82% |
Stage #1: 3,6-dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 1h; Inert atmosphere;
Stage #2: 3-bromomethylheptane In N,N-dimethyl-formamide at 130℃; Inert atmosphere; |
2,5-bis(2-ethylhexyl)-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (3).
Compound 2 (6.0 g, 19.98 mmol) andK2CO3 (8.3 g, 59.98 mmol) were added in a 250 mL round-bottom flask under argon. A degassed anhydrous solution of DMF (100mL) were added to the mixture. The reaction solution was refluxed for 1 hour at 120 °C. 2-ethylhexyl bromide (10.3 mL, 59.98mmol) was then added dropwise, and the reaction mixture was further refluxed overnight at 130 °C. After cooling to roomtemperature (RT), the resulting solution was diluted with CHCl3 (200 mL) and washed with H2O (5 × 200 mL). The organic layerwas collected and evaporated via rotary evaporator. The remaining crude product was purified by column chromatography (silicagel) using a single solvent (CH2Cl2) as eluent to give compound 3 (8.6 g, 16.38 mmol, 82%) as brown solid. 1H NMR (400 MHz,CDCl3) δ (ppm): 8.90 (dd, J = 3.6, 1.2 Hz, 2H), 7.63 (dd, J = 5.2, 1.2 Hz, 2H), 7.27 (dd, J = 5.2, 4.0 Hz, 2H), 4.03 (m, 4H), 1.86(m, 2H), 1.38-1.22 (m, 16H), 0.89-0.83 (m, 12H). |
79% |
With potassium carbonate In N,N-dimethyl-formamide at 140℃; for 12h; Inert atmosphere; |
1.1 (1) Synthesis of 2,5-diethylhexyl-3,6-dithiophen-2-ylpyrrolo[3,4-c]pyrrole-1,4-dione
Under a nitrogen atmosphere, 3,6-dithiophen-2-yl-2,5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione (13 g, 43.3 mmol) dissolved in 300 mL of dimethylformamide (DMF) was added to a 500 ml two-necked round bottom flask. After stirring the mixture with heating, potassium carbonate (K2CO3) (4 eq.) was added and stirred at 140°C. Then, 2-ethylhexylbromomide (4.6 eq.) was added thereto and stirred for 12 hours. After stopping the reaction by thin film chromatography (TLC) confirmation, the resulting mixture was washed with ice water and solids were filtered through a filter and purified by silica column eluted with chloroform to obtain 2,5-diethylhexyl-3,6-dithiophen-2-ylpyrrolo[3,4-c]pyrrole-1,4-dione (18.01 g, Y=79%). |
75% |
Stage #1: 3,6-dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 1h; Inert atmosphere;
Stage #2: 3-bromomethylheptane With 18-crown-6 ether In N,N-dimethyl-formamide at 150℃; Inert atmosphere; |
|
75% |
Stage #1: 3,6-dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 1h; Inert atmosphere;
Stage #2: 3-bromomethylheptane In N,N-dimethyl-formamide at 130℃; for 24h; Inert atmosphere; |
|
75% |
With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 24h; |
|
72% |
With 18-crown-6 ether; potassium carbonate In N,N-dimethyl-formamide at 120 - 150℃; for 12h; Inert atmosphere; |
1.2
in a nitrogen atmosphere of formula (5) Compound 5 (3. 00g, 9. 99mmol), anhydrous potassium carbonate (6. 22g, 45mmol) was added to a solution containing 50ml N, N- dimethylformamide (DMF ) the reaction flask was heated to 120 ° C, and then dissolved in a minimum of DMF of 1-bromo-2-ethylhexanoate was added dropwise to the burning reaction flask while adding a small amount of 18-crown-6 ether, dropwise after the addition is complete warm to 150 ° C, for 12 hours. Then cooled to room temperature, the reaction solution was poured into four volumes of distilled water, the aqueous phase was extracted with methylene chloride to colorless, and then the organic phase was washed three times with distilled water, the organic solvent was removed under reduced pressure after boiling range 60 ° C -90 ° C petroleum ether as eluent over a silica gel column, to give the formula shown in (5) compound 6 3. 77g, yield 72%. ; |
72% |
With 18-crown-6 ether; potassium carbonate In N,N-dimethyl-formamide at 120℃; for 12h; Inert atmosphere; |
1.2
(2) 1.024 g of compound (I),2.7642 g of potassium carbonate and 4.2991 g of 18-crown ether 6 were added to a round bottom flask.Start degassing and then fill with nitrogen for three consecutive times,Then add 20mL of N, N-dimethylformamide (DMF), stir,Then 2.84 mL of bromoisooctane was added and reacted at 120 ° C for 12h.The resulting solution was first distilled under reduced pressure and then purified through a chromatography column.The eluent has a ratio of methylene chloride to petroleum ether of 1: 3.Compound (II) can be obtained by distillation under reduced pressure, and the mass of the obtained compound is about 1.52 g.The yield is 72%; its chemical reaction equation is as follows: |
70.9% |
Stage #1: 3,6-dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 1.5h; Inert atmosphere;
Stage #2: 3-bromomethylheptane In N,N-dimethyl-formamide at 130℃; for 24h; Inert atmosphere; |
|
63% |
Stage #1: 3,6-dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione With potassium carbonate In N,N-dimethyl-formamide at 145℃; for 0.166667h;
Stage #2: 3-bromomethylheptane In N,N-dimethyl-formamide at 100 - 145℃; |
2,5-bis(2-ethylhexyl)-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4-dione
3,6-Dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione (cmpd describedhere above)(3.922 g, 13.06 mmol) and potassium carbonate (7.226 g, 52.28 mmol,4 equiv) were dried under vacuum. DMF (65 mL) was added and the medium was stirredat 145 °C for 10 min resulting in a deeper purple color medium. 2-Ethylhexylbromide (11.6 mL, 65.23 mmol,5 equiv) was added slowly at 100 °C. The medium was stirred further at 145 °C overnight, then cooled to rt.The reaction medium was quenched with an ice/water solution (150 mL), then extracted with CH2Cl2 andwashed with water, finally dried with brine and over Na2SO4. Purification by column chromatography onsilica using a gradient of CH2Cl2/petroleum ether as eluent (50/50 to 100/0) afforded cmpd 1 as a purple solid(4.336 g, 63%). |
52.4% |
With potassium carbonate In N,N-dimethyl-formamide at 70℃; |
2 Synthesis Example 2
Charge a 500-ml eggplant-shape flask with the above- prepared compound (a) (5.0 g, 13.3 mmol), 2-ethylhexyl bromide (8.0 g, 41.6 mmol), dry DMF (100 ml), and potassium carbonate (6.0 g). Agitate the flask content all night long at 70° C. Afier distilling the solvent away under reduced pressures, add a mixed solvent of methanol and water (MeOH/water=1/1, 100 ml) to the flask. Separate the precipitate by filtration and purify it by a silica gel colunm chromatography (solvent: toluene). Thus, a red powder (4.5g, 52.4%) is obtained. mlz=525.3 (M+H) |
51% |
With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 24h; |
Synthesis of Compound 2
The compound 1 (10.0g, 33.3mmol), 2- ethylhexyl bromide ( 19. 3g, 99.9mmol), and K2CO3 (18.4g, 133mmol) dry DIt was mixed in MF (300mL), stirred for 24 hours at 120. ° C. . After cooling to room temperature , precipitationThe reaction mixture was poured into a large amount of ice water to form a palace compound . The resulting precipitate was times by filtrationTo yield , and washed with water and methanol .The resulting product was purified by silica gel column chromatography ( eluent : CHCl3 / hexaDown = 1: 1, v purified on / v ) , then recrystallized from CHCl3 / methanol , and dried under vacuumTo give compound 2 as a red- brown solid ( 8.89 g , yield = 51% ) . |
49% |
With potassium carbonate In N,N-dimethyl-formamide at 145℃; for 15h; |
|
45% |
With potassium-t-butoxide In 1-methyl-pyrrolidin-2-one for 16h; Inert atmosphere; Reflux; |
1.2; 2.2
10 mmol of 3,6-dithienylpyrrolopyrroledione and 10 mmol of bromoisooctane were added to 20 mmol of potassium t-butoxide and 100 mL of dry Ν-methylpyrrolidone solution. Under the protection of argon, the mixture was heated to reflux for 16 h, cooled to room temperature, suction filtered, and the filtrate was evaporated under reduced pressure to remove most of the N-methylpyrrolidone. CH2Cl2 extraction, anhydrous NaSO4 drying, column chromatography gave 2,5-diisooctyl-3,6-dithienylpyrrolopyridinone as a red solid with a yield of 45%. |
39% |
Stage #1: 3,6-dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione With potassium carbonate In N,N-dimethyl-formamide at 145℃; for 2h; Inert atmosphere;
Stage #2: 3-bromomethylheptane In N,N-dimethyl-formamide at 145℃; for 12h; Inert atmosphere; |
|
35% |
With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 40h; |
|
33% |
With potassium carbonate In N,N-dimethyl-formamide at 145℃; Inert atmosphere; |
3.2.1. 5-Diethylhexyl-3,6-dithiophen-2-ylpyrrolo-[3,4-c]pyrrole-1,4-dione (2)
Compound 1 (1.00 g, 3.30 mmol, 1 eq.) and anhydrous potassium carbonate (1.84 g, 13.3 mmol,4 eq.) were dissolved into dry N,N-dimethylformamide (25 mL) in a two-neck round flask and heatedto 145 C under nitrogen protection. 2-Ethylhexyl bromide (2.96 g, 15.3 mmol, 4.6 eq.) was injected inone portion by syringe. The reaction mixture was stirred for 20 h at 145 C, then the solution was cooledto room temperature (rt.) and poured into ice water (50 mL). The aqueous layer was extracted withCH2Cl2 (3 50 mL). The combined organic extracts were dried over Na2SO4, filtered and concentratedunder reduced pressure. The resulting material was purified by silica gel column chromatographyusing hexane:EtOAc (9:1) leading to 2 (0.57 g, 1.08 mmol, 33%) as a black red solid. 1H-NMR (400 MHz,CDCl3, 298 K): 8.91 (d, J = 8.9 Hz, 2H), 7.62 (d, J = 7.6 Hz, 2H), 7.27 (d, J = 7.3 Hz, 2H), 4.03-4.00 (m,4H), 1.88-1.85 (m, 2H), 1.38-1.24 (m, 16H), 0.89-0.83 (m, 12H). 13C-NMR (100 MHz, CDCl3, 298 K): 161.7, 140.3, 135.2, 130.5, 129.8, 128.4, 107.8, 77.3, 77.0, 76.7, 45.8, 39.0, 30.2, 30.1, 28.3, 23.5, 23.0, 14.0,10.4. HRMS (TOF ASAP+, m/z): observed 525.2600, calculated for C30H41N2O2S2 [M + H]+ 525.2604.The 1H-NMR data was in accordance with reported literature [40]. |
31% |
With potassium carbonate In N,N-dimethyl-formamide at 130℃; Inert atmosphere; |
|
31.5% |
With Cs2CO3 In acetonitrile at 90℃; for 15h; |
1.2; 2.2; 3.2; 4.2
2) Add compound (I) (1.00g, 3.33mmol) to a 250mL three-necked round bottom flask,Bromoisooctane (5.14g, 26.7mmol), cesium carbonate (6.43g, 19.7mmol),Then add 50mL of acetonitrile, and reflux at 90 ° C for 15h. After the reaction,Spin-dry acetonitrile, extract with a large amount of water and dichloromethane, spin-dry the organic phase, and then pass the column with a volume ratio of 1: 1 dichloromethane and petroleum ether mixture to collect pure product points to obtain 0.55g of compound ( II), yield 31.5% |
26% |
With potassium carbonate In N,N-dimethyl-formamide at 130℃; |
|
26% |
Stage #1: 3,6-dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 1h; Inert atmosphere; Schlenk technique;
Stage #2: 3-bromomethylheptane In N,N-dimethyl-formamide at 120℃; Inert atmosphere; Schlenk technique; |
|
25% |
Stage #1: 3,6-dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione In N,N-dimethyl-formamide at 119.84℃; for 0.5h; Inert atmosphere;
Stage #2: 3-bromomethylheptane With potassium carbonate at 129.84 - 139.84℃; Inert atmosphere; |
2,5-Bis(2-Ethylhexyl)-3,6-Di(Thiophene-2-Yl)-2,5-Dihydropyrrolo[3,4-c]Pyrrole-1,4-Dione (3)
Compound 2(3.36 g, 10.8 mmol) and 100 mL of dry DMF were added to a 250 mL two-neck round-bottom flask, equipped with a condenserand stir-bar and placed under N2 atmosphere. The mixturewas heated to 393 K, stirred for 30 min, and 2-ethylhexylbromide (6.05 g, 31.3 mmol) was then addedquickly (while at 393 K).The reaction mixture was subsequently stirred at 413 K forca. 6 h, and cooled to room temperature. The organic phasewas extracted with diethyl ether and washed with water. Thediethyl ether was evaporated, and the resulting tacky solid(red) was purified by column chromatography using CHCl3as eluent. 1.30 g of 3 was isolated (25 % yield). 1H NMR(500MHz, CDCl3): (ppm) = 8.33 (d, J = 3.6 Hz, 2 H), 7.61 (d,J = 1.3 Hz, 2 H), 6.69 (dd, J = 1.7 Hz, 3.6 Hz, 2 H), 4.04 (d,J = 7.8 Hz, 4 H), 1.80-1.68 (m, 2 H), 1.39-1.26 (m, 16 H), 0.95-0.85 (m, 12 H). 13C (75 MHz, CDCl3): (ppm) = 161.4,145.0, 144.8, 134.1, 120.4, 113.6, 106.6, 46.3, 40.1, 30.7,28.8, 24.0, 23.2, 14.2, 10.9. |
24% |
Stage #1: 3,6-dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 1h; Inert atmosphere;
Stage #2: 3-bromomethylheptane In N,N-dimethyl-formamide at 120℃; for 24h; Inert atmosphere; |
2 2.2 2,5-Dioctyl-3,6-di(thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (1a)
General procedure: This compound was synthesized according to a literature procedure [41] 3,6-Di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (3) (0.45 g, 1.5 mmol) and K2CO3 (0.83 g, 6.0 mmol) were added to the reaction vessel. The reaction vessel was fitted with a silicon septum, evacuated, and back-filled with argon. This sequence was repeated twice. Anhydrous DMF (16 mL) was added under a stream of argon, and the resulting mixture was stirred at 120 °C for 1 h. Then, 1-iodooctane (4a) (1.44 g, 6.0 mmol) was added in one portion, and the mixture was stirred at 120 °C for 24 h. After cooling to room temperature, the reaction mixture was poured into ice-cold water (100 mL), and extracted with CH2Cl2 (4 x 25 ml). The organic fractions were collected, dried over Na2SO4, filtered, and concentrated at reduced pressure. The residue was purified by flash chromatography on silica gel with a mixture of CH2Cl2 and petroleum ether (1:1) as eluent. The chromatographic fractions containing the required compound were collected and concentrated at reduced pressure to give 1a as a dark pink solid (0.46 g, 58% yield) |
20% |
With potassium carbonate In N,N-dimethyl-formamide at 150℃; Inert atmosphere; |
|
16.66% |
With 18-crown-6 ether; potassium carbonate In N,N-dimethyl-formamide at 120℃; for 24h; Inert atmosphere; |
|
16% |
Stage #1: 3,6-dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione With 18-crown-6 ether; potassium carbonate In N,N-dimethyl-d<SUB>6</SUB>-formamide at 120℃; for 3h; Inert atmosphere;
Stage #2: 3-bromomethylheptane In N,N-dimethyl-formamide at 130℃; for 20h; Inert atmosphere; |
|
15% |
Stage #1: 3,6-dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 3h;
Stage #2: 3-bromomethylheptane In N,N-dimethyl-formamide at 140℃; Inert atmosphere; |
|
|
With potassium carbonate In 1-methyl-pyrrolidin-2-one at 140℃; for 6h; |
1.a
Examples Example 1; a) A solution of 4.5 g of DPP 1 , 6.23 g of K2CO3 and 8.68 g of 1 -broιmo-2-ethyl-hexyl in 60 ml of N-methyl-pyrrolidone (NMP) is heated to 14O0C for 6h. The mixture is washed with water and extracted with dichloromethane. The organic phase is then dried and filtered on a double layer of silica gel and Hyflo (CAS 91053-39-3; Fluka 56678) before it is concentrated. The residue is dissolved in 100 ml of chloroform, cooled down to O0C and 2 equivalents of N-bromosuccinimide are then added portion wise over a period of 1 h. After the reaction has been completed, the mixture is washed with water. The organic phase is extracted, dried and concentrated. The compound is then purified over a silica gel column to give 1.90 g of a violet powder of DPP 2. |
|
With potassium carbonate In 1-methyl-pyrrolidin-2-one at 140℃; for 6h; |
1.a
A solution of 4.5 g of the 1 ,4-diketopyrrolo[3,4-c]pyrrole (DPP) derivative of the formula 1 , 6.23 g of K2CO3 and 8.68 g of 1 -bromo-2-ethyl-hexyl in 60 ml of N-methyl-pyrrolidone (NMP) is heated to 14O0C for 6h. The mixture is washed with water and extracted with dichloromethane. The organic phase is then dried and filtered on a double layer of silica gel and Hyflo (CAS 91053-39-3; Fluka 56678) before it is concentrated. The residue is dissolved in 100 ml of chloroform, cooled down to 0 0C and 2 equivalents of N- bromosuccinimide are then added portion wise over a period of 1 h. After the reaction has been completed, the mixture is washed with water. The organic phase is extracted, dried and concentrated. The compound is then purified over a silica gel column to give 1.90 g of a violet powder of the DPP derivative of the formula 2. |
2.05 g |
With 18-crown-6 ether; potassium carbonate In N,N-dimethyl-formamide at 120℃; for 20h; |
|
1.24 g |
Stage #1: 3,6-dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione With Cs2CO3 In N,N-dimethyl-formamide at 120℃; for 3h;
Stage #2: 3-bromomethylheptane In N,N-dimethyl-formamide at 130℃; for 20h; |
|
|
With potassium carbonate In N,N-dimethyl-formamide |
|
|
In N,N-dimethyl-formamide at 110℃; |
|
|
With potassium carbonate In N,N-dimethyl-formamide at 145℃; for 15h; Inert atmosphere; |
|
4.7 g |
With 18-crown-6 ether; potassium carbonate In N,N-dimethyl-formamide at 120℃; |
|
|
With potassium carbonate In N,N-dimethyl-formamide |
|
|
With potassium carbonate In N,N-dimethyl-formamide at 60℃; |
|
4.6 g |
Stage #1: 3,6-dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 1h;
Stage #2: 3-bromomethylheptane In N,N-dimethyl-formamide at 80 - 120℃; for 24h; |
2 Synthesis of compound (c):
In a 250mL two-necked bottle,Crude product 2 (3.5 g, 11.5 mmol) and anhydrous potassium carbonate (12.7 g, 92 mmol) and N,N dimethyl amide (DMF) 100 mL,The mixture was heated to reflux at 120 ° C for 1 hour under argon gas.When cooled to about 80 ° C, bromoisooctane (16.5 mL, 57 mmol) was slowly added dropwise.After completion of the dropwise addition, the reaction was carried out at 120 ° C for 24 hours.The heating was stopped, and after cooling to room temperature, 50 mL of ethyl acetate was added and then suction filtered.The filtrate was extracted with ethyl acetate. The organic phases were combined and dried over anhydrous sodium sulfate.The solvent was distilled off under reduced pressure, and the crude product was separated by column chromatography.The eluent was petroleum ether (PE) and ethyl acetate (EA) (50:1).A purple-red solid of 4.6 g was obtained with a yield of 34%. |
1.39 g |
With potassium carbonate In N,N-dimethyl-formamide for 15h; Inert atmosphere; Heating; |
|
|
With potassium carbonate In N,N-dimethyl-formamide |
|
|
With 18-crown-6 ether; potassium carbonate In N,N-dimethyl-formamide at 120℃; for 12h; |
|