Structure of 21252-69-7
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Zeger, Victoria R ; Thapa, Bhawana ; DeLair, Jessica F ; Bell, David S ; Shollenberger, Daniel ; Chakraborty, Moubani , et al.
Abstract: The chemical structure of nine imidazolium sulfonate and triflimide zwitterionic liquids (ZILs) were systematically tuned to increase their thermal stability for gas chromatography (GC)separations. Substituents for imidazolium and 2-phenylimidazolium cation systems, comprised of alkyl, benzyl, and oligoether groups of varying chain lengths, were studied as stationary phases in GC. Propanesulfonate, ethanesulfonate, and propanetriflimide anions were examined to understand the effect of linker length and nucleophilicity on ZIL thermal stability. Studies were conducted to assess film stability and thermal lability of ZIL stationary phases on fused silica capillaries when exposed to elevated temperatures for prolonged time periods. All stationary phases exhibited relatively poor film stability on untreated capillary surfaces, but most showed repeatable chromatographic retention after stepwise heating from 100 to 200°C. To understand the thermal degradation pathways of the ZILs, mass spectrometry (MS) was used to monitor the degradation/volatilization of the stationary phase when heated from 40-250°C. Salt-deactivated surfaces were effective at mitigating stationary phase instability, but were observed to participate in the degradation of alkyl functionalized ZILs via nucleophilic attack of the alkyl substituent. This was not observed for oligoether substituted ZILs. Imidazolium propanesulfonate ZILs all underwent degradation through the detachment of the anion system, resulting in the reformation of 1,3-propanesultone. Most ZIL stationary phases degraded below 230°C, but the cation substituent was observed to play a significant role in overall ZIL thermal stability. For the imidazolium propanetriflimide ZIL, degradation of the anion system occurred prior to the detachment of the entire anion system via elimination and occurred at around 245°C.
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Keywords: gas chromatography ; stationary phase ; zwitterionic liquid ; thermal stability ; mass spectrometry
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Mesoporous Silica-Supported Ionic Liquids as Catalysts for Styrene Carbonate Synthesis from CO2
Agnieszka Siewniak ; Adrianna Forajter ; Katarzyna Szymańska ;
Abstract: Various types of mesoporous silica were used as carriers to synthesize a series of immobilized imidazolium-based ionic liquids. Their activity was tested in the synthesis of styrene carbonate from CO2 and styrene. This is one-pot process, whereby two stages are carried out in one reactor and there is no need to isolate the intermediate product, epoxide. A systematic study on the influence of parameters such as temperature, the reaction time, CO2 pressure, as well as the amount and type of catalyst used was carried out. A strong synergistic catalytic effect of ionic liquid and Lewis acid was observed in promoting this reaction. The addition sequence of regents and amount of immobilized catalyst were considered crucial for the synthesis of styrene carbonate from CO2 and styrene. The tested silica-supported ionic liquids gave an easily-recyclable system which under the most favorable conditions ([mtespim]Cl/@SiO2; ZnBr2, 0.1 mol%; 110 °C, 4 h, 1 MPa) can be reused without a significant loss of catalytic activity nor selectivity.
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Keywords: cyclic carbonates ; silica-supported ionic liquids ; carbon dioxide ; mesoporous silica
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CAS No. : | 21252-69-7 |
Formula : | C11H20N2 |
M.W : | 180.29 |
SMILES Code : | CCCCCCCCN1C=CN=C1 |
MDL No. : | MFCD00467256 |
InChI Key : | KLMZKZJCMDOKFE-UHFFFAOYSA-N |
Pubchem ID : | 161351 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
Num. heavy atoms | 13 |
Num. arom. heavy atoms | 5 |
Fraction Csp3 | 0.73 |
Num. rotatable bonds | 7 |
Num. H-bond acceptors | 1.0 |
Num. H-bond donors | 0.0 |
Molar Refractivity | 57.14 |
TPSA ? Topological Polar Surface Area: Calculated from |
17.82 Ų |
Log Po/w (iLOGP)? iLOGP: in-house physics-based method implemented from |
2.8 |
Log Po/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by |
3.36 |
Log Po/w (WLOGP)? WLOGP: Atomistic method implemented from |
3.24 |
Log Po/w (MLOGP)? MLOGP: Topological method implemented from |
1.92 |
Log Po/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by |
2.67 |
Consensus Log Po/w? Consensus Log Po/w: Average of all five predictions |
2.8 |
Log S (ESOL):? ESOL: Topological method implemented from |
-2.9 |
Solubility | 0.228 mg/ml ; 0.00127 mol/l |
Class? Solubility class: Log S scale |
Soluble |
Log S (Ali)? Ali: Topological method implemented from |
-3.41 |
Solubility | 0.0698 mg/ml ; 0.000387 mol/l |
Class? Solubility class: Log S scale |
Soluble |
Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by |
-3.63 |
Solubility | 0.0424 mg/ml ; 0.000235 mol/l |
Class? Solubility class: Log S scale |
Soluble |
GI absorption? Gatrointestinal absorption: according to the white of the BOILED-Egg |
High |
BBB permeant? BBB permeation: according to the yolk of the BOILED-Egg |
Yes |
P-gp substrate? P-glycoprotein substrate: SVM model built on 1033 molecules (training set) |
No |
CYP1A2 inhibitor? Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set) |
Yes |
CYP2C19 inhibitor? Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set) |
Yes |
CYP2C9 inhibitor? Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set) |
No |
CYP2D6 inhibitor? Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set) |
Yes |
CYP3A4 inhibitor? Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set) |
No |
Log Kp (skin permeation)? Skin permeation: QSPR model implemented from |
-5.01 cm/s |
Lipinski? Lipinski (Pfizer) filter: implemented from |
0.0 |
Ghose? Ghose filter: implemented from |
None |
Veber? Veber (GSK) filter: implemented from |
0.0 |
Egan? Egan (Pharmacia) filter: implemented from |
0.0 |
Muegge? Muegge (Bayer) filter: implemented from |
1.0 |
Bioavailability Score? Abbott Bioavailability Score: Probability of F > 10% in rat |
0.55 |
PAINS? Pan Assay Interference Structures: implemented from |
0.0 alert |
Brenk? Structural Alert: implemented from |
0.0 alert: heavy_metal |
Leadlikeness? Leadlikeness: implemented from |
No; 1 violation:MW<1.0 |
Synthetic accessibility? Synthetic accessibility score: from 1 (very easy) to 10 (very difficult) |
1.73 |
* 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 |
---|---|---|
89% | A mixture of imidazole (1 .36 g, 20.0 mmol) and sodium hydroxide (0.80 g, 20.0 mmol) in DMSO was heated to 90 C for 2 h, and then cooled to room temperature. A solution of 1 -bromooctane (3.46 g, 19.0 mmol) in DMSO was added dropwise to the mixture. After stirring at room temperature for 3 h, the mixture was heated up slowly to 65 C for 16 h with constant stirring. The solution obtained was mixed with water and the product was extracted 4 times with diethyl ether. The diethyl ether phases were combined and dried with sodium sulfate. Diethyl ether was removed under vacuum and the intermediate (9) was obtained as yellow liquid (2.89 g, 89 %). 1 H NMR (DMSO-d6): delta 7.61 (s, 2H), 7.15 (s, 1 H), 6.87 (s, 1 H), 3.93 (t, 2H), 1 .68 (m, 2H), 1 .25 (m, 10H), 0.85 (t, 3H). | |
87.7% | With sodium hydroxide; In dimethyl sulfoxide; at 20 - 25℃;Inert atmosphere; | To a flask equipped with a stirrer, Add the thermometer to the three necked flask 0 · 440 g (11.0 mmol) of NaOH, 0.714 g (10.5 mmol) of imidazole and 10 mL of dimethylsulfoxide (DMSO) were stirred under nitrogen at 20 C to 25 C to give a clear solution. To this was added dropwise 1.93 g (10.0 mmol)Bromo octane, reaction 4 ~ 6 h, the reaction into 10 mL of water extracted with chloroform 3 X 10 mL, and then washed with water chloroform layer 4 ~ 5 times, and then dried with anhydrous MgS04, filtered to get the filtrate, Removal of chloroform yielded a pale yellow liquid, 1.58 g of N-octylimidazole, in 87.7% yield. |
85% | With sodium hydroxide; In tetrahydrofuran; water;Reflux; | General procedure: A solution of imidazole 3 (30 mmol) in THF (60 mL) was treated with NaOH (25 mL, 40% aq) and the alkyl bromide (30 mmol), and the reaction was refluxed overnight. The solvent was evaporated and the crude reaction mixture was extracted with CH2Cl2 against water. The organic layer was washed with water, dried over MgSO4 and concentrated. The final product was distilled under vacuum (~5 mbar) to provide 4 as yellow oily liquid in 80-85% yield. |
82.3% | General procedure: A mixture of imidazole (30 mmol, 2.04 g), potassiumhydroxide (30 mmol, 1.68 g) and dimethyl sulfoxide(10 mL) was stirred for 2 h at room temperature. Afterthat, alkyl bromide (25.0 mmol of 1-bromohexane, 1-bromooctane,1-bromodecane, 1-bromododecane, 1-bromotetradecane,1-bromohexadecane, or 1-bromooctadecane)was dropped in slowly and the mixture was stirred for anadditional 4 h. Upon completion, water (30 mL) was addedto the resulting mixture followed by extraction with chloroform(5 x 30 mL). The combined organic layer wasdried over anhydrous magnesium sulfate and the filtratewas concentrated under reduced pressure. The residue wassubjected to flash chromatography with ethyl acetate aseluent to give N-alkyl imidazole. The respective yields ofN-hexyl imidazole, N-octyl imidazole, N-decyl imidazole,N-dodecyl imidazole, N-tetradecyl imidazole, N-hexadecylimidazole and N-octadecyl imidazole are 84.6, 82.3, 81.2,80.5, 80.4, 79.8 and 79.6 %. | |
60% | Imidazole (3.41 g, 50 mmol) and NaH (1.34 g, 54 mmol) were dissolved in THF (10 mL) under N2 in an ice bath for 45 min, followed by addition of 1-bromooctane (9.65 g, 50 mmol). The solution was stirred for 24 h at room temperature and then concentrated under reduced pressure after filtration.The residue was purified by flash chromatography (SiO2; petroleum ether/ethyl acetate5 : 1 as eluent) to give 1 as alight yellow oil (5.97 g, 60 %). deltaH (CDCl3, 400 MHz) 7.42 (1H, s), 7.01 (1H, s), 6.87 (1H, s), 3.89 (2H, t, J 8.0), 1.76-1.73 (2H, m), 1.31-1.25 (10H, m), 0.87 (3H, t, J 7.2). deltaC (CDCl3, 100 MHz) 136.2, 128.4, 118.1, 46.4, 31.2, 30.6, 28.6, 28.5,26.0, 22.1, 13.6. m/z (ESI) 181 ([M + H]+). m/z 181.1708. HRMS (ESI) Anal. Calc. for C11H21N2 ([M + H]+) 181.1705. | |
General procedure: These compoundswere obtained fromthe reaction of the sodium salt of imidazole and 1-bromoalkanes, as follows: to a 3-necked round-bottom flask, provided with a reflux condenser, dropping funnel, and inlet for dry nitrogen was added a solution of imidazole (7.49 g; 0.11 mol) in dry ethanol (25 mL). Small pieces of sodium (2.53 g, 0.11 mol), were slowly introduced, the mixture was vigorously stirred until the metal has dissolved and then heated under reflux for 2 h. The mixture was cooled to room temperature; the appropriate 1-bromoalkane (0.10 mol; 16.50 g, 17.91 g, 19.31 g, 22.12 g for R ¼ C6; C7; C8 and C10, respectively)was added slowly (ca. 30 min); then the mixture was refluxed for 2 h. The mixture was cooled to room temperature, the precipitated NaBr was filtered off; the ethanol evaporated, the residual oilwas washed with water, and then dried with anhydrous MgSO4. The N-(1-alkyl)imidazoles were purified by fractional distillation (yields before distillation ca. 98%); their purity was confirmed with 1H NMR spectroscopy (results not shown). | ||
General procedure: N-Hexadecylbromide (11.35 g, 37.2 mmol) was dissolved in dimethylformamide (DMF, 50 mL) and then added to a solution of the sodium salt of imidazole, which was formed by the reaction of imidazole (5.0 g, 74 mmol) with sodium hydride (2.66 g, 111 mmol) in DMF (50 mL). The mixture was heated at 60 C for 6 h, cooled, and diluted with water. After extraction with ethyl acetate (EtOAc), the extract was washed with brine and water, and then dried with sodium sulfate. The solvent was separated by reduced pressure distillation and N-alkylimidazole was obtained as a pale yellow oily product. | ||
With potassium hydroxide; In acetonitrile; for 4h;Reflux; | General procedure: N-Butylimidazole and N-octylimidazole were synthesized fol-lowing the procedure of literature [44]: To a round-bottomedflask, imidazole (6.0 g, 88 mmol), 1-bromobutane/1-bromooctane(90 mmol), acetonitrile (50 mL) and potassium hydroxide (9.9 g,177 mmol), were added in sequence. The reaction mixture wasrefluxed for 4 h and then cooled down to room temperature. Afterevaporating the solvent, the residue was purified by a flash col-umn chromatography utilizing ethyl acetate/methanol (v/v = 25:1)as eluent. The pure product of 1-butylimidazole/1-octylimidazolewas isolated as a pale yellow oil (?83%). N-Octylimidazole:1H NMR: (CDCl3): (ppm) = 0.87 (t, J = 6.5 Hz,3H, CH3), 1.28 (br, 10H, CH2), 1.77 (br, 2H, CH2), 3.92 (t, J = 7.2 Hz,2H, CH2), 6.90 (s, 1H, ImH), 7.04 (s, 1H, ImH), 7.45 (s, 1H, ImH).13CNMR (CDCl3): (ppm) = 13.9, 22.5, 26.4, 28.9, 29.0, 31.0, 31.6, 46.9,118.7, 129.2, 136.9. | |
With sodium hydroxide; In acetone; at 20℃; for 12h; | N-alkylimidazoles were synthesized using a previously reported method with minor modification. Typically, to a solution of imidazole (1 mol equiv.) and sodium hydroxide (1 mol equiv.) in acetone (50 mE) was added 1 -bromoalkane (0.8 mol equiv.). After stirring at room temperature for 12 h, a Nal3r precipitate was filtered and acetone removed under reduced pressure. A residual oily mass was re-dissolved in dichloromethane and extracted three times with water. Finally, an organic phase was dried on anhydrous sodium sulfate and dicholoromethane was removed under reduced pressure to produce brown oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | In einen 2 I Schlenkkolben werden 830,5 g (5 mol) 1-Octylimidazol vorgelegt und 630,5g (5 mol) Dimethylsulfat portionsweise zugegeben. Der Ansatz wird danach 15 Minuten nachgeruehrt. Der Kolbeninhalt wird danach in ein 5I Becherglas ueberfuehrt und zu einer Mischung von 548,0g (5 mol) Natriumtetrafluoroborat in 2 Liter Wasser gegeben. Sofort bildetsich das Produkt als zweite, fluessige Phase. . Nach einer Phasentrennung wird die waessrige Phase noch einmal mit 1 Liter CH2Cl2extrahiert, und das organische Extrakt von Methylenchlorid befreit. Beide Produktfraktionen werden vereinigt und ueber Nacht bei 60°C am HV getrocknet. Man erhaelt 1-Octyl-3-methylimidazoliumtetrafluoroborat in 94 percentiger Ausbeute. Zum qualitativen Nachweis auf Chloridreste, werden ca. 1 ml des Produktes mit ca. 5 ml Wasser versetzt und mit 2 Tropfen konzentrierter Salpetersaeure angesaeuert. Zu dieser Loesung werden dann ca. 3-4 Tropfen Silbernitrat gegeben um etwaig vorhandenes Chlorid als Silberchlorid auszufaellen. Das Ausbleiben eines Silberchlorid-Niederschlags spricht fuer die komplette Abwesenheit von Chloridresten. [26.1] 1H-NMR (300 MHz, CDCl3):delta=9.3 ppm (s,1H,Ha); delta=7.26 ppm (d,1H,Hc); delta=7.24 ppm (d,1H,Hd); delta=4.1 ppm (t,2H,He); delta=3.9 ppm (s,2H,Hb); delta=1.6 ppm (m,2H,Hf); delta=1.2 ppm (m,10H,Hg,h,i,j,k); delta=0.8 ppm (t,3H,HI).13C-NMR (75 MHz, CDCl3):delta=137 ppm (C1); delta=124-122 ppm (C3,C4); delta=48 ppm (C5); delta=35 ppm (C2); delta=29-24 ppm (C6-C10); delta=20 ppm (C11); delta=13 ppm (C12).19F-NMR (281 MHz, CDCl3):delta= -151,3 ppm (d, 1J(BF)= 22 Hz) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71.3% | In propan-1-ol; | EXAMPLE 3 Preparation of 1-octylimidazole 64.6 parts of n-octylamine and 34 parts of 25percent strength aqueous ammonia aredissolved in 186 parts of propanol and are introduced dropwise over 30 minutes, simultaneously with a mixture of 72.5 parts of 40percent strength aqueous glyoxal solution and 37.5 parts of 40percent strength aqueous formaldehyde solution, into a stirred flask. The temperature is kept at 65° C. After all has been introduced, stirring is continued for 20 minutes at 65° C., and the mixture is then worked up by distillation. 64.2 parts of 1-octylimidazole (boiling point 110° C./1 mm Hg) are obtained, corresponding to a yield of 71.3percent of theory. |