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Structure of 13731-82-3

Chemical Structure| 13731-82-3

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Horbalová, Julia ;

Abstract: In this report, terephthalonitriles substituted with nitrile groups are explored as anolyte compounds for their applications in non-aqueous redox flow batteries. Green solvents such as propylene carbonate (PC), γ-butyrolactone (GBR) and γ-valerolactone (GVL) are explored as possible alternatives for acetonitrile (ACN) to achieve lower toxicity and price of the electrolyte solutions utilized in the flow batteries. Three derivatives of terephthalonitriles, dimethyl 2,5-dicyanoterephthalate (C1), diethyl 2,5-dicyanoterephthalate (C2) and bis(2-methoxyethyl) 2,5-dicyanoterephthalate (C3) are investigated as anolytes. Their electrochemical properties and longterm stability are explored using cyclic voltammetry, symmetric H-cell cycling coupled with UV-Vis spectroscopy. Coin cell cycling and symmetric mixed flow battery cycling are completed to investigate the behavior of the active compounds under static and flow conditions, respectively. Experimental results obtained reveal a positive effect of the nitrile group on the redox potential achieving less deep reduction. Furthermore, diffusion coefficients alongside the electron-transfer rate constant are determined presenting values in the range of 1.0x10-5 cm2 /s to 1.0x10-7 cm/s. Additionally, electrontransfer rate constants indicate the systems to be of a quasi-reversible nature the lowest value being in an order of 1.1x10-3 cm/s. Improved diffusivity and electron-transfer rate is further explored in γ-GVL at 54°C and 74°C achieving diffusivity of 2.2x10-4 for C2 making it faster than in ACN. Exploring the compatibility of the anolyte compounds with a catholyte is obtained through coin cell cycling achieving retained capacity of 84% of 50 mM C2 and N-[2-(2-methoxyethoxy)ethyl]phenothiazine (MEEPT) in γ-GVL over 1000 cycles. This particular combination is further investigated under dynamic conditions in flow battery cycling observing the importance of incorporating ACN as a co-solvent to obtain feasible cycling. Various of performing parameters and components of the flow cell were explored and require further optimization to obtain reasonable cyclability limiting the capacity fade of the flow battery. Last, but not least, flow batteries of 10 mM C2 with 10 mM MEEPT in TBAPF6 and one-to-one solution of GVL:ACN achieving retained capacity of 65% and the same flow battery was carried out with C3 as an anolyte obtaining 85% capacity retention, making C3 a good candidate as an anolyte in GVL:CAN flow battery system. Finally, long-term stability measurements of C2 were performed and have presented no indication of decomposition or presence of newly formed species for the length of over one month, indicating a good stability of C2 for long-term measurements.

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Product Details of [ 13731-82-3 ]

CAS No. :13731-82-3
Formula : C8H4Br2O4
M.W : 323.92
SMILES Code : C1=C(Br)C(=CC(=C1C(O)=O)Br)C(O)=O
MDL No. :MFCD00204593
InChI Key :VUTICWRXMKBOSF-UHFFFAOYSA-N
Pubchem ID :83690

Safety of [ 13731-82-3 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Computational Chemistry of [ 13731-82-3 ] Show Less

Physicochemical Properties

Num. heavy atoms 14
Num. arom. heavy atoms 6
Fraction Csp3 0.0
Num. rotatable bonds 2
Num. H-bond acceptors 4.0
Num. H-bond donors 2.0
Molar Refractivity 55.76
TPSA ?

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

74.6 Ų

Lipophilicity

Log Po/w (iLOGP)?

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

1.11
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

2.36
Log Po/w (WLOGP)?

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

2.61
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.

2.64
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

2.01
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

2.15

Water Solubility

Log S (ESOL):?

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

-3.52
Solubility 0.0978 mg/ml ; 0.000302 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.

-3.57
Solubility 0.0878 mg/ml ; 0.000271 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

-2.83
Solubility 0.484 mg/ml ; 0.00149 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

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)
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.

-6.6 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

0.0
Bioavailability Score?

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

0.56

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

0.0 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<0.0
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)

1.65

Application In Synthesis of [ 13731-82-3 ]

* 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.

  • Downstream synthetic route of [ 13731-82-3 ]

[ 13731-82-3 ] Synthesis Path-Downstream   1~2

  • 1
  • europium(III) chloride hexahydrate [ No CAS ]
  • [ 865169-07-9 ]
  • [ 13731-82-3 ]
  • Eu(3+)*C20H11N4O2(1-)*C8H2Br2O4(2-) [ No CAS ]
  • 2
  • [ 1004-38-2 ]
  • [ 13731-82-3 ]
  • 2C4H7N5*C8H4Br2O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
63% In ethanol; water; for 0.5h; General procedure: To a 10 ml of ethanol-H2O mixed solution containing H2NPA(0.20 mmol) and <strong>[1004-38-2]TAP</strong>I (0.10 mmol) was stirred for half an hourcontinually. The resulting clear solution was evaporated at20e25 C, and an irregular, colorless bulk crystal was obtained afterseven days. The resulting crystals were filtered and dried afterrinsed with ethanol-H2O mixed solution. Yield: 70%. Analysiscalculated for C12H14N6O7: C, 40.64; H, 3.95; N, 23.71%. Found: C,40.35; H, 4.00; N, 23.51%. Infrared spectrum (KBr disc, cm1):3441s, 3409s, 3208m, 3082m, 2416w, 1679s, 1651s, 1607s, 1569s,1538s, 1454m, 1431m, 1413m, 1351s, 1261m, 1155m, 1133w, 1077w,972w, 912m, 843w, 830m, 810m, 782s, 763m, 705s, 661w, 587m,532s.
 

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