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CAS No. : | 1774-47-6 | MDL No. : | MFCD00011899 |
Formula : | C3H9IOS | Boiling Point : | - |
Linear Structure Formula : | ((CH3)3SO)I | InChI Key : | BPLKQGGAXWRFOE-UHFFFAOYSA-M |
M.W : | 220.07 | Pubchem ID : | 74498 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With sodium hydride; In dimethyl sulfoxide; at 20 - 65℃; for 3h; | 1-Oxa-6-aza-spiro[2.5]oct-6-yl-phenyl-methanone (A4) was synthesized according to literature (Vacher et al. J Med Chem, (1999), 42, 1648). In detail, 19.6 g (490 mmol) NaH (60percent in oil) was suspended in 600 ml DMSO and stirred at 65° C for 2 hrs. After cooling to room temperature 108 g (490 mmol) trimethylsulfoxonium iodide was added and the mixture was stirred for 15 min at room temperature. Then, 95 g (470 mmol) 1- benzoylpiperidin-4-one dissolved in 300 ml DMSO was added to the mixture and the solution was stirred for 45 min. The reaction mixture was poured in water and extracted with ethyl acetate for three times. The combined organic layers were washed with water and brine, dried over Na2SO4 and evaporated in vacuo to yield the product. Yield: 84 g (83 percent) yellow oil.MS (APCI): m/z 218 (M+1)*. 1H NMR (CDCI8, 600 MHz) delta (ppm): 1.35-1.60 (m, 2H, piperidine); 1.76-2.68 (m, 2H, piperidine); 2.74 (bs, 2H1 oxirane); 3.43-3.72 (m, 3H, prperidine); 4.18-4.36 (m, 1H, piperidine); 7.37-7.46 (m, 5H, phenyl). |
54% | Trimethylsulfoxonium iodide (11.2 g, 51.0 mmol), dimethyl sulfoxide (15 mE) and sodium hydride (60percent in mineral oil, 157 mg, 6.54 mmol) were added to a 50-mE round-bottom flask fitted with a magnetic stit The resulting mixture was stirred for 30 mm at room temperature. 1-ben- zoylpiperidin-4-one (500 mg, 2.18 mmol) was added and the resulting solution was stirred at room temperature for 4 h. The reaction was quenched by the addition of water (30 mE) and extracted with dichloromethane (3x30 mE). The organic layers were combined, dried over anhydrous sodium sulfate, filtered and concentrated under vacuum. The residue was purified by colunm chromatography using ethyl acetate to afford phenyl(1 -oxa-6-azaspiro[2.5]octan-6-yl)methanone (Intermediate 2-36, 2.00 g, 54percent). LCMS: (ESI) mlz 218 [M+H]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydroxide; In acetonitrile; at 50℃; for 2.5h; | Ground 85% potassium hydroxide (5.2 g) was added to a suspension of <strong>[50606-58-1]1-benzyl-3-piperidone hydrochloride</strong> hydrate (5.0 g) and trimethylsulfoxonium iodide (5.3 g) in anhydrous acetonitrile (220 mL), followed by stirring at 50C under nitrogen atmosphere for two and half hours. After cooling to room temperature, insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was mixed with ethyl acetate (100 mL) and water (50 mL) and was separated. The organic layer was sequentially washed with water (50 mL) and brine (50 mL) and was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to yield the titled compound (4.07 g) as an oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; In ice-water; dimethyl sulfoxide; | (1) Ethyl 2,3-methanohexanoate 15.6 g. of sodium hydride (content 65.1percent, 0.423 mol) were suspended in 800 ml. of dimethyl sulphoxide, and there were added, with stirring, 154 g. (0.7 mol) of trimethyloxosulphonium iodide in small portions at 20° to 30°C. over a period of 20 minutes. An exothermic reaction took place with the evolution of hydrogen. After stirring for 10 minutes, there was added, dropwise, a solution of 60 g. (0.423 mol) of ethyl hex-trans-2-enoate in 70 ml. of dimethyl sulphoxide at 20° to 30°C. The reaction mixture was stirred at 40°C. for 3 hours and then poured into 2 litres of ice-water and extracted with diethyl ether. The aqueous layer was treated with 60 ml. of concentrated hydrochloric acid and extracted with diethyl ether. The combined ethereal layer was washed with water, dried with magnesium sulphate and concentrated under reduced pressure. Distillation of the crude product gave 23.2 g. of ethyl 2,3 -methanohexanoate having the following physical characteristics:- b.p. 57° to 60°C./6 mm.Hg; NMR (CDCl3 and CCl4 solution); delta: 4.05 (2H, q), 0.95 (3H, t) and 0.70-0.48 (2H, dd); IR (liquid film); nu: 2950, 1720, 1450, 1405, 1370, 1330, 1265, 1200, 1180, 1100, 1040, 860 cm-1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
2.2 eq NaH (60% dispersion in oil) and 2.5 eq trimethylsulfoxonium iodide were weighed into a dry flask under nitrogen. 20 ml anhydrous DMSO was added and the reaction stirred one hour at room temperature. The intermediate acid E117b (6.8 mmol), dissolved in 6 ml anhydrous DMSO was added dropwise. After 2.5 hours at room temperature, the reaction was poured into 1N HCl and extracted with EtOAc. The combined organic layers were washed with a minimal amount of aqueous sodium thiosulfate then brine. The combined organic layers were then dried over MgSO4, filtered and concentrated to provide the intermediate cyclopropane E117c. The material E117c was used without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With potassium tert-butylate; In dimethyl sulfoxide; at 20℃;Product distribution / selectivity; | Intermediate 9; Ethyl 1 -oxaspiror2.51octane-6-carboxylate; Procedure 9a; To a mixture of trimethylsulfoxonium iodide and potassium tert-butoxide (as reported in Synthetic Communications, 33(12), 2135-2143; 3.9 g, 11.76 mmol) was added a solution of ethyl 4-oxocyclohexanecarboxylate (1 g, 5.87 mmol, Aldrich) in DMSO (20ml). The mixture was left to stir overnight at room temperature. The mixture was poured into water and extracted with diethyl ether; the organic phase was dried on Na2SO4, filtered and evaporated in vacuo to afford the title compound (704.5 mg, 65%), which was used without purification.Another batch of the same compound prepared using an analogous method showed the following NMR spectra:1H NMR (400 MHz, CDCI3): delta 4.06 (2H, q), 2.49-2.59 (2H, m), 2.26-2.28 (1 H, m), 1.63- 2.04 (6H, m), 1.27-1.49 (2H, m), 1.20 (3H, t) cis/trans 65:35 |
With potassium tert-butylate; In dimethyl sulfoxide; at 20℃;Product distribution / selectivity; | Intermediate delta: Ethyl 1-oxaspiror2.5loctane-6-carboxylate; To a mixture of trimethylsulfoxonium iodide and potassium tert-butoxide (as reported in Synthetic Communications, 33(12), 2135-2143; 3.9 g, 11.76 mmol) was added a solution of ethyl 4-oxocyclohexanecarboxylate (1 g, 5.87 mmole, Aldrich) in DMSO (20 ml). The mixture was left to stir overnight at room temperature. The mixture was poured into water and extracted with diethyl ether; the organic phase was dried on Na2SO4, filtered and evaporated in vacuo to afford ethyl 1-oxaspiro[2.5]octane-6-carboxylate (704.5 mg, 65%), which was used without purification. Another batch of the same compound prepared using an analogous method gave 1 H-NMR (400 MHz, CDCI3): delta 1.20 (t, 3 H), 1.27-1.49 (m, 2 H), 1.63-2.04 (m, 6 H), 2.26-2.28 (m, 1 H), 2.49-2.59 (m, 2 H), 4.06 (q, 2 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | General procedure: Sodium hydride (60percent), (1.88 g, 0.047 mol), washed twice withhexane to remove the paraffin oil, was added to a clean well driedRB flask. Traces of solvent were removed by applying nitrogenusing evacuated carousel or ampoules. To the dried sodiumhydride, dry DMF (30 mL) was added under nitrogen atmosphere,followed by trimethylsulfoxonium iodide (10.35 g, 0.047 mol) insingle lot and the contents were stirred for 60 min at 40?45 C.This solution was added to a mixture of the compound 3a (10 g,0.046 mol) in DMF (5 mL) at 0 C under nitrogen atmosphere overa period of 15 min. The completion of reaction was checked by TLC.Then the reaction mixture was maintained for a period of 1?2 h atroom temperature and quenched by adding the reaction mixtureinto a solution of aqueous hydroiodic acid (10percent) solution at 0 C.The aqueous mixture was extracted with chloroform and theorganic layer was washed with 10percent sodium thiosulfate solutionto remove the excess iodine. The organic layer was concentratedand purified using column chromatography on silica gel (hexane/EtOAc) to afford the iodo compound 5a, as pale yellow colouroily liquid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
13% | To a mixture of trimethylsulfoxonium iodide (30.6 g, 150 mmol) in THF (100 mL) was added NaH (5.98 g, 60percent in miniral oil, 150 mmol) in portions at 0°C under N2. The mixture was stirred at 0°C for 30 mins. Dihydrofuran-3(2H)-one (10 g, 116 mmol) in DMSO (100 mL) was added dropwise at 0°C. The reaction mixture was stirred at 0°C for 2 hours. The mixture was poured into ice-water (500 mL) in portions, extracted with DCM (2 x 500 mL). The combined organic phase was washed with brine (500 mL), dried over Na2S04, filtered and concentrated at 30°C. The residue was purified by Combi-flash (EtOAc in PE, 0percent~40percent) to afford J-l (1.5 g, 13 percent) as an oil. 1H NMR (400 MHz, CDC13) delta 4.11-3.90 (m, 3H), 3.66 (d, / = 10.0 Hz, 1H), 3.03 (d, / = 4.4 Hz, 1H), 2.94 (d, / = 4.0 Hz, 1H), 2.34-2.23 (m, 1H), 2.00-1.88 (m, 1H). |
[ 5034-06-0 ]
trimethyloxosulphonium chloride
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