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Chemical Structure| 586-35-6

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Hanna Głowienke ; Anna Pancielejko ; Magdalena Miodyńska ; Anna Gołąbiewska ; Emilia Gontarek-Castro ; Tomasz Klimczuk , et al.

Abstract: Perovskites are attractive structures for photocatalytic hydrogen generation, but also are limited by low stability, which can be improved by combination with other materials. Perovskite structures have potential for photocatalytic hydrogen generation; however, their practical application is hindered by inherent low stability. This limitation can be effectively mitigated through strategic combinations with complementary materials. Therefore, hybrids consisting of the perovskite CsPbX3 (X = Br, I) and the metal–organic framework (Ce)UiO-66-Y (Y = H, Br, NH2) were successfully synthesized for the first time, using a straightforward ligand-assisted reprecipitation synthesis at room temperature. To develop a room temperature synthesis for CsPbX3@(Ce)UiO-66-Y hybrid nanomaterials, herein, we optimized the synthesis of perovskite firstly (considering factors such as the choice of solvents, the drying of stabilizers, and the purification) and then developed an efficient way to combine both materials. Six types of hybrid materials, differing in the type of perovskite and functional group in the MOFs linker, were synthesized by the introduction of MOFs powder into a solution containing perovskite precursors (CsX and PbX2 in DMF stabilized by oleyamine and oleic acid) followed by antisolvent addition. We demonstrated that the hybrids containing perovskite in combination with MOF (Ce)UiO-66-NH2 in a molar ratio of 13:1 exhibited significantly higher activity and twice as long reaction stability time compared to the individual components of the hybrids when tested separately. This outcome underscores the presence of a synergistic effect, highlighting the potential of these hybrid materials in catalyzing hydrogen generation.

Keywords: Perovskite ; MOFs ; Hybrids ; LARP ; H2 generation ; Photocatalysis

Purchased from AmBeed:

Miller, Lars ;

Abstract: This work explores the synthesis and characterization of redox active rare-earth (RE) metal–organic frameworks (MOFs). MOFs are of interest due to their unique properties including permanent porosity, high surface area, and stability. Redox active MOFs have shown promise in a variety of applications including catalysis and molecular electronics. The second chapter will explore materials composed of Ce(IV) clusters bridged by ditopic carboxylate-based linkers. The synthesis of a series of UiO-66 analogues using the redox active metal Ce(IV) is completed with the original linker benzene-1,4-dicarboxylic acid as well as with various functionalized linkers including: 2-aminobenzene-1,4-dicarboxylic acid, 2-fluorobenzene1,4-dicarboxylic acid, 2-bromobenzene-1,4-dicarboxylic acid, 2,5-dihydroxybenzene-1,4- dicarboxylic acid, and 2,3,5,6-tetrafluorobenzene-1,4-dicarboxylic acid. The electrochemical differences between the analogues is explored via cyclic voltammetry. The third chapter delves into the synthesis of a series of redox active MOFs using the tetratopic tetrathiaflvalene-3,4,5,6-tetrakis(4-benzoic acid) (TTFTBA) redox active linker. Synthesis of a 3D cluster based MOF is attempted using Ce(III/IV), Yb(III), and Lu(III). Two new MOFs with shp topology are synthesized using TTFTBA and Yb(III) or Lu(III). The materials are characterized, and their redox properties are explored.

Purchased from AmBeed: ; ; ; ; ; ; ;

Alternative Products

Product Details of [ 586-35-6 ]

CAS No. :586-35-6
Formula : C8H5BrO4
M.W : 245.03
SMILES Code : O=C(O)C1=CC=C(C(O)=O)C=C1Br
MDL No. :MFCD00002403
InChI Key :QPBGNSFASPVGTP-UHFFFAOYSA-N
Pubchem ID :68513

Safety of [ 586-35-6 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H317-H319
Precautionary Statements:P280-P305+P351+P338

Computational Chemistry of [ 586-35-6 ] Show Less

Physicochemical Properties

Num. heavy atoms 13
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 48.06
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.

1.02
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

1.7
Log Po/w (WLOGP)?

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

1.85
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.

1.93
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

1.3
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

1.56

Water Solubility

Log S (ESOL):?

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

-2.64
Solubility 0.562 mg/ml ; 0.00229 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.

-2.88
Solubility 0.322 mg/ml ; 0.00131 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

-2.0
Solubility 2.43 mg/ml ; 0.00993 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.

-6.59 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<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)

1.51

Application In Synthesis of [ 586-35-6 ]

* 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 [ 586-35-6 ]

[ 586-35-6 ] Synthesis Path-Downstream   1~4

  • 1
  • [ 67-56-1 ]
  • [ 586-35-6 ]
  • [ 18643-86-2 ]
YieldReaction ConditionsOperation in experiment
98% With sulfuric acid; for 5h;Reflux; 2-Bromo terephthalic acid (204 mmol,Methanol (MeOH) 0.4M and20 mmol of sulfuric acid (H2SO4) was added to a round flask, and the mixture was refluxed for 5 hours. Next, the reaction solution was filtered and washed to obtain a reaction product in a yield of 98%
93% With thionyl chloride; at 0 - 20℃; Example 13Dimethyl 2-bromoterephthalate; Intermediate-4 To a round bottom flask was added 2-bromoterephthalic acid (10.0 g, 40.8 mmol) in methanol (120 mL). The suspension was cooled to 0 C. and thionyl chloride (11.9 mL, 163 mmol) was added dropwise. The reaction mixture was allowed to warm to rt and was stirred overnight. The mixture was concentrated, sat. NaHCO3 was added and extracted with DCM (3×). The combined organic phases were then washed with water, and brine, dried over anhydrous Na2SO4, filtered and concentrated to afford dimethyl 2-bromoterephthalate (10.4 g, 93%). LC-MS: (FA) ES+274; 1H NMR (400 MHz, CDCl3) δ 8.31 (d, J=1.6 Hz, 1H), 8.00 (dd, J=8.1, 1.6 Hz, 1H), 7.81 (d, J=8.1 Hz, 1H), 3.96 (s, 3H), 3.95 (s, 3H).
93% With thionyl chloride; at 0 - 20℃; for 16h; To a stirred solution of 2-bromoterephthalic acid (15.0 g, 61.2 mmol) in methanol (150.0 mL) was added dropwise thionyl chloride (4.91 mL, 67.3 mmol) at 0C. The reaction mixture was allowed to warm to room temperature and stirred further for 16 h. The rection was monitored by TLC, the reaction mixture was concentrated. Added saturated solution of sodium bicarbonate to the residue and extracted using dichloromethane (3 x 150.0 mL). The combined organic phase was washed with water (200.0 mL), brine (100.0 mL) and dried over anhydrous sodium sulphate. Concentrate this reaction mixture to afford 26.7 g crude, which was purified by column chromatography using eluent 0-30% of ethyl acetate in n-hexane to afford the titled compound dimethyl 2-bromoterephthalate (15.5 g, 93 % yield) as off white solid. MS (ES+) m/z = 274.04 (M+1). 1H NMR (400 MHz, Chloroform-d) δ 8.33 (d, J = 1.6 Hz, 1H), 8.02 (dd, J = 8.1, 1.6 Hz, 1H), 7.83 (d, J = 8.2 Hz, 1H), 3.98 (s, 3H), 3.97 (s, 3H).
92% With sulfuric acid; at 60℃; for 6h;Inert atmosphere; Large scale; In nitrogen atmosphere, 2-bromoterephthalic acid (30.0 kg, 122.4mol) was suspened in methanol (95 kg), cooled to about 5 C, and 98 weight % sulfuric acid (33.0 kg) was added and the mixture was stirred at 60 C for 6 hours. TLC is confirmed for the end of reaction, the reaction mixture is then cooled to the room temperature, methyl tert-butyl ether (220.0 kg) was added and the organic layer was washed with water (180.0 kg), and NaHCO3 aqueous solution (8 weight %, 180.0 kg) and salt water (24 weight %, 180.0 kg) , dried using anhydrous magnesium sulfate (6.0 kg) , concentrated under reduced pressure to obtain the title compound as pale yellow crystals (30.40 kg, yield 92.0%).
92.2% With sulfuric acid; In water; at 65℃; As shown in Scheme 1, MOF-ligand (see the Fig.S5 for the 1H and 13CNMR spectra of the MOF-ligand) and UiO-66-C≡CH could be synthesized by following a similar published procedure [28].Compound 1 to a solution of 2-bromoterephthalic acid (7.5 g,40 mmol) in 250 mL methanol, conc. H2SO4 (15 mL) was added slowly.Then being stirred at 65C overnight. After methanol was removed by evaporation, 300 mL ethyl acetate (EA) was added. The mixture was washed with K2CO3 solution (1 M) and dried with Na2SO4. Finally, the crude product 1 was purified by flask silica gel column chromatography(white solid 7.7 g, yield 92.2 %). 1H NMR (400 MHz, CDCl3) δ 8.30 (d, J=1.8 Hz, 1 H), 8.12 - 7.93 (m, 1 H), 7.81 (t, J =6.7 Hz, 1 H), 4.00 3.93(m, 6 H). 13C NMR (600 MHz, CDCl3) δ 167.96, 164.36, 137.47, 134.56,132.18, 129.76, 126.96, 122.04, 47.07.
83% With thionyl chloride; at 0 - 20℃;Inert atmosphere; To a solution of 2-bromoterephthalic acid (2.0 g, 8.2 mmol) in MeOH (20 mL) at 0 00 underN2was added thionyl chloride (5.8 g, 49 mmol) dropwise. The resulting mixture was stirred atroom temperature overnight. The mixture was concentrated and the residue partitioned between DCM (20 mL) and saturated aqueous NaHCO3 (15 mL). The aqueous phase was extracted with DCM (3 x 10 mL). The combined organic fractions were washed with saturated aqueous NaHCO3 (3 x 10 mL), brine (3 x 10 mL), dried (Na2SO4), filtered and concentrated to give the title compound (1.85 g, 83%) as a white solid. 1H NMR (400 MHz,ODd3) 6 8.30 (d, J = 1.6 Hz, 1 H), 7.99 (dd, J = 8.0, 1.2 Hz, 1 H), 7.80 (d, J = 8.0 Hz, 1 H),3.95 (s, 3H), 3.94 (s, 3H); LCMS RT 2.63 mm; m/z 273,275 [M+H]+
44% With thionyl chloride; for 4h;Reflux; 2-Bromoterephthalic acid (2.0 g, 8.2 mmol) was dissolved in 50.0 mL of methanol and 7.0 mL SOCl2. The mixture was heated to reflux for 4.0 h. After cooling to room temperature, MeOH was removed by evaporation and then 60 mL (20.0 mL * 3) of CH2Cl2 was added. The solution was washed water. Then the organic solution was dried with MgSO4. After solution was removed by evaporation, raw solid was obtained. Vacuum thermal sublimation and deposition was performed for a further purity (1.0 g, 0.44%).
To a mixture of 2-bromoterephthalic acid (2.0 g, 8.2 mmol) and DMF (0.3 mL) in DCM (20 mL) was added oxalyl chloride (15.6 g, 123 mmol) and the mixture stirred at room (0570) temperature overnight. The reaction was then concentrated and the residue diluted with MeOH (50 mL) at 0 C and stirred for 10 min. The solvent was removed under reduced pressure to give the title product as a yellow oil that was used for the next step directly. LCMS: RT 2.61 min; m/z 273.0, 275.0 [M+H] +.

  • 2
  • [ 586-35-6 ]
  • [ 18643-86-2 ]
YieldReaction ConditionsOperation in experiment
With thionyl chloride; triethylamine; In methanol; diethyl ether; Step A: Preparation of Dimethyl-2-bromoterephthalate 2-Bromoterephthalic acid (14.2 g) was treated with thionyl chloride (35 ml) and the reaction mixture was heated at reflux overnight. The reaction mixture was cooled and the excess SOCl2 was removed under reduced pressure. The residue was treated with methanol (174 ml) at -10 C. over a one-half hour period followed by triethylamine (17.4 ml). After 15 minutes at room temperature, the methanol was removed under reduced pressure. The residue was then taken up in ethyl ether, washed with water, dried and evaporated which gave a white solid (14.65 g). 1 H-NMR (CDCl3, 200 MHz): δ3.87 (s, CH3); 7.8-8.32 (m, ArH). IR (CH2 Cl2, cm-1): 1720. STR423
  • 3
  • [ 586-35-6 ]
  • [ 74-88-4 ]
  • [ 18643-86-2 ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; Scheme 19DIBAL-HDCM Step 1[00262] To the solution of 2-bromoterephthalic acid (CIV) (5.0 g, 20.40 mmol) in DMF was added K2C03 (7.9 g, 57.13 mmol) and CH3I (3.56 mL, 57.13 mmol). The reaction mixture was stirred overnight at room temperature. The reaction mixture was diluted with DCM, washed with 1 N aqueous HCI, 1 M aqueous K2C03, 10% aqueous Na2S203, brine, dried over anhydrous MgS04, and concentrated under vacuum to give dimethyl 2-bromoterephthalate (CV) (4.82 g, 17.65 mmol, 99% purity, 80% yield). ESIMS found for Ci0H9BrO4 mlz 275.2 (M+2H).
  • 4
  • [ 586-35-6 ]
  • [ 149-73-5 ]
  • [ 18643-86-2 ]
 

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