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CAS No. : | 625-82-1 | MDL No. : | MFCD00192088 |
Formula : | C6H9N | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | MFFMQGGZCLEMCI-UHFFFAOYSA-N |
M.W : | 95.14 | Pubchem ID : | 39539 |
Synonyms : |
|
Num. heavy atoms : | 7 |
Num. arom. heavy atoms : | 5 |
Fraction Csp3 : | 0.33 |
Num. rotatable bonds : | 0 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 30.72 |
TPSA : | 15.79 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.83 cm/s |
Log Po/w (iLOGP) : | 1.55 |
Log Po/w (XLOGP3) : | 1.48 |
Log Po/w (WLOGP) : | 1.63 |
Log Po/w (MLOGP) : | 0.84 |
Log Po/w (SILICOS-IT) : | 2.35 |
Consensus Log Po/w : | 1.57 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -1.89 |
Solubility : | 1.22 mg/ml ; 0.0129 mol/l |
Class : | Very soluble |
Log S (Ali) : | -1.42 |
Solubility : | 3.63 mg/ml ; 0.0381 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | -2.29 |
Solubility : | 0.483 mg/ml ; 0.00508 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.0 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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 |
---|---|---|
80% | Stage #1: at 0℃; for 0.333333 h; Stage #2: at 0℃; for 0.5 h; Heating / reflux Stage #3: With sodium acetate In 1,2-dichloro-ethane for 0.333333 h; Heating / reflux |
A. 2-formyl-3,5-dimethylpyrrole To dimethylformamide (4.5 mL, 57.8 mmol) under argon at 0° C. was added phosphorus oxychloride (57.8 mmol) dropwise over 5 min. The cooling bath was removed and after 15 min. 1,2-dichloroethane (15 mL) was added. The reaction mixture was again cooled to 0° C. and a solution of 2,4-dimethylpyrrole (52.6 mmol) in 1,2-dichloroethane (15 mL) was added dropwise over 15 min. The reaction was heated to reflux for 15 min, and then cooled to rt. A solution of sodium acetate (24 g) in water (75 mL) was added slowly to the reaction mixture and the resulting mixture was again heated to reflux for 20 min. After the reaction mixture was cooled to rt it was diluted with CH2Cl2, and the aqueous phase was washed with CH2Cl2 (2*50 mL). The combined organic fractions were washed with saturated NaHCO3, dried (Na2SO4), and concentrated in vacuo. The crude material was purified by chromatography on silica gel eluding with 10percent ethyl acetate in hexane to provide 5.2 g (80percent) of the desired compound 2-formyl-3,5-dimethylpyrrole. [M+H]+=124.1, [M-H]-=122.0 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | Stage #1: at 0 - 20℃; Inert atmosphere Stage #2: at 0 - 40℃; Inert atmosphere |
POCl3 (1.00mL, 11 mmol) was added dropwise at 0°C to DMF (20mL) and the resulting mixture was stirred for 5min. The solution was then stirred at rt for 30min before being cooled back down to 0°C. The solution was then treated with 3,5-dimethyl-1H-pyrrole (1.0mL, 10mmol). The resulting mixture was allowed to warm up to rt, and then heated to 40°C until completion as indicated by TLC analysis (18h). The reaction was then cooled down to rt and diluted with EtOAc (30mL). The resulting solution was washed with H2O (8×50mL), brine (3×50mL), dried (Na2SO4) and concentrated in vacuo to afford the crude as a dark brown solid. Column chromatography (silica gel, 50percent Et2O/petroleum ether) afforded (1.1g, 82percent) of the desired pyrrole carbaldehyde 8 as an off white solid. 1H NMR (CDCl3, 400MHz) δ: 10.14 (1H, br s), 9.49 (1H, s), 5.89 (1H, s), 2.32 (3H, s), 2.30 (3H, s). 13C NMR (CDCl3, 100MHz) δ: 176.0, 138.5, 134.8, 128.8, 112.1, 13.2, 10.5. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 16 h; | To a solution of 2,4-dimethyl-lH-pyrrole (24 mg, 0.25 mmol) and mesitylsulfonyl chloride (218 mg, 1.0 mmol) in 5 mL of THF was added 60percent NaH (40 mg, 1.0 mmol) at 0 °C. The resulting mixture was stirred at r.t. for 16 h. The solution was diluted with EtOAc (50 mL), washed with 1 N HC1 (aq.) (10 mL) and brine (10 mL). The organic layer was dried over anhydrous Na2S04 and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (Hexane/EtOAc = 10/1) to give the desired product as a pale red solid (40 mg, 58percent). H NMR (600 MHz, CDC13) δ 7.01 (s, 1H), 6.95 (s, 2H), 5.77 (s, 1H), 2.49 (s, 6H), 2.31 (s, 3H), 2.00 (s, 3H), 1.99 (s, 3H). 13C NMR (150 MHz, CDCI3) δ 143.8, 140.2, 133.8, 132.2, 130.2, 119.7, 119.2, 114.5, 23.4, 21.1, 12.6, 11.8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
26% | With potassium hydroxide; In water; at 140 - 160℃; for 11h; | Diethyl 3,5-dimethyl-1H-pyrrole-2,4-dicarboxylate (6) (15.0 g, 63 mmol) and potassium hydroxide (85%, 7.389 g, 132 mmol) were suspended in water (110 mL) and heated to reflux for 3 h. Within this time, most of the reactants were dissolved. The mixture was then heated to 160 C and kept at this temperature for 8 h. Subsequently, the mixture was cooled down and the reflux condenser was replaced by a steam distillation setup. After excessive steam distillation using argon as inert gas, the condensed liquids were extracted with diethyl ether. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate and solvents were removed under reduced pressure. The brown residue was purified by vacuum-distillation to obtain the pure product as a colorless liquid which is light- and oxidation sensitive. Yield: 1.566 g (26%). 1H NMR (300 MHz, CDCl3): delta = 2.07 (s, 3H, CH3), 2.21 (s, 3H, CH3), 5.74 (s, 1H, ArCH), 6.38 (s, 1H, ArCH), 7.56 (bs, 1H, NH). 13C NMR (75 MHz, CDCl3): delta = 11.9, 13.0, 107.6, 113.9, 119.1, 127.8. HR-MS (ESI): Calculated for [C6H9N]H+: 96.08078. Found: 96.08078. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Compound 3c. 1c (17.4 mmol, 11.4 g) and 2,4-dimethylpyrrole (34.88 mmol, 3.32 g) were dissolved in 1200 mL of dry CH2CI2 in a 2000-mL three-neck flask. Eight drops of TFA were added to the reaction mixture, and resulting mixture was stirred in dark for 12 hours under nitrogen atmosphere at room temperature. After the complete consumption of aldehyde (1c) (which was conformed by TLC), DDQ (2,3-dichloro-5,6- dicyano-1,4-benzoquinone) (17.4 mmol 3.95 g) in 100 mL of CH2CI2 was added to the reaction mixture. When the mixture was stirred for 30 minutes, 35 mL of diisopropylethylamine (DIEA) and 35 mL of BF3OEt2 were added to the mixture. After the mixture was further stirred for 30 minutes, it was concentrated to 200 mL and filtered. The filtrate was washed once with sodium bicarbonate solution and twice with water, dried over anhydrous MgSO4 and concentrated under reduced pressure. The crude product was purified by column chromatography using hexane/ EtOAc (95/5 v/v) to obtain dark brown crystalline solid (4.5 g, 30 %). 1H NMR (400 MHz, CDCI3) δ 6.45 (s, 2H), 5.97 (S, 2H), 3.99 (t, J = 6.4 Hz, 2H), 3.90 (t, J = 6.4 Hz, 4H), 2.53 (s, 6H), 1.75 (q, J = 6.8 Hz, 6H), 1.52 (s, 6H), 1.48-1.42 (m, 6H), 1.40-1.24 (m, 48H), 0.88-0.85 (m, 9H); 13C NMR (100 MHz, CDCI3) δ 155.6, 154.3, 143.3, 142.0, 138.9, 131.6, 129.8, 121.2, 106.6, 73.9, 69.6, 32.1 , 30.5, 29.9, 29.8, 29.6, 29.5, 26.3, 26.2, 22.9, 14.7, 14.4, 14.3; IR (cm"1): 2922, 2853, 1544, 1509, 1467, 1417, 1373, 1327, 1307, 1156, 1113, 1086, 1026, 977, 834, 804, 758, 721. ESI-MS. M+ (C55H91BF2N2O3) Calcd: m/z = 877.1 , Found: m/z = 877.5. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | Stage #1: 2,4-dimethyl pyrrole; p-(hydroxymethyl)benzaldehyde With trifluoroacetic acid In dichloromethane at 20℃; for 12h; Inert atmosphere; Stage #2: boron trifluoride diethyl ether complex With triethylamine; 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 0 - 20℃; for 3h; Inert atmosphere; | 1.1 (1) Synthesis of 1,3,5,6-tetramethyl 8- (4 (hydroxymethylphenyl)) boron fluoride dipyrrole (2) Take a dry 500ml two-necked flask, the bottle was replaced with nitrogen, 2,4-dimethylpyrrole (2.2mL,Benzaldehyde (1.4 g, 10.0 mmol), trifluoroacetic acid (0.11 mL, 1 mmol) and CH2Cl2 (150 mL) were stirred at room temperature for 12 h before 2,3-dichloro-5,6-dicyanobenzene Quinone (2.3 g, 10.0 mmol), stirred for 1 h at room temperature,Et3N (30 mL) was added and the mixture was cooled to 0 ° C. in an ice bath. BF 3 .Et 2 O (30 mL) was added and the mixture was stirred at rt for 3 h, washed with saturated NaHCO 3 and extracted with CH 2 Cl 2.The combined organic phases were dried over anhydrous magnesium sulfate, filtered and concentrated.Purification by silica gel column chromatography (petroleum ether: dichloromethane = 2: 1) gave a yellow solid (0.9 g, 2.5 mmol) in a yield of 50%. |
41.3% | With CF3COOH; 2,3-dichloro-5,6-dicyano-1,4-benzoquinone; (C2H5)3N In dichloromethane (N2); drop of TFA was added to soln. of aldehyde and pyrrole in CH2Cl2, stirred overnight, treated with DDQ, stirred for 30 min, Et3N was added,after15 min BF3*Et2O was added at 0°C, stirred at r.t. for 3 h; washed with satd. aq. NaHCO3, organic layer was eparated, dried over MgSO4, filtered, concd., column chromy., (silica, CH2Cl2/hexane); | |
26% | Stage #1: 2,4-dimethyl pyrrole; p-(hydroxymethyl)benzaldehyde With trifluoroacetic acid In dichloromethane at 20℃; Inert atmosphere; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane for 0.5h; Inert atmosphere; Stage #3: boron trifluoride diethyl ether complex Further stages; | Synthesis of compound 3 . To a stirred solution of compound 2 (1.36 g, 10 mmol) and 2,4-dimethylpyrrole (1.60 g, 20.0 mmol) in anhydrous CH 2 Cl 2 (100 mL), one drop of TFA was added as a catalyst. The resulting mixture was stirred overnight under N 2 at room temperature. DDQ (2.28 g, 10 mmol) was added to the reac- tion mixture, and stirred for additional 30 min. Et 3 N (30 mL) was added and stirred for 15 min. BF 3 ·Et 2 O (60 mL) was added at 0 °C, and the mixture was stirred for 3 h. 50 mL of water was added to the reaction mixture and exacted with DCM, the organic layer was washed with aq. NaHCO 3 and brine, dried over anhydrous MgSO 4 . Evaporation of the solvent under reduced pressure, the residue was purified by chromatography using CH 2 Cl 2 /hexane as an eluent to afford compound 3 (0.92 g, 26%). 1 H NMR (600 MHz, CDCl 3 ) : 7.49 (d, J = 8.2 Hz, 2H), 7.28 (d, J = 8.1 Hz, 2H), 5.98 (s, 2H), 4.81 (d, J = 5.5 Hz, 2H), 2.55 (s, 6H), 1.38 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ) 155.45, 143.16, 141.99, 141.63, 134.06, 132.26, 131.47, 128.09, 127.40, 127.00, 121.25, 64.63, 14.58, 14.49. Anal. calcd for C 20 H 21 BF 2 N 2 O: C, 67.82; H, 5.98; N, 7.91; found: C, 67.79; H, 6.01; N, 7.89. |
Stage #1: 2,4-dimethyl pyrrole; p-(hydroxymethyl)benzaldehyde With trifluoroacetic acid In dichloromethane at 20℃; Inert atmosphere; Stage #2: boron trifluoride diethyl ether complex With triethylamine; 2,3-dicyano-5,6-dichloro-p-benzoquinone | ||
With triethylamine; trifluoroacetic acid; 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; for 24h; | ||
With 2,3-dimethyl-5,6-dicyanobenzoquinone; triethylamine In dichloromethane at 0 - 50℃; | (1) Mix methylpyrrole (206mg, 2.2mmol), benzaldehyde (106mg, 1.0mmol), and triethylamine (0.5ml) into dichloromethane, stir overnight at room temperature, and slowly add trifluoride at 0°C. Boron diethyl ether (0.5ml), stir for 10 minutes, add 2,3-dimethyl-5,6-dicyanobenzoquinone (227mg, 1mmol), extract with dichloromethane, dry with anhydrous Na2SO4, and spin at 50°C under vacuum. The solvent is evaporated, and a chromatographic column is used for separation and purification to obtain the orange-yellow solid product BODIPY. | |
Stage #1: 2,4-dimethyl pyrrole; p-(hydroxymethyl)benzaldehyde With triethylamine In dichloromethane at 20℃; Stage #2: boron trifluoride diethyl ether complex In dichloromethane at 0℃; for 0.166667h; | 1 The NB preparation method used in the following examples is as follows: (1) 2,4-dimethylpyrrole (1.1 mmol), p-methylhydroxybenzaldehyde (0.5 mmol), and triethylamine (0.2 ml) were mixed and dissolved in dichloromethane, stirred at room temperature overnight, and slowly added dropwise at 0°C with borontrifluoride etherate (0.2ml), stirred for 10 minutes, added 2,3-dimethyl-5,6-dicyanobenzoquinone (0.5mmol), extracted with dichloromethane, dried over anhydrous Na2SO4, and vacuum rotary evaporated at 50°C. The solvent was removed, and the product was separated and purified by a chromatographic column to obtain BODIPY as an orange-yellow solid product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | Add 1ml acetyl chloride, 3mL 2,4-dimethylpyrrole, 100ml dichloromethane to a 250ml three-necked flask, and stir the reaction at room temperature under the protection of light and nitrogen. The reaction is detected by TLC, and 6ml triethylamine is added. Add 9 ml of boron trifluoride ether complex, and the reaction was detected by TLC. The mixture was cooled to room temperature.Petroleum ether ethyl acetate was passed through a column to obtain 1.5 g of a red solid.Yield 40%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | A 1L round bottom flask under a nitrogen atmosphere charged with 2,4-dimethyl-pyrrole 15.0 g (158 mmol), acetyl chloride 6.2 g (79mmol) and dichloromethane (DCM) 450 ml were added and stirred at room temperature for 24 hours. Then, triethylamine (TEA) 55 ml, boron trifluoride diethyl ether (BF3OEt2) 55 ml was added and stirred for 4 hours at room temperature. Subsequently, by introducing water and the layers were separated and the organic layer was concentrated and then a mixed solvent of dichloromethane and hexane (1: 2 (v / v)) by performing column chromatography to give red solid of intermediate (1) 9.4 g of a (yield: 45%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluoroacetic acid; In dichloromethane;Inert atmosphere; | General procedure: 3-Iodo-4,5-dimethoxybenzaldehyde (1.5 mmol) and 2,4-dimethyl-3-ethylpyrrole (3.3 mmol) were dissolved in absolute CH2Cl2 (30 mL) under N2 atmosphere, 10 drops of TFA were added and the solution was stirred at rt overnight or until TLC analysis showed complete consumption of the aldehyde. At this time of DDQ (2.5 mmol) were added and stirring continued for 20 min. Then, Et3N (4 mL) and BF3·OEt2 (4 mL) were added. The mixture was stirred for 12 h then the organic layer containing the crude product was subsequently washed three times with water; the organic solution was dried over Na2SO4, and evaporated to dryness. The raw material was chromatographed (SiO2, petroleum ether/CH2Cl2, 6:4) affording 280 mg (yield: 33%) of 1a in the form of orange needles |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | Stage #1: 2,4-dimethyl-1H-pyrrole; 4-(prop-2-ynyloxy)benzaldehyde With trifluoroacetic acid In tetrahydrofuran at 26℃; for 6h; Inert atmosphere; Stage #2: boron trifluoride diethyl etherate With triethylamine; 2,3-dicyano-5,6-dichloro-p-benzoquinone In tetrahydrofuran at 0℃; Inert atmosphere; | |
36% | Stage #1: 2,4-dimethyl-1H-pyrrole; 4-(prop-2-ynyloxy)benzaldehyde With trifluoroacetic acid In dichloromethane at 20℃; Inert atmosphere; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane for 4h; Inert atmosphere; Stage #3: boron trifluoride diethyl etherate Further stages; | Synthesis of BODIPY 2 According to the literature [2], to a solution of 1 (0.84 g, 5.26 mmol) and 2,4-dimethylpyrrole (1.03 g, 10 mmol) in anhydrous dichloromethane was added three drops of TFA under ice bath. The resulting mixture was stirred overnight at room temperature. 2,3-Dichloro-5,6-dicyano-p-benzoquinone (DDQ, 1.19 g, 5.26 mmol) was dissolved in dichloromethane and added into the mixture and stirred for 4 h. Next, triethylamine (12 mL) was added dropwise and stirred for 0.5 h with ice bath cooling. Then, boron trifluoride-etherate (12 mL) was added dropwise and stirred overnight. The solution was then extracted with dichloromethane three times and the combined organic extracts were collected and dried over anhydrous MgSO4. The solvent was evaporated under reduced pressure. The crude product was further purified by silica gel column chromatography (petroleum ether:dichloromethane = 1: 1, v/v) to give 2 as a red solid (0.72 g, 36%). 1H NMR (400 MHz,CDCl3): = 7.20 (d, J = 7.6 Hz, 2 H, ArH), 7.09 (d, J = 7.6 Hz, 2 H, ArH), 5.98 (s, 2 H,pyrrole-H), 4.76 (s, 2 H, OCH2), 2.55 (s, 7 H, CH3 and -C≡CH), 1.42 (s, 6 H, CH3). |
35% | Stage #1: 2,4-dimethyl-1H-pyrrole; 4-(prop-2-ynyloxy)benzaldehyde With trifluoroacetic acid In dichloromethane at 20℃; for 24h; Inert atmosphere; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane for 1h; Cooling with ice; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane for 5h; | 1.2.2 (2) Synthesis of Compound 5 Under inert gas protection,Compound 4 (0.934 g) and 2,4-dimethylpyrrole (1.11 g) were dissolved in dichloromethane (100 mL), and 3 portions of trifluoroacetic acid were added and stirred at room temperature for 24 hours.Under ice bath, add DDQ (1.97g) and stir for one hour.Additional triethylamine (10 mL) andThe boron trifluoride etherate (10 mL) was stirred for 5 hours. After the reaction,200 mesh acidic silica gel column chromatography gave product 5,The yield was 35%. |
31% | Stage #1: 2,4-dimethyl-1H-pyrrole; 4-(prop-2-ynyloxy)benzaldehyde With trifluoroacetic acid In dichloromethane at 20℃; for 6h; Stage #2: With chloranil In dichloromethane at 20℃; for 1h; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane at 20℃; for 2h; | |
30% | Stage #1: 2,4-dimethyl-1H-pyrrole; 4-(prop-2-ynyloxy)benzaldehyde With trifluoroacetic acid In dichloromethane Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone Stage #3: boron trifluoride diethyl etherate With triethylamine | |
24% | Stage #1: 2,4-dimethyl-1H-pyrrole; 4-(prop-2-ynyloxy)benzaldehyde With trifluoroacetic acid In dichloromethane at 20℃; Inert atmosphere; Darkness; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; for 0.75h; Darkness; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane for 2h; Cooling with ice; | 1.4 4. Synthesis and Characterization of Intermediate Dye The BOD-Q synthesis route is shown in Figure 5. Under nitrogen protection, QQ (1g, 6.2mmol) was dissolved in 150mL of nitrogen-saturated anhydrous DCM, and then 2,4-dimethylpyrrole (1.2g (12.6 mmol) was injected with a syringe.Add 100 μL of trifluoroacetic acid, the solution turns colorless to brown-red, cover the reaction system with tin foil to protect from light, and stir at room temperature overnight.After adding DDQ (1.4 g, 6.2 mmol), it was stirred at room temperature for 45 min in the dark.The reaction was then placed in an ice bath. After 15 min, 6 mL of triethylamine and 6 mL of boron trifluoride ether were slowly added dropwise, and stirring was continued for 2 h.After the reaction was completed, 200 mL of water was added, and the mixture was shaken vigorously for 5 min. The organic layer was collected, and the organic layer was washed with saturated brine and water three times in that order.The organic layer was subsequently dried over anhydrous magnesium sulfate, and the filtrate was filtered to remove excess organic solvent by distillation under reduced pressure.The obtained crude product was dissolved in a small amount of dichloromethane, and then separated and purified by silica gel column chromatography (petroleum ether / dichloromethane as eluent) gradient elution to obtain 0.57 g of a purple-red powder, yield: 24%. |
22% | Stage #1: 2,4-dimethyl-1H-pyrrole; 4-(prop-2-ynyloxy)benzaldehyde With trifluoroacetic acid In dichloromethane for 5h; Inert atmosphere; Stage #2: With chloranil In dichloromethane for 1h; Inert atmosphere; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane Inert atmosphere; | |
22% | Stage #1: 2,4-dimethyl-1H-pyrrole; 4-(prop-2-ynyloxy)benzaldehyde With trifluoroacetic acid Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone Stage #3: boron trifluoride diethyl etherate | |
18% | Stage #1: 2,4-dimethyl-1H-pyrrole; 4-(prop-2-ynyloxy)benzaldehyde With trifluoroacetic acid In dichloromethane at 20℃; Inert atmosphere; Darkness; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; for 1h; Inert atmosphere; Darkness; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane for 2h; Inert atmosphere; Darkness; Cooling with ice; | |
16% | Stage #1: 2,4-dimethyl-1H-pyrrole; 4-(prop-2-ynyloxy)benzaldehyde With trifluoroacetic acid In dichloromethane at 20℃; Inert atmosphere; Cooling with ice; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; for 7h; Inert atmosphere; Stage #3: boron trifluoride diethyl etherate Further stages; | |
16% | With triethylamine; trifluoroacetic acid; 2,3-dicyano-5,6-dichloro-p-benzoquinone at 20℃; for 2h; Inert atmosphere; | |
11% | With triethylamine Inert atmosphere; | |
With triethylamine; trifluoroacetic acid; 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane | ||
With triethylamine; trifluoroacetic acid; 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | Ref. 9 Dimethylpyrrole(1 g, 10 mmol) was put in a round bottom flask under nitrogenatmosphere, and 22 mL of dried dichloromethane were added. Theresulting mixture was sparged with nitrogen bubbling for 90 min.Then 3-(trimethylsilyl)-2-propynal (0.733 mL, 5 mmol) was addeddrop wise at 70 C over a period of 30 min. The solution becamepurple. After the addition, stirring was carried on for 15 more minutesand removed. The solution was allowed to come to room temperatureduring 3 h. The solution became orange. First, p-Chloranil(1.23 g, 10 mmol) was added, the reaction mixture was stirred for1 h until it turned purple. Then, triethylamine (6.74 mL, 50 mmol)was added, the reaction was stirred for 30 min at room temperature.Finally, boron trifluoride diethyl etherate was added drop wise andthe reaction was stirred for 16 h. Dichloromethane was added to themixture and the organic phase was extracted with dichloromethane,washed with water and dried over magnesium sulphate.The solvent was removed under reduced pressure. Acetone wasadded until there was no more smoke emission, and was removedunder reduced pressure. The solid obtained was subjected to columnchromatography (silica gel, using a petroleum ether: dichloromethanemixture (70:30 vol) as the eluent). Yield = 70%.1H NMR (300 MHz, CDCl3, 300 K): d (ppm) = 0,27 (s, 9H); 2.5 (s,6H); 2.4 (s, 6H); 6.04 (s, 2H). 13C NMR {1H} (75 MHz, CDCl3, 300 K):d (ppm) = 0.56; 14.73; 15.65; 100.62; 115.11; 120.20; 120.91;133.21; 142.37; 154.55. ESI-MS: m/z = 345 [M+H]+; 325 [MF]+;367 [M+Na]+ (calcd for C18H23BF2N2Si: 344.17 (exact mass);344.28 (FW)). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | Stage #1: 2,4-dimethyl-1H-pyrrole; 4-(N-methyl-N-hydroxyethylamino)benzaldehyde With trifluoroacetic acid In dichloromethane at 20℃; for 0.833333h; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane Stage #3: boron trifluoride diethyl etherate Further stages; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
39% | 4,4-Difluoro-8-(2-methoxy-5-nitrophenyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (9) Compound 9 was prepared from 2,4-dimethylpyrrole and <strong>[25016-02-8]2-methoxy-5-nitrobenzaldehyde</strong> in 39% yield for three steps. C20H20BF2N3O3, dark red solids, mp 178-180 C.; TLC (EtOAc/hexane, 1:4) Rf=0.31; 1H NMR (600 MHz, CDCl3) delta 8.42 (1H, dd, J=9.1, 2.7 Hz), 8.17 (1H, d, J=2.7 Hz), 7.12 (1H, d, J=9.1 Hz), 6.02 (2H, s), 3.93 (3H, s), 2.59 (6H, s), 1.46 (6H, s); 13C NMR (150 MHz, CDCl3) delta 161.7, 156.1, 141.9, 135.0, 131.1, 126.9, 126.0, 124.8, 121.5, 118.9, 111.0, 56.7, 14.6, 14.2; HRMS calcd for C20H21BF2N3O3: 400.1644. found: m/z 400.1640 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | A 1L round bottom flask under a nitrogen atmosphere charged with 2,4-dimethyl-pyrrole 15.0 g (158 mmol), n-octyl chloride 14.0 g (79mmol) and dichloromethane (DCM) 450 ml were added and stirred at room temperature for 24 hours. Then, triethylamine (TEA) 55 ml, boron trifluoride diethyl ether (BF3OEt2) 55 ml was added and stirred for 4 hours at room temperature. Subsequently, by introducing water and the layers were separated and the organic layer was concentrated and then a mixed solvent of dichloromethane and hexane (1: 2 (v / v)) by performing column chromatography to give a red solid of intermediate (2) 9.4 g (yield: 45%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | Stage #1: 2,4-dimethyl-1H-pyrrole; 4-bromobutyroyl chloride In dichloromethane for 8h; Inert atmosphere; Cooling with ice; Reflux; Stage #2: boron trifluoride diethyl etherate With triethylamine In dichloromethane; toluene at 20 - 50℃; Cooling with ice; | 1 Example 1 A round bottom flask was charged with 2,4-dimethyl-1H-pyrrole(2.2 eq.), dissolved in anhydrous dichloromethane, nitrogen protection, ice bath, with a constant pressure low liquid funnel dropping 4-bromobutyryl chloride (1.0eq.). After completion of the dropwise addition, the reaction was refluxed for 8 hours, dried to dryness of methylene chloride. Add toluene and dichloromethane (toluene and methylene chloride volume ratio = 19: 1), ice bath, triethylamine (7.0 eq.) and the boron trifluoride-ether complex (7.0 eq.) was dropped by a constant pressure low - fluid funnel. After completion of the drop, remove the ice bath, room temperature reaction 10-20min, 50 °C heating reaction 3h. The reaction solution was cooled, poured into ice water, quenched, extracted with methylene chloride, dried over sodium sulfate, dried solvent, purified by column to obtain product, reddish brown solid, yield 30%. |
30% | Stage #1: 2,4-dimethyl-1H-pyrrole; 4-bromobutyroyl chloride In dichloromethane at 50℃; for 8h; Inert atmosphere; Cooling with ice; Stage #2: boron trifluoride diethyl etherate With triethylamine In dichloromethane; toluene at 20 - 50℃; Cooling with ice; | 1 The synthesis route is the same as Chinese Patent 201510418869.2 (application number).Add 2,4-Dimethyl-pyrrole (2.2eq.) into a round bottom flask, dissolved in anhydrous dichloromethane, protected by nitrogen, ice bath,Add 4-bromobutyryl chloride (1.0eq.) in a constant-pressure low-liquid funnel. After the addition is complete, heat and reflux for 8h.Spin to dry the dichloromethane, add toluene and dichloromethane (volume ratio of toluene to dichloromethane = 19:1),In an ice bath, add triethylamine (7.0eq.), add boron trifluoride-ether complex (7.0eq.) dropwise with a constant pressure low liquid funnel,After the addition is complete, remove the ice bath, react at room temperature for 10-20 minutes, and heat at 50°C for 3 hours.The reaction solution was cooled, poured into ice water for quenching, extracted with dichloromethane, dried over sodium sulfate, and spinned to dry the solvent.Purification by column to obtain product 3a, reddish brown solid, yield 30%, |
30% | Stage #1: 2,4-dimethyl-1H-pyrrole; 4-bromobutyroyl chloride In dichloromethane at 50℃; for 8h; Cooling with ice; Inert atmosphere; Stage #2: boron trifluoride diethyl etherate With triethylamine In dichloromethane; toluene at 20 - 50℃; Cooling with ice; Inert atmosphere; | 1 Example 1 Synthesis of compound 3a Add 2,4-Dimethyl-pyrrole (2.2eq.) into the round bottom flask, dissolve in anhydrous dichloromethane, nitrogen protection, ice bath, drop 4-bromobutyryl chloride (1.0eq. .), after the dropwise addition is completed, heat and reflux for 8h, spin off the dichloromethane, add toluene and dichloromethane (volume ratio of toluene to dichloromethane = 19:1), ice bath, add triethylamine (7.0eq.) , Use a constant-pressure low-liquid funnel to drop the boron trifluoride-ether complex (7.0eq.). After the addition is complete, remove the ice bath, react at room temperature for 10-20min, heat at 50°C for 3h, cool the reaction solution, and pour Quenched in ice water, extracted with dichloromethane, dried with sodium sulfate, spin-dried the solvent, and purified by column to obtain product 3a, a reddish brown solid, with a yield of 30%, |
20.2% | Stage #1: 2,4-dimethyl-1H-pyrrole; 4-bromobutyroyl chloride In dichloromethane at 0 - 25℃; for 1h; Stage #2: With triethylamine In dichloromethane at 25℃; for 0.166667h; Cooling with ice; Stage #3: boron trifluoride diethyl etherate In dichloromethane at 25℃; | 3.3 Synthesis of intermediate 5 Dimethylpyrrole (2.0 mL, 19 mmol) and 4-bromobutyryl chloride (1.0 mL, 8.8 mmol) were dissolved in 20ML in dichloromethane. The reaction was stirred at 0 ° C for 30 min and then at 25 ° C for 30 min. In the iceTriethylamine (3.7 mL, 26 mmol) was added dropwise and stirred at 25 & lt; 0 & gt; C for 10 min.Boron trifluoride diethyl ether (5.5 mL, 44 mmol) was added dropwise and the mixture was stirred overnight at 25 ° C. The solvent was distilled off under reduced pressure, and the intermediate was isolated by column chromatography5 (546 mg, 20.2%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | Stage #1: 2,4-dimethyl-1H-pyrrole; mesytaldehyde With trifluoroacetic acid In dichloromethane at 20℃; for 3h; Inert atmosphere; Darkness; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 0℃; for 0.166667h; Inert atmosphere; Darkness; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane for 2h; Inert atmosphere; Darkness; | |
80.8% | Stage #1: 2,4-dimethyl-1H-pyrrole; mesytaldehyde With trifluoroacetic acid In dichloromethane at 20℃; for 3h; Inert atmosphere; Stage #2: With chloranil In dichloromethane at 20℃; for 1h; Inert atmosphere; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane at 20℃; for 1h; Inert atmosphere; | |
72% | Stage #1: 2,4-dimethyl-1H-pyrrole; mesytaldehyde With trifluoroacetic acid In dichloromethane at 0℃; for 3h; Inert atmosphere; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone at 0 - 20℃; for 1.33333h; Inert atmosphere; Stage #3: boron trifluoride diethyl etherate With triethylamine at 20℃; for 12h; Inert atmosphere; |
62% | Stage #1: 2,4-dimethyl-1H-pyrrole; mesytaldehyde With trifluoroacetic acid In dichloromethane at 20℃; for 6h; Inert atmosphere; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; for 0.5h; Inert atmosphere; Stage #3: boron trifluoride diethyl etherate Further stages; | |
44% | Stage #1: 2,4-dimethyl-1H-pyrrole; mesytaldehyde With trifluoroacetic acid In dichloromethane at 20℃; for 3h; Darkness; Inert atmosphere; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; for 1.16667h; Inert atmosphere; Cooling with ice; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane at 20℃; for 2h; Inert atmosphere; | 4.2.1. Compound 1 [50] A solution of trifluoroacetic acid (50 μL, 0.65 mmol) in dry dichloromethane(2.5 mL) was added slowly to a solution of 2,4,6-trimethylbenzaldehyde(0.73 mL, 5.00 mmol) and 2,4-dimethyl-1H-pyrrole(1.28 mL, 12.5 mmol) in dry dichloromethane (250 mL) at roomtemperature in the shield of light under Ar. After stirring for 3 h, 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 1.13 g, 5 mmol) wasadded and stirred under ice bath for 10 min. The reaction mixture wasstirred for an additional 1 h at room temperature. NEt3 (10 mL,72 mmol) was added to the reaction solution, following by slow additionof BF3•OEt2 (10 mL, 74 mmol). After 2 h of stirring at room temperature,the reaction solution was washed with saturated aqueousNa2CO3 solution (3×50 mL), dried over Na2SO4, and concentratedunder reduced pressure. The oily residue was purified by columnchromatography on silica with n-hexane/CH2Cl2=3:1 as the eluent.The product fraction with greenish fluorescence was dried to yield ared-brown solid compound 1. Yield (0.81 g, 44%). 1H NMR (600 MHz,CDCl3, ppm), δ 6.95 (s, 2 H), 5.96 (s, 2 H), 2.56 (s, 6 H), 2.33 (s, 3 H),2.09 (s, 6 H), 1.38 (s, 6 H) (Fig. S11). HRMS (ESI+): m/z calcd forC22H26BF2N2 [M + H+]: 367.2155; found: 367.2161(Fig. S20). |
43% | Stage #1: 2,4-dimethyl-1H-pyrrole; mesytaldehyde With trifluoroacetic acid In dichloromethane for 3h; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; for 1h; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane at 20℃; for 2h; | Synthesis of compound 1 2,4,6-Trimethylbenzaldehyde (0.592 g, 4 mmol) and 2,4-dimethyl-1H-pyrrole (0.856g, 9 mmol) were dissolved in dry CH2Cl2 (200 mL), Trifluoroacetic acid (50 μL, 0.65mmol) was slowly added to the reaction solution at room temperature.2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (0.908 g, 4 mmol) was then added after 3h stirring under ice bath cooling and stirred for further 10 min. The solution wasstirred for an additional 1 h at room temperature. Triethylamine (8 mL) was added,followed by slow addition of BF3·Et2O (8 mL). The reaction mixture was washedafter 2 h of stirring at room temperature with saturated aqueous Na2CO3 solution(3×40 mL), dried over anhydrous Na2SO4, and concentrated on a rotary evaporator.The brown, oily residue was purified by column chromatography on silica gel withpetroleum ether/CH2Cl2 = 3:1 as eluent. The product fraction with greenishfluorescence was collected and dried to obtain a red-brown solid. Yield: 0.63 g, 43%. |
40% | Stage #1: 2,4-dimethyl-1H-pyrrole; mesytaldehyde With trifluoroacetic acid In dichloromethane at 20℃; for 5h; Inert atmosphere; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 0 - 20℃; for 1h; Inert atmosphere; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane at 20℃; for 5h; Inert atmosphere; | 1 Preparation of Compound P1: After mixing 2,4-dimethylpyrrole (10 g, 0.10 mol), mesityl aldehyde (7.8 g, 0.052 mol), trifluoroacetic acid (2 drops), and dry dichloromethane (500 mL) in a flask, the result was stirred for 5 hours at room temperature under nitrogen. After checking the disappearance of the starting materials using TLC, DDQ (12 g, 0.052 mol) was added thereto at 0° C. The result was stirred for 1 hour at room temperature, and then triethylamine (26 g, 0.25 mol) was slowly added dropwise thereto. After the result was stirred for 30 minutes at room temperature, a boron trifluoride ethyl ether complex (65 g, 0.46 mol) was slowly added dropwise thereto. The reactants were stirred for 5 hours at room temperature, water was added thereto, and the result was extracted using dichloromethane. The result was dried with anhydrous magnesium sulfate and filtered, and then vacuum distilled to remove the solvent. A red compound P1 (7.8 g, 40%) was obtained through a silica-gel column (hexane/ethyl acetate). |
40% | Stage #1: 2,4-dimethyl-1H-pyrrole; mesytaldehyde With trifluoroacetic acid In dichloromethane at 20℃; for 5h; Inert atmosphere; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 0 - 20℃; for 1h; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane at 20℃; for 5h; | 5 Preparation of Compound P4: After mixing 2,4-dimethylpyrrole (10 g, 0.10 mol), mesityl aldehyde (7.8 g, 0.052 mol), trifluoroacetic acid (2 drops) and dry dichloromethane (500 mL) in a flask, the result was stirred for 5 hours at room temperature under nitrogen. After identifying that the starting materials disappeared using TLC, DDQ (12 g, 0.052 mol) was added thereto at 0° C. The result was stirred for 1 hour at room temperature, and then trimethylamine (26 g, 0.25 mol) was slowly added dropwise thereto. The result was stirred for 30 minutes at room temperature, and a boron trifluoride ethyl ether complex (65 g, 0.46 mol) was slowly added dropwise thereto. The reactant was stirred for 5 hours at room temperature, and extracted with dichloromethane after adding water thereto. The result was dried with anhydrous magnesium sulfate, filtered, and vacuum distilled to remove the solvent. Red Compound P4 (7.8 g, 40%) was obtained through a silica-gel column (hexane/ethyl acetate). (0210) [M-F]+=347 |
Stage #1: 2,4-dimethyl-1H-pyrrole; mesytaldehyde With trifluoroacetic acid In dichloromethane at 25℃; for 3h; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 0 - 25℃; for 1h; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane at 25℃; for 5h; | 8 Preparation of Organic Dots Represented by Formula 2-1 To a three-necked flask, 0.59 ml (4 mmol) of 2,4,6-trimethylbenzaldehyde was added, followed by evacuating. Dried CH2Cl2 was added thereto, followed by stirring. (0115) Then, 1.029 ml (10 mmol) of 2,4-dimethyl-1H-pyrrole was added thereto, and trifluoroacetic acid (44 UI) and dried CH2Cl2 were diluted and added thereto slowly. (0116) After that, the reaction mixture was stirred at 25° C. for 3 hours, and 0.90 g (4 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was injected thereto at 0° C., followed by elevating the temperature to 25° C. and stirring for 1 hour. (0117) Then, 8.1 ml (57.6 mmol) of triethylamine (NEt3) was injected, and 8.6 ml (68 mmol) of BF3.Et2O was slowly injected, followed by stirring at 25° C. for 5 hours to finish the reaction. (0118) The reaction product was treated with an Na2CO3 solution and an Na2SO4 solution to capture water, and dried using a rotary evaporator. After that, the dried reaction product was separated using column chromatography to obtain a compound represented by the following Formula 2-1. (0119) 1H NMR (CDCl3, 400 MHz): 6.967 (s, 2H), 5.983 (s, 2H), 2.579 (s, 6H), 2.355 (s, 3H), 2.114 (s, 6H), 1.402 (s, 6H) | |
Stage #1: 2,4-dimethyl-1H-pyrrole; mesytaldehyde With trifluoroacetic acid In dichloromethane at 25℃; for 3h; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 0 - 25℃; for 1h; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane at 25℃; for 5h; | 1-1 Preparation Example 1-1: Preparation of a green-based organic-dot represented by the formula 1-1 [0132] 0.59 ml of 2,4,6-trimethylbenzaldehyde (4 mmol) was added to a three-necked flask, and the mixture was made into a vacuum state , then the dried CH2Cl2 was added and stirred. [0133] Next, here, after 2,4- dimethyl -1H- pyrrole (2,4-dimethyl-1H-pyrrole, 10 mmol) 1.029 was inserted into the trifluoroacetic acids (trifluoroacetic acid, 44 Ul) and the dried CH2Cl2were attenuated and it was slowly injected. [0134] Next, after the mixture was stirred for 3 hours at 25 , after 0.90 g of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (4 mmol) was added at 0 ° C, then the mixture was stirred at 25 for 1 hour.[0135] Next, after 8.1 ml of triethylamine (NEt3, 57.6 mmol) was added, 8.6 ml of BF3.Et2O (68 mmol) was slowly added thereto, then the mixture was stirred at 25 for 5 hours to complete the reaction.[0136]Next, after the reaction product was processed as the Na2CO3solution water was caught as the Na2SO4solution and it was dried using the Rotavapor. Next, the dried reaction product the compound indicated as the chemical formula 1 -1 was obtained in the column. | |
Stage #1: 2,4-dimethyl-1H-pyrrole; mesytaldehyde With trifluoroacetic acid In dichloromethane Inert atmosphere; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane Inert atmosphere; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane Inert atmosphere; | ||
With triethylamine; trifluoroacetic acid; 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
To a three-necked flask, 1.0 g (6.246 mmol) of <strong>[58551-83-0]2,4,6-trifluorobenzaldehyde</strong> was added, followed by evacuating. Dried CH2Cl2 was added thereto, followed by stirring. (0138) Then, 1.48 g (15.615 mmol) of 2,4-dimethyl-1H-pyrrole was added thereto, and trifluoroacetic acid (44 UI) and dried CH2Cl2 were diluted and added thereto slowly. (0139) After that, the reaction mixture was stirred at 25 C. for 3 hours, and 1.42 g (6.246 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was injected thereto at 0 C., followed by elevating the temperature to 25 C. and stirring for 1 hour. (0140) Then, 12.0 ml (89.942 mmol) of triethylamine (NEt3) was injected, and 13.0 ml (106.182 mmol) of BF3.Et2O was slowly injected, followed by stirring at 25 C. for 5 hours to finish the reaction. (0141) The reaction product was treated with an Na2CO3 solution and an Na2SO4 solution to capture water, and dried using a rotary evaporator. After that, the dried reaction product was separated using column chromatography to obtain a compound represented by the following Formula 2-4. (0142) 1H NMR (CDCl3, 400 MHz): 6.40 (s, 2H), 5.84 (s, 2H), 2.72 (s, 6H), 1.49 (s, 6H) | ||
[0162]In a three-necked flask, 1.0 g of trifluorobenzaldehyde 2,4,6-trimethylbenzaldehyde, (6.246 mmol) was put into a vacuum state, then the dried CH2Cl2 was added and stirred. [0163] Next, here, 1.37 g of 2,4-dimethyl-1H-pyrrole (2,4-dimethyl-1H-pyrrole, 15.869 mmol) was added then Trifluoroacetic acid (44 UI) was dried and CH2Cl2 was diluted and slowly added. [0164] Next, after the mixture was stirred for 3 hours at 25 , 1.42 g of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (6.246 mmol) was added at 0 C, then the temperature was raised to 25 and the mixture was stirred for 1 hour. [0165] Next, 12.0 ml of triethylamine (NEt3, 89.942 mmol) was added , then 13.0 ml of BF3.Et2O (106.182 mmol) was slowly, and then the mixture was stirred at 25 DEG C for 5 hours to complete the reaction. [0166] Next the reaction product was then treated with Na2CO3 solution after that, water was added to the solution with Na2SO4 and dried using a rotary evaporator. The dried reaction product was then subjected to column chromatography to obtain a compound represented by the following chemical Formula 1-4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
To a three-necked flask, 1.0 g (5.984 mmol) of <strong>[467442-15-5]3,5-difluoro-4-formylbenzonitrile</strong> was added, followed by evacuating. Dried CH2Cl2 was added thereto, followed by stirring. (0162) Then, 1.42 g (14.960 mmol) of 2,4-dimethyl-1H-pyrrole was added thereto, and trifluoroacetic acid (44 UI) and dried CH2Cl2 were diluted and added thereto slowly. (0163) After that, the reaction mixture was stirred at 25 C. for 3 hours, and 1.36 g (5.984 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was injected thereto at 0 C., followed by elevating the temperature to 25 C. and stirring for 1 hour. (0164) Then, 12.0 ml (86.169 mmol) of triethylamine (NEt3) was injected, and 13.0 ml (101.728 mmol) of BF3.Et2O was slowly injected, followed by stirring at 25 C. for 5 hours to finish the reaction. (0165) The reaction product was treated with an Na2CO3 solution and an Na2SO4 solution to capture water, and dried using a rotary evaporator. After that, the dried reaction product was separated using column chromatography to obtain a compound represented by the following Formula 2-7. (0166) 1H NMR (CDCl3, 400 MHz): 6.94 (s, 2H), 5.80 (s, 2H), 2.70 (s, 6H), 1.49 (s, 6H) | ||
[0192] In a three-necked flask, 1.0 g of <strong>[467442-15-5]3,5-difluoro-4-formylbenzonitrile</strong>, 5.984 mmol was put into a vacuum state, then the dried CH2Cl2 was added and stirred. [0193] Next, here, 1.42 g of 2,4-dimethyl-1H-pyrrole (2,4-dimethyl-1H-pyrrole, 14.960 mmol) was added then Trifluoroacetic acid (44 UI) was dried and CH2Cl2 was diluted and slowly added. [0194] Next, after the mixture was stirred for 3 hours at 25 , 1.36 g of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (5.984 mmol) was added at 0 C, then the temperature was raised to 25 and the mixture was stirred for 1 hour. [0195] Next, 15.0 ml of triethylamine (NEt3,86.169 mmol) was added , then 13.0 ml of BF3·Et2O(101.728 mmol) was slowly, and then the mixture was stirred at 25 DEG C for 5 hours to complete the reaction. [0196] Next the reaction product was then treated with Na2CO3 solution after that, water was added to the solution with Na2SO4 and dried using a rotary evaporator. Next, the dried reaction product was subjected to column to obtain a compound represented by the following formula 1-7 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42.6% | General procedure: To a 30 mL solution of <strong>[6361-22-4]2-chloro-6-nitrobenzaldehyde</strong> (213 mg,1.15 mmol) and 2,4-dimethylpyrrole (260 muL, 2.53 mmol) in dry CH2Cl2, kept under N2 atmosphere,were added ten drops of TFA. The solution was then stirred at RT for the time necessary to obtain the complete consumption of the aldehyde (from 6 to 12 h) as determined by TLC analysis. Thereafter the oxidation of the dipyrrolylmethane to dipyrrolylmethene was carried out, in the same flask, by the additionof DDQ (391.6 mg, 1.725 mmol) and the mixture was stirred for 30 min. The last step of the BODIPY synthesis requires the addition of Et3N (3 mL) and BF3 · OEt2 (3 mL) thus producing the desired borinated final compound. This step requires about 12 h, then the organic layer was washed two times with water, two times with a HCl 1 M solutionand then other three times with water. The organic solution was dried over Na2SO4, filtered and evaporated to dryness. The raw material was purified by column chromatography (SiO2 50 g, ether-CH2Cl2, 3:7) affording 197 mg (0.49mmol, yield: 42.6%) of 14a in the form of orange needles, mp = 190 C. UV-vis (CH3CN): 513 nm (epsilon = 63,600); Phifluo (526 nm): 0.68; 1H NMR (CDCl3) delta 1.46 (s, 6H, 2 × CH3), 2.59 (s, 6H,2 × CH3), 6.03 (s, 2H), 7.66 (t, 1H, J = 12 Hz), 7.85 (d, 1H, J = 12 Hz),8.03 (d, 1H, J = 12Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
13.3% | General procedure: To a 30 mL solution of 2-chloro-6-nitrobenzaldehyde (213 mg,1.15 mmol) and 2,4-dimethylpyrrole (260 muL, 2.53 mmol) in dry CH2Cl2, kept under N2 atmosphere,were added ten drops of TFA. The solution was then stirred at RT for the time necessary to obtain the complete consumption of the aldehyde (from 6 to 12 h) as determined by TLC analysis. Thereafter the oxidation of the dipyrrolylmethane to dipyrrolylmethene was carried out, in the same flask, by the additionof DDQ (391.6 mg, 1.725 mmol) and the mixture was stirred for 30 min. The last step of the BODIPY synthesis requires the addition of Et3N (3 mL) and BF3 · OEt2 (3 mL) thus producing the desired borinated final compound. This step requires about 12 h, then the organic layer was washed two times with water, two times with a HCl 1 M solutionand then other three times with water. The organic solution was dried over Na2SO4, filtered and evaporated to dryness. The raw material was purified by column chromatography (SiO2 50 g, ether-CH2Cl2, 3:7) affording 197 mg (0.49mmol, yield: 42.6%) of 14a in the form of orange needles, mp = 190 C. UV-vis (CH3CN): 513 nm (epsilon = 63,600); Phifluo (526 nm): 0.68; 1H NMR (CDCl3) delta 1.46 (s, 6H, 2 × CH3), 2.59 (s, 6H,2 × CH3), 6.03 (s, 2H), 7.66 (t, 1H, J = 12 Hz), 7.85 (d, 1H, J = 12 Hz),8.03 (d, 1H, J = 12Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | (1) The compound (1.40 g, 5.78 mmol), (1.22 g, 12.80 mmol) was added To 100 mL of anhydrous dichloromethane, add 0.05 mL of trifluoroacetic acid (TFA), stir under nitrogen at room temperature overnight;2,3-dichloro-5,6-dicyanoacetophenone (DDQ) (1.32 g, 5.80 mmol) was dissolved in 150 mL of dichloromethane and then added The reaction mixture was stirred at room temperature for 4 h; triethylamine (Et3N, 12 mL) and boron trifluoride diethyl ether (BF3 · Et2O,12 mL) was slowly added dropwise to the above mixture, and the mixture was stirred overnight at 0 ° C. After completion of the reaction, the mixture was filtered off with diatomaceous earth The black solid was washed successively with saturated NaHCO3 solution and water twice. The combined organic layers were dried over anhydrous Na2SO4 and depressurized (0.86 g, 32percent) was obtained by silica gel column chromatography using methylene chloride - petroleum ether (1: 2, v / v) as eluant. | |
23% | General procedure: To the solution of 4?trifluoromethylbenzaldehyde (1.50 g, 9.30 mmol) and 2,4?dimethylpyrrole(1.82 g, 19.08 mmol) in anhydrous dichloromethane (80 mL) was added one drop of trifluoroaceticacid. The mixture was stirred overnight at ambient temperature and then the solution of2,3?dichloro?5,6?dicyano?p?benzoquinone (2.12 g, 9.35 mmol) in anhydrous dichloromethane (150mL) was added. The resulting mixture was stirred continuously for another 4 h. After the additionof triethylamine (18 mL, 0.13 mol), BF3*Et2O (18 mL, 0.15 mol) was dropwise added into the mixture,which was cooled in an ice?water bath. The mixture was stirred overnight at ambient temperatureand then filtered through a celite pad to remove black solid impurities. The filtrate was then washedwith saturated NaHCO3 aqueous solution (200 mL × 2), followed by saturated NaCl aqueoussolution (200 mL × 2). The organic fraction was dried over anhydrous Na2SO4 and then concentratedto dryness under vacuum. The crude product was purified by silica gel column chromatographyusing CH2Cl2 /petroleum ether (1:2, v/v) as the eluent to give 1a as the orange?yellow solid (1.10 g,30percent). |
Yield | Reaction Conditions | Operation in experiment |
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35% | Stage #1: 2,4-dimethyl-1H-pyrrole; 4-(N-methyl-N-hydroxyethylamino)benzaldehyde With trifluoroacetic acid In dichloromethane for 24h; Inert atmosphere; Stage #2: With boron trifluoride diethyl etherate; triethylamine; 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane for 24h; Inert atmosphere; | 2.2 Synthesis of BODIPY dye (1) A 500ml round bottomed flask was charged with dichloromethane (150ml) and purge with N2 for 20min. (0.25g, 1.39mmol) 4-((2-hydroxyethyl)(methyl)amino)benzaldehyde were added to reaction flask and 2,4-dimethyl-1H-pyrrole (0.3ml, 2.8mmol) were dissolved in 30ml of dichloromethane and poured to that. One drop of trifluoroacetic acid was added to mixture and stirred for one day. Then, 2,3-dichloro-5,6-dicyano-p-benzoquinon (DDQ) (0.32g, 1.4mmol) was dissolved in dichloromethane and slowly poured to reaction flask with separating funnel after this reaction mixture was stirred for 30min at room temperature. Subsequently, 1.3ml of triethyl amine (NEt3) (9mmol) was added to reaction mixture drop by drop after 2ml of BF3 .OEt2 (15.4mmol) was slowly added to reaction mixture and stirred for one day. This reaction mixture was filtered from G4 sintered fitler. Then, solid matter was purified with aluminum oxide column chromatography, using diethyl eter as eluent. Yield: (195mg, 35%), melting point: 122-124°C (0007) IR (ATR) ν (cm-1): 3222 (O-H), 3079 (Ar-H), 2919-2866 (Aliph. C-H), 1690, 1598, 1569, 1516, 1436, 1369, 1281, 1186, 1118, 968, 807, 697. 1H NMR (400MHz, CDCl3), (δ:ppm): 7.65 (d, 2H, J=8, Ar-H), 7.15 (d, 2H, J=8, Ar-H), 6.43 (s, 1H, -CH), 5.95 (s, 1H, -CH), 3.85 (m, 2H, CH2-O), 3.54 (m, 2H, CH2-N), 3.05 (s, 3H, CH3-N), 2.38 (s, 3H, CH3), 2.30 (s, 3H, CH3), 2.10 (s, 3H, CH3), 2.08 (s, 3H, CH3). 13C NMR (100MHz, CDCl3), (δ:ppm): 172.18, 149.57, 145.07, 133.86, 131.89, 131.46, 127.95, 125.55, 121.75, 119.13, 116.05, 111.55, 110.93, 60.02, 55.40, 38.93, 29.68, 25.21, 24.98, 14.11. UV-Vis (CHCl3) λmax nm (log ε): 474 (5.03). MALDI-TOF-MS m/z calc. 397.26; found: 348.71 [M-BF2]+. |
Yield | Reaction Conditions | Operation in experiment |
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43% | Stage #1: 2-benzofuran-1(3H)-one With triethyloxonium fluoroborate In dichloromethane at 20℃; for 24h; Inert atmosphere; Molecular sieve; Stage #2: 2,4-dimethyl-1H-pyrrole In dichloromethane at 0 - 20℃; for 3h; Inert atmosphere; Molecular sieve; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere; Molecular sieve; | |
40% | Stage #1: 2-benzofuran-1(3H)-one With triethyloxonium fluoroborate In dichloromethane for 24h; Inert atmosphere; Reflux; Stage #2: 2,4-dimethyl-1H-pyrrole In dichloromethane at 0℃; for 4h; Inert atmosphere; Reflux; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere; | 4.1. 8-(2-Hydroxymethylphenyl)-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (2) To a solution of phthalide 1 (1 eq, 0.750 mmol, 100 mg) in0.75 mL of anhydrous dichloromethane under N2 was added a solution of triethyloxonium tetrafluoroborate (5M in dichloromethane,2 eq, 1.5 mmol, 0.30 mL). The resulting solution wasstirred under reflux for 24 h. After cooling down to 0 C, 2,4-dimethylpyrrole (3 eq, 2.25 mmol, 0.230 mL) was added and theresulting mixture was stirred under reflux for 4 h. After coolingdown to 0 C, triethylamine (6 eq, 4.5 mmol, 0.63 mL) and borontrifluoridediethyl etherate complex (9 eq, 6.75 mmol, 1.80 mL) were added dropwise, and the reaction mixturewas stirred at rt for2 h. The reaction mixture was diluted with dichloromethane and washed three times with water and with a saturated aqueous solution of sodium chloride. The organic layer was dried over Na2SO4and concentrated under reduced pressure. Then, in order to remove the unreacted phthalide 1, the residue was stirred in a mixture of dichloromethane and an aqueous solution of NaOH (1 M) at roomtemperature overnight. The organic layer was separated, washedwith water and with a saturated aqueous solution of sodiumchloride, dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate: 8/2) to give thedesired BODIPY 2 (104 mg, 40%) as orange crystals; Rf (cyclohexane/ethyl acetate/: 8/2) 0.17; 1H NMR (300 MHz CDCl3) d (ppm): 7.65(dd, J 6.3 Hz, J 1.3 Hz, 1H), 7.52 (td, J 7.6 Hz, J 1.5 Hz, 1H), 7.42(td, J 7.5 Hz, J 1.3 Hz, 1H), 7.20 (dd, J 7.6 Hz, J 1.5 Hz, 1H), 5.98(s, 2H), 4.60 (s, 2H), 2.56 (s, 6H), 1.36 (s, 6H). The spectral data wasin accordance with the literature [16] |
Yield | Reaction Conditions | Operation in experiment |
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With trifluoroacetic acid; In dichloromethane; at 20℃; for 2h;Inert atmosphere; | <strong>[1123-56-4]2,6-dimethylbenzaldehyde</strong> 670 mg (5 mmol) and under a nitrogen atmosphere2,4-dimethylpyrrole 950mg (10mmol)Dissolved in 200ml of re-distilled dichloromethane,Add 2 drops of trifluoroacetic acid,The molar amount of trifluoroacetic acid is 0.5% of the molar amount of <strong>[1123-56-4]2,6-dimethylbenzaldehyde</strong>.Room temperature reaction 2h,TLC monitored the complete reaction of <strong>[1123-56-4]2,6-dimethylbenzaldehyde</strong>;Add dropwise 1.2g DDQ (5.3mmol) to the reaction solutionDichloromethane solution,After 30 minutes of reaction,120 ml of water was added to the reaction system.The organic phase was extracted with methylene chloride, dried over anhydrous Na 2 SO 4 and filtered.The eluent is a mixed solution of dichloromethane and methanol, and the volume ratio of dichloromethane to methanol is 99:1 to obtain a product.650 mg, yield 43%. |
Yield | Reaction Conditions | Operation in experiment |
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60% | With trifluoroacetic acid In dichloromethane at 20℃; for 4h; Inert atmosphere; | 2.2. Preparation of probe BDY-1 [51,52] 2, 4, 6-trimethylbenzaldehyde (0.73 mL, 5 mmol) and 2, 4-dimethylpyrrole(1.28 mL, 12.5 mmol) were dissolved in dichloromethane (100mL). Then, one drop of TFA (trifluoroacetic acid) was then added, andthe resulting solution was stirred under N2 at room temperature for 4 h.The solvent was removed under vacuum, and the residue was purified bysilica column chromatography (PE/EA), 9/1 to 4/1, v/v) to give thedipyrrole intermediate (BDI) as a yellow solid (970 mg, 60%). 1H NMR(400 MHz, CDCl3) δ 7.24 (s, 2H), 6.83 (s, 2H), 5.73 (s, 1H), 5.71-5.64(m, 2H), 2.26 (s, 3H), 2.13 (s, 6H), 2.02 (s, 6H), 1.74 (s, 6H). To the solution of dipyrrole intermediate (BDI) (960 mg, 3.0 mmol)in dichloromethane (100 mL), 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone(DDQ, 1.128 g, 5 mmol) was added under ice bath conditions,which was stirred for another 2 h. Then, N, N-diisopropylethylamine(DIPEA, 10 mL) and BF3•OEt2 (10 mL) were added slowly into the solution,and the reaction mixture was continued for 2 h. The reactionmixture was washed with brine, dried over anhydrous sodium sulfate,filtered, and concentrated. The crude product was purified by silicacolumn chromatography (PE/EA, 15/1 to 4/1, v/v) to give the BDY-1 asa red solid (0.795 g, 70%). 1H NMR (400 MHz, CDCl3) δ6.94 (s, 2H),5.96 (s, 2H), 2.56 (s, 6H), 2.33 (s, 3H), 2.09 (s, 6H), 1.38 (s, 6H). |
With trifluoroacetic acid In dichloromethane at 20℃; for 2h; Inert atmosphere; | 1 2,4,6-trimethylbenzaldehyde 742 mg (5 mmol) and under a nitrogen atmosphere2,4-dimethylpyrrole 950mg (10mmol)Dissolved in 200ml of re-distilled dichloromethane,Add 2 drops of trifluoroacetic acid,The molar amount of trifluoroacetic acid is 0.5% of the molar amount of 2,4,6-trimethylbenzaldehyde, and the reaction is carried out at room temperature for 2 h.Thin layer chromatography (TLC) was used to monitor the completion of 2,4,6-trimethylbenzaldehyde;Then add 1.2g DDQ (5.3mmo) to the reaction solution.Dichloromethane solution,After 30 minutes of reaction,120 ml of water was added to the reaction system.Dichloromethane extraction, combined organic phase, dried over anhydrous Na2SO4, filtered, concentrated filtrate, column chromatography purification,The eluent used in column chromatography is a mixed solution of dichloromethane and methanol.The volume ratio of dichloromethane to methanol is 99:1,The product 1.2g was obtained with a yield of 55%. | |
With trifluoroacetic acid In dichloromethane for 3h; Cooling with ice; |
With trifluoroacetic acid In dichloromethane at 20℃; Inert atmosphere; | ||
With trifluoroacetic acid In dichloromethane at 20℃; Inert atmosphere; | ||
With trifluoroacetic acid In dichloromethane at 20℃; for 24h; Inert atmosphere; | 2.3.1. (Z)-2-((3,5-Dimethyl-2H-pyrrol-2-ylidene)(mesityl)methyl)-3,5-dimethyl-1H-pyrrole 2,4,6-Trimethylbenzaldehyde (200 mg, 1.35 mmol) and 2,4-dimethylpyrrole(322 mg, 3.38 mmol) were dissolved in dry dichloromethane(30 mL) under N2 atmosphere. Trifluoroacetic acid(100 μL) was added and the reaction mixture was stirred at roomtemperature for 24 h. After this time, tetrachloro-p-benzoquinone(332 mg, 1.35 mmol) was added and the reaction mixture stirred additional4 h. Afterwards the solution was filtered and the solvent evaporated.The crude product was purified by column chromatography onneutral alumina with a gradient of dichloromethane/hexane. Thefractions containing the product were united and the solvent was removed.The solid was washed with Et2O and dried. The compound wasused for the next synthetic step without further purification. | |
With trifluoroacetic acid In dichloromethane Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
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58% | 4.95 g (52 mmol) of 2,4-dimethyl-pyrrole was dissolved in 20 mL of dry dichloromethane, and 9.5 g (121 mmol) of acetyl chloride was added dropwise at room temperature, and refluxed at 50 C for 1 hour , after adding 100 mL of n-hexane and spinning the solvent, 240 mL of dichloromethane was added at room temperature, and 15.2 g (150 mmol) of triethylamine was added thereto, and the mixture was stirred for 10 minutes, then 31.9 g (225 mmol) of boron trifluoride etherate was added dropwise, reaction was stirred for 1 hour. After the reaction, it was quenched with water, and washed with a saturated aqueous solution of sodium carbonate for 4 times, extracted with dichloromethane, dichloromethane extract was dried over anhydrous sodium sulfate, evaporated to dryness under reduced pressure, and separated by silica gel column chromatography to obtain 3.9 g of pure product of BODIPY 2a, yield 58%. |
Yield | Reaction Conditions | Operation in experiment |
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65% | Stage #1: 2,4-dimethyl-1H-pyrrole; 5-bromovaleroyl chloride In dichloromethane for 2h; Inert atmosphere; Reflux; Stage #2: boron trifluoride diethyl etherate With triethylamine In dichloromethane; toluene at 50℃; for 1.5h; | 3.2.1. Synthesis of the BODIPY Core The BODIPY core was synthesized according to our previously reported procedure [61]. In a250-mL dry, round-bottomed flask, 5-bromovaleryl chloride (1.14 mL, 8.52 mmol) and 2,4-dimethylpyrrole (1.75 mL, 17.04 mmol) were dissolved in dry CH2Cl2 (100 mL) at room temperature anddegassed with a stream of Ar gas for 2 min. The resulting mixture was refluxed for 2 h and thesolvents were then removed in vacuo. The residual mixture was re-dissolved in a mixture of tolueneand CH2Cl2 (10:1, v/v), then TEA (4.8 mL) and BF3·Et2O (4.2 mL) were added. After heating at 50 °Cfor 1.5 h, the solvents were evaporated and the crude product was purified by columnchromatography to afford the BODIPY core as an orange solid (2.12 g, 65% yield).1H-NMR (300 MHz, CDCl3, δ, ppm): 6.07 (s, 2H), 3.48-3.43 (t, 2H), 3.02-2.96 (t, 2H), 2.52 (s, 6H), 2.43(s, 6H), 2.08-2.04 (m, 2H), 1.87-1.82 (m, 2H). |
65% | Stage #1: 2,4-dimethyl-1H-pyrrole; 5-bromovaleroyl chloride In dichloromethane for 2h; Inert atmosphere; Reflux; Stage #2: boron trifluoride diethyl etherate With triethylamine In dichloromethane; toluene at 50℃; for 1.5h; Inert atmosphere; | 2.2.1. Synthesis of the BODIPY dye 1 The BODIPY dye 1 was synthesized in accord to our previouslydescribed procedure [30] . Briefly, 5-bromovaleryl chloride (1.14 mL,8.52 mmol) and 2,4-dimethyl pyrrole (1.75 mL, 17.04 mmol) weredissolved in dry CH 2 Cl 2 (100 mL). The resulting mixture was thendegassed with a stream of Ar gas for 2 min, refluxed for 2 h, andthe solvents were then evaporated on a rotary evaporator . A mixtureof toluene and CH 2 Cl 2 (10:1, v/v) was added to the residualmixture, followed by TEA (4.8 mL) and BF 3 •Et 2 O (4.2 mL). Themixture was heated at 50 °C for 1.5 h and the solvents were subsequentlyevaporated. The crude product was purified by silica gelcolumn chromatography employing dichloromethane/hexane (1:1)solvent system to obtain the BODIPY dye as an orange solid (2.12 g,65% yield).1 H NMR (300 MHz, CDCl 3 , , ppm): 6.07 (s, 2H), 3.37 (t,J = 6.0 Hz, 2H), 2.98 (m, 2H), 2.52 (s, 6H), 2.42 (s, 6H), 1.75 (m,4H).13 C NMR (75 MHz, CD 3 OD, , ppm): 154.28, 145.55, 140.63,131.55, 121.94, 47.25, 44.35, 33.13, 32.85, 30.16, 28.88, 27.51, 16.40,16.36, 14.47, 14.44, 8.74. |
49% | Stage #1: 2,4-dimethyl-1H-pyrrole; 5-bromovaleroyl chloride In dichloromethane at 50℃; for 2h; Stage #2: With triethylamine In dichloromethane; toluene for 0.5h; Inert atmosphere; Stage #3: boron trifluoride diethyl etherate In dichloromethane; toluene for 1.5h; Inert atmosphere; Reflux; | 2.1.1. BODIPY-(CH2)4-Br The halogenated dye was prepared according to a previously publishedmethod [25]. 5-Bromovaleryl chloride (0.352 ml, 1.00 eq) wasadded dropwise to a stirred solution of 2,4-dimethylpyrrole (0.500 g,2.00 eq) in anhydrous dichloromethane at 50 °C for 2 h. After the solventwas evaporated, the residual solid was dissolved in toluene (35 ml)and dichloromethane (15 ml). Triethylamine (1.54 ml, 4.20 eq) wasadded, and the mixture was stirred under argon atmosphere for 30 min,and then boron trifluoride diethyl etherate (1.62 ml, 5.00 eq) was added dropwise. The reaction mixture was refluxed for 1.5 h at 50 °Cand the solvent was vacuum evaporated. The crude product was purifiedby silica gel column chromatography eluting with CH2Cl2-hexane.Yield 49%. 1H NMR (CDCl3, 400 MHz): δ=6.07 (s, 2 H), 3.46 (t, 2 H),2.99 (t, 2 H), 2.52 (s, 6 H), 2.43 (s, 6 H), 2.06 (t, 2 H), 1.82 (t, 2 H) ppm. |
46% | Stage #1: 2,4-dimethyl-1H-pyrrole; 5-bromovaleroyl chloride In dichloromethane for 5h; Reflux; Stage #2: boron trifluoride diethyl etherate With triethylamine In dichloromethane; toluene at 50℃; for 1h; | 14.1 General procedure: 2,4-Dimethylpyrrole (7.0g, 73.6mmol) was dissolved in 200mL of anhydrous dichloromethane (DCM), 4-bromobutyryl chloride (6.75g, 36.4mmol) was added dropwise under ice bath, and the reaction was refluxed. 5h.Rotate the solvent to dryness, dissolve the residue with a mixed solvent of 200mL toluene/DCM=19:1, add triethylamine (TEA, 18.4g, 182mmol) and boron trifluoride ether complex in turn(BF3·Et2O, 36.2g, 255mmol), react at 50 for 1h,The reaction solution was poured into 400 mL of ice water, 200 mL of dichloromethane was added for extraction, the organic phase was washed twice with water, dried over anhydrous sodium sulfate, spin-dried the solvent, and separated by column chromatography to obtain the product (4.0 g, 36%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | A solution of 4-(formylphenyl)pyridine (2.5 g,13.6 mmol, 1 eq.) in CH2Cl2 (90 mL) was degassed with Ar for 5 min.2,4-dimethylpyrrole (2.8 mL, 27.3 mmol, 2 eq.) was added, then trifluoroaceticacid (15 drops). The reaction mixture was protected fromlight and stirred at room temperature under argon for 18 h. The resultingorange solution was washed with saturated NaHCO3 solutionwith the mixture turning yellow, then with water. The organic layerwas dried on MgSO4, filtered and evaporated. The resulting yellow--brown foam was dissolved in THF (120 mL), cooled to 0 C and protectedfrom light. A solution of DDQ (3.4 g, 15.0 mmol, 1.1 eq.) in THF(120 mL) was added dropwise and the mixture was stirred at roomtemperature for 64 h. The reaction mixture was concentrated to halfvolume and the precipitate was dissolved by addition of CH2Cl2 andNEt3 before adsorption on silica for purification by column chromatography(SiO2, CH2Cl2/NEt3: 100/1 then CH2Cl2/MeOH/NEt3: 97/3/1)to afford dipyrrin 2 (2.3 g, 48% yield) as a brown solid. deltaH (500 MHz,CDCl3) 13.16 (s, 1H, NH), 8.75-8.63 (m, 2H, pyH), 7.75 (d, J=8.3 Hz,2H, PhH), 7.64-7.56 (m, 2H, pyH), 7.44 (d, J=8.3 Hz, 2H, PhH), 5.91(s, 2H, CH3), 2.36 (s, 6H, CH3), 1.34 (s, 6H, CH3). deltaC (125 MHz, CDCl3)151.99, 150.51, 147.66, 140.24, 139.23, 137.91, 137.82, 136.33,130.31, 127.15, 121.60, 119.87, 16.18, 14.86. HRMS (ESI): [MH]+,found 354.1943. C24H24N3 requires 354.1965. UV-Vis: lambdamax(DMF)/nm(epsilon/mol-1.L.cm-1): 449 (35100). |
Yield | Reaction Conditions | Operation in experiment |
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17.4% | Stage #1: 2,4-dimethyl-1H-pyrrole; methyl adipoyl chloride In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere; Stage #2: With triethylamine In dichloromethane at 20℃; for 0.166667h; Inert atmosphere; Stage #3: boron trifluoride diethyl etherate In dichloromethane Inert atmosphere; | 2.2. Synthesis of BODIPY BF2-ms-(4-methoxycarbonylbutyl)-3,3′,5,5′-tetramethyl-2,2′-dipyrromethene(M = 362.22) was synthesized under argon atmospherewith stirring on a magnetic stirrer according to the procedure presentedin [29]. 1.0 ml (0.927 g, 9.74 mmol) 2,4-dimethylpyrrole slowly, dropby drop was added dropwise to a solution (1.52 ml, 1.73 g, 9.74 mmol)of methyladipoyl chloride in 40 ml of dried and cooled (up to 0 °C)methylene chloride. The mixture was allowed to warm to room temperature,and the solution of the resulting dipyrromethene was usedwithout further purification. The solution was allowed to stir at roomtemperature for 2 hours. Then, 2 ml of triethylamine was added to thesolution at room temperature and stirring on a magnetic stirrer, then1.5 ml of BF3Et2O (∼12 mmol) was added after 10 min. Complex formationwas monitored by changes of ABS. The solvent was distilled offunder reduced pressure, and the solid residue was dissolved in dichloromethaneand chromatographed on silica gel, eluting by 1:1 hexane:methylene chloride. The eluate was evaporated, and the productwas precipitated with methanol from a concentrated solution in dichloromethaneunder cooling. Yield 0.307 g (0.847 mmol, 17.4 %). 1HNMR spectrum (CDCl3), δ, ppm: 6.07 s (2H, 4.4′-H); 3.69 s (3H, OCH3:2.95-3.00m (2H, ms-CH2); 2.53 s (6H, CH3); 2.43 s + 2.41 t (6+2H,J=7.4 Hz, CH3+CH2CO); 1.84qv (2H, J=7.4 Hz, CH2); 1.64-1.72m(2H, CH2). Mass spectrum, m/z: 343.52 [M-F]+. Found, %: H 6.99, C62.95, N 7.79. BF2. BF2C19H25N2O2. Calculated, %: H 6.96, C 63.00, N7.73. |
17.4% | Stage #1: 2,4-dimethyl-1H-pyrrole; methyl adipoyl chloride In dichloromethane at 0 - 20℃; for 4h; Inert atmosphere; Stage #2: boron trifluoride diethyl etherate With triethylamine In dichloromethane at 0 - 20℃; for 3h; Inert atmosphere; | 2.2 Synthesis of meso-BODIPY dyes General procedure: BF2-meso-(4-methoxycarbonylpropyl)-3,3′,5,5′-tetramethyldipyrromethene (5) (BF2C18H23N2O2; M=348.2) was obtained in an argon atmosphere with stirring on a magnetic stirrer according to the method described in [18]. To a solution of 0.65ml (4.73mmol) of methyl 4-chloroformylbutyrate in 40ml of methylene chloride dried and cooled to 0°C, 0.97ml (9.45mmol) of 2,4-dimethylpyrrole was slowly (∼1h) dropwise added. The mixture was allowed to warm to room temperature and stirred for an additional 4h. The color of the solution changes to reddish brown. The solution was again cooled to 0°C, and 2ml (∼14mmol) of triethylamine were added, followed by 1.5ml (∼12mmol) of boron triboride etherate, and stirring was continued at room temperature for 3h. The end of the reaction was determined by the change in the electronic absorption spectrum. Then the solvent was removed on a rotary evaporator under vacuum. The solid residue was purified by chromatography on silica gel, eluting with a 1 : 1hexane/methylene chloride mixture. The eluate was partially evaporated, the product precipitate was filtered off and dried under vacuum. The yield was 0.243g (0.697mmol, 14.7%). 1H NMR spectrum (CDCl3), δ, ppm: 6.08s (2H, 4,4-H); 3.72s (3H, OCH3); 2.99-3.05m (2H, meso-CH2); 2.53s+2.52t (6+2H, J=7.2Hz, CH3+CH2CO); 2.45s (6H, CH3); 1.94-2.02m (2H, CH2). Mass spectrum, m/z: 329.50 [M-F]+. Found, %: H 6.69, C 62.01, N 8.13. Calculated, %: H 6.66, C 62.09, N 8.05. CCDC number 2011215. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluoroacetic acid In dichloromethane at 20℃; Inert atmosphere; | 2.1.1 4,4-Difluoro-8-[4-(3-(N,N-dimethylamino))propoxiphenyl]-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (BDP 1) 2,4-Dimethylpyrrole (500μL, 4.85mmol) and 4-(3-(N,N-dimethylamino)propoxy)benzaldehyde (400μL, 1.99mmol) were treated with trifluoroacetic acid (TFA, 30μL, 0.39mmol) in 75mL of dichloromethane (DCM). The solution was deoxygenated with argon and stirred overnight at room temperature. Then, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 461mg, 2.03mmol) in 25mL of DCM was added drop by drop in the reaction flask and the mixture was kept under stirring for 6h. After that, it was placed in a cold bath to decrease the temperature to about -1°C and an excess of triethylamine (TEA, 5mL, 35.9mmol) was incorporated and boron trifluoride diethyl etherate (BF3.OEt2, 5mL, 40.5mmol) was added after 15min and the solution was stirred for 12h. The mixture was washed with water and the organic phase was dried over Na2SO4. The crude product was obtained by solvent evaporation under reduced pressure. The product was purified by flash column chromatography (silica gel) using DCM:n-hexane (80:20) with 1% TEA as eluent provided 127mg (14%) of BDP 1. TLC (DCM: TEA 1%) Rf=0.54. 1HNMR (CDCl3, TMS) δ [ppm] 1.49 (s, 6H), 1.96 (m, 2H), 2.30 (s, 6H, -N(CH3)3), 2.51 (t, 2H, J=6.8Hz, -CH2-N), 2.55 (s, 6H), 4.11 (t, 2H, J=6.1Hz, -CH2-O), 5.97 (s, 2H, pyrrole), 7.00 (d, 2H, J=8.7Hz, Ar), 7.17 (d, 2H, J=8.7Hz, Ar). ESI-MS [m/z] 426.2521 (426.2528 calculated for (M+H)+, M=C24H30BF2N3O). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
15.4% | Stage #1: 2,4-dimethyl-1H-pyrrole; 1,10-phenanthroline-2,9-dicarboxaldehyde In dichloromethane for 12h; Inert atmosphere; Darkness; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane for 1h; Inert atmosphere; Darkness; Stage #3: boron trifluoride diethyl etherate With triethylamine In dichloromethane for 2h; Inert atmosphere; Darkness; | 2.2.2. 2,9-BDP-Phen To a three necked-flask, 2, 9-dicarbaldehyde (0.69 g, 2.91 mmol) and2, 4-dimethyl pyrrole (1.2 mL, 11.62 mmol) were added in 150 mLCH2Cl2. The solution was purged with nitrogen for 30 min to removeoxygen. Then two drops of trifluoracetic acid were added. The reactionmixture was stirred for 12 h under dark. After adding 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (1.32 g, 5.81 mmol), the mixture wasallowed to stir for another hour. Then triethylamine (11.64 mL, 82.82mmol) and BF3.Et2O (11.62 mL, 94.16 mmol) was added sequentially.The reaction mixture was stirred for another two hours. After removingthe solid by filtration and solvent of the filtrate, the residual wasredissolved in CH2Cl2 and applied to a silica gel column for purification.An orange solid was obtained. Yield: 0.30 g, 15.4%.1H NMR (400 MHz,CDCl3): = 8.46 (d, 1H), 8.00 (s, 1H), 7.79 (d, 1H), 5.94 (s, 2H), 2.54 (s,6H), 1.19 (s, 6H). 13C NMR (400 MHz, CDCl3): = 14.11, 14.67, 121.24,124.37, 127.46, 128.73, 131.78, 137.20, 138.88, 142.42, 146.17,154.65, 156.31 HRMS (ESI) Found, m/z: 673.3058 [M+H]+,C38H35B2F4N6, Calculated: 673.3045 |
Tags: 625-82-1 synthesis path| 625-82-1 SDS| 625-82-1 COA| 625-82-1 purity| 625-82-1 application| 625-82-1 NMR| 625-82-1 COA| 625-82-1 structure
[ 517-22-6 ]
2,4-Dimethyl-3-ethyl-1H-pyrrole
Similarity: 0.88
[ 2199-58-8 ]
3,5-Dimethyl-1H-pyrrole-2-carbaldehyde
Similarity: 0.78
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