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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. : | 201802-67-7 |
Formula : | C18H16BNO2 |
M.W : | 289.14 |
SMILES Code : | OB(O)C1=CC=C(C=C1)N(C1=CC=CC=C1)C1=CC=CC=C1 |
MDL No. : | MFCD06798117 |
InChI Key : | TWWQCBRELPOMER-UHFFFAOYSA-N |
Pubchem ID : | 12166934 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335-H413 |
Precautionary Statements: | P261-P273-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 |
---|---|---|
76% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In tetrahydrofuran; methanol; water; for 24h;Inert atmosphere; Reflux; | General procedure: A mixture of compound B1 (0.70 g, 2.00 mmol), 4-(diphenylamino)phenylboronic acid (0.70 g, 2.40 mmol), tetrakis(triphenylphosphine)palladium (0.12 g, 0.10 mmol), and aqueous sodium carbonate (2 M, 10 mL) in tetrahydrofuran (40 mL) and methanol (10 mL) was heated to reflux in a nitrogen atmosphere for 24 h. After the reaction mixture was concentrated in vacuo, the resulting mixture was extracted with dichloromethane. The organic layer was washed with water and brine and dried using anhydrous sodium sulfate. The filtrate was concentrated in vacuo to give a crude mixture, which was then subjected to column chromatography on silica gel using dichloromethane and hexane (v/v 1:1) as the eluent to afford analytically pure N,N-diphenyl-4'-(1-phenyl-1H-benzo[d]imidazol-2-yl)biphenyl-4-amine as a yellow solid (0.78 g, 76%). 1H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8 Hz, 1H), 7.61 (d, J = 8.4 Hz, 2H), 7.52 (d, J = 8 Hz, 4H), 7.45 (d, J = 8.8 Hz, 2H), 7.35 (d, J = 7.8 Hz, 2H), 7.27-7.23 (m, 8H), 7.10 (dd, J = 8.8, 2 Hz, 6H), 7.02 (t, J = 7.2 Hz, 2H). 13C NMR (CDCl3, 100 MHz) δ 152.18, 147.65, 147.51, 141.39, 137.29, 137.09, 133.66, 129.89, 129.79, 129.28, 128.57, 127.62, 127.47, 127.24, 124.53, 123.62, 123.28, 123.09, 122.98, 119.75, 110.38. MALDI-TOF MS: calcd for C37H27N3 513.22 g/mol, found 513.26 g/mol. HRMS (FAB+) [M + H: C37H28N3]: calcd for 514.2283, found 514.2283. Anal. Calcd. For C37H27N3: C, 86.52; H, 5.30; N, 8.18. Found: C, 86.05; H, 5.18; N, 8.11. |
62% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 100℃;Inert atmosphere; | [0104] Compound 26: A mixture of Compound 25 (4- (diphenylamino)phenyl)boronic acid (900 mg, 3.1 mmol), Compound 9 (1.09 g, 3.1 mmol), Pd(PPh3)4 (180 mg, 0.16 mmol) and K2CO3 (1.38 g, 10 mmol) in 1,4- dioxane/H2O (25 mL/5 mL) was degassed and the resulting mixture was heated at about 100 0C overnight under an argon atmosphere. After cooling to room temperature, the resulting mixture was poured into water, extracted with ethyl acetate (100 mL x 2). The organic phase was dried over Na2SO4 and filtered. After addition of hexanes (100 mL), a yellow precipitate formed after about one hour. Filtration gave a yellow solid (760 mg) and the filtrate was absorbed on silica gel and purified by flash chromatography to give a yellow solid (200 mg). The total amount of product (Compound 26) was 960 mg in 62% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium phosphate;tris-(dibenzylideneacetone)dipalladium(0); tricyclohexylphosphine; In 1,4-dioxane; water; at 80 - 100℃;Inert atmosphere; | Example 10; This example illustrates the preparation of phenanthroline derivative Compound 14, using Suzuki coupling of <strong>[5394-23-0]4,7-dichloro-1,10-phenanthroline</strong> with the boronic ester shown below. Take 2.0 g of dichloro-phen (8 mM) in glove box and add 4.7 g (17 mM) boronic acid. Add 0.15 g Pd2 DBA3 (0.15 mM), 0.1 g tricyclohexylphosphine (0.35 mM) and 3.75 g potassium phosphate (17 mM) and dissolve all into 30 mL dioxane and 15 mL water. Mix and heat in glove box in mantle at 100 C for 1 hr then warm gently (minimum rheostat setting) under nitrogen overnight. Solution immediately is dark purple but on reaching 80 C it is a tan brown slurry which slowly becomes clear brown. As the solution refluxes (air condensor) it remains clear brown. Cool and work up by removing from glove box and evaporate out the dioxane then add more water. Filter off light brown gummy solid and wash with water. Solid dissolves well in toluene and DCM. The structure was confirmed by NMR analysis to be Compound 14: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 80℃; for 16.5h;Inert atmosphere; | Example 1.12.16 4-(8-(3,5-bis(benzo[d]oxazol-2-yl)phenyl)dibenzo[b,d]furan-2-yl)-N,N-diphenylaniline (Compound 16) A mixture of (4-(diphenylamino)phenyl)boronic acid (2.00 g, 6.92 mmol), <strong>[10016-52-1]2,8-dibromodibenzo[b,d]furan</strong> (3.95 g, 12.10 mmol), tetrakis(triphenylphosphine) palladium(0) (0.40 g, 0.35 mmol), potassium carbonate (2.87 g, 20.80 mmol), 1,4-dioxane (60.00 mL), and water (12.00 mL) was degassed with bubbling argon for 1 hour. The reaction mixture was then heated to 80° C. and was stirred overnight (16.5 hours), maintaining an argon atmosphere. Consumption of the starting material was confirmed by thin-layer chromatography and the reaction was cooled to room temperature. After adding water, the precipitated product was filtered, dried, and purified by silica gel column chromatography with dichloromethane in hexanes as the eluent. The product fractions were then dried and the product was collected to yield Compound 16 (1.84 g, 54percent). |
General procedure: In a 100 mL three-necked round-bottom flask, a mixture of compound 4a (2.0g, 4.89mmol) , K2CO3 (2.76 g, 20 mmol), Pd(PPh3)4 (70 mg, 0.07mmol), water (10 mL), and THF (20 mL) were heated to 45 oC for 1 h under an argon atmosphere. Then, compound 3 (1.4g, 4.89 mmol) dissolved in 20 mL THF was added dropwise and the reaction mixture was heated to reflux for 4 h and then allowed to cool down to r.t. The mixture was washed with water and extracted with CH2Cl2. The combined organic layer was dried over anhydrous MgSO4 and concentrated using a rotary evaporator. The resident was purified by column chromatography on silica (petroleum ether/dichloromethane=8:1, v/v) to yield the crude product as a white powder (1.2 g, 43percent). The crude product was going to the next reaction without further purification. Compound 5band 5c was synthesized by the similar procedure as 5a. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88.1% | With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In water; toluene; for 40.5h;Reflux; Irradiation; | A mixture of 2Br2T (0.32g, 1.00mmol), 4-(diphenylamino)phenylboronic acid (1.16g, 4.00mmol), cesium carbonate (1.30g, 4.00mmol), [Pd(PPh3)4] (0.06g, 0.05mmol), toluene (20mL), and water (5mL) was degassed for 0.5h and heated to reflux for 40h under argon atmosphere. The mixture was then allowed to cool to the room temperature and extracted with chloroform. The resulting organic layer was dried over anhydrous sodium sulfate and filtered. The filtrate was evaporated, and the residue was purified by column chromatography over silica gel using hexane and dichloromethane (1:1) as eluent to give 0.57g (88.1%) of 2TPA2T as a yellow solid. The yellow single crystals of 2TPA2T suitable for X-ray diffraction measurement were grown and isolated from DMF by slow evaporation in air at room temperature for 2 weeks. Melting point: >300C. Anal. Calcdfor [C44H32N2S2]: C, 80.95; H, 4.94; N, 4.29%. Found: C, 80.71; H, 5.12; N, 4.13%. Main FTIR absorptions (KBr pellets, cm-1): 3450 (b), 2361 (m), 1590 (s), 1490 (vs), 1327 (m), 1283 (s), 1183 (w), 1070 (w), 830 (w), 796 (w), 757 (m), 694 (m), 512 (w). 1H NMR (500MHz, CDCl3) δ: 7.46 (d, 4H, J=8.5Hz, ph), 7.28 (t, 8H, ph), 7.13 (d, 12H=8H+4H, J=7.5Hz, ph+thio), 7.07 (d, 4H, J=8.3Hz, ph), 7.04 (t, 4H, ph). 13C NMR (125MHz, CDCl3) δ: 147.5, 147.4, 142.9, 136.0, 129.3, 128.1, 126.4, 124.6, 124.3, 123.6, 123.2, 122.9. EI-TOF-MS (m/z): calcdfor [C44H32N2S2]+: 652.2 (100.0%), 653.2 (49.9%). Found: 652.0 (100.0%), 653.0 (11.6%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | With bis-triphenylphosphine-palladium(II) chloride; caesium carbonate; In water; N,N-dimethyl-formamide; at -5℃; for 6h; | The dimethyl formamide (DMF) 10 ml and H 2 O 1ml were mixed with 4 (N,Ndiphenylamino)phenyl bronic acid (4(N,NDiphenylamino)phenylboronic acid) 0.5 g (1.73 mmol), 5,5'dibromo2,2'bithiophene bromothiophene (5,5'dibromo2,2'bithiophene) 1.68 g (5.18 mmol), and the mixture of thecesium carbonate (cesium carbonate) 1.41 g (4.32mmol) and bis (triphenylphosphine) palladium (II)dicloride (bis(triphenylphosphine)palladium(II) dichloride) 0.121 g (0.173 mmol) and it was stirred in5for 6 hours. The solid compound which did notmelt in the dimethyl formamide (DMF) after the completion of reaction filtered and it removed and the dimethyl formamide solvent was evaporated. Next, after the solid mixture was mixed using thehydrochloride (HCl) 20 ml and dichloromethane 20ml for 10 minutes after the solvent disappeared the dichloromethane layer and aqueous solution liquid were separated. Next, the dichloromethane solution was dried using the Magnesium Sulfate Anhydrous (MgSO(sub)4(/sub)) and after it filtered the solvent was evaporated. Consequently, the product was refined using the dry column chromatography (dry column chromatography) (dichloromethane hexane: = 1:4) with the separation and product 4 (5bromothiophene2yl)N,Ndiphenylaniline (4(5Bromothiophene2yl)N,Ndiphenylaniline)(0.294 g, 34 %) of yellow were obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; sodium hydroxide; In toluene; at 120℃; for 48h; | 1. 1 mmol of 5-bromobenzothiadiazole,1 mmol of triphenylamine-4-boronic acid pinacol ester,0.05 mmol of tetrakis(triphenylphosphine)palladium, 0.1 mmol of tetrabutylammonium bromide,6mmol sodium hydroxide andMix 10 ml of toluene, react at 120 C for 48 h, extract with water and dichloromethane, and combine the organic layers.After drying, the organic solvent is removed, and purified by using a mixed solvent of dichloromethane and petroleum ether as a solvent column chromatography.Obtaining 4-(benzo[c][1,2,5]thiadiazol-5-yl)-N,N-diphenylaniline |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41% | With water; caesium carbonate; In 1,4-dioxane; water; for 8h;Inert atmosphere; Reflux; | General procedure: Compound 1: A mixture of 2-Br-phen (0.80 g, 3.10 mmol), 2-thiophenylboronic acid (0.42 g, 3.28 mmol), Pd(PPh3)4 (0.12 g, 0.10 mmol) and Cs2CO3 (3.03 g, 9.30 mmol) was dissolved in a mixture of dioxane (40 mL) and H2O (8 mL), placed into a degassed three-necked flask and refluxed under an argon atmosphere for 8 h. After the solution was cooled to room temperature, the solvent was removed under reduced pressure and the residue was dissolved in CHCl3 (50 mL), washed with excess water, and dried with anhydrous Na2SO4. The desired compound 1 was finally separated as light yellow solid by silica gel column chromatography using CHCl3/petroleum ether (v:v 5:1) as the eluent in a yield of 0.71 g (87%). Compound L2 was prepared according to a procedure similar to that for 1 except that 3-Br-phen and 4-(diphenylamino)phenylboronic acid were used in place of 2-Br-phen and 2-thiophenylboronic acid. Yield: 0.27 g (41%). Mp: 234-236C. Main FTIR absorptions (KBr pellets, cm-1): 3035 (m), 1592 (s), 1516(s), 1488 (s), 1422 (m), 1331 (m), 1272 (s), 1181 (w), 834 (m), 753(m), 696 (m). 1H NMR (300 MHz, CDCl3) delta: 9.43 (d, 1H, J=2.3 Hz,phen), 9.20 (dd, 1H, J=4.3 and 1.6 Hz, phen), 8.36 (d, 1H, J=2.3 Hz,phen), 8.27 (dd, 1H, J=6.5 and 1.6 Hz, phen), 7.83 (m, 2H, phen), 7.67 (d, 2H, J=8.5 Hz, triphenylamino), 7.63-7.61 (m, 1H, phen), 7.33-7.28 (m, 4H, triphenylamino), 7.24-7.16 (m, 6H, triphenylamino),7.10-7.05 (m, 2H, triphenylamino). 13C NMR (75 MHz, CDCl3) delta: 150.3, 149.0, 148.2, 147.3, 146.1, 144.6, 135.9, 135.2, 132.3, 130.7,130.3, 129.3, 128.5, 128.4, 128.1, 126.8, 126.6, 124.7, 123.4, 123.3,122.7. EI-TOF-MS (m/z): Calcd for [C30H21N3]: 423.2 (100.0%);Found, 423.1 (100.0%). Anal. Calcd for C30H21N3: C, 85.08; H, 5.00; N,9.92%. Found: C, 84.88; H, 5.14; N, 9.81%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; toluene; at 80℃;Inert atmosphere; | <strong>[2050-48-8]4,4'-sulfonylbis(bromobenzene)</strong> (10g, 26.6mmol),4-(Diphenylamino)phenylboronic acid (8.5 g, 29.26 mmol), Potassium carbonate (K2CO3) ( 16.2 g, 117.04 mmol), tetrakistriphenylphosphine palladium (0.1 g),Intermediate 5-1 (10.8 g, 75%) was prepared using the same experimental procedure as Compound 1. Compound 1-5 (15 g, 32.44 mmol), toluene (350 ml), under nitrogenCompound 1-4 (15.94 g, 38.93 mmol) was added.Calcium carbonate (K2CO3) (19.7 g, 142.74 mmol), adding deionized water to the reaction mixture,Tetrahydrofuran (200 ml), tetrakistriphenylphosphine palladium (0.1 g) was added, and the mixture was stirred, and the reaction was refluxed at 80 C.After extraction, it was recrystallized from dichloromethane / n-hexane to give Compound 1 (13.5 g, 63%). |
55% | With potassium carbonate; palladium; In tetrahydrofuran; water; at 80℃;Inert atmosphere; | In N2in the gas purification system, the 4-bromobenzyl sulfone soluble in toluene solvent, and by adding 4 - (diphenyl amino) phenyl boronic acid (1.1 equivalent). The K2CO3 (4.4 equiv) dissolved in distilled water in and added to the mixed solution. By adding tetrahydrofuran solvent, and by adding palladium (0.05 equiv). The mixture at 80 C and the temperature of the refluxing under stirring. After the reaction is finished, by ethyl acetate extraction mixture. From the extraction of using magnesium sulphate remove the moisture in the organic layer, and removing the remaining organic solvent. The material through the use of methylene chloride and hexane to carry out wet refining column chromatography, thereby obtaining compound "k". (Yield: 55%) |
With potassium carbonate; palladium; In tetrahydrofuran; water; toluene;Inert atmosphere; Reflux; | In N2Gas purification system, the compound H is dissolved in toluene, added compound K (1.1 eq).Will be dissolved in deionized water K2CO3(4.4 equiv.) Was added to the mixture.After the addition of tetrahydrofuran was added Pd (0.05 equiv).The mixture was stirred at reflux at a temperature of 80 .Will try to isolate the crystalline compound H, compound K and byproduct mixture.The resultant was passed through the column with dichloromethane and hexane to obtain the compound L. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With potassium carbonate; palladium; In water; toluene; at 80℃;Inert atmosphere; | In N2in the gas purification system, the 5,8- [...][...] soluble in toluene solvent, and by adding 4 - (diphenyl amino) phenyl boronic acid (1.1 equivalent). The K2CO3 (4.4 equiv) dissolved in distilled water in and added to the mixed solution. By adding tetrahydrofuran solvent, and by adding palladium (0.05 equiv). The mixture at 80 C and the temperature of the refluxing under stirring. After the reaction is finished, by ethyl acetate extraction mixture. From the extraction of using magnesium sulphate remove the moisture in the organic layer, and removing the remaining organic solvent. The material through the use of methylene chloride and hexane to carry out wet refining column chromatography, thereby obtaining compound "m". (Yield: 43%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); | 2,3-dibromo-benzothiophene and 4- (diphenylamino) phenylboric acid intermediates through the Suzuki coupling reactionAfter obtaining the M12-1-1 according to a conventional method of producing a boric acid to give the intermediate M12-1. | |
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; | <strong>[6287-82-7]2,3-dibromobenzothiophene</strong> with4-boronic acid triphenyl phosphate was obtained by Suzuki coupling Intermediate M12-1-1, and the intermediate M12-1 was obtained by the general preparation method of boronic acid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); potassium pivalate; In N,N-dimethyl acetamide; at 110℃; for 1.03333h;Inert atmosphere; | General procedure: In a flask of 20 ml, the diboronic acid and the 1,3-Dibromo-5-(2-ethylhexyl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione are placed, subsequently 3 molar equivalents of potassium pivalate (PIVOK) are addedand finally 0.05 mol % of catalyst tetrakistriphenylphosphine Pd(PPh3)4 was added. The mixture wasplaced under nitrogen atmosphere, then 5 mL of dimethylacetamide (DMA) is added; the mixture wasstirred for 2 min and then heated up in the microwave at 110 C with a power of 100 W. After 1 h,the reaction was cooled down to 50 C and 50 mL of cold EtOH are added, a solid precipitate isobserved, which is filtered and washed first with 50 mL of EtOH and then with 50 mL of hexane.The solid was recovered and recrystallized using a mixture of ketone/EtOH 40:60. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium hydroxide;Inert atmosphere; Reflux; | Put 9,10-dibromoindole, triphenylamine boric acid and 4-(1-phenyl-1-H-benzimidazol-2-)benzeneboronic acid in a three-necked flask, solvent 40 ml, and install a mechanical stir bar. Nitrogen gas for 10 minutes,The catalyst PdCl2 (dppf) was added under 0.25 mol% to 3 mol%, and the 2M alkali solution was 0.018 mol, and the mixture was heated under reflux for 5-7 hours.After the reaction, suction filtration, toluene washing, and ethanol washing.After recrystallization from xylene, a powder having a purity of 99% or more was obtained, and the product yield was 78%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; for 12.0h;Inert atmosphere; | In the flask, <strong>[1109284-33-4]3-iodo-6-bromopyrazolo[1,5-a]pyrimidine</strong> (1 g, 3.1 mmol) was added.4-diphenylaminophenylboronic acid (1.8 g, 6.2 mmol),Potassium carbonate (0.86g, 6.2mmol),Tetrakistriphenylphosphine palladium (50mg),Tetrahydrofuran (20 mL) and water (10 mL),Under the protection of nitrogen,Heated for 12 hours,cool down,Extracted with dichloromethane,dry,concentrate,The crude product was purified by column chromatography to yield 1.59 g of product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; sodium hydroxide; In toluene; at 120℃; for 48h; | 1. 1 mmol of 4-bromobenzothiadiazole,1 mmol of triphenylamine-4-boronic acid pinacol ester,0.05 mmol of tetrakis(triphenylphosphine)palladium, 0.1 mmol of tetrabutylammonium bromide,Mix 6mmol sodium hydroxide and 10ml toluene, react at 120 C for 48h,Extract with water and dichloromethane, combine the organic layers, and remove the organic solvent after drying.Purified by column chromatography using a mixed solvent of dichloromethane and petroleum ether.Obtaining 4-(benzo[c][1,2,5]thiadiazol-4-yl)-N,N-diphenylaniline |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 20 - 110℃; for 24.166h;Inert atmosphere; | Specifically: under the protection of argon, triphenylamine borate (2.24 g, 7 mmol), 4-pyridine bromobenzene (1.8 g, 7.7 mmol), tetrakis(triphenylphosphine)palladium (0.4 g, 0.35 mol) and carbonic acid Sodium (2.2 g, 21 mmol) was added to a 250 mL three-necked flask. After adding toluene (70 mL), ethanol (20 mL) and water (7 mL), the mixture was evaporated and evaporated at room temperature for 10 minutes, then heated to reflux.Stir at 110 C for 24 h. Then, it was filtered, concentrated, extracted with saturated brine, dried, and purified by column chromatography to give 4-pyridinetriphenylamine benzene (yield 69%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; at 75℃;Inert atmosphere; | General procedure: In 25 mL round bottom flask equipped with reflux condenser, 0.0004 mol of 4-chloro-3,5-dimethylphenol mixed with appropriate quantity of arylboronic acid (1-6) and 0.05 g of Pd(PPh3)4 were added into the flask containing 20 mL of absolute ethanol under inert atmospheric condition (N2) gas. The mixture was stirred and heated and 5 mL of solution (5% Na2CO3) were added into the flask.The reaction mixture was stirred and heated at 75 C for 5-6 h then followed by TLC and monitor reactions using (n-hexane and ethyl acetate) in 2:3 ratio v/v. The mixture was filtrated off to remove the inorganic salt and the residue of pallidum catalyst, washed by cooled ethanol and the solvent was removed and decanted by cooled ether (Scheme-I). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In toluene; at 100℃;Inert atmosphere; | In a 25 ml round bottom two-necked flask,Add Intermediate 1-1 (1mmol), compound S2 (1mmol), potassium carbonate (1.2mmol), toluene (8ml), water (1ml), tetrakis(triphenylphosphine)palladium (0.05mmol), nitrogen protection After the reaction is completed, it is heated to 100C, quenched by adding water, extracted with dichloromethane, and the organic layer is dried with anhydrous magnesium sulfate, filtered, and spin-dried.The crude product was purified by column chromatography (dichloromethane/n-hexane/methanol (volume ratio 20:10:1)) to obtain Intermediate 2-1 (yield 88%). |