Structure of 28611-39-4
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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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Rajapaksha, Ishanka N. ; Wang, Jing ; Leszczynski, Jerzy ; Scott, Colleen N. ;
Abstract: NIR dyes have become popular for many applications, including biosensing and imaging. For this reason, the mol. switch mechanism of the xanthene dyes makes them useful for in vivo detection and imaging of bioanalytes. Our group has been designing NIR xanthene-based dyes by the donor-acceptor-donor approach; however, the equilibrium between their opened and closed forms varies depending on the donors and spacer. We synthesized donor-acceptor-donor NIR xanthene-based dyes with an alkyne spacer via the Sonogashira coupling reaction to investigate the effects of the alkyne spacer and the donors on the maximum absorption wavelength and the mol. switching (ring opening) process of the dyes. We evaluated the strength and nature of the donors and the presence and absence of the alkyne spacer on the properties of the dyes. It was shown that the alkyne spacer extended the conjugation of the dyes, leading to absorption wavelengths of longer values compared with the dyes without the alkyne group. In addition, strong charge transfer donors shifted the absorption wavelength towards the NIR region, while donors with strong π-donation resulted in xanthene dyes with a smaller equilibrium constant DFT/TDDFT calculations corroborated the exptl. data in most of the cases. Dye 2 containing the N,N-dimethylaniline group gave contrary results and is being further investigated.
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Keywords: donor-acceptor-donor ; NIR dyes ; xanthene dyes ; amine donors ; alkyne spacers
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Purchased from AmBeed: 589-87-7 ; 768-60-5 ; 201802-67-7 ; 262861-81-4 ; 57102-42-8 ; 17573-94-3 ; 1066-54-2 ; 205877-26-5 ; 28611-39-4 ; 1195931-66-8
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CAS No. : | 28611-39-4 |
Formula : | C8H12BNO2 |
M.W : | 165.00 |
SMILES Code : | CN(C1=CC=C(B(O)O)C=C1)C |
MDL No. : | MFCD01074642 |
InChI Key : | RIIPFHVHLXPMHQ-UHFFFAOYSA-N |
Pubchem ID : | 2734344 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* 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 |
---|---|---|
Ethyl 5-bromo-1-benzothiophene-2-carboxylate (2.0 g), 4-dimethylaminophenylboronic acid (1.27 g), 1 M potassium carbonate aqueous solution (15 mL) and ethanol (15 mL) were added to toluene (50 mL), and stirred for 30 minutes at room temperature in an argon atmosphere. Tetrakis(triphenylphosphine)palladium (0.24 g) was added and refluxed for 8 hours. The mixture was extracted with ethyl acetate, the organic layer was washed with water and sodium chloride solution and dried over magnesium sulfate, and the solvent was evaporated. The residue was purified by silica gel column chromatography (elution solvent: ethyl acetate/hexane) to obtain ethyl 5-[4-(dimethylamino)phenyl]-1-benzothiophene-2-carboxylate (1.36 g) as yellow crystals. 1H-NMR (300MHz, CDCl3) δ 1.43 (3H, t, J = 7.1 Hz), 3.01 (6H, s), 4.42 (2H, q, J = 7.1 Hz), 6.83 (2H, d, J = 8.9 Hz), 7.65 (2H, d, J = 8.9 Hz), 7.68 (1H, dd, J = 1.7, 8.5 Hz), 7.87 (1H, d, J = 8.5Hz), 8.00 (1H, d, J = 1.7 Hz), 8.08 (1H, s) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
500 mg (2.5 MMOL) 5-bromo-benzo [1,2, 5] oxadiazole and 313 mg (0.1 eq. ) tetrakis- (triphenylphosphine) palladium are stirred for 30 minutes at room temperature in 10 mL 1,2- dimethoxyethane. 533 mg (2 eq. ) sodium carbonate are dissolved in 1.8 mL water and added to the reaction mixture, followed by 663 mg (1.6 eq. ) 4- (dimethylamino) phenylboronic acid. After stirring at REFLUX FOR 18H, the reaction mixture is cooled to room temperature and extracted with ethyl acetate and water. The organic phases are combined, dried with magnesium sulfate, filtered and evaporated. The residue is column chromatographed (hexane, then HEXANE/ETHYL acetate 8: 1 then 5: 1) to yield the desired product as a yellow solid. MS (ES+): 240 (M+1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In methanol; water; toluene;Inert atmosphere; Reflux; | General procedure: To a solution of bromobiphenylaldehyde (6, 260 mg, 1 mmol) and various phenyl boronic acids (7a-j, 1 mmol) in 2 M aqueous sodium carbonate (2 mL) and toluene/ethanol (9:3 mL) is added a catalytic amount (0.4% mol) of tetrakis-triphenylphosphine palladium, and the mixture was reflux under argon atmosphere for 2-3 h. After completion of reaction, the suspension is cooled and extracted with ethyl acetate (3 × 30 mL) and the organic phase was washed with water and brine, dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure to get the crude product. This residue was further purified by column chromatography using ethyl acetate and hexane to afford the pure terphenylaldehydes (8). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,2-dimethoxyethane; water; at 0 - 80℃; for 24h; | To a solution of 2 (1 g, 5.3 mmol) and 4-(dimethylamino)phenylboronicacid (0.74 g, 5.3 mmol) in mixture of 2 M sodium carbonate aq (10 mL) and DME(1,2-dimethoxyethane) (10 mL), tetrakis-(triphenylphosphine)palladium (0) (0.3g, 0.26 mmol) was added by keeping the temperature at 0 C. Thereaction mixture was stirred at 80 C for 24 h. Upon completion, thereaction mixture was poured into ice-cold water. The mixture was diluted withEtOAc, and the insoluble material was filtered off through Celite. The organiclayer of the filtrate was washed with brine, dried anhydrous magnesium sulfate,and concentrated. The residue was chromatographed (SiO2, EtOAc/n-hexane, 1/9,v/v) to afford compound 3 (0.9 g, 3.9 mmol, 73%). 1H NMR (500 MHz, CDCl3,delta, ppm): 2.49 (3H. s), 3.02 (6H. s), 6.56 (1H, d, J = 3.7 Hz), 6.72 (2H, d, J= 9.1 Hz), 7.25 (1H, d, J = 3.7 Hz),7.67 (2H, d, J = 9.1 Hz). MS m/z 230 (M + H)+. |
71% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,2-dimethoxyethane; for 12h;Reflux; Inert atmosphere; | 5-Bromo-2-acetylfuran (Compound a) (1.6 g, 8.5 mmol)To the dissolved DME solution 4- (dimethylamino) benzeneboronic acid (Sigma-Aldrich, St. Louis, Mo., USA) was added.2M Na2CO3(10 mL) was addedAfter dissolving Pd (PPh3) 4 (0.98 g, 0.85 mmol)Further added to the solution and refluxed under nitrogen for 12 hours.The solution was extracted with ethyl acetate,After washing with water, it was dried over MgSO4.After evaporation of the solvent in vacuo,The residue was chromatographed (SiO2, EtOAc / n-hexane = 4/1 (v / v)) to give compound b (1.3 g, 71%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With potassium phosphate; hydrazine hydrate; at 80℃; for 8h; | 25 mL of the reaction flask was added hydrazine hydrate (0.25 mmol)4-N, N-dimethylbenzeneboronic acid (0.5 mmol)Potassium phosphate (1.0 mmol)And polyethylene glycol-400 (2.0 g).The mixture was reacted at 80 C until the reaction was complete. The reaction mixture was cooled to room temperature and the solvent was evaporated under reduced pressure. The product was isolated by column chromatography in a yield of 92%. |
89% | With copper(II) sulfate hydrate; potassium hydroxide; In water; at 20℃; for 24h; | General procedure: A flask was charged with 3,4-dimethoxyphenylboronic acid (1.0 mmol),CuSO4*H2O (0.02 g, 0.1 mmol), CNT-Chit film (10.0 mg), KOH (0.17 g, 3.0mmol), and H2O (5.00 mL). Then, the flask was stirred at room temperature in open air for 24 hours. At the end of the reaction, the reaction mixture was filtered and washed with water. Then, the filtrate was acidified with dilute aqueous HCl and extracted with diethyl ether (3 10 mL). The organic phases were combined, and the volatile components were evaporated under reduced pressure. Purification by flash column chromatography on silica gel (70%hexanes/ 30% ethyl acetate) afforded 0.1433 g of 3,4-dimethoxyphenol (2f) in 93% isolated yield as an off-white solid |
34% | With copper(I) oxide; potassium hydroxide; In water; at 20℃; for 24h;Green chemistry; | General procedure: a flask was charged with 4-methylphenylboronic acid (1.0 mmol), Cu2O (0.008 g, 0.1 mmol), CTS-Py (100.0 mg), KOH (0.17 g, 3.0 mmol), and H2O (5.00 mL). Then, the flask was stirred at room temperature in open air for 24 h. At the end of the reaction, the reaction mixture was filtered and washed with water. Then, the filtrate was acidified with dilute aqueous HCl and extracted with diethyl ether (3 × 10 mL). The organic phases were combined. Combined organic layers were washed with brine, and then dried over anhydrous Na2SO4. The volatile components were evaporated under reduced pressure. Filtering through short pad of silica (80percent hexanes/ 20percent ethyl acetate) afforded 0.0671 g of p-cresol (2d) in 62percent isolated yield as a colorless oily liquid. |