Structure of 5335-87-5
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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
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Synthesis of N-Sulfenylimines from Disulfides and Primary Methanamines
Robert Kawȩcki ;
Abstract: N-Sulfenylimines (sulfenimines, thiooximes, N-alkylidenesulfenamides) were efficiently synthesized through the reaction of primary amines and disulfides with NBS or bromine. This reaction can be carried out in an open flask at room temperature without the need for any transition-metal-containing additives. The use of thiols instead of disulfides gave similar results. A wide range of amines were reacted with aryl and alkyldisulfides, resulting in the formation of sulfenimines in a yield of 44–99%.
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CAS No. : | 5335-87-5 |
Formula : | C14H14O2S2 |
M.W : | 278.39 |
SMILES Code : | COC1=CC=C(SSC2=CC=C(OC)C=C2)C=C1 |
MDL No. : | MFCD00041358 |
InChI Key : | PZQGLCGLPMWYBT-UHFFFAOYSA-N |
Pubchem ID : | 79258 |
GHS Pictogram: |
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Signal Word: | Danger |
Hazard Statements: | H318-H410 |
Precautionary Statements: | P273-P280-P305+P351+P338-P501 |
Class: | 9 |
UN#: | 3077 |
Packing Group: | Ⅲ |
* 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 |
---|---|---|
84% | With sodium dithionite; water; potassium carbonate; In dimethyl sulfoxide; at 60℃; for 0.75h; | General procedure: A mixture of isatoic anhydride 1 (0.6 mmol), disulfide 2 (0.2 mmol), and Na2S2O4 (0.9 mmol) in undried DMSO (2 mL) was stirred at 60 C for respective time in Table 2 and Scheme 2. After the completion of the reaction, as monitored by TLC and GC-MS analysis, the reaction mixture washed with brine and extracted with ethyl acetate. The organic phase was separated and dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated and the resulting residue was purified by column chromatography on silica gel (300-400 mesh) with petroleum ether-EtOAc as eluent to provide the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With potassium iodide; In dichloromethane; at 20℃; | General procedure: DIB (0.6 mmol, 193 mg), ArSSAr (0.3 mmol), and KI (0.5 mmol, 83 mg) were added to a styrene (or their derivatives) solution in CH2Cl2 (0.5 mmol in 2 mL of CH2Cl2), and the suspension mixture was vigorously stirred at room temperature for 2 h. Upon completion, the reaction mixture was quenched by the addition of saturated aqueous sodium thiosulfate (Na2S2O3) (5 mL), and basified with saturated aqueous sodium hydrogen carbonate (NaHCO3) (5 mL). Further stirring was followed by extraction with ethyl acetate (3*15 mL). The combined organic extracts were washed with water (20 mL), brine (20 mL), dried (anhydrous MgSO4), filtered, and concentrated (aspirator). The residue was purified by column chromatography (SiO2) to furnish analytically pure product. 4.2.25 1-(3-Formylphenyl)-2-((4-methoxyphenyl)thio)ethyl acetate (3kc) m-Vinylbenzaldehyde (1k) (67 mg, 0.50 mmol). Column chromatography (silica gel; 5-12% EtOAc/hexanes) yields 3kc (119 mg, 72%); light yellow viscous oil; Rf (20% EtOAc/hexanes) 0.26; IR (neat): νmax 2730, 1743, 1699, 1246 cm-1; 1H NMR (300 MHz, CDCl3): δ 9.98 (s, 1H, CHO), 7.82-7.76 (m, 2H, ArH), 7.56 (dt, J=7.8, 1.5 Hz, 1H, ArH), 7.49 (br t, J=7.8 Hz, 1H, ArH), 7.34 (br d, J=8.8 Hz, 2H, ArH), 6.83 (br d, J=8.8 Hz, 2H, ArH), 5.88 (dd, J=7.7, 5.8 Hz, 1H, ArCH), 3.78 (s, 3H, OCH3), 3.32 (dd, J=14.0, 7.7 Hz, 1H, CHH), 3.14 (dd, J=14.0, 5.8 Hz, 1H, CHH), 2.06 (s, 3H, CH3); 13C NMR (75 MHz, CDCl3): δ 191.8, 169.8, 159.2, 140.2, 136.4, 133.9, 132.7, 129.7, 129.1, 127.5, 125.0, 114.6, 73.8, 55.2, 41.7, 20.9; HRMS (ESI-TOF): MNa+, found: 353.0834; error=3 ppm requires C18H18NaO4S 353.0823. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With [{Ti(salophen)H2O}2O][OSO2C4F9]2; zinc; In tetrahydrofuran; at 20℃; for 2h;Inert atmosphere; | General procedure: Under N2 atmosphere, a solution of complex 1 (68.7 mg, 5 mol%) in THF (3.0 mL), zinc dust (80 mg, 1.2 mmol), diphenyl disulfide (109 mg, 0.5 mmol), and ethyl 2-bromoacetate (184 mg, 1.1 mmol) were added. Then the mixture was stirred for 2 h at room temperature, monitored by thin-layer chromatography (TLC). The resulting reaction mixture was diluted with diethyl ether (10 mL x 3), filtered, and evaporated, and then the residue was subjected to column chromatography using petroleum ether:ethyl acetate as eluent (30:1) to afford the pure product 6a. |
70% | With iron; In N,N-dimethyl-formamide; at 90℃; for 20h;Inert atmosphere; | General procedure: In a round-bottomed flask, activated iron dust (168 mg,3 mmol) was added to a solution of α-bromo carbonyl compounds (1.0 mmol) and diaryl disulfides (0.5 mmol) in DMF (3.0mL). The reaction mixture was stirred at 90C under N2 atmosphere for 15 h. Then ethyl acetate (20 mL) was added, stirred, and filtered. To filter liquor, the water (15 mL) was added and the mixture was extracted with ethyl acetate (15 mL × 3). The combined organic phase was washed with water (20 mL × 2), dried over anhydrous Na2SO4 , and concentrated under vacuum. The crude product was purified by column chromatography on silica gel (petroleum ether /ethyl acetate = 30:1). |
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