Structure of 4-Bromobenzoic acid
CAS No.: 586-76-5
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Qing Yun Li ; Leigh Anna Hunt ; Kalpani Hirunika Wijesinghe ; Christine Curiac ; Ashley Williams ; Amala Dass , et al.
Abstract: Strong photoinduced oxidants are important to organic synthesis and solar energy conversion, to chemical fuels or electric. For these applications, visible light absorption is important to solar energy conversion and long-lived excited states are needed to drive catalysis. With respect to these desirable qualities, a series of five 5,6-dicyano[2,1,3]benzothiadiazole (DCBT) dyes are examined as organic chromophores that can serve as strong photooxidants in catalytic systems. The series utilizes a DCBT core with aryl groups on the periphery with varying electron donation strengths relative to the core. The dyes are studied via both steady-state and transient absorption and emission studies. Additionally, computational analysis, voltammetry, crystallography, and absorption spectroelectrochemistry are also used to better understand the behavior of these dyes. Ultimately, a strong photooxidant is arrived at with an exceptionally long excited state lifetime for an organic chromophore of 16 µs. The long-lived excited state photosensitizer is well-suited for use in catalysis, and visible light driven photosensitized water oxidation is demonstrated using a water-soluble photosensitizer.
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Purchased from AmBeed: 54512-79-7 ; 5798-75-4 ; 328-70-1 ; 586-76-5 ; 22385-77-9 ; 3109-63-5 ; 23783-42-8 ; 3375-31-3 ; 1122-58-3 ; 479094-62-7 ; 75-98-9 ; 51364-51-3 ; 538-75-0 ; 584-08-7 ; 1122-91-4 ; 123-30-8 ; 108-88-3 ; 109-77-3 ; 64-19-7 ; 603-35-0
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CAS No. : | 586-76-5 |
Formula : | C7H5BrO2 |
M.W : | 201.02 |
SMILES Code : | C1=CC(=CC=C1C(O)=O)Br |
MDL No. : | MFCD00002529 |
InChI Key : | TUXYZHVUPGXXQG-UHFFFAOYSA-N |
Pubchem ID : | 11464 |
GHS Pictogram: |
![]() |
Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
Num. heavy atoms | 10 |
Num. arom. heavy atoms | 6 |
Fraction Csp3 | 0.0 |
Num. rotatable bonds | 1 |
Num. H-bond acceptors | 2.0 |
Num. H-bond donors | 1.0 |
Molar Refractivity | 41.1 |
TPSA ? Topological Polar Surface Area: Calculated from |
37.3 Ų |
Log Po/w (iLOGP)? iLOGP: in-house physics-based method implemented from |
1.55 |
Log Po/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by |
2.86 |
Log Po/w (WLOGP)? WLOGP: Atomistic method implemented from |
2.15 |
Log Po/w (MLOGP)? MLOGP: Topological method implemented from |
2.36 |
Log Po/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by |
1.9 |
Consensus Log Po/w? Consensus Log Po/w: Average of all five predictions |
2.16 |
Log S (ESOL):? ESOL: Topological method implemented from |
-3.27 |
Solubility | 0.109 mg/ml ; 0.000542 mol/l |
Class? Solubility class: Log S scale |
Soluble |
Log S (Ali)? Ali: Topological method implemented from |
-3.3 |
Solubility | 0.1 mg/ml ; 0.000499 mol/l |
Class? Solubility class: Log S scale |
Soluble |
Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by |
-2.63 |
Solubility | 0.473 mg/ml ; 0.00236 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 |
Yes |
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 |
-5.5 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 |
0.0 |
Bioavailability Score? Abbott Bioavailability Score: Probability of F > 10% in rat |
0.56 |
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) |
1.0 |
* 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 |
---|---|---|
99% | With potassium carbonate; palladium dichloride; In PEG400; water; at 20℃; for 0.133333h;Air atmosphere; | General procedure: A mixture of arylboronic acid (0.5 mmol), aryl bromides/iodides (0.6 mmol), PdCl2 (0.0025 mmol), K2CO3 (1.75 mmol), PEG400 1.5 mL, and H2O 1.5 mL were added to a 50 mL round-flask, and stirred at room temperature for the desired time until complete consumption of starting material as judged by TLC. Then, the reaction mixture was extracted with ether (10 mL×4) and the combined organic layers were dried over anhydrous MgSO4 (acidification was needed for carboxyl substituted substrates before extraction). The solvent was removed by evaporation under reduced pressure to afford the crude products, which were further purified by column chromatography on silica gel using petroleum ether and ethyl acetate as the eluent. |
98% | With potassium carbonate; In water; at 20℃; for 4h;Green chemistry; | General procedure: A 50 mL flask was charged with an aryl halide (1.0 mmol), anaryl boronic acid (1.2 mmol), K2CO3 (2.0 mmol), nanocatalyst(0.05 mol% Pd) and deionized water (5 mL). The reactionwas stirred at room temperature for 4 h. The progress ofthe reaction was monitored by thin-layer chromatography After the reaction was completed, distilled water (25 mL) wasadded to the mixture and dilute 2 mol/L HCl was added dropwiseto pH 3.0-4.0 with stirring, and the mixture was heatedto 100 C for 10 min. The white solid that had formed wasfiltered off and washed with hot water. After drying, it wasdissolved in ether (5 mL) and was rapidly separated using asilica gel column. Elution with ether left behind small amountsof impurities and traces of palladium black to give a crudeproduct. The ether solution was evaporated to 3-5 mL andrecrystallized to obtain a pure product. All the products 3a-uare known compounds and were characterized by comparingtheir melting points and 1H NMR spectra with those preparedrecently by using a water-soluble glycine-based Pd catalyst,PdCl2(NH2CH2CO2H)2.10 The melting points and 1H NMRdata of 3a-u are listed in the supplemental material. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23% | General procedure: EDCI (1.7 mmol) was added in small batches to a solution of the carboxylic acid (1.4 mmol) and HOBt (1.7 mmol) in dry DCM or DMF (5 ml), and the reaction mixture was stirred for 10 minutes at room temperature. A solution of the appropriate amine (1.1 mmol) in 5 ml of dry DCM or DMF was added in small portions and the reaction mixture left to stir for 24 hr at room temperature (monitored by TLC until completion). The reaction mixture was then washed with saturated aqueous sodium bicarbonate (3 x 10ml), saturated aqueous sodium chloride (2 x 10ml), dried with anhydrous Na2SO4 and concentrated under reduced pressure. Purification by column silica gel chromatography (EtOAc/Hexane, 40:60) afforded the products as solids |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | a. Preparation of4-bromo-N-(?4-cyanopyridin-2-yl)benzamide (626-1) [00560j 4-Bromo-N-4-cyanopyridin-2-yl)benzamide (626-1) (11.5 g, 77percent) was obtained as a white solid from 4-bromobenzoic acid (10 g, 49.75 mmol) and <strong>[42182-27-4]4-cyanopyridin-2-amine</strong> (5.9 g, 49.75 mmol). LC-MS (ESI): m/z (M/M+2) 302.1/304.1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In a scintillation vial, 4-bromobenzoic acid (75 mg, 0.373 mmol) was dissolved in DCM (3 mL). EDC hydrochloride (100 mg, 0.523 mmol), and DMAP (30 mg, 0.245 mmol) were added and the reaction was allowed to stir for 5 min. Cyclopropanesulfonamide (100 mg, 0.826 mmol) was added, and the reaction was allowed to stir at rt for 16 h, after which time the reaction was determined to be complete by LCMS. The reaction was diluted into DCM/H20 (30 mL, 1 : 1). The organic layer was separated, and the aqueous layer was extracted with DCM (2 x 20 mL). The combined organic extracrts were dried over MgS04, filtered, and then concentrated in vacuo. The crude material was purified by flash column chromatography (ISCO, Hex/EtOAc 0-100% gradient) to afford the title compound in 96 mg (0.316 mmol, 85% yield) as a white solid. MS (ES) 338.2 (M+H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66.4% | To a mixture of 4-boronobenzoic acid (0.10 g, 0.603 mmol) and DMF (1.21 ml) at 0 C. was added HATU (0.25 g, 0.66 mmol) and DIPEA (0.316 ml, 1.81 mmol). The mixture stirred for 30 min, then dimethyl 2,2'-azanediyldiacetate, hydrochloride (0.155 g, 0.78 mmol) was added. The reaction stirred for 72 hours. The reaction was diluted with 1N HCl and extracted with EtOAc (4*). The organic layers were combined, passed through a phase separator, concentrated, and purified via flash chromatography (ISCO, 12 g silica column, 0-40% MeOH:EtOAc) to give the title compound (0.143 g, 66.4% yield). MS (m/z) 310.0 (M+H+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With 4-methyl-morpholine; HATU; In N,N-dimethyl-formamide; at 20℃; for 12.0h; | Step 1: Preparation of tert-butyl (R)-4-(4-bromobenzoyl)-2-(hydroxymethyl)piperazine-1-carboxylate 4-Bromobenzoic acid (541 mg, 2.69 mmol), HATU (1.2 g, 3.23 mmol) and <strong>[169448-87-7](R)-tert-butyl 2-(hydroxymethyl)piperazine-1-carboxylate</strong> (582 mg, 2.69 mmol) were dissolved in DMF (8.9 mL) in a 40 mL vial. NMM (0.59 mL, 5.38 mmol) was added and the reaction was stirred at RT for 12 h then diluted with water (20 mL) and EtOAc (20 mL). The layers were separated and the organic layer was washed with water (2*10 mL) and brine (1*10 mL), then dried over sodium sulfate, filtered and concentrated. The crude mixture was purified by FCC (0-7% MeOH in DCM) to afford tert-butyl (R)-4-(4-bromobenzoyl)-2-(hydroxymethyl)piperazine-1-carboxylate (961 mg, 89%). LC-MS Rt=1.99 min (Condition C), MS (M-54)=345.1. |
Tags: 586-76-5 synthesis path| 586-76-5 SDS| 586-76-5 COA| 586-76-5 purity| 586-76-5 application| 586-76-5 NMR| 586-76-5 COA| 586-76-5 structure
A1440395 [1173020-93-3]
4-Bromobenzoic-1,2,3,4,5,6-13C6 acid
Reason: Stable Isotope
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