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Chemical Structure| 55120-76-8 Chemical Structure| 55120-76-8

Structure of 55120-76-8

Chemical Structure| 55120-76-8

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Product Citations

Product Citations

Siqi Li ;

Abstract: Upcoming depletion of non-renewable fossil fuels provides an urgent prompt for reshaping the current structure of both direct energy sources and processing for industrial chemicals. Biorefinery hints an alternative pathway especially in processing industrial chemicals through oxidation of bio-derivable alcohols towards aldehydes and carboxylic acids that may serve as precursors to esters and polymers. With development in photovoltaic electrolyzers, renewable-energy compatible electrocatalysis serves as a promising tool to perform the selective oxidation reaction under the principles of green chemistry. Aldehydes are considered relevant industrial chemicals that are usually evolved from fossil-fuel dependent procedures. Alcohol oxidation towards aldehyde products usually suffers from poor selectivity, remains challenging in the field and relies heavily on noble metal complexes or electrocatalysts. Here, this thesis outlines strategies to use inorganic mediators and noble-metal-free inorganic materials to achieve selective ethanol oxidation towards acetaldehyde. Solvent-free electrolysis, with ethanol as both the solvent and the substrate, is heavily implemented, where acetalization allows the generated acetaldehyde to be protected. This scheme is however understudied with ethanol being thought of as a difficult solvent for electrochemistry. Under these circumstances, Chapter 2 investigates the use of chloride as redox mediator for solvent-free ethanol oxidation. On glassy carbon (GC), cyclic voltammetry (CV) shows chloride oxidation originates at lower potential compared to oxidation in chloride-free electrolyte. Constant potential chronoamperometry (CPC) shows 2-electron ethanol oxidation to 1,1-diethoxyethane (DEE) proceeds with >95% faradaic efficiency (FE) with chloride electrolyte. DEE arises from acetalization of acetaldehyde and protects acetaldehyde from overoxidation. UV–vis spectroscopy shows that ethyl hypochlorite (EtOCl) is the sole chloride oxidation product, which is known to decompose unimolecularly to form HCl and acetaldehyde. Finally, kinetic experiments show steady-state formation of EtOCl during electrolysis. Chapter 3 seeks to understand the mechanism of the chloride oxidation reaction (COR) in ethanol. CV carried out at varying scan rate in inert dichloromethane solvent establishes a Volmer step, where solution chloride ion adsorbs as chlorine(0) on GC. At higher applied potential, a second electron transfer from ethanol solvent occurs, forming EtOCl. Rotating ring-disk electrode (RRDE) measurement and in situ spectroelectrochemical measurements corroborate the mechanism by showing no EtOCl is produced in lower potential (<0.8V), despite anodic current being observed. Thus, the 2-electron COR mechanism is confirmed to be Volmer step followed by a subsequent reaction between ethanol and adsorbed chlorine(0). Koutecky-Levich (K-L) analysis quantifies the kinetic rate constant of the COR to be 10–5 to 10–6 s–1, which is 2 – 3 orders of magnitude faster than direct alcohol oxidation. Chapter 4 develops a noble-metal-free electrocatalyst for neat ethanol oxidation. MnOx is deposited on FTO by electrochemical deposition. The material is amorphous by X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) reveals a mixed-valent manganese (between Mn3+ and Mn4+). Similar linear-sweep voltammetry (LSV) current responses are observed when tested with Cl--, NO3¬--, and OTf-- containing electrolytes, indicating direct ethanol oxidation occurs on MnOx. After 16-hour CPC, >90% FE for DEE is observed by gas chromatrography in both Bu4NOTf and HOTf electrolytes. Elemental analysis of the electrolyte solution shows <1% Mn dissolved after long-term electrolysis, highlighting its operational stability. With no potential applied, Mn dissolution occurs, and we propose the chemical oxidation of ethanol by Mn3+ is the rate limiting step, supported by Tafel analyses in electrolytes of varying acidity.

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Product Details of [ 55120-76-8 ]

CAS No. :55120-76-8
Formula : C2F6MnO6S2
M.W : 353.08
SMILES Code : O=S(C(F)(F)F)([O-][Mn+2][O-]S(C(F)(F)F)(=O)=O)=O
MDL No. :MFCD17015267
InChI Key :HEYNLDRKZOOEDN-UHFFFAOYSA-L
Pubchem ID :15436487

Safety of [ 55120-76-8 ]

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H302-H314
Precautionary Statements:P261-P280-P305+P351+P338-P310
Class:8
UN#:3261
Packing Group:

Computational Chemistry of [ 55120-76-8 ] Show Less

Physicochemical Properties

Num. heavy atoms 17
Num. arom. heavy atoms 0
Fraction Csp3 1.0
Num. rotatable bonds 6
Num. H-bond acceptors 12.0
Num. H-bond donors 0.0
Molar Refractivity 31.41
TPSA ?

Topological Polar Surface Area: Calculated from
Ertl P. et al. 2000 J. Med. Chem.

119.18 Ų

Lipophilicity

Log Po/w (iLOGP)?

iLOGP: in-house physics-based method implemented from
Daina A et al. 2014 J. Chem. Inf. Model.

0.0
Log Po/w (XLOGP3)?

XLOGP3: Atomistic and knowledge-based method calculated by
XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry

1.69
Log Po/w (WLOGP)?

WLOGP: Atomistic method implemented from
Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.

5.32
Log Po/w (MLOGP)?

MLOGP: Topological method implemented from
Moriguchi I. et al. 1992 Chem. Pharm. Bull.
Moriguchi I. et al. 1994 Chem. Pharm. Bull.
Lipinski PA. et al. 2001 Adv. Drug. Deliv. Rev.

-0.34
Log Po/w (SILICOS-IT)?

SILICOS-IT: Hybrid fragmental/topological method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

1.02
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

1.54

Water Solubility

Log S (ESOL):?

ESOL: Topological method implemented from
Delaney JS. 2004 J. Chem. Inf. Model.

-2.7
Solubility 0.708 mg/ml ; 0.00201 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Soluble
Log S (Ali)?

Ali: Topological method implemented from
Ali J. et al. 2012 J. Chem. Inf. Model.

-3.81
Solubility 0.055 mg/ml ; 0.000156 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Soluble
Log S (SILICOS-IT)?

SILICOS-IT: Fragmental method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

-1.13
Solubility 26.0 mg/ml ; 0.0736 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Soluble

Pharmacokinetics

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)
and tested on 415 molecules (test set)
10-fold CV: ACC=0.72 / AUC=0.77
External: ACC=0.88 / AUC=0.94

No
CYP1A2 inhibitor?

Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.83 / AUC=0.90
External: ACC=0.84 / AUC=0.91

No
CYP2C19 inhibitor?

Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.80 / AUC=0.86
External: ACC=0.80 / AUC=0.87

No
CYP2C9 inhibitor?

Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set)
and tested on 2075 molecules (test set)
10-fold CV: ACC=0.78 / AUC=0.85
External: ACC=0.71 / AUC=0.81

No
CYP2D6 inhibitor?

Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set)
and tested on 1068 molecules (test set)
10-fold CV: ACC=0.79 / AUC=0.85
External: ACC=0.81 / AUC=0.87

No
CYP3A4 inhibitor?

Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set)
and tested on 2579 molecules (test set)
10-fold CV: ACC=0.77 / AUC=0.85
External: ACC=0.78 / AUC=0.86

No
Log Kp (skin permeation)?

Skin permeation: QSPR model implemented from
Potts RO and Guy RH. 1992 Pharm. Res.

-7.25 cm/s

Druglikeness

Lipinski?

Lipinski (Pfizer) filter: implemented from
Lipinski CA. et al. 2001 Adv. Drug Deliv. Rev.
MW ≤ 500
MLOGP ≤ 4.15
N or O ≤ 10
NH or OH ≤ 5

0.0
Ghose?

Ghose filter: implemented from
Ghose AK. et al. 1999 J. Comb. Chem.
160 ≤ MW ≤ 480
-0.4 ≤ WLOGP ≤ 5.6
40 ≤ MR ≤ 130
20 ≤ atoms ≤ 70

None
Veber?

Veber (GSK) filter: implemented from
Veber DF. et al. 2002 J. Med. Chem.
Rotatable bonds ≤ 10
TPSA ≤ 140

0.0
Egan?

Egan (Pharmacia) filter: implemented from
Egan WJ. et al. 2000 J. Med. Chem.
WLOGP ≤ 5.88
TPSA ≤ 131.6

0.0
Muegge?

Muegge (Bayer) filter: implemented from
Muegge I. et al. 2001 J. Med. Chem.
200 ≤ MW ≤ 600
-2 ≤ XLOGP ≤ 5
TPSA ≤ 150
Num. rings ≤ 7
Num. carbon > 4
Num. heteroatoms > 1
Num. rotatable bonds ≤ 15
H-bond acc. ≤ 10
H-bond don. ≤ 5

2.0
Bioavailability Score?

Abbott Bioavailability Score: Probability of F > 10% in rat
implemented from
Martin YC. 2005 J. Med. Chem.

0.55

Medicinal Chemistry

PAINS?

Pan Assay Interference Structures: implemented from
Baell JB. & Holloway GA. 2010 J. Med. Chem.

0.0 alert
Brenk?

Structural Alert: implemented from
Brenk R. et al. 2008 ChemMedChem

2.0 alert: heavy_metal
Leadlikeness?

Leadlikeness: implemented from
Teague SJ. 1999 Angew. Chem. Int. Ed.
250 ≤ MW ≤ 350
XLOGP ≤ 3.5
Num. rotatable bonds ≤ 7

No; 1 violation:MW<1.0
Synthetic accessibility?

Synthetic accessibility score: from 1 (very easy) to 10 (very difficult)
based on 1024 fragmental contributions (FP2) modulated by size and complexity penaties,
trained on 12'782'590 molecules and tested on 40 external molecules (r2 = 0.94)

3.34
 

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