Structure of 79060-88-1
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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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Feliciano-Carmona, Alberto ; Wang, Xiqu ; Hughes, Russell P ; Daugulis, Olafs ; Brookhart, Maurice ;
Abstract: We have prepared cationic palladium complexes possessing a new zwitterionic ligand bis-N,N’−1-(2,4,6-triphenylpyridyl) oxalamide [(N∧N)Pd(Me)(L)]+ [BArF]−, (BArF = 3,5-(CF3)2C6H3, L = NCMe, CO). The structure of [(N∧N)Pd(Me)(CO)]+ [BArF]− was determined by X-ray diffraction analysis. Energy Decomposition Analysis (EDA) indicates this N∧N zwitterionic ligand is more electron-donating relative to bidentate diimine ligands. Low temperature NMR analysis shows the existence of linkage isomers with the N∧N isomer the most stable. Structures were assigned using NMR and DFT analysis. Barriers to interconversion of isomers are ΔG‡ = 10−12 kcal/mol. Kinetics of acetonitrile displacement from [(N∧N)Pd(Me)-(NCCH3)]+ [BArF]− by CD3CN, ethylene and t Bu3P were measured and mechanisms of exchange determined. The ethylene complex, [(N∧N)Pd(Me)(C2H4)]+ was generated at −45 °C, and the barrier of migratory insertion was determined at 0 °C (ΔG‡ = 23.4 kcal/mol) and compared to related diimine complexes. The methyl carbonyl complex undergoes migratory insertion in the presence of CO at −70 to −55 °C (ΔG‡ = ca. 15.7 kcal/mol) to yield the acyl carbonyl complex. The neutral bistrimethylsilylmethyl complex, (N∧N)Pd(CH2SiMe3)2 was prepared and characterized by X-ray diffraction analysis. It displays dynamic behavior at very low temperatures in the NMR spectrum (−90 °C, ΔG‡ = 7.9 kcal/mol) which, supported by DFT analysis, is ascribed to rotation of the bulky −CH2SiMe3 groups.
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Plasticizer-based and polymer-free ion-selective optodes on cellulose paper
Long Li ; Carlin Thompson ; Xuewei Wang ;
Abstract: Paper-based ion-selective optodes (ISOs) allow for low-cost ion measurements using widely accessible optical detectors such as smartphones, representing an attractive analytical platform for medical testing and environmental monitoring. Previously reported paper-based ISOs rely on plasticized PVC membranes or PVC/plasticizer-free adsorption layers containing hydrophobic sensing chemicals. In this paper, we studied a new format of paper-based ISOs, in which a plasticizer phase containing sensing chemicals is deposited onto cellulose paper without using a hydrophobic polymer like PVC. Compared to ISOs without plasticizers and polymers, the plasticizer-based ISOs show much higher pH sensitivity when using chromoionophore I and tetrakis[3,5-bis(trifluoromethyl)phenyl]borate as the sensing chemicals. When the sensing layer further contains a solid ionophore with high molecular rigidity, the plasticizer-based ISOs for cations also exhibit enhanced sensitivity than the plasticizer-free ISOs. However, when the ionophore is a liquid at room temperature or has a long alkyl chain, the plasticizer-based and plasticizer-free ISOs have comparable responses because the ionophore behaves as a pseudo-plasticizer. Compared to ISOs with both plasticizers and polymers, the elimination of hydrophobic polymers like PVC makes inkjet printing more efficient and preserves the capillary action of the porous paper. By using the newly launched Samba cartridge with smaller nozzles, the plasticizer-based and polymer-free optodes for sodium, potassium, and calcium ions are prepared by inkjet printing for the first time. In an example application, the inkjet-printed plasticizer-based and polymer-free ISOs are used for colorimetric measurements of urine calcium.
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Keywords: Ionophore ; Ion-selective optode ; Cellulose paper ; Inkjet printing ; Colorimetric
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Polymerization of Terminal Acetylenes by a Bulky Monophosphine-Palladium Catalyst
Chen, Zhi-Hao ; Daugulis, Olafs ; Brookhart, Maurice ;
Abstract: A well-defined Pd complex [(tBuXPhos)Pd(Me)(BArf)] bearing a bulky monophosphine ligand was synthesized and fully characterized. X-ray diffraction anal. shows that the 1,3,5-triisopropylaryl group of the dialkylbiaryl phosphine ligand exhibits a weak η6-interaction with the Pd(II) center. This catalyst exhibits excellent functional group tolerance and polymerizes propargyl esters containing benzoyl and acetyl groups, propargyl Me ether, propargyl alc., benzyl acetylene, and Ph acetylene to yield polymers with Mn values at 5-15 kDa with monomodal mol. weight distributions between ∼1.4 and 2.1.
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Charge‐activated TADDOLs: Recyclable organocatalysts for asymmetric (hetero‐) Diels–Alder reactions
George F. Riegel ; Keiji Takashige ; Alex Lovstedt ; Steven R. Kass ;
Abstract: Several charge-containing TADDOL salts were synthesized and used as organocatalysts in asymmetric Diels–Alder and hetero-Diels–Alder reactions. Their catalytic activity was found to exceed that of a noncharged analog while maintaining or improving upon the enantioselectivity. The enhanced activities of the TADDOL salts enabled them to act as presumed hydrogen bond donor catalysts in the Diels–Alder and hetero-Diels–Alder reactions of 1,3-cyclohexadiene with methyl vinyl ketone at 40°C and 2-phenoxy-1,3-butadiene with ethyl glyoxylate at room temperature, respectively. Given the ionic nature of these charge-activated catalysts, it also proved possible to recycle and reuse the TADDOL without chromatography or the need for a recrystallization.
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CAS No. : | 79060-88-1 |
Formula : | C32H12BF24Na |
M.W : | 886.20 |
SMILES Code : | FC(C1=CC(C(F)(F)F)=CC([B-](C2=CC(C(F)(F)F)=CC(C(F)(F)F)=C2)(C3=CC(C(F)(F)F)=CC(C(F)(F)F)=C3)C4=CC(C(F)(F)F)=CC(C(F)(F)F)=C4)=C1)(F)F.[Na+] |
MDL No. : | MFCD00043323 |
InChI Key : | LTGMONZOZHXAHO-UHFFFAOYSA-N |
Pubchem ID : | 23681909 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
Num. heavy atoms | 58 |
Num. arom. heavy atoms | 24 |
Fraction Csp3 | 0.25 |
Num. rotatable bonds | 12 |
Num. H-bond acceptors | 24.0 |
Num. H-bond donors | 0.0 |
Molar Refractivity | 150.07 |
TPSA ? Topological Polar Surface Area: Calculated from |
0.0 Ų |
Log Po/w (iLOGP)? iLOGP: in-house physics-based method implemented from |
0.0 |
Log Po/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by |
14.17 |
Log Po/w (WLOGP)? WLOGP: Atomistic method implemented from |
20.43 |
Log Po/w (MLOGP)? MLOGP: Topological method implemented from |
11.02 |
Log Po/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by |
13.7 |
Consensus Log Po/w? Consensus Log Po/w: Average of all five predictions |
11.86 |
Log S (ESOL):? ESOL: Topological method implemented from |
-13.78 |
Solubility | 0.0 mg/ml ; 0.0 mol/l |
Class? Solubility class: Log S scale |
Insoluble |
Log S (Ali)? Ali: Topological method implemented from |
-14.26 |
Solubility | 0.0 mg/ml ; 0.0 mol/l |
Class? Solubility class: Log S scale |
Insoluble |
Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by |
-16.38 |
Solubility | 0.0 mg/ml ; 4.17e-17 mol/l |
Class? Solubility class: Log S scale |
Insoluble |
GI absorption? Gatrointestinal absorption: according to the white of the BOILED-Egg |
Low |
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) |
Yes |
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 |
-1.65 cm/s |
Lipinski? Lipinski (Pfizer) filter: implemented from |
2.0 |
Ghose? Ghose filter: implemented from |
None |
Veber? Veber (GSK) filter: implemented from |
1.0 |
Egan? Egan (Pharmacia) filter: implemented from |
1.0 |
Muegge? Muegge (Bayer) filter: implemented from |
4.0 |
Bioavailability Score? Abbott Bioavailability Score: Probability of F > 10% in rat |
0.17 |
PAINS? Pan Assay Interference Structures: implemented from |
0.0 alert |
Brenk? Structural Alert: implemented from |
1.0 alert: heavy_metal |
Leadlikeness? Leadlikeness: implemented from |
No; 1 violation:MW<3.0 |
Synthetic accessibility? Synthetic accessibility score: from 1 (very easy) to 10 (very difficult) |
4.59 |
* 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 |
---|---|---|
62% | In chloroform; at 35℃; for 24h; | General procedure: A mixture of amino acid ester hydrochloride (1.0 equiv., 100 mg) and sodiumtetrakis [3,5-bis(trifluoromethyl)phenyl] borate (NaBArF) (1.1 equiv.) was added tochloroform (40 mL) in a 100 mL round-bottom flask. This was then stirred at 35 for 24h. The progress of the reaction was monitored by taking an aliquot from the clear solution.The anion exchange reaction was deemed complete when no further precipitation(AgCl) was observed upon addition of an aqueous solution of AgNO3 to the aliquot. Theresulting white precipitate was removed by filtering twice. The solvent of the filtrate wassubjected to rotary evaporation under reduced pressure. The resultant yellow viscoussolid was dried in a vacuum at 45 for two days, to generate the target products. |
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