Structure of 584-13-4
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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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Kopacka, Gabriela ; Wasiluk, Kinga ; Majewski, Pawel W. ; Kopyt, Michal ; Kwiatkowski, Piotr ; Megiel, Elzbieta
Abstract: The fixation of carbon dioxide with epoxides is one of the most attractive methods for the green utilization of this greenhouse gas and leads to many valuable chems. This process is characterised by 100% atom efficiency; however, an efficient catalyst is required to achieve satisfactory yields. Metal-organic frameworks (MOFs) are recognized as being extremely promising for this purpose. Nevertheless, many of the proposed catalysts are based on ions of rare elements or elements not entirely safe for the environment; this is notable with com. unavailable ligands. In an effort to develop novel catalysts for CO2 fixation on an industrial scale, we propose novel MOFs, which consist of aluminum ions coordinated with commercially available 1,4-naphthalene dicarboxylic acid(Al@NDC) and their nanocomposites with gold nanoparticles entrapped inside their structure (AlAu@NDC). Due to the application of 4-amino triazole and 5-amino tetrazole as crystallization mediators, the morphol. of the synthesized materials can be modified. The introduction of gold nanoparticles (AuNPs) into the structure of the synthesized Al-based MOFs causes the change in morphol. from nano cuboids to nanoflakes, simultaneously decreasing their porosity. However, the homogeneity of the nanostructures in the system is preserved. All synthesized MOF materials are highly crystalline, and the simulation of PXRD patterns suggests the same tetragonal crystallog. system for all fabricated nanomaterials. The fabricated materials are proven to be highly efficient catalysts for carbon dioxide oxide; and propylene oxide. Applying the synthesized catalysts enables the reactions to be performed under mild conditions (90℃; 1 MPa CO2) within a short time and with high conversion and yield (90% conversion of glycidol towards glycerol carbonate with 89% product yield within 2 h). The developed nanocatalysts can be easily separated from the reaction mixture and reused several times (both conversion and yield do not change after five cycles). The excellent performance of the fabricated catalytic materials might be explained by their high microporosity (from 421 m2 g-1 to 735 m2 g-1); many catalytic centers in the structure exhibit Lewis acids' behavior, increased capacity for CO2 adsorption, and high stability. The presence of AuNPs in the synthesized nanocatalysts (0.8% weight/weight) enables the reaction to be performed with a higher yield within a shorter time; this is especially important for less-active epoxides such as propylene oxide (two times higher yield was obtained using a nanocomposite, in comparison with Al-MOF without nanoparticles).
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Keywords: metal-organic frameworks ; cyclic carbonates ; heterogeneous catalysts ; gold nanoparticles ; CO2 fixation ; epoxides
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CAS No. : | 584-13-4 |
Formula : | C2H4N4 |
M.W : | 84.08 |
SMILES Code : | C1=NN=C[N]1N |
MDL No. : | MFCD00003099 |
InChI Key : | FMCUPJKTGNBGEC-UHFFFAOYSA-N |
Pubchem ID : | 11432 |
GHS Pictogram: |
![]() |
Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
Num. heavy atoms | 6 |
Num. arom. heavy atoms | 5 |
Fraction Csp3 | 0.0 |
Num. rotatable bonds | 0 |
Num. H-bond acceptors | 2.0 |
Num. H-bond donors | 1.0 |
Molar Refractivity | 20.16 |
TPSA ? Topological Polar Surface Area: Calculated from |
56.73 Ų |
Log Po/w (iLOGP)? iLOGP: in-house physics-based method implemented from |
0.34 |
Log Po/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by |
-0.82 |
Log Po/w (WLOGP)? WLOGP: Atomistic method implemented from |
-1.0 |
Log Po/w (MLOGP)? MLOGP: Topological method implemented from |
-0.87 |
Log Po/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by |
-0.55 |
Consensus Log Po/w? Consensus Log Po/w: Average of all five predictions |
-0.58 |
Log S (ESOL):? ESOL: Topological method implemented from |
-0.46 |
Solubility | 29.1 mg/ml ; 0.346 mol/l |
Class? Solubility class: Log S scale |
Very soluble |
Log S (Ali)? Ali: Topological method implemented from |
0.11 |
Solubility | 108.0 mg/ml ; 1.28 mol/l |
Class? Solubility class: Log S scale |
Highly soluble |
Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by |
0.43 |
Solubility | 227.0 mg/ml ; 2.7 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 |
No |
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) |
No |
CYP2C19 inhibitor? Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set) |
No |
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) |
No |
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 |
-7.4 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 |
2.0 |
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) |
1.78 |
* 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 |
---|---|---|
50% | at 100℃; for 96h;High pressure; Autoclave; | Atr (16.8 mg, 0.2 mmol), Cu(OAc)2H2O (40.0 mg, 0.2 mmol), and <strong>[68-04-2]sodium citrate</strong> (29.4 mg, 0.1 mmol) were dissolved in doubly deionized water (8.0 mL). The resulting mixture was then transferred into a Parr Teflon-lined stainless steel vessel (23.0 mL) and heated at 100 C for 96 h under autogenous pressure. After the mixture was cooled to room temperature at a rate of 3.3 C h1, blue block-shaped crystals suitable for X-ray analysis were generated directly, washed with water, and dried in air. Yield: 50% based on CuII salt. Anal. Calc. for C16H28Cu4N8O20: C, 21.20; H, 3.11; N,12.36. Found: C, 20.20; H, 3.10; N, 12.37%. FT-IR (KBr, cm-1):3339 (br), 1606 (s), 1561 (s), 1423 (s), 1394 (s), 1319 (s), 1262(w), 1217 (m), 1081 (m), 1064 (m), 1022 (w), 914 (m), 859 (w), 706 (m), 625 (m), 551 (w), 472 (w), 413 (w). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With triethylamine; In methanol; at 100℃; for 96h;High pressure; Autoclave; | To a methanol solution (5.0 mL) containing atr (25.2 mg,0.3 mmol), H4cit (20.9 mg, 0.1 mmol), and triethylamine (40.4 mg, 0.4 mmol) was slowly added an aqueous solution (5.0 mL) of Cu(NO3)2*6H2O (48.4 mg, 0.2 mmol) with constant stirring. The resulting mixture was filtered after further stirring for half an hour. Blue block-shaped crystals suitable for X-ray diffraction were grown by slow evaporation of the filtrate within aweek. Yield: 67% based on CuII salt. Anal. Calc. for C10H16N8O9Cu2: C, 23.13; H, 3.10; N, 21.57. Found: C, 23.11; H, 3.10; N, 21.56%. FT-IR (KBr, cm1): 3442 (br), 1636 (s), 1362 (s), 1222 (w), 1125(m), 1062 (m), 1007 (m), 936 (m), 858 (m), 761 (s), 620 (m),501 (w), 438 (w). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With lithium hydroxide; In methanol; at 100℃; for 96h;High pressure; Autoclave; | To a methanol solution (5.0 mL) containing atr (16.8 mg,0.2 mmol), H4cit (21.0 mg, 0.1 mmol), and lithium hydroxide (8.4 mg, 0.2 mmol) was slowly added an aqueous solution(5.0 mL) of Cu(NO3)2*6H2O (72.3 mg, 0.3 mmol) with constant stirring. The resulting mixture was filtered after further stirring for half an hour. Blue block-shaped crystals suitable for X-ray diffraction were generated by slow evaporation of the filtrate within a week. Yield: 50% based on H4cit. Anal. Calc. for C8H16.50Cu2N4O11.25: C, 20.19; H, 3.50; N, 11.77. Found: C, 20.20; H, 3.48; N, 11.79%. FT-IR (KBr, cm-1): 3468 (br), 1639 (s), 1617 (s), 1421 (s), 1307(m), 1249 (m), 1086 (m), 1049(m), 1008 (m), 957 (s), 926 (w),699 (w), 619 (w), 698 (w), 514 (w). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With 2,6-di-t-butyl catechol; acetic acid; In ethanol; for 3h;Reflux; | General procedure: A mixture of equal volumes of heterocyclic amine (0.02 mol), and vinylbenzaldehyde (1p and 1m) (0.02 mol) in the presence of some traces of 2,6-di-t-butyl catechol as the polymerization inhibitor, and 4-5 drops of glacial acetic acid used as reaction catalyst in 30 mL of absolute ethanol was refluxed for 3 h in water bath as shown in the Scheme 1. The resulting solution was concentrated in vacuum and cooled down in a freezer for 24 h. The precipitated product was filtered, washed with cold absolute ethanol and then dried. |
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