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CAS No. : | 299962-88-2 | MDL No. : | N/A |
Formula : | C14Br4O6 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | AYAULFUIPANQMY-UHFFFAOYSA-N |
M.W : | 583.76 | Pubchem ID : | 3089245 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P264-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+P313 | UN#: | N/A |
Hazard Statements: | H315-H319 | 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 |
---|---|---|
100% | With fuming sulphuric acid; sulfuric acid; bromine at 140℃; for 672h; | The synthesis of NDI-AQ (1) was achieved by reacting 1,4,5,8-naphthalenetetracarboxylic dianhydride (NDA) with 5.3 equiv ofBr2 in a mixture of sulfuric acid and oleum (v:v, 4:1) at 140 C for4 weeks. 2,3,6,7-Tetrabromonaphthalene diimide (3) was preparedover two steps by the reaction of 2 and 4 equiv of n-octylamine inrefluxing acetic acid for 30 min to give 2,3,6,7-tetrabromo-4,8-bis(octylcarbamoyl) naphthalene-1,5-dicarboxylic acid, whichwas further treated with excess PBr3 in refluxing toluene for 12 hto afford 3 in 31% overall yield.1 |
99% | Stage #1: 1,4,5,8-naphthalenetetracarboxylic dianhydride With sulfuric acid at 55℃; for 2h; Stage #2: With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione at 80℃; for 48h; | |
96% | With sulfuric acid; sulfur trioxide; bromine at 140℃; for 672000h; |
94% | Stage #1: 1,4,5,8-naphthalenetetracarboxylic dianhydride With fuming sulphuric acid at 55℃; for 2h; Stage #2: With dibromoisocyanuric acid at 85℃; for 50h; | |
93% | With sulfuric acid; dibromoisocyanuric acid at 25℃; for 3h; | |
93% | With dibromoisocyanuric acid In oleum(20% SO3) at 25℃; for 3h; | |
93% | With sulfuric acid; sulfur trioxide; sodium bromide at 130℃; | |
93% | With fuming sulphuric acid; dibromoisocyanuric acid at 25℃; for 3h; | |
93.3% | With sulfuric acid; bromine at 140℃; for 672h; Cooling with ice; | 1.1 (1) Add 50 mL of fuming sulfuric acid to a 100 mL three-necked flask under ice bath, and add NDI-01-A (16.08 g, 0.060 mol).Bromine (48.0 g, 0.30 mol) was added dropwise, stirred for 10 minutes, and then warmed to 140 ° C for 4 weeks, and cooled.Pour into a large amount of ice water, precipitate solids, filter, and wash the solid water twice (150mL*2).The crude product was beaten twice with PE (petroleum ether): DCM (dichloromethane) = 1:1 (100 mL: 100 mL), filtered, and dried at 80 ° C for 16 hours.The product NDI-01-B was obtained as a yellow solid (32.7 g, yield 93.3%). |
89.5% | With sulfuric acid; dibromoisocyanuric acid at 90℃; for 6h; | Synthesis of intermediate compound a: Under mechanical stirring at room temperature, dibromoisocyanuric acid (DBI) (13.2g, 46mmol) was added in portions to 1,4,5,8-naphthalenetetracarboxylic anhydride (3.5g, 11.5mmol) and fat in two hours Niacin sulfuric acid (20% SO3, 25 mL).Then the temperature of the reaction system was raised to 90°C and stirring was continued for 6h.The reaction mixture was slowly poured into ice, filtered, and the solid was washed with deionized water to be neutral,Wash with methanol three more times. The collected solid was vacuum dried at 60°C for 12h,6.0 g of yellow powder compound a was obtained with a yield of 89.5%. Because the compound has very poor solubility,Therefore, it was directly used in the next reaction without further purification. |
88% | With sulfuric acid; sulfur trioxide; sodium bromide at 180℃; for 4h; | |
87% | With 1,3,5-tribromo-1,3,5-triazinane-2,4,6-trione; sulfuric acid at 20 - 80℃; for 16h; regioselective reaction; | General procedure for regioselective bromination of NDA: General procedure: In single necked round bottomed flasks 1,4,5,8-naphthalenetetracarboxylic dianhydride (NDA,10 mmol) was slurried in concd H2SO4 (25 mL) at ambient temperature, the mixtures were stirred for 5 min to obtain dissolution. To the resulting solutions, TBCA (0.5, 1.0 and 2.5 equiv respectively) was added in portions and stirred at room temperature for 8, 12 and 8 h respectively for regioselective bromination to obtain mono-, di- and tetra-bromo-NDAs (1-3) respectively. The room temperature reaction mixture with 2.5 equiv of TBCA was further stirred for 8 h at 80 °C to improve the reaction efficiency. The reaction mixtures were poured into crushed ice and the precipitated solids were filtered, washed with water then with methanol, and finally dried in vacuo to obtain corresponding brominated NDAs (1-3). All the compounds were recrystallized from dimethylformamide to obtain mono-, di-, and tetrabrominatedNDAs 1-3 in their highest purity. |
60% | With sulfuric acid; sulfur trioxide; dibromoisocyanuric acid at 20℃; for 4 - 21h; | 1; 3 Example 1; 2,3,6,7-tetrabromonaphthalene-1,4:5,8-tetracarboxylic dianhydride; A solution of 2.68 g (10 mmol) of naphthalene-1,4:5,8-tetracarboxylic bisanhydride is added dropwise within 4 hours to a solution of 2.86 g (10 mmol) of dibromocyanuric acid in 30% oleum. After the addition has ended, the mixture is stirred at room temperature for another hour before it is poured onto 500 ml of ice-water. The precipitate is filtered off and washed to neutrality with water, washed with methanol and dried under reduced pressure. 3.5 g (60%) of the 2,3,6,7-tetrabromonaphthalene-1,4:5,8-tetracarboxylic dianhydride are obtained in the form of a yellowish solid.; Example 3; 2,3,6,7-Tetrabromonaphthalene-1,8;4,5-Tetracarboxylic Bisanhydride (further example for the preparation of the compound specified in example 1); 5.36 g (20 mmol) of 1,8;4,5-naphthalenetetracarboxylic bisanhydride are dissolved in 100 ml of 30% oleum within one hour. At room temperature, a solution of 12.6 g (44 mmol) of dibromoisocyanuric acid in 100 ml of 30% oleum is added to this solution within four hours. After the addition has ended, the reaction mixture is stirred for 16 hours and then poured cautiously onto 1000 ml of ice-water, in the course of which a solid precipitates out. The residue is washed with dilute hydrochloric acid and a little methanol and dried under reduced pressure. 10.8 g (92%) of a yellow solid are obtained. |
With sulfuric acid; bromine at 50℃; | ||
With fuming sulphuric acid at 20℃; for 7h; Inert atmosphere; | ||
With sulfuric acid; dibromoisocyanuric acid at 90℃; for 8h; | Synthesis of 2,3,6,7-tetrabromonaphthalene tetracarboxylic dianhydride (2) To a 250 mL three-neck flask was added NTCA (1) (14g, 46mmol) and Oleum (20% SO3, 100mL),and after mixed up with a mechanical agitator 4equiv. DBI was added to the reaction system byportions in 2 hours. Then the whole system was heated up to 90 and stirred for another 6hours. The reaction mixture was then carefully poured into ice. The precipitated solid was filteredoff, and washed with water and methanol successively. The cake was dried in vacuo to giveCompound 2 as a yellow powder. All characterization data are the same as literature.(3) | |
With fuming sulphuric acid; dibromoisocyanuric acid at 20℃; for 3h; | ||
With fuming sulphuric acid; dibromoisocyanuric acid at 20 - 90℃; for 8h; | ||
With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione at 80℃; for 18h; | ||
With sulfuric acid; sulfur trioxide; dibromoisocyanuric acid | ||
With carbromal; sulfuric acid at 100℃; for 120h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With acetic acid at 120℃; for 0.5h; | ||
With acetic acid at 120℃; for 0.5h; | The synthesis of NDI-AQ (1) was achieved by reacting 1,4,5,8-naphthalenetetracarboxylic dianhydride (NDA) with 5.3 equiv ofBr2 in a mixture of sulfuric acid and oleum (v:v, 4:1) at 140 C for4 weeks. 2,3,6,7-Tetrabromonaphthalene diimide (3) was preparedover two steps by the reaction of 2 and 4 equiv of n-octylamine inrefluxing acetic acid for 30 min to give 2,3,6,7-tetrabromo-4,8-bis(octylcarbamoyl) naphthalene-1,5-dicarboxylic acid, whichwas further treated with excess PBr3 in refluxing toluene for 12 hto afford 3 in 31% overall yield.1 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
29% | With acetic acid at 120℃; for 6h; | |
15% | With acetic acid at 120℃; for 6h; | 9 Example 9; N,N'-Di(2,6-diisopropylphenyl)-2,3,6,7-tetrabromonaphthalene-1,8;4,5-tetracarboximide; Napthalene-1,8;4,5-tetracarboxylic acid (200 mg, 0.343 mmol) and 2,6-diisopropylaniline (425 mg, 2.40 mmol) are initially charged in concentrated acetic acid (5 ml) and stirred at 120° C. for 6 h. This is followed by addition of water (50 ml), neutralization with saturated sodium hydrogencarbonate solution and extraction with chloroform. The combined organic phases are dried over sodium sulfate and freed of the solvent. The residue is eluted with pentane/dichloromethane=2/1 on silica gel. The target compound is isolated as the second, pale yellow fraction. It can be obtained in pure form by preparative HPLC (RP18) with dichloromethane/methanol=16/84.Yield: 51 mg (0.051 mmol, 15%)ESI-MS: calc. for C50H53Br3N3O4 [M+H]+: 1000.1558, found: 1000.1478; calc. for C50H52Br3NaN3O4 [M+Na]+: 1022.1378, found: 1022.1303.m.p.: 344.5-346° C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: AcOH / 0.5 h / 120 °C 2: 672 mg / PBr3 / toluene / 12 h / Heating | ||
Multi-step reaction with 2 steps 1: acetic acid / 0.5 h / 120 °C 2: phosphorus tribromide / toluene / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In xylene at 85 - 110℃; for 7h; Heating / reflux; | 8 Example 8; N,N'-Bis(phenylethyl)-2,6-dibromonaphthalene-1,8;4,5-tetracarboximide N,N'-Bis(phenylethyl)-2,7-dibromonaphthalene-1,8;4,5-tetracarboximide by imidation of 2,3,6,7-tetrabromonaphthalene-1,4;5,8-tetracarboxylic bisanhydride; A mixture of 25 ml of xylene, 2.3 g (4 mmol) of 2,3,6,7-tetrabromonaphthalene-1,8;4,5-tetracarboxylic bisanhydride, 1.94 g (16 mmol) of phenethylamine is heated to 85° C. for 6 hours and then to 110° C. for one hour. The reaction mixture is cooled to room temperature and filtered, and the residue is washed with ethanol. 2.3 g of a solid product are obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In 1,4-dioxane; sulfolane at 100℃; for 119h; Heating / reflux; | 7 Example 7; 2,3,6,7-Tetracyanonaphthalene-1,8;4,5-tetracarboxylic bisanhydride; A mixture of 0.58 (1 mmol) of 2,3,6,7-tetrabromonaphthalene-1,8;4,5-tetracarboxylic dianhydride in 50 ml of dioxane is admixed with 1.76 g (15 mmol) of zinc cyanide, 70 mg (0.143 mmol) of 1,1'-bis(diphenylphosphinoferrocene) and 79 mg (143 mmol) of tris(dibenzylideneacetone)dipalladium. The mixture is stirred at 100° C. for 22 hours. 5 ml of sulfolane are added and the mixture is stirred at reflux for a further 97 hours. Subsequently, the reaction mixture is diluted with water and the residue which forms is filtered off, washed with water and dried. 0.46 g of a solid is obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium fluoride In sulfolane at 100 - 145℃; for 4h; | 2 Example 2; Mixture of Difluoro- and Tetrafluoronaphthalenetetracarboxylic Anhydrides; 5 ml of thionyl chloride are added to 32 ml of anhydrous sulfolane, the mixture is heated to 130° C. and the volatile constituents are distilled off. The mixture is cooled to 100° C. Subsequently, 0.85 g (1 mmol) of the above-described tetrabromo bisanhydride compound is added thereto, and also 0.1 g of 18-crown-6 and 1.4 g (12 mmol) of dried potassium fluoride. The mixture is heated at 120° C. and kept at this temperature for 2 hours. Subsequently, the mixture is heated to 145° C. and kept at this temperature for 2 hours. The reaction mixture is cooled to room temperature, precipitated in water, filtered and washed with water. According to mass spectroscopy analysis, a mixture of difluoro- and tetrafluoronaphthalic bisanhydride, which comprises a trace of trifluoronaphthalic bisanhydride, is obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | With ammonium acetate; acetic acid for 2h; Heating / reflux; | 10 Example 10; 2,3,6,7-Tetrabromonaphthalene-1,8;4,5-tetracarboximide; Naphthalene-1,4,5,8-tetracarboxylic acid (500 mg, 0.857 mmol) and ammonium acetate (1.32 g, 17.1 mmol) are heated to reflux with concentrated acetic acid to initially form a yellow solution. Later, an orange solid precipitates out, which is filtered off while hot after 2 h. The substance is washed with concentrated acetic acid (3 ml), water (5 ml), sat. sodium hydrogencarbonate solution (3 ml) and water again (5 ml), and then dried over phosphorus pentoxide.Yield: 150 mg (0.258 mmol, 30%)EI-MS: calc. for C14H2Br4N2O4 [M]+: 581.7, found: 581.7m.p. >350° C. |
30% | With ammonium acetate; acetic acid for 2h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | Stage #1: n-Octylamine; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride In dichloromethane for 2h; Reflux; Stage #2: With phosphorus tribromide In dichloromethane for 1h; Reflux; | 4,5,9,10-tetrabromo-2,7-dioctylbenzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)- tetraone (2) A suspension of TBNDA (100 mg, 0.17 mmol), n-octylamine (0.06 mL, 0.36 mmol) in dichloromethane (20 mL) was refluxed for 2h. Then PBr3 was added to the reaction solution and further refluxed for 1h. After cooled to room temperature, the mixture was poured into water (100 mL), dichloromethane was used to extract the product, and the combined organic solution was dried with anhydride MgSO4. The solvent was evaporated under reduced pressure, and the crude product was purified by silica gel chromatography with petroleum ether/dichloromethane (1:1) as eluent. 2 was obtained as a yellow solid (100 mg, 72%). When THF was used instead of dichloromethane as a solvent, a slightly lower yield (69%) was obtained. MS (MALDI-TOF) m/z 807.0 (M+H)+; 1H-NMR(300MHz, CDCl3) δ (ppm): 0.857-0.900 (m, 3H, -CH3), 1.26d1-1.386 (br,10H, -CH2-), 1.704-1.804 (m, 2H, -CH2-), 4.176-4.226 (t,2H, -CH2-N); Anal. Calcd. For C30H34Br4N2O4: C, 44.69; H, 4.25; N, 3.47; Found: C,45.00; H, 4.43; N, 3.19 |
38% | Stage #1: n-Octylamine; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride With acetic acid at 80℃; for 0.666667h; Inert atmosphere; Stage #2: With phosphorus tribromide In toluene for 10h; Inert atmosphere; Reflux; | |
30% | With acetic acid at 90℃; |
With acetic acid at 110℃; for 0.5h; | ||
1.5 g | Stage #1: n-Octylamine; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride With acetic acid for 1.5h; Reflux; Stage #2: With phosphorus tribromide In toluene for 4h; Reflux; | |
Stage #1: n-Octylamine; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride With acetic acid at 120℃; Stage #2: With phosphorus tribromide In toluene Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 35% 2: 26% 3: 21% | In acetic acid at 130℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 65% 2: 14% | In acetic acid at 150℃; for 0.5h; Microwave irradiation (100 W); |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
19% | Stage #1: 2-decyl-1-tetradecylamine; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride With acetic acid Reflux; Stage #2: With phosphorus tribromide In toluene Reflux; | |
19% | Stage #1: 2-decyl-1-tetradecylamine; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride With acetic acid at 120℃; for 0.5 - 1h; Inert atmosphere; Stage #2: With phosphorus tribromide In toluene for 1h; Reflux; | Synthesis of N,N'-di(2-decyltetradecyl)-2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic acid diimide (22): TBNDA (3.3 g, 5.7 mmol) and 2-decyl-tetradecyl amine (6.5 g, 18.4 mmol) were added into acetic acid (50 mL) under nitrogen atmosphere, heated to 120°C. Heating was terminated when the reaction liquid turned clear and before the color got dark (the heating lasted for about 0.5∼1 hour). After cooled to room temperature, the reaction solution was poured into water (400 mL) and filtered. The resulting precipitate was washed with water (200 mL), and dried under vacuum to obtain a yellow solid. The yellow solid and phosphorus tribromide (2.0 mL, 21.1 mmol) were added into anhydrous toluene (120 mL) and heated to reflux for 1 hour. After cooled to room temperature, the reaction liquid was poured into water (400 mL) and extracted with toluene (200 mL × 3). The organic phases were combined and the solvent was evaporated under reduced pressure. The crude product was purified by silica gel chromatography column using dichloromethane/petroleum ether (1/2) as an eluent to give 1.35 g of a yellow solid (22), and the yield was 19% (calculated based on TBNDA as a starting material). MS (MALDI-TOF) m/z 1257.6 (M+); 1H-NMR (300 MHz, CDCl3) δ (ppm): 0.852-0.894 (m, 6H, -CH3), 1.287-1.409 (m, 8H, CH2), 1.235 (b, 40H, CH2), 1.970-2.005 (m, 1H, CH), 4.159-4.184 (d, J = 7.50 Hz, 2H, -CH2-N); 13C-NMR (100 MHz, CDCl3): δ 14.10, 22.67, 26.25, 29.33, 29.56, 29.64, 30.01, 31.50, 31.90, 36.50, 46.60, 125.75, 126.32, 135.23, 160.18 (CO). |
19% | In acetic acid at 120℃; Inert atmosphere; | TBNDA (3.3 g, 5.7 mmol) and 2-decyl-tetradecyl amine (6.5 g, 18.4 mmol) were added into acetic acid (50 mL) under nitrogen atmosphere, heated to 120° C. Heating was terminated when the reaction liquid turned clear and before the color got dark (the heating lasted for about 0.51 hour). After cooled to room temperature, the reaction solution was poured into water (400 mL) and filtered. The resulting precipitate was washed with water (200 mL), and dried under vacuum to obtain a yellow solid. The yellow solid and phosphorus tribromide (2.0 mL, 21.1 mmol) were added into anhydrous toluene (120 mL) and heated to reflux for 1 hour. After cooled to room temperature, the reaction liquid was poured into water (400 mL) and extracted with toluene (200 mL×3). The organic phases were combined and the solvent was evaporated under reduced pressure. The crude product was purified by silica gel chromatography column using dichloromethane/petroleum ether (1/2) as an eluent to give 1.35 g of a yellow solid (22), and the yield was 19% (calculated based on TBNDA as a starting material).MS (MALDI-TOF) m/z 1257.6 (M+);1H-NMR (300 MHz, CDCl3) δ (ppm): 0.852-0.894 (m, 6H, -CH3), 1.287-1.409 (m, 8H, CH2), 1.235 (b, 40H, CH2), 1.970-2.005 (m, 1H, CH), 4.159-4.184 (d, J=7.50 Hz, 2H, -CH2-N);13C-NMR (100 MHz, CDCl3): δ 14.10, 22.67, 26.25, 29.33, 29.56, 29.64, 30.01, 31.50, 31.90, 36.50, 46.60, 125.75, 126.32, 135.23, 160.18 (CO). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | Stage #1: 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride; 2,4,6-trimethylaniline In dichloromethane for 2h; Reflux; Stage #2: With phosphorus tribromide In dichloromethane for 1h; | |
13% | With acetic acid at 80 - 95℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | Stage #1: 2-(2,4-dithia-1,5-disodapentan-3-ylidene)propanedinitrile; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride In N,N-dimethyl-formamide at 50℃; for 1h; Inert atmosphere; Stage #2: N-(2-aminoethyl)-3,4,5-tris(dodecyloxy)benzamide In N,N-dimethyl-formamide at 50℃; for 6h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
21% | Stage #1: 2-(2,4-dithia-1,5-disodapentan-3-ylidene)propanedinitrile; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride In N,N-dimethyl-formamide at 50℃; for 1h; Inert atmosphere; Stage #2: 2-decyl-1-tetradecylamine; N-(2-aminoethyl)tricosa-10,12-diynamide In N,N-dimethyl-formamide at 50℃; for 6h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | Stage #1: 2-(2,4-dithia-1,5-disodapentan-3-ylidene)propanedinitrile; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride In N,N-dimethyl-formamide at 50℃; for 1h; Inert atmosphere; Stage #2: 2,2-bis(octyloxy)ethanamine In N,N-dimethyl-formamide at 50℃; for 6h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | Stage #1: 2-(2,4-dithia-1,5-disodapentan-3-ylidene)propanedinitrile; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride In N,N-dimethyl-formamide at 50℃; for 1h; Inert atmosphere; Stage #2: 4-tert-Butylaniline In N,N-dimethyl-formamide at 50℃; for 6h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
29% | Stage #1: 2-(2,4-dithia-1,5-disodapentan-3-ylidene)propanedinitrile; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride In N,N-dimethyl-formamide at 50℃; for 1h; Inert atmosphere; Stage #2: (3,4,5-tris(dodecyloxy)phenyl)methanamine In N,N-dimethyl-formamide at 50℃; for 6h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
18% | Stage #1: 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride; (3,4,5-tris(dodecyloxy)phenyl)methanamine In propionic acid Inert atmosphere; Reflux; Stage #2: With phosphorus tribromide In toluene for 0.333333h; Inert atmosphere; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: acetic acid / 0.67 h / 80 °C / Inert atmosphere 1.2: 10 h / Inert atmosphere; Reflux 2.1: N,N-dimethyl-formamide / 6 h / 135 °C | ||
Multi-step reaction with 2 steps 1.1: acetic acid / 120 °C 1.2: Reflux 2.1: 120 °C / Schlenk technique |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: N,N-dimethyl-formamide 2: triethylamine / N,N-dimethyl-formamide / 6 h 3: trifluoroacetic acid / 1 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: N,N-dimethyl-formamide 2: triethylamine / N,N-dimethyl-formamide / 6 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | In N,N-dimethyl-formamide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With tetraoctyl ammonium bromide; potassium carbonate In water for 2h; Reflux; | Synthesis of 2,3,6,7-tetrabromo-1,4,5,8-tetrabutoxylcarbonyl naphthalene (3) To a suspension of Compound 2 (6.36g, 10 mmol) in water was added K2CO3 to adjust the PHvalue of the solution to 10. Subsequently, tetra-n-octylammonium bromide (TOAB) (547mg,1mmol) and n-BuBr (5.35mL, 50mmol) was added to the above system. After that, thewhole reaction system was heated to reflux for 2 hours. The resulting solution wasextracted with dichloromethane and the organic phase was washed with water for 3 times,then dried with anhydrous MgSO4, evaporated under reduced pressure to give the crudeproduct which was further purified by silica gel column chromatography with CH2Cl2 andpetroleum ether(2:1) as eluent. Compound 3 was obtained as a white solid (8.15g, yield97%, melting point: 85.2-86.0 ). 1H NMR (400 MHz, CDCl3): δ=0.96 (m, 12H), 1.50 (m,8H), 1.75 (m, 8H), 4.32 (m, 8H) ppm. 13C NMR (100 MHz, CDCl3): δ= 13.8, 19.4, 30.1,67.0, 125.1, 125.8, 135.3, 165.9 ppm. HRMS (MALDI-TOF) m/z calculated forC30H36O8Br4Na 866.9041, found: 866.9084 ([M+Na]+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | Stage #1: 2-(3,4,5-tris(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy)phenyl)ethanamine; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride With acetic acid In N,N-dimethyl-formamide; toluene at 100℃; for 0.5h; Inert atmosphere; Stage #2: With phosphorus tribromide In N,N-dimethyl-formamide; toluene for 12h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | Stage #1: 3-(3,4,5-tris(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy)phenyl)propan-1-amine; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride With acetic acid In N,N-dimethyl-formamide; toluene at 100℃; for 0.5h; Inert atmosphere; Stage #2: With phosphorus tribromide In N,N-dimethyl-formamide; toluene for 12h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | Stage #1: 3-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy)propan-1-amine; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride With acetic acid In N,N-dimethyl-formamide; toluene at 100℃; for 0.5h; Inert atmosphere; Stage #2: With triphenylphosphine In N,N-dimethyl-formamide; toluene for 12h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | Stage #1: (3,4,5-tris(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy)phenyl)methanamine; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride With acetic acid In N,N-dimethyl-formamide; toluene at 100℃; for 0.5h; Inert atmosphere; Stage #2: With phosphorus tribromide In N,N-dimethyl-formamide; toluene for 12h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1.1: acetic acid / 1 h / Reflux 1.2: 2 h / Reflux 2.1: 18-crown-6 ether; cesium fluoride / 1,4-dioxane / 13 h / Inert atmosphere; Reflux 3.1: sodium hydride / tetrahydrofuran / 24 h / 20 °C 4.1: lead dioxide / dichloromethane / 2 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: acetic acid / 1.5 h / Reflux 1.2: 4 h / Reflux 2.1: 18-crown-6 ether; cesium fluoride / 1,4-dioxane / 12 h / 200 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: acetic acid / 1 h / Reflux 1.2: 2 h / Reflux 2.1: 18-crown-6 ether; cesium fluoride / 1,4-dioxane / 13 h / Inert atmosphere; Reflux 3.1: 1,4-dioxane / 3 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: acetic acid / 1 h / Reflux 1.2: 2 h / Reflux 2.1: 18-crown-6 ether; cesium fluoride / 1,4-dioxane / 13 h / Inert atmosphere; Reflux 3.1: sodium hydride / tetrahydrofuran / 24 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
10% | Under nitrogen protection, 2,3,6,7-tetrabromonaphthalenetetracarboxylic dianhydride (TBNDA) (300 mg, 0.51 mmol) and Sodium dicyanoethylene-2,2-dithiolate (288 mg, 1.54 mmol) was added to 50 mL of DMF and heated to 50 C.After stirring for 1 h, 2-octyl-dodecylamine (228 mg, 0.77 mmol) and 4-tert-butylbenzylamine (125 mg, 0.77 mmol) were added and the reaction was continued for 5 h at 50 C.The reaction mixture was cooled to room temperature, poured into 100 mL of saturated ammonium chloride solution, filtered, washed with water, dried in vacuo, and eluted with dichloromethane / petroleum ether (2: 1) The crude product was isolated and purified to give Compound 1 as a brown-red solid (50 mg, yield 10%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With potassium carbonate In ethanol Inert atmosphere; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69.2% | Stage #1: n-Pentylamine; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride With acetic acid In N,N-dimethyl-formamide; toluene at 100℃; for 0.5h; Inert atmosphere; Stage #2: With phosphorus tribromide In N,N-dimethyl-formamide; toluene for 12h; Reflux; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | Stage #1: 1-amine-3-decylpentadecane; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride In dichloromethane for 2h; Reflux; Stage #2: With phosphorus tribromide In dichloromethane for 1h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
10% | Under ambient conditions, a solution of 3 (500 mg, 0.86 mmol) and sodium 1,1-dicyanoethene-2,2-dithiolate (480 mg, 2.57 mmol) in DMF (25 mL) was stirred at 55 C for 1 hour. Then 2-decyltetradecylamine (394 mg, 1.11 mmol) and 3,5-difluoroiodoaniline[2] (371 mg, 1.46 mmol) were added to the reaction mixture. The resulting purple black solution was stirred at 55 C for 12 hours, and water (200 mL) was added to quench the reaction. The product was extracted with CH2Cl2 (3 × 50 mL), and the combined organic solution was washed with water, brine, and dried over anhydrous MgSO4. After removing the solvent under reduced pressure, the crude product was purified by silica gel column chromatography with CH2Cl2 as eluent. Compound 1 was obtained as a purple red solid (yield: 10 %). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
10% | Stage #1: 2-(2,4-dithia-1,5-disodapentan-3-ylidene)propanedinitrile; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride In N,N-dimethyl-formamide at 55℃; for 1h; Stage #2: 2-decyl-1-tetradecylamine; 3,5-difluoroaniline In N,N-dimethyl-formamide at 55℃; for 12h; | 2,2-[2-(3,5-difluoro-4-iodo)phenyl-8-(2-decyltetradecyl)-1,2,3,7,8,9-hexahydro-1,3,7,9-tetraoxo[1,3]benzodithiolo[4,5,6,7-lmn][1,3]dithiolo[4,5-f][3,8]phenanthroline-5,11-diylidine]bis(malononitrile) (1). General procedure: Under ambient conditions, a solution of 3 (500 mg, 0.86 mmol) and sodium 1,1-dicyanoethene-2,2-dithiolate (480 mg, 2.57 mmol) in DMF (25 mL) was stirred at 55 °C for 1 hour. Then 2-decyltetradecylamine (394 mg, 1.11 mmol) and 3,5-difluoroiodoaniline[2] (371 mg, 1.46 mmol) were added to the reaction mixture. The resulting purple black solution was stirred at 55 °C for 12 hours, and water (200 mL) was added to quench the reaction. The product was extracted with CH2Cl2 (3 × 50 mL), and the combined organic solution was washed with water, brine, and dried over anhydrous MgSO4. After removing the solvent under reduced pressure, the crude product was purified by silica gel column chromatography with CH2Cl2 as eluent. Compound 1 was obtained as a purple red solid (yield: 10 %). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With acetic acid at 120℃; for 0.416667h; | 1 A compound 2 is synthesized according to a method provided in, J. Org. Chem. 2007, 72, P. 8074. 1 g (1.7 mmol) of the compound 2 is suspended in 17 ml of acetic acid, 6.8 mmol of n-hexylamine is added thereto, and the mixture is heated at 120° C. for 25 minutes. Then, the resultant is cooled down to 24° C., and 130 ml of water is added thereto. The obtained precipitate is cleaned with water, obtaining a compound 3. The compound 3 is dissolved in 44 ml of dehydrated toluene, 30.66 ml (7.0 mmol) of PBr is added thereto, and the mixture is heated and refluxed for 12 hours under an argon atmosphere. Then, the resultant is cooled down to 24° C., 50 ml of water is added thereto, and the mixture is extracted with toluene. An organic layer obtained therefrom is then purified through silica gel column chromatography (development solvent: toluene:hexane=a volume ratio of 3:2), obtaining a compound 4. 0.2 mmol of the compound 4 and 0.06 mmol of sodium 1,1-dicyanoethene-2,2-thiolate are dissolved in 30 ml of tetrahydrofuran (THF), and the solution is heated and agitated at 50° C. for 1 and a half hours. Then, a solid obtained by taking a precipitate therefrom is cleaned in THF, obtaining 92 mg of a compound represented by Chemical Formula 1a (yield: 55%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81.5% | Stage #1: zinc(II) cyanide; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride With 1,1'-bis-(diphenylphosphino)ferrocene; tris-(dibenzylideneacetone)dipalladium(0) In 1,4-dioxane at 100℃; for 22h; Inert atmosphere; Stage #2: With sulfolane In 1,4-dioxane at 100℃; for 97h; Inert atmosphere; | 1.2 (2) Add NDI-01-B (11.6 g, 20.0 mmol) to a three-necked flask and add 1,4-dioxane (200 mL).Add Zn(CN) 2 (35.2 g, 0.30 mol), then add Pd2 (dba) 3 (790 mg, 1.43 mmol) and dppf (1.43 mmol).The reaction was carried out at 100 ° C for 22 hours under a nitrogen atmosphere. Further, 5 mL of sulfolane was added, and the reaction was continued at 100 ° C for 97 hours.After cooling, dilute with water (300 mL), precipitate a solid, filter, and wash the solid twice with water (100 mL*2).The crude product was further beaten twice with PE: DCM = 1:1 (50 mL: 50 mL), filtered, and baked at 80 degrees for 16 hours.The product NDI-01-C was obtained as a brown solid (6.0 g, yield 81.5%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94.3% | With triethylamine; In N,N-dimethyl-formamide; at 40℃; for 48h; | (1) NDI-01-B (11.68 g, 0.020 mol) was added to a three-necked flask, and DMF (80 mL) was added.Trifluoroethylamine hydrochloride (5.96 g, 0.040 mol), followed by dropwise addition of triethylamine (8.08 g, 0.080 mol).The reaction was raised to 40 degrees and stirred for 48 hours.After cooling, 50 mL of water was added to precipitate a solid, which was filtered, and the solid was washed twice with ethyl acetate (60 mL*2).The crude product was further beaten twice with THF: DCM = 1:1 (40 mL: 40 mL), filtered, and the product was baked at 70 degrees for 16 hours.The product NDI-13-A was obtained as a tan solid (14.06 g, yield 94.3%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80.8% | Stage #1: 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride With n-butyllithium In tetrahydrofuran at -78℃; for 2h; Inert atmosphere; Stage #2: carbon dioxide In tetrahydrofuran at -10℃; for 2h; Inert atmosphere; | 5.1 (1) NDI-01-B (11.68 g, 20.0 mmol) was dissolved in anhydrous tetrahydrofuran (300 mL).Under nitrogen protection, the temperature was lowered to -78 °C, and n-butyllithium (40.0 mL, 0.10 mol) was added dropwise.After stirring at -78 °C for 2 hours, it was raised to -10 °C and passed through dry carbon dioxide for 2 hours.Pour into ice water, add hydrochloric acid to adjust the pH to 1, and spin the water to give a solid. Add methanol (300 mL) to dissolve.The inorganic salt was removed by filtration, the organic phase was spun dry, and the crude product was beaten twice with PE:DCM=1:1 (50 mL: 50 mL).Filtered and the solid was dried at 70 degrees for 16 hours.The product NDI-15-A was obtained as a yellow solid (7.18 g, yield 80.8%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90.3% | With potassium acetate; In N,N-dimethyl-formamide; at 120℃; for 24h; | (1) NDI-01-B (11.68 g, 20.0 mmol) was added to DMF (300 mL),4,5-Diaminophthalonitrile (6.32 g, 40.0 mmol) was added and potassium acetate (3.92 g, 40.0 mmol) was added.The reaction was stirred at 120 degrees for 24 hours.After cooling to room temperature, DMF was sparged with an oil pump, and a small amount of water (100 mL) was added to the solid, filtered, and washed with water (100 mL*2).The crude product was further beaten twice with PE: DCM = 1:1 (50 mL: 50 mL), filtered, and the product was baked at 80 degrees for 16 hours.The product NDI-17-A (10.4 g, yield 90.3%) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90.3% | With potassium acetate In N,N-dimethyl-formamide at 120℃; for 24h; | 7.1 (1) NDI-01-B (11.68 g, 20.0 mmol) was added to DMF (300 mL),Add 2,3-diaminomaleonitrile(4.32 g, 40.0 mmol),Potassium acetate (3.92 g, 40.0 mmol) was added and the reaction was stirred at 120 °C for 24 hours.Cool to room temperature, spin dry DMF with oil pump, add a small amount of water (100 mL), filter, Washed (100mL * 2), the crude product was beaten twice with PE: DCM = 1:1 (50mL: 50mL), filtered, The product is baked at 80 degrees for 16 hours.The product NDI-18-A (8.58 g, yield 90.3%) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
31% | Stage #1: 2-n-hexyldecan-1-amine; 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride In tetrahydrofuran for 2h; Reflux; Inert atmosphere; Stage #2: With phosphorus tribromide In tetrahydrofuran for 1h; Reflux; Inert atmosphere; | Synthesis of intermediate compound b: Under nitrogen protection, the suspension of compound 1 (5.84 g, 10 mmol) and 2-hexyldecylamine (7.23 g, 30 mmol) in 70 mL of tetrahydrofuran was heated to reflux for 2 h.Then, phosphorus tribromide (8.1 g, 30 mmol) was slowly added dropwise to the above suspension, and the reaction was continued to reflux for 1 h.After cooling, slowly add water to quench the reaction, and extract three times with dichloromethane,The organic phases were combined and dried over anhydrous magnesium sulfate. Spin off the solvent under reduced pressure and separate and purify by column chromatography.A petroleum ether/dichloromethane volume ratio of 4/1 was used as the eluent to obtain 3.2 g of compound b (yield 31%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride; N-butylamine With acetic acid at 120℃; Stage #2: With phosphorus tribromide In toluene Reflux; | |
33% | Stage #1: 2,3,6,7-tetrabromonaphthalene-1,4,5,8-tetracarboxylic dianhydride; N-butylamine In dichloromethane for 2h; Reflux; Stage #2: With phosphorus tribromide In dichloromethane for 1h; |
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