (50 ml). (+)-Diethyl L-tartrate (1.71 ml, 10 mmol), titanium(IV) isopropoxide (1.5 ml, 5 mmol) and water (90 mul, 5 mmol) were added with stirring. The resultant mixture was stirred at room temperature for 20 minutes. Thereafter, cumene hydroperoxide (80percent, 1.05 g, 5.5 mmol) were added at room temperature and the solution was stirred at room temperature for 90 minutes. The crude mixture was shown to consist of 38.9percent sulphide, 8.4percent sulphone and 47.6percent sulphoxide with an optical purity of 32percent e.e. The product was not isolated.
With isopropylbenzene hydroperoxide;titanium(IV) isopropylate; In water; toluene; Example 8 Asymmetric synthesis of (+)-5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridinyl)-methyl]sulphinyl]-1H-benzimidazole, (+)-(Ia). 5-Methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridinyl)methyl]thio]-1H-benzimidazole (0.5 g, 1.5 mmol) was suspended in toluene (2.5 ml). Water 9.2 mul (0.5 mmol), (+)-Diethyl L-tartrate (0.39 ml, 2.3 mmol) and titanium(IV) isopropoxide (0.27 ml, 0.91 mmol) were added at 50° C. The mixture was warmed at 50° C. for 90 minutes whereupon 0.25 ml of the solution was transferred to a test-tube. To this tube was then added 25 mul of cumene hydroperoxide (80percent) and almost immediately thereafter this mixture consisted of 41percent desired sulphoxide with an optical purity of 69.5percent ee. The product was not isolated.

 

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