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CAS No. : | 82-45-1 | MDL No. : | MFCD00001213 |
Formula : | C14H9NO2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | KHUFHLFHOQVFGB-UHFFFAOYSA-N |
M.W : | 223.23 | Pubchem ID : | 6710 |
Synonyms : |
|
Num. heavy atoms : | 17 |
Num. arom. heavy atoms : | 12 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 0 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 64.15 |
TPSA : | 60.16 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | Yes |
Log Kp (skin permeation) : | -5.01 cm/s |
Log Po/w (iLOGP) : | 1.67 |
Log Po/w (XLOGP3) : | 3.74 |
Log Po/w (WLOGP) : | 2.05 |
Log Po/w (MLOGP) : | 1.25 |
Log Po/w (SILICOS-IT) : | 2.81 |
Consensus Log Po/w : | 2.3 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -4.1 |
Solubility : | 0.0176 mg/ml ; 0.000079 mol/l |
Class : | Moderately soluble |
Log S (Ali) : | -4.7 |
Solubility : | 0.0045 mg/ml ; 0.0000202 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -4.89 |
Solubility : | 0.00287 mg/ml ; 0.0000129 mol/l |
Class : | Moderately soluble |
PAINS : | 2.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 2.18 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302 | 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 |
---|---|---|
99.3% | With sodium hydrogen sulphide | 4 EXAMPLE 4 EXAMPLE 4 A 1-nitroanthraquinone (98.0% purity) and water mixture with slurry concentration of 17.2% and a 12.0% aqueous solution of sodium hydrosulfide were added dropwise into a 2,000-volume-part glass-made vessel under agitation while maintaining the internal temperature of the vessel at 94°-96° C. The feeding rates of the 1-nitroanthraquinone-water mixture and the 12.0% sodium hydrosulfide solution were maintained constant at 1,055 part/hr and 945 part/hr, respectively. One hour after start of pouring, withdrawal of the reaction mixture from the bottom of the flask was started, with the efflux rate being maintained constant at 2,000 part/hr. The flow rate of 1-aminoanthraquinone (98.5% purity) in the effluent obtained from the 6th hour and afterward was 158 part/hr. 1-aminoanthraquinone was obtained in the yield of 99.3% based on the starting material 1-nitroanthraquinone, and the crystals of 1-aminoanthraquinone had very excellent filterability. |
98.9% | With disodium sulphide; lithium hydroxide monohydrate; sulphur at 90 - 105℃; for 6h; | 1 In a 500 ml flask, 350 ml of industrial sodium sulfide (28 g) and industrial sulfur (6 g) were added in an amount of 60%, and the temperature was raised to 80 to 90 ° C and stirred for 1 hour until the sulfur was completely dissolved. Washed and washed together into the mother liquor, the filtrate into 500ml four-necked flask, adding 99. 0% purity of 1-nitroanthraquinone 35g, and then add appropriate amount of water to the total volume of about 400ml, about 2 hours slowly and gradually heated to 90 ° C, and then continue to heat up to 102 ~ 105 ° C reflux insulation reaction 4 hours, after the end of insulation to 90 ~ 95 ° C, hot filter, filter cake with about 90 ° C heat Water to the filtrate to clarify the colorless, pH test paper to detect the filtrate was neutral again after the full dry, remove the filter cake dried 1 - amino anthraquinone 30. 5g, the yield of 98. 9%, 99. 1% purity. |
98% | With hydrogen In methanol at 60℃; for 8h; Autoclave; Large scale; | 2 Preparation of 1-aminoanthraquinone Add the solvent methanol (40 kg) and 1-nitroanthraquinone (150 kg) to the 1L autoclave in sequence, add 450g of superparamagnetic nanoparticle-supported nickel carbonyl catalyst under stirring, replace with nitrogen 3 times, and replace with hydrogen 3 times. Enter hydrogen, keep the pressure 0.35-0.4Mpa, Stir and raise the temperature to 60°C, react for 8 hours, and sample for testing. Reduce the temperature to 40-50°C, add a magnetic field to recover the catalyst, transfer the reaction liquid to the acidification kettle, add 15wt% hydrochloric acid 80 kg dropwise to adjust the pH to 5.5-6.0, stir and cool to room temperature, and filter by pressure to obtain 1-aminoanthraquinone The wet product was vacuum dried at 85-90°C for 8 hours to obtain 129 kg of 1-aminoanthraquinone with a yield of 98% and a purity of 99.8% (detected by HPLC). |
97.2% | With hydrogen In lithium hydroxide monohydrate at 45 - 95℃; Autoclave; Alkaline conditions; Industrial scale; | 1 The total amount of 100 kg produced 1-nitro-anthraquinone 1-aminoanthraquinone as an example, the catalyst used is a noble metal loading of 3wt% / C, in the production process of the catalyst was 3% of the starting material (3 kg), the total amount of water 10 times the raw material (1000 kg), at the time of continuous production, the slurry, water and a catalyst and 1-nitro-anthraquinone in accordance with the flow rate of the aqueous base added, the specific process is as follows. 1. Start the feed pump, adjust the flow rate of 540L / h, the flow rate leads to a reduction Click vessel 1 while the catalyst (3wt% of raw materials) and water (10 times the mass of raw materials) also leads to a reduction kettle 1, adjust the speed of a stirring autoclave at 300 rev / min or so, and then pass into the hydrogen reduction reaction, in this embodiment, the hydrogen pressure is maintained at 0.6-0.8Mpa reduction reaction occurs. While the hydrogenation reaction gives off heat, adjust the pot temperature by cooling water, so that the pot temperature is always controlled at between 45-95°C. 2. when a reduction of an overflow tank, the analysis also liquid content, the conversion rate of 95%, starting two pot stirrer, kept under stirring speed of 300 rev / min or so, and the reaction liquid from a tank continuous inflow of two stage 2 tank, holding two hydrogen pressure in the autoclave, a kettle with a uniform temperature, and the reaction was continued in the secondary reaction vessel 2 in an autoclave reactor along with a catalyst solution into the secondary vessel 2, Therefore, in the secondary vessel 2 is generally no additional catalyst is added, if the outlet when the reaction liquid can be added to the catalyst test failed in two additional vessel 2. 3. when two tank when there is an overflow from the sampling port to take further stock solution, requiring no further liquid suspension of 1-nitro-anthraquinone, no yellow circle infiltration qualified, and also analyze liquid content, the conversion rate of 98% above, starting three stirred tank means, kept under stirring at the speed of 300 rev / min or so, the reaction liquid from the secondary vessel 2 continuously flows into three tank 3 to maintain the hydrogen pressure in the autoclave three, consistent with a kettle temperature, so that the reaction was continued in the three reaction vessel 3, the reaction liquid in the vessel 3 has three substantially complete reaction, the presence of only a small portion of unreacted starting material, three tank 3 is to enhance the role of the reaction time, the full conversion of the starting material completely in the reaction solution from three overflow tank 3, the detection of the conversion rate has reached 99%, there is no reaction of 1-nitro-anthraquinone by settling with separated catalyst is returned with the first stage hydrogenation reactor 1. 4.from three out of the reaction vessel 3 liquid overflow to the settler 4, entrained catalyst further liquid-liquid separation after settling, when settler 4 level grew to 83%, the open valve settler 4 , self-adjusting valve opening, a lower solids content within the settler 4 into the filter layer of the liquid, entrained in the filtered liquid also small amounts of liquid into the oxidation catalyst vessel; open the valve at the bottom of the settling vessel, the flowing liquid layer containing more solid as a catalyst. 5. after the above-mentioned liquid further into the oxidation vessel 5, open mixing, open air pump, the oxidation is completed, i.e., the filter cake was taken as the 1-aminoanthraquinone. The remaining filtrate directly into a vessel 1 as the solvent circulating apply.The method according to the above obtained product was analyzed to give 1-nitro-anthraquinone conversion rate of 100%, the selectivity of 1-aminoanthraquinone 99.2%, 1-amino-anthraquinone content of 98.8%, a yield of 97.2%. |
93% | With urea; 1,1,3,3-tetramethylurea at 130℃; for 8h; | |
93% | With sodium hydroxide; nitrogen In lithium hydroxide monohydrate; hydrogen | 4 EXAMPLE 4 EXAMPLE 4 A 1-liter electromagnetically stirred glass reactor was charged with 2.53 g (0.01 mole) of 1-nitroanthraquinone (roughly purified product with no impurity detected by thin-layer chromatography), 52 g of water and 0.051 g of 5% palladium-carbon. The inside of the reactor was purged with nitrogen, and with stirring at room temperature, the 1-nitroanthraquinone was hydrogenated. In 4.5 hours when 0.03 mole of hydrogen was absorbed, the hydrogen inside the reactor was replaced by nitrogen, and 2.1 g (0.052 mole) of sodium hydroxide was added. The inside of the reactor was purged with hydrogen, and the hydrogenation was continued at room temperature. In 1 hour, the absorption of hydrogen was stopped. The amount of hydrogen absorbed until then was 0.01 mole. The reaction mixture completely dissolved. The inside of the reactor was purged with nitrogen, and the reaction mixture was filtered in an atmosphere of nitrogen to separate the catalyst. The filtrate was oxidized with air at 20° to 30° C. for 2 hours with stirring to afford 2.08 g of 1-aminoanthraquinone having a purity of 98% by weight in a yield of 93% of theory. By a thin-layer chromatographic analysis, no impurity was detected. |
92% | With gold nanoparticles supported on titanium dioxide (TiO<SUB>2</SUB>); ammsnium formate In methanol at 25℃; for 1.7h; Inert atmosphere; chemoselective reaction; | |
81% | With bis(η5-cyclopentadienyl) titanium dichloride; indium powder In tetrahydrofuran at 20℃; for 4h; | |
71% | In formamide | 8 German Offenlegungsschrift (German Published Specification) 2,211,411, Example 1. EXAMPLE 8 German Offenlegungsschrift (German Published Specification) 2,211,411, Example 1. 26.3 g of 1-nitroanthraquinone (96% pure) are suspended in 110 g of formamide. Ammonia gas is passed in at 155°. After 4 hours, the solvent is distilled off and the residue is washed with water. After drying in vacuo, 22.5 g of 70% pure 1-aminoanthraquinone (71% of theory) are obtained. |
With ammonium sulfide | ||
With sodium hydrogen sulphide | ||
With disodium sulphide | ||
With tin oxidepotash; lithium hydroxide monohydrate | ||
With potassium hydroxide; D-glucose at 40 - 60℃; | ||
With acid bei der elektrolytischen Reduktion; | ||
With alkali bei der elektrolytischen Reduktion; | ||
With potassium sulphide; lithium hydroxide monohydrate | ||
With sodium hydrogen sulphide; calcium(II) chloride; benzene | ||
With ammonium hydroxide at 195℃; | ||
With tetrahydropyrrole; carbon monoxide; lithium hydroxide monohydrate In methanol at 150℃; for 5h; | ||
With sodium hydroxide; carbon monoxide In 2-methoxy-ethanol at 25℃; for 10h; Yield given; | ||
With hydrogen In ethanol at 35℃; for 7h; | ||
With sodium hydroxide; carbon monoxide In 2-methoxy-ethanol at 25℃; for 10h; variation of conditions; other aromatic nitro compounds; | ||
With hydrogen In ethanol at 35℃; for 7h; influence of solvent, activation enrgy (E), ΔS(excit.); | ||
With nitrogen; hydrogen | 4 EXAMPLE 4 EXAMPLE 4 1 Part of crude nitroanthraquinone with a content of 90 percent of 1-nitroanthraquinone, 9 parts of phenetol and 0.33 parts of hydrogenation catalyst (2,4 percent Pd on Al2 O3) are heated in an autoclave with a stroke agitator, to 130°. While heating, rinsing is effected with nitrogen which is followed by hydrogen when the final temperature has been reached. The stroke agitator is then activated and hydrogenation effected for 35 minutes at a pressure of 3 atm., upon which the hydrogen is followed by nitrogen, and afterwards by air at 5 atm. The agitator is run for 15 minutes. The catalyst is separated and the filtrate cooled down to room temperature on which 1-aminoanthraquinone precipitates in easily filtrable crystals. | |
With sodium hydroxide; hydrazine hydrate monohydrate In lithium hydroxide monohydrate | 1 EXAMPLE 1 EXAMPLE 1 500 Parts of water, 20 parts of hydrazine hydrate and 100 parts of 30% sodium hydroxide solution are heated to 70°. 51 Parts of 1-nitro-anthraquinone are entered over the course of 1 hour. The temperature of the reaction mixture is kept at between 70° and 75°. After the addition of the whole amount of 1-nitroanthraquinone, the suspension is heated to 80° and stirred for 1 hour. 70 Parts of 40% sodium hydroxide solution are subsequently added. The reaction mass is then stirred at 90° over the course of 90 minutes and filtered. The precipitate is washed with water until the filtrate is colourless and neutral, and then dried. 43 Parts of 1-amino-anthraquinone are obtained. | |
With anhydrous sodium sulphite | 7 EXAMPLE 7 EXAMPLE 7 To a suspension (about 60 parts) which is obtained by treatment of crude 1-nitroanthraquinone (A) (10 parts) with sodium sulfite as in Example 2, sodium sulfide flakes (purity, 60 %) (9.4 parts) are added, and the mixture is stirred at 45° C. for 3 hours and then at 95° C. for 2 hours whereby reduction proceeds almost quantitatively. After cooling, the reaction mixture is filtered, and the product is washed and dried to obtain 1-aminoanthraquinone with a high purity of 98 % (6.3 parts). | |
With NaSH In lithium hydroxide monohydrate | 2.b EXAMPLE 2 (b) The 1-amino-anthraquinone employed in (a) was obtained as follows: 54 kg of 1-nitro-anthraquinone (75.6% pure) was introduced into a mixture of 50 l of water and 27 kg of NaSH solution (18.5% strength) at 90° C. in the course of 1 hour, whilst stirring, and the mixture is stirred at 90°-95° C. for a further 1/2 hour. The reaction mixture is filtered hot and the residue is washed with 1% strength sodium hydroxide solution and finally with hot water until neutral and dried. 46.3 kg of 1-amino-anthraquinone of the following composition are obtained: 74.3% of 1-amino-anthraquinone=95.6% of theory, 3.3% of anthraquinone, 4.8% of 2-amino-anthraquinone, 3.2% of 1,5-diamino-anthraquinone, 2.9% of 1,8-diamino-anthraquinone, 3.6% of 1,6-diamino-anthraquinone, 3.6% of 1,7-diamino-anthraquinone and 0.5% of 2,6-+2,7-diamino-anthraquinone=96.2%. | |
With carbon monoxide; Au/TiO2-VS; lithium hydroxide monohydrate In N,N-dimethyl-formamide at 25℃; for 4h; Autoclave; chemoselective reaction; | ||
With triethylamine In acetonitrile Irradiation; Inert atmosphere; | ||
With hydrogen In N,N-dimethyl-formamide at 100℃; for 3h; Autoclave; | 5 Example 5 Nano-Cu / Ni catalyst was prepared in the same manner as in Example 1,Catalytic 1-nitro-anthraquinone hydrogenation,Only change the hydrogen pressure were 0.5MPa,1.5MPa and 2.0MPa,You can get the hydrogen pressure of 1 - nitro-anthraquinone catalytic hydrogenation reaction,The results are shown in Table 4.; _ In a 500 ml autoclave equipped with a stirrer were charged 10 g of 1-nitroanthraquinone and 150 ml of N, N-dimethylformamide,Then add 0.3g nano copper / nickel binary alloy catalyst;Install the reaction device,Purged with nitrogen purge 10min emptying,And then into the high purity hydrogen row N2,Then turn on the mixing device,Stirring speed 400rpm,When the reaction temperature rose to 100 ° C,Pass 1.0MPa H2 reaction 3h;After the reaction,Cooling to below 45 ,The reaction product is diluted,Using high performance liquid chromatography analysis and calculation,The results are shown in Table 1. | |
Multi-step reaction with 2 steps 1: Methyl chlorosulfonate; pyridine-base; copper atom / 30 - 35 °C / und die waessr.Loesung des Reaktionsprodukts mit Kaliumchlorid versetzt; entsteht das Kaliumsalz eines sauren Schwefelsaeureesters | ||
102.91 g | With sodium hydrogen sulphide In lithium hydroxide monohydrate at 25 - 95℃; for 5h; | 1.2; 1.3; 2.2; 2.3; 3.2; 3.3 (2) The solid mixture obtained in the above (1) is added in portions to a solution of 33.6 g of sodium hydrosulfide and 120 g of water. Maintain a reaction at 25 ° C for 3 hours. After the temperature is raised to 90 ° C ~ 95 ° C, the reaction is continued for 2 hours. filter, Washed, A solid mixture of 126.91 g was obtained. Wherein the 1-aminoanthracene content is 81.09%, The anthracene content was 18.91%. (3) The solid mixture obtained in the above (2) is added in portions to 55% phosphoric acid (volume fraction) 300 ml, Stirring at 45 ° C ~ 55 ° C, filter, The filter residue was washed with water to obtain 24 g of purity, 99% purity (measured by gas chromatography); the filtrate was adjusted to pH=8-9 with 15% NaOH (mass fraction). The solid was precipitated to give 1-aminoanthraquinone 102.91 g, purity 99.8%. |
With hydrogen In N,N-dimethyl-formamide at 140℃; for 4h; Autoclave; | 2.4. Evaluation of Catalytic Performance Catalytic hydrogenation of 1-nitroanthraquinone with H2was performed in a 500 mL stainless steel autoclave andstirred with a magnetic driven stirrer. The autoclave wascharged with 3 g of 1-nitroanthraquinone in 150 mL ofDMF solution and appointed amount of CuPtx nanoparticles.The autoclave was purged with N2 for 10 minto replace air inside. And then, pure H2 was pressurizedinto the autoclave and the reaction solution washeated to specified reaction temperatures. When the reactiontemperature reached the specified value, the stirringrate was increased to 400 rpm. After reacting for a periodof time, the reaction was quenched by running coolingwater through a cooling coil in the autoclave. The productswere analyzed using high performance liquid chromatography(HPLC). A reverse-phase column (Innoval ASB C18,5 mm, 4.6 mm×250 mm) and a UV detector (λ=254 nm)were used for analysis at 30 °C. A mixture of water andmethanol of chromatographic grade (v/v, 20/80) was usedas a mobile phase at a flow rate of 1.0 mL min-1. The concentrationsof the products and 1-nitroanthraquinone wereanalyzed by the external standard method. | |
With hydrazine monohydrate; Co(OH)2 In acetonitrile at 60℃; for 1.16667h; Sonication; | ||
With hydrogen In lithium hydroxide monohydrate at 70℃; for 0.833333h; | 25-26 Example 25 Example 25 investigates the performance of different nickel nanoparticle catalysts prepared in Examples 1-15 and Comparative Examples 1-16 in the reaction of catalytic hydrogenation to synthesize 1-aminoanthraquinone.In a 50ml stainless steel reaction kettle, add 20ml of absolute ethanol, 2g of 1-nitroanthraquinone, 0.05g of carbon material-coated nickel nanoparticle catalyst prepared in different embodiments or comparative examples, close the reaction kettle, and replace the air in the reaction kettle with hydrogen 5 times, and then replace the nitrogen with hydrogen for 3 times, raise the temperature to 70°C, the hydrogen pressure is 1.0MPa, start stirring, the stirring rate is 1000r/min, and the reaction is 50min.The reaction was stopped, and after the temperature was lowered to room temperature, the supernatant liquid of the reaction solution was taken, and after the catalyst was filtered off, the supernatant liquid was taken and analyzed by gas chromatography.The experimental results are shown in Table 12: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | In benzene for 7h; Heating; | |
77% | With pyridine In toluene at 60℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With hydrogenchloride; sodium nitrite In water at 5℃; for 1h; Cooling with ice; | |
With sulfuric acid; acetic acid; sodium nitrite Erhitzen des Reaktionsprodukts mit wss.NaOH; | ||
With sulfuric acid; sodium nitrite Diazotization.Darstellung; und folgendes Erhitzen auf 120-130grad; |
Diazotization.Zersetzung der Diazoloesung; | ||
With sulfuric acid; acetic acid; sodium nitrite 1.) 5 deg C, 20 min, 2.) reflux; Yield given. Multistep reaction; | ||
Diazotization.Zersetzung der Diazoloesung; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With bromine; acetic acid; at 40 - 100℃; for 24h; | 1-Amino-9,10-dioxo-9,10-dihydroanthracene (3) (1.10 g, 5 mmol) was dissolved in 20 mL glacial acetic acid, the solution was heated to 40 C, and bromine (11 mL, 10 mmol) was then dropwise added. The resulting mixture was stirred at this temperature for 16 hS17followed by 8 h at 100 C. The reaction was stopped by pouring it into 50 mL of a NaHSO3 solution (40 % in H2O) to form a dark orange precipitate of product 15. The precipitate was filtered off, washed with water and dried overnight in an oven at 75 C to yield 1.90 g (100 %) of compound 15 as a dark orange solid; m.p. 225 - 227 C (lit. m.p. 223 C) [6]. HPLC-UV (254 nm) ESI-MS, purity: 98.1 %. LC-MS (m/z): 380 [M - H]-. 1H NMR (500 MHz, DMSO-d6) δ 7.87 (m, 2H, 6-H, 7-H), 8.09 (m, 1H, 5-H or 8-H), 8.16 (m, 1H, 5-H or 8-H), 8.20 (s, 1H, 3H). 13C NMR (126 MHz, DMSO) δ 107.2 (C-4), 114.6 (C-9a), 117.2 (C-2), 126.3, 126.5 (C-5, C-8), 130.5 (C-4a), 133.1 (2C, C-8a, C-10a), 134.1, 134.4 (C-6, C-7), 143.6 (C-3), 148.4 (C-1), 181.9 (C-10), 183.8 (C-9). HRMS (ESI-TOF) m/z: [M + H]+ calcd. for C14H8Br2NO2 381.8901, found 381.8899. |
98% | With bromine; In methanol; at 50 - 60℃;Large scale; | 30.0 kg of 4-Amino-i 0-hydroxyanthracen-9(1OH)- one (starting material 1) was suspended in MeOH (70 L). To the suspension, 53.7 kg of bromine was added to the suspension at 600 C. about 1 hr. After the addition of bromine, the reaction mixture was stirred at 5O6O0 C. for about 18-24 hours. The reaction mixture was then cooled. The resulting suspension was filtered, washed with MTBE. The red solid was dried to give Intermediate 2 as a red solid (.-50.0 kg, yield 9 8%). HPLC analysis showed 96% purity. ‘H-NMR (CDC13, 300 Hz) ö 8.26 (m, 2H), 8.09 (s, 1H), 7.80 (m, 2H). |
98% | With bromine; In methanol; at 50 - 60℃;Large scale; | 30.0 kg of 4-Amino-10-hydroxyanthracen-9(10H)-one was suspended in MeOH (70 L). To the suspension, 53.7 kg of bromine was added slowly to the suspension at 60 C about lhr. After the addition of bromine, the reaction mixture was vigorously stirred at 50-60 C for about 18-24 hours. The reaction mixture was then cooled to around 18 C. The resulting suspension was filtered, washed with 210 L of MTBE. The red solid was dried in air to give product 2 as a red solid (-50.0 kg, yield 98%). HPLC analysis showed 96% purity. 1H- MR (CDC13, 300Hz) δ 8.26 (m, 2H), 8.09 (s, 1H), 7.80 (m, 2H). |
92% | With nonanebis(peroxoic acid); acetic acid; potassium bromide; at 30 - 32℃; for 2.3h; | General procedure: In a 100 mL round bottomed flask equipped with a mercury sealed stirrer, 5 mL acetic acid was placed to which aminoanthracene-9,10-dione (1, 1 equiv), and KBr (0.5 to 2 equiv) were added under stirring. To this slurry, nonanebis(peroxoic acid) (1 to 2 equiv) was added cautiously over a period of 10 min at room temperature. The reaction mass was stirred at room temperature/50-55 C and was monitored by TLC. After completion, the reaction mass was poured into 10% sodium bicarbonate solution to neutralize the acids. The solid obtained was filtered and washed with water till neutral pH was obtained. The crude product was purified by column chromatography on a silica gel with hexane/ethyl acetate (95:5) as an eluent to give purified product 2. |
92% | With hydrogen bromide; 3-chloro-benzenecarboperoxoic acid; In methanol; at 30 - 32℃; for 0.166667h; | The procedure used for bromination of 1-aminoanthracene-9,10-dione 1a by using m-CPBA-HBr system is similar to that of H2O2-HBr system. The oxidant, m-CPBA was taken 2 equivalents and the reaction was stirred for 10 min at room temperature. |
88% | With bromine; In methanol; at 50 - 60℃; for 17h; | 1-Aminoanthraquinone 1 (10 g, 1 eq, 44.8 mmol) was suspended in 250 mL of dry MeOH in a 500 mL three neck-round-bottom flask that was equipped with a mechanical stirrer and an addition funnel. Bromine (17.92 g, 2.5 eq, 112 mmol) was added dropwise at 60 C to this suspension with vigorous stirring. The reaction mixture was stirred at 50-60 C overnight (-17 h). Product formation was confirmed by MS analysis. The reaction was allowed to come to attain ambient temperature and the mixture was filtered through a sintered funnel, washed with methyl t-butyl ether (MTBE, 250 mL), and dried in air to give Compound 2 (15 g, 88% yield) as a bright red solid. NMR (300 MHz, CDC13) δ 8.19-8.27 (m, 2H), 8.07 (s, 1H), 7.71-7.78 (m, 2H).; m/z [negative ion] = 378.9, 380.9, 382.9. |
65% | With bromine; acetic acid; at 20℃; for 12h;Molecular sieve; | The anilinoanthroquinone (78mg, 0.35mmol) was dissolved in Sml of glacial acetic acid predried using 3A molecular sieves to which bromine was added (72u1, 1 .4mmol) and the reaction stirred at room temperature for 1 2hr. The solution was extracted against DCM and brine, the organic layers combined, dried, and concentrated as described above with the isolated red solid purified by ISCO silica chromatography using a hexanetDCM gradient (20%DCM- 1 00%DCM). The isolated fractions were concentrated with the crude brominated anthroquinone product crystallized out of DCMMeOH resulting in the isolation of pure dibromo-anilinoanthroquinone Tin 65% yield ‘H NMR (600 Mhz, Chloroform-d) 8.24 (td, J= 7.5, 2.2 Hz, 2H), 8,08 (s, 1H), 7.76 (ddd, J= 6,4, 3,8, 1.8 Hz, 2H). ‘3C NMR (151 Mhz, CDC13) 184.37, 182.27, 147.97, 143.97, 133.94, 133.82, 133.45, 133.26, 130.67, 127.08, 126.60, 117.50, 115.33, 108.71. HEMS (ES+) calc’dfor C14H8Br2NO2 (M+H)m/z379.8844Found. 379.8841 |
With potassium iodide; sulfuric acid; bromine; sodium hydrogen sulphite; In water monomer; | EXAMPLE 2 A mixture of 100 parts of 90% sulfuric acid, 20 parts of 1-aminoanthraquinone and 0.1 part of potassium iodide was heated to 120 C., and 30 parts of bromine was added dropwise over 6 hours at the same temperature. The reaction mixture was kept at the same temperature for further 2 hours, cooled to 50 C. and discharged into 500 parts of water containing 5 parts of sodium bisulfite. The precipitated crystals were filtered, washed and dried to obtain 33.8 parts of a 1-amino-2,4-dibromoanthraquinone cake (m.p. 223-225 C.). | |
With sulfuric acid; bromine; sodium hydrogen sulphite; acetic acid; In water monomer; | EXAMPLE 3 A mixture of 160 parts of 96% sulfuric acid and 20 parts of 1-aminoanthraquinone was heated to 80 C., and at the same temperature a mixture of 20 parts of bromine and 5 parts of acetic acid was added dropwise over 3 hours. The reaction mixture was kept at the same temperature for further 3 hours. Thereafter, a mixture of 15 parts of bromine and 4 parts of acetic acid was added dropwise to the reaction mixture over 2 hours, and the mixture was kept at the same temperature for further 2 hours. The mixture was then kept at 100 C. for 3 hours, cooled to room temperature and discharged into 1000 parts of water containing 7 parts of sodium bisulfite. The precipitated crystals were filtered, washed and dried to obtain 34.2 parts of the same 1-amino-2,4-dibromoanthraquinone cake as in Example 1. | |
With sulfuric acid; bromine; at 0 - 60℃; for 23h; | Example 1 : 1 -aminoanthraquinone (46.0 parts) commercial available such as from Sigma Aldrich, is dissolved in concentrated sulfuric acid (98%, 200 mL) at 60 C. When the product is completely dissolved, the temperature is decreased to room temperature before slow addition of ice (800.0 parts) with efficient stirring. To the resulting slurry at 0-5 ' is then added drop wise bromine (72.4 parts) over a period of 3 hours. The resulting mixture is stirred at room temperature for 20 hours. Excess bromine is then removed by bubbling nitrogen in the reaction mixture. The precipitate is then filtered and washed with water (1000 mL). The wet press-cake is stirred in 8wt% aqueous sodium hydroxide solution (1000 mL) for one hour, filtered, successively washed with water (1000 mL), 20wt% aqueous sodium bisulfite solution (400 mL), water (1000 mL) and finally dried overnight at 50 C under vacuum to afford 70.0 parts of compound (1 ) as a red solid. NMR- H (DMSO-d6, 300 MHz, ppm): 8.2 (s, 1 H), 8.2-8.1 (m, 2H), 7.8 (m, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tert.-butylnitrite; copper(II) bromide In acetonitrile for 1h; Reflux; | |
36% | Stage #1: 1-aminoanthracene-9,10-dione With tert.-butylnitrite; copper (II) bromide In acetonitrile at 65℃; for 6h; Stage #2: With hydrogenchloride In lithium hydroxide monohydrate; acetonitrile for 3h; | 12.1.i [Embodiment 12]; [0450]In this embodiment, a synthetic method of9,10-diphenyl-l-[JV-(9-phenylcarbazol-3-yl)-iV-phenylamino]anthracene (abbreviation: IPCAPA), which is the anthracene derivative of the present invention represented by Structural Formula (202), is specifically described. [0451](202)[0452][Step 1] Synthesis of l-bromo-9,10-diphenylanthracene.; [0453](i) Synthesis of l-bromo-9,10-anthraquinone.A synthetic scheme of l-bromo-9,10-anthraquinone is shown in (C-23). 20.0 g (88.8 mmol) of l-amino-9,10-anthraquinone, 36.7 g (164 mmol) of copper bromide (II), and 240 mL of acetonitrile were put into a 500 mL three-neck flask, and the atmosphere of the flask was substituted with nitrogen. Thereafter, 15.8 mL (133 mmol) of tert-butyl nitrite was added, and the mixture was stirred for 6 hours at 65 0C. After the reaction was completed, the reaction mixture was poured into 1.3 L of 3 mol/L hydrochloric acid, which was followed by additional stirring for 3 hours at room temperature. A precipitate in the mixture was collected by suction filtration, and the precipitate was washed with water and then with ethanol. Then, the obtained solid was dissolved in a mixed solvent of toluene and chloroform, and the solution was subjected to suction filtration through Florisil, celite, and then alumina. The filtrate was concentrated, and the residue was purified by silica gel column chromatography (eluent: toluene). The obtained solid was recrystallized with a mixed solvent of chloroform and hexane, giving 9.37 g of l-bromo-9,10-anthraquinone as yellow powder in 36% yield. |
With sulfuric acid; NaNO2 Diazotization.Ausfaellen der Diazoniumverbindung durch Eis und Behandlung mit CuBr und Bromwasserstoffsaeure; |
(i) (diazotization), (ii) CuBr; Multistep reaction; | ||
With tert.-butylnitrite; copper (II) bromide In acetonitrile at 65 - 90℃; for 4h; Inert atmosphere; | ||
Multi-step reaction with 2 steps 1: nitrite / lithium hydroxide monohydrate / 1.5 h / 0 °C 2: NBS / methanol / 1.5 h / 15 °C / Sealed tube; Irradiation |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With toluene-4-sulfonic acid; potassium iodide; sodium nitrite In acetonitrile at 20℃; for 1h; | |
72% | Stage #1: 1-amino-9,10-anthracenedione With sulfuric acid; acetic acid In water Stage #2: With sodium nitrite In water at 10℃; Stage #3: With potassium iodide In water at 90℃; | |
54% | With toluene-4-sulfonic acid; sodium iodide In water; acetonitrile at 10 - 20℃; for 2h; Inert atmosphere; |
With sulfuric acid; water; sodium nitrite Diazotization.Behandeln der Diazoniumsulfatloesung mit KI; | ||
Multi-step reaction with 2 steps 1: 100 percent / NO2 / 3 h / 20 °C / 525.05 Torr 2: 100 percent / KI / 24 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | Stage #1: 1-amino-9,10-anthracenedione With copper(II) sulfate In 1,2-dichloro-ethane Large scale; Stage #2: With chlorosulfonic acid at 83 - 85℃; for 3h; Large scale; | 1.1 Example 1 sulfonation reaction:In a sulfonation reactor, 450 kg of dichloroethane was added,Copper sulfate 4.5kg,Further, 112 kg (content: 96%) of 1-aminoanthraquinone,Closed feeding port,Heated to boiling,Evaporation of water and dichloroethane condensate through the condenser,Into the oil-water separator,The upper oil phase dichloroethane was returned to the reaction system, and the lower layer water was separated out of the reaction system to observe that there was no water separation in the oil-water separator, and the dehydration was concluded to be about 1 hour. After the completion of the dehydration, 64kg of chlorosulfonic acid was slowly added to carry out the sulfonation reaction, and the reaction temperature was controlled at 830C to 850C. After the completion of the dropwise addition, the reaction was continued for about 3 hours. After completion of the reaction, the reaction solution was cooled to 300C to 500C,Adding 98% concentrated sulfuric acid 400kg, stirring for 1.5 hours, the organic phase of 1-amino anthraquinone-2-sulfonic acid dissolved in concentrated sulfuric acid, standing layered, the lower acid phase,Amino-anthraquinone-2-sulfonic acid concentrated sulfuric acid solution separated into the bromination reactor,The upper oil phase was left to be the next reaction solvent, the reaction yield was 98%. |
With sulfuric acid anschliessendes Erhitzen mit Chloroschwefelsaeure auf 110grad; | ||
With chlorosulfonic acid In nitrobenzene at 115 - 120℃; |
With sulfuric acid In chlorobenzene at 180℃; for 15h; Large scale; | 3 In a 20L reactor,Add 10kg of chlorobenzene,2.28kg content of 98% of 1-aminoanthraquinone (10 mol) and 1.05kg mass fraction of 98% sulfuric acid (10.5mol),Sufficiently stirred to effect sufficient mixing sulfuric acid and 1-amino-anthraquinone,A salt,Simultaneously,Distilling chlorobenzene at elevated temperature,Then heat up to 180 ° C,Vacuuming to an absolute vacuum of 10 mmHg,Bringing out the water vapor generated by the reaction,Keep the reaction for 15h,The content of 1-aminoanthraquinone-2-sulfonic acid in the product was determined by liquid chromatography to be 99.4%.The 1-aminoanthraquinone content was 0.6% (area normalization method). | |
Multi-step reaction with 2 steps 1: 140 °C | ||
With sulfuric acid; sodium sulfate at 120℃; | ||
With chlorosulfonic acid In 1,2-dichloro-benzene at 75 - 130℃; for 3.25h; Green chemistry; | 1.1-1.5; 2.1-2.5; 3.1-3.5; 4.1-4.5; 1.1-1.4; 2.1-2.4 Example 4 (1) Add 1-aminoanthraquinone and o-dichlorobenzene solvents to the reaction flask, control the concentration of 1-aminoanthraquinone to 25g/L, and perform beating treatment at 130°C for 60 minutes;(2) Add chlorosulfonic acid dropwise to the solution after beating treatment at 75°C, and control the dropping acceleration rate to 1g/min.Among them, the mass ratio of 1-aminoanthraquinone and chlorosulfonic acid is 100:72, stirring for 15min, and then carrying out sulfonation reaction at 130 for 3h,Follow the reaction process by TLC thin layer chromatography until the remaining amount of 1-aminoanthraquinone is less than 3%;(3) After the reaction is completed, the temperature is reduced to 110°C, distilled water is added for pretreatment for 10 minutes, and then distilled water is added for dilution and stirring for 30 minutes.(4) The diluted solution is allowed to stand for 15 hours, and then the extraction process is carried out.Take the upper water phase, then add distilled water to the lower oil phase, and perform extraction and separation 4 times.The separated aqueous phases are then combined to obtain an aqueous solution of sulfonated 1-aminoanthraquinone.(5) Rotary evaporate the aqueous solution of sulfonated 1-aminoanthraquinone to remove the solvent, and add the mixed solvent,Among them, the combination of ethyl acetate and ethanol, the combination of ether and ethanol, the combination of chloroform and ethanol,Any one of the combination of acetone and ethanol is subjected to recrystallization purification treatment to obtain 1-aminoanthraquinone-2-sulfonic acid, the molecular formula is C14H9NO5S,The product was tested for purity by gas chromatography-mass spectrometry. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: copper(II) sulfate / 1,2-dichloro-ethane / Large scale 1.2: 3 h / 83 - 85 °C / Large scale 2.1: bromine / water / 1.5 h / 53 - 55 °C / Large scale | ||
With sulfuric acid at 120℃; Behandeln des Reaktionsprodukts mit Brom in Wasser; | ||
Multi-step reaction with 3 steps 1: sulfuric acid; sodium sulfate / 1,2-dichloro-benzene / 3 h / 150 °C 2: iodine; bromine / 1,2-dichloro-benzene / 8 h / 80 °C 3: sodium hydroxide / water / 8 h / 90 °C / pH 8 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With sodium hydroxide; zinc at 85℃; for 24.5h; Inert atmosphere; | 1.1 Step 1. Synthesis of 1-aminoanthracene compound (referred to as compound 1): In a 25 mL three-necked flask, add 3.00 g of 1-aminoanthraquinone,By continuously evacuating nitrogen for 3 to 5 cycles,Exhaust the oxygen and moisture in the system to reach a nitrogen atmosphere.Then 100 mL of a 10% NaOH solution was added as a solvent.Add 8g of Zn powder in portions and stir for 30min.Slowly raise the temperature to 85 ° C and keep stirring at 85 ° C for 24h. After the reaction was completed, the reaction was stopped and cooled to room temperature.Filter and wash until the filtrate is colorless. Dissolve the filter residue in acetone.Filtration, spin-drying the filtrate, recrystallization from ethanol,Obtained 2.30 g of compound 1 as a yellow-green crystalline solid,The yield was 92%. |
88% | Stage #1: 1-amino-9,10-anthracenedione With sodium hydroxide; zinc at 20 - 85℃; for 0.5h; Inert atmosphere; Stage #2: With zinc at 85℃; for 24.5h; | 1.1 Step 1. Synthesis of compound 2: In a 250mL three-necked flask, add 3.00g of uniformly ground compound 1,By continuously evacuating nitrogen for 3 to 5 cycles,Exhaust the oxygen and moisture in the system to reach a nitrogen atmosphere.Add 100mL of 10% NaOH aqueous solution and stir well at room temperature.Add 4.00 g of zinc powder and stir for 30 minutes, slowly raise the temperature to 85 ° C, then add 4.00 g of zinc powder, stir for 30 minutes, maintain the temperature at 85 ° C, and stir for 24h. After the reaction is complete, stop stirring, cool to room temperature, wash with suction until the filtrate is colorless, dissolve the filter cake with acetone, remove most of the acetone by rotary evaporation, and recrystallize with ethanol to obtain the filtrate. DCM) to give 2.20 g of red-brown compound 2 in a 88% yield. |
With sodium hydroxide; zinc |
Multi-step reaction with 2 steps 1: zinc; copper; aqueous ammonia / 100 - 110 °C / R4:Kalilauge; unter Druck 2: beim Aufbewahren an der Luft allmaehlich | ||
With zinc Alkaline conditions; | ||
With sodium tetrahydroborate; sodium hydroxide In isopropyl alcohol at 80 - 90℃; for 100h; Inert atmosphere; | ||
With copper-zinc catalyst at 325 - 335℃; im Wasserstoffstrom; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | Stage #1: 1-amino-9,10-anthracenedione With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; sodium hydroxide In water at 100℃; for 24h; Flow reactor; Stage #2: With sodium dithionite; sodium hydroxide In water at 60℃; for 0.5h; | |
80% | With cesium hydroxide; DBN In 1,2-dichloro-benzene at 160℃; for 12h; | 1 Embodiment 1 In the 500 ml round-bottom flask cesium hydroxide is added in (134.9g, 0 . 90mol), 1,5-diaza macrobicyclic [4.3.0] nona-5-ene (148.7,1 . 20mol) and ortho-dichlorobenzene (180g), nitrogen protection, heating under stirring to 100 °C, when the solid completely dissolved, add 1-amino-anthraquinone (66.9g, 0 . 30mol), is omitted, raising the temperature to 160 °C reaction, silica gel thin layer chromatography (TLC) tracking to the raw point disappeared (about 12h), stop heating, natural cooling to room temperature, after diluting adds the methyl alcohol filtering, the filter cake is washed with methanol washing to no obvious odor, obtained after drying 54g dark blue solid, yield 80%. |
With chlorine at 220℃; |
With bromine at 220℃; | ||
With potassium chlorate; potassium phenolate | ||
With sodium chlorate | ||
With manganese(IV) oxide | ||
In 1,3,4-trimethylimidazolidin-2-one | 3 EXAMPLE 3 EXAMPLE 3 102.6 g of 1-aminoanthraquinone (97.5% pure) were condensed in the presence of 200 g (190 ml) of N,N'-dimethylpropyleneurea as described in Example 1 to form indanthrone (I). | |
In 1,3,4-trimethylimidazolidin-2-one | 4 EXAMPLE 4 EXAMPLE 4 102.6 g of 1-aminoanthraquinone (97.5% pure) were condensed in the presence of 200 g (190 ml) of N,N'-dimethylpropyleneurea as described in Example 1 to form indanthrone (I). | |
With bromine at 220℃; | ||
With chlorine at 220℃; | ||
With metal salt at 230 - 260℃; im Rohr; | ||
With mineral acid at 200 - 250℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With sodium sulfite In pyridine; water at 22℃; for 6h; Irradiation; yield with different additives; | |
100% | With sodium sulfite In pyridine; water at 51 - 53℃; for 6h; Irradiation; | |
96% | With chlorosulfonic acid In nitrobenzene at 130℃; for 3h; |
87% | With chlorosulfonic acid In nitrobenzene at 85 - 130℃; for 1.66667h; | Sodium 1-amino-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate (4) 1-Amino-9,10-dioxo-9,10-dihydroanthracene (3) (2.23 g, 10 mmol) was dissolved in nitrobenzene (250 mL) and heated at 120 °C for 15 min to remove traces of water. The solution was then cooled to 85 °C, followed by dropwise addition of chlorosulfonic acid (0.864 mL, 13 mmol) within 10 min. The reaction mixture was subsequently heated at 130 °C for 1.5 h. When the reaction was complete (as monitored by TLC), it was cooled down to rt before the addition of 0.64 g of Na2CO3. Ca. 300 mL water was added to the reaction mixture, which was subsequently extracted with diethyl ether (3 500 mL) to remove nitrobenzene. The water layer was then concentrated in vacuo and subsequently purified by flash column chromatography using reversed phase (RP-18) silica gel, starting with water followed by a gradient of 5% then 20 % of acetone / water to yield compound 4 (2.80 g, 87.0 %) as orange solid; m.p. 280 °C. HPLC-UV (220 - 600 nm) ESI-MS, purity: 99.4 %. LC-MS (m/z): 302 [M - Na]-, 304 [M - Na + 2H]+, 321 [M - Na + NH4 + H]+. 1H NMR (600 MHz, DMSO-d6) δ 7.41 (d, 1H, 4-H, 3J3,4 7.7 Hz), 7.84 (td, 1H, 6-H or 7-H, 4J6,8 = 4J5,7 1.2 Hz, 3J5,6 = 3J6,7 = 3J7,8 7.7 Hz), 7.91 (td, 1H, 6-H or 7-H, 4J6,8 = 4J5,7 1.2 Hz, 3J5,6 = 3J6,7 = 3J7,8 7.7 Hz), 7.95 (d, 1H, 3-H 3J3,4 7.7 Hz), 8.14 (dd, 1H, 5-H or 8-H, 4J6,8 = 4J5,7 1.2 Hz, 3J5,6 = 3J7,8 7.7 Hz), 8.23 (dd, 1H, 5-H or 8-H, 4J6,8 = 4J5,7 1.2 Hz, 3J5,6 = 3J7,8 7.7 Hz). 13C NMR (151 MHz, DMSO) δ 112.6 (C-9a), 114.2 (C-4), 126.2, 126.5 (C-5, C-8), 132.4 (C-2), 132.8, 133.5 (C-6, C-7), 134.1 (C-8a or C-10a), 134.5 (C-3), 134.6 (C-8a or C-10a), 138.2 (C-4a), 148.5 (C-1), 182.7 (C-10), 184.0 (C-9). HRMS (ESI-TOF) m/z: [M - Na]- calcd. for C14H8NO5S 302.0123, found 302.0134. |
Multi-step reaction with 2 steps 1: Na2S nonahydrate / H2O; pyridine / 6 h / 22 °C / Irradiation 2: hydrogen peroxide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | Stage #1: N,N-dimethyl acetamide With trichlorophosphate In acetonitrile at 20℃; for 1h; Stage #2: 1-amino-9,10-anthracenedione In acetonitrile at 50℃; for 8h; Further stages.; | |
94% | With trichlorophosphate at 50℃; for 6h; | |
94% | In acetonitrile at 20 - 60℃; for 7h; | 1-Amino anthraquinone (2.23 g, 10 mM) was added to a solution of DMA (2.18 g, 25 mM) and POCl3 (1.86 mL, 20 mM) in acetonitrile and stirred at room temperature for 1 h and then heated to 50 °C for 6 h. After the reaction was over, the reaction was poured into ice water. Then mixture was neutralized with 10% NaOH. The precipitate was filtered off to offer intermediate (2.74 g, 94%) as a red powder. 1H NMR (CDCl3): δ 1.80 (s, 3 H), 3.13 (s, 6 H), 7.07 (d, 1 H, J = 7.2 Hz), 7.55 (t, 1H, J = 7.2 Hz), 7.67-7.71 (m, 2 H), 7.93 (d, 1H, J = 7.2 Hz), 8.18-8.24 (m, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | In acetic acid at 20 - 95℃; | VI.B.1 0.01 mol of 1-aminoanthraquinone and 0.01 mol of epichlorohydrin in 20 mL acetic acid were kept for 9 hours at 95°C. During the first 6 hours, additional 0.01 mol of epichlorohydrin was added to the reacting system slowly. The reaction was monitored by TLC using hexane/ethyl acetate (2.5:1 volume ratio) as the eluent. Afterward, the reaction mixture was cooled to room temperature and stirred overnight. The product was precipitated with water and purified by recrystallization from methanol with a yield of 75%. The structure of the product was confirmed by NMR. [0096] Then, 0.01 mol of the purified product, together with 0.1 mol tertiary amine, was dissolved in 15 mL n-propanol. The mixture was refiuxed at 1150C for 24 hours monitored by TLC in methanol. The suspension was precipitated by ethyl ether and then vacuum filtered. The crude product was recrystallized with alcohol-ether co-solvent (2:1 volume ratio). Yield: 95%. 1H-NMR spectra data (DMSO): δ 9.872 (s, IH, -NH-CH2); 8.220-8.206, 8.147-8.133, 7.935-7.907, 7.871-7.843, 7.697-7.665, 7.488-7.474, 7.393-7.375 (d, J = 7.0 Hz, d, J = 7.0 Hz, t, J = 7.0 Hz, t, J = 7.0 Hz, t, J = 7.0 Hz, d, J = 8.0 Hz, d, J - 7.0 Hz, 7H, protons attached to C2, C3, C4, C5, C6, C7, C8); 6.165-6.153 (d, J = 9.0 Hz, IH, CH-OH); 4.375 (m, J = 6.0 Hz, IH, CH-OH); 3.537-3.363 (m, 6H, CH2-CH (OH)-CH2-N+(CH3)2-CH2); 3.137-3.125 (d, J = 6.0 Hz, 6H, N+(CHj)2-CH2-CH2-CH2-CH3); 1.725-1.602 (m, 2H, N+(CHs)2-CH2-CH2-CH2-CH3); 1.267-1.256 (m, 2H, N+(CH3)2-CH2- CH2-CH2-CH3); 0.897-0.868 (t, J = 7.3 Hz, 3H, N+(CH3^-CH2-CH2-CH2-CH3). |
63.5% | With acetic acid at 75 - 80℃; for 25h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | Stage #1: 1-amino-9,10-anthracenedione With sulfuric acid; sodium nitrite In water at 45℃; for 8h; Stage #2: With sodium metabisulfite; sodium hydroxide In water at 10 - 90℃; for 17h; | 1.1-6.3 A method for producing pyrazoxanthone by using 1-aminoanthraquinone, including the following steps: (1) Add 200 mol sulfuric acid with a mass fraction of 93% to the reaction kettle. Add while stirring while the sulfuric acid is added. After the sulfuric acid is added, continue to stir and cool down. When the temperature reaches room temperature, add 150 mol sodium nitrite and heat up to 70°C. , Heat preservation for 2h, then add 100mol 1-aminoanthraquinone to the reaction kettle, and diazotize the reaction at 45 for 8h; after the reaction, the temperature is lowered, and the materials are added to the reduction kettle;(2) The solution in the reduction kettle was cooled to 10°C, and 75% sodium metabisulfite solution was added to start the reduction reaction. The reduction reaction time was 5 hours. During the reduction reaction, liquid caustic soda was added to control the pH between 12.5 and 12.8; The dosage is 500mol;(3) Add 98% sulfuric acid to the reaction kettle, and the amount is 7% of the reaction liquid mass in step 2). The cyclization reaction is continued by means of programmed temperature rise and time-phased reaction. : First raise the temperature in the kettle to 35°C, and react with temperature control for 7h; then heat to 50°C for 3h; then raise the temperature to 90°C for temperature control and react for 2h. After the reaction, pyrazoxanthone is obtained. The product was weighed and tested, and the yield of the product was 99% and the purity was 99.99%. |
Multi-step reaction with 2 steps 1: 1) NaNO2, conc. H2SO4; 2) sodium acetate / 1) 12 - 15 deg C, 4 h; 2) water, 0 - 3 deg C, 24 h 2: 85 percent / 37percent hydrochloric acid / acetic acid / 60 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With sodium acetate; potassium carbonate In methanol; N,N-dimethyl-formamide at 150℃; for 25h; | 3 This Example describes the preparation of 1-[4-(biphenyl-4-carbonyl)]phenylaminoanthraquinone colorant composition from 1-[4-(biphenyl-4-carbonyl)]bromobenzene. A 250 ml round-bottomed flask equipped with a thermometer, a double surface condenser with chilled water circulation, and a calcium chloride guard tube was charged with dry N,N-dimethylformamide (75 ml), 7.2 g 1-[4-(biphenyl-4-carbonyl)]bromobenzene, 1-amino anthraquinone (4.7 g), copper(I) iodide (426 mg), copper metal powder (426 mg), potassium carbonate (426 mg), and sodium acetate (2.98 g), in the indicated order. The resulting reaction mixture was heated to about 150° C. under nitrogen with stirring for about 25 hours, by which time TLC analysis indicated complete consumption of the starting material. After cooling to room temperature, the reaction mixture was poured onto 500 ml de-ionized water. The solid thus precipitated was filtered, washed with 1500 ml de-ionized water to remove residual DMF, and then with 250 ml methanol. The residual solid was dried in a vacuum oven (100 mm Hg at 60° C.) to furnish 1-[4-(biphenyl-4-carbonyl)]phenylaminoanthraquinone in a yield of 8.7 g, or 80% of theoretical yield. HPTLC analysis indicated that the purity of the product was about 90%. The nuclear magnetic resonance spectrum of the material was consistent with the structure of the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium acetate; sodium carbonate In 1,2-dichloro-benzene at 180℃; for 18h; Heating / reflux; | 1 Example 1 This Example describes the preparation of 3'-Phenyl-2-methyl-4-(aminoanthraquinone)-1,9-anthrapyridone. A mixture of 3'-phenyl-2-methyl-4-bromo-1,9-anthrapyridone (28 grams), 1-aminoanthraquinone (15 grams), sodium carbonate (8.4 grams), sodium acetate (1.8 grams), cuprous chloride (0.3 grams), and 1,2-dichlorobenzene (350 milliliters) was stirred under reflux (solution temperature was about 180° C.) for about 18 hours. The reaction mixture was then cooled to about 60° C., diluted with methanol (60 milliliters), and stirred for about 2 hours. Then the mixture was filtered, and the filter cake was washed successively with hot dilute hydrochloric acid, water, methanol, and air-dried. The filter cake was suspended in N,N-dimethyl formamide (80 milliliters), heated to about 80° C., and stirred for about 1 hour. The solid product was then filtered, washed successively with water, and methanol, and dried in a vacuum oven maintained at about 120° C. for about 8 hours to give the desired product in a yield of 24 grams. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99.5% | With potassium hydroxide; acetic acid In water; nitrobenzene | 1 EXAMPLE 1 EXAMPLE 1 A mixture of 1-aminoanthraquinone (purity 99.6%, 22.4 g), nitrobenzene (224 g), 96% potassium hydroxide (11.7 g), tetra-n-butyl ammonium bromide (1.7 g) and dimethylsulfuric acid (25 g) was stirred, while being maintained at 30° C. for 24 hours. Then, after water (150 g) was added, the solution was stirred for one hour while being maintained at 50° C. The aqueous phase had pH of 10 or higher. After acetic acid (0.5 g) was added for neutralization until pH of the aqueous phase was 7, nitrobenzene was recovered. The solution was cooled down to 50° C., and filtered. The solid material was washed and dried, to obtain 1-methylaminoanthraquinone (23.7 g, purity: 99.5%, yield 99.5%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89.5% | With bromine; boric acid In water | 1 EXAMPLE 1 EXAMPLE 1 9.0 kg of bromine are added to a mixture of 10.0 kg of 1-aminoanthraquinone (97%) and 15 l of 98% strength sulphuric acid at 50° C. in a pressure vessel. The reaction vessel is then tightly closed and the contents of the vessel are vigorously stirred at 70° C. for 1 hour, at 80° C. for 1 hour and finally at 90° C. for 2 hours. The vessel is then cooled to 50° C. and the pressure is slowly released. Without intermediate isolation, 5.5 kg of boric acid and 27 l of oleum (20%) are added consecutively and cautiously to the bromination mixture, the temperature being maintained at 50°-60° C. with cooling, before it is heated at 75° C. (1 hour) and then at 90° C. and 100° C. for 1 hour each. It is finally heated to 115° C. and stirred at this temperature for 6 hours, the bromine which is produced distilling out. After cooling to 30°-40° C., excess bromine is removed in vacuo, and the reaction mixture is discharged onto 80 l of water. During this, the temperature rises to 90° C. The temperature is increased to 95° C. by blowing in steam. The mixture is allowed to stir at this temperature for 2 hours, and then the product is filtered off through a suction filter. After washing with hot water and drying, 12.4 kg--converted to 100% pure material--of 1-amino-2-bromo-4-hydroxyanthraquinone are obtained, which corresponds to a yield of 89.5%--the product contains less than 0.5% of 1-amino-4-hydroxyanthraquinone and about 1% each of 1-amino-2,4-dihydroxyanthraquinone and 1-amino-2,4-dibromoanthraquinone, together with traces of other bromo derivatives. |
With sulfuric acid; bromine; boric acid In ice-water | 3 EXAMPLE 3 EXAMPLE 3 A stirring autoclave is charged consecutively with 40 kg of sulphuric acid (80% strength), 10 kg of 1-aminoanthraquinone (97% pure) and 3.4 l of bromine. After closure of the pressure vessel, it is heated stepwise to 90° C. and maintained at this temperature for 2 hours. The vessel is allowed to cool to room temperature and the pressure is released. Then 5.5 kg of boric acid are introduced and the mixture is vigorously stirred. Subsequently, with efficient cooling, 66 kg of oleum (65% strength) are cautiously allowed to run in. The internal temperature rises to 70° C. during this. The mixture is then heated stepwise to 115° C. and is stirred at this temperature for 6 hours. The reaction melt is then discharged onto 80 l of ice-water. The mixture thereby obtained is stirred at 95° C. for 2 hours and then discharged onto a filter press. After washing to neutrality and drying, 12.06 kg--converted to 100% pure material--(87% of theory) of a product consisting of 91.4% of 1-amino-2bromo -4-hydroxyanthraquinone and 2.3% of 1-amino-2, are obtained. The remainder was not identified on analysis. | |
With sulfuric acid; bromine; boric acid; acetic acid In water | 6 EXAMPLE 6 EXAMPLE 6 A mixture of 160 parts of 96% sulfuric acid and 20 parts of 1-aminoanthraquinone was heated to 80° C., and at the same temperature a mixture of 20 parts of bromine and 5 parts of acetic acid was added dropwise over 3 hours. The reaction mixture was kept at the same temperature for further 3 hours. Thereafter, a mixture of 15 parts of bromine and 4 parts of acetic acid was added dropwise to the reaction mixture over 2 hours, and the mixture was kept at the same temperature for further 2 hours. The mixture was then kept at 100° C. for 3 hours and cooled to room temperature. Thereafter, 10 parts of boric acid was added to the reaction mixture which was then kept at 130° C. for 8 hours. Eighty parts of water was added dropwise at 90° to 100° C. over 2 hours to the mixture which was then cooled to 55° C. and filtered. The filtered cake was washed with 100 parts of 60% sulfuric acid and then water and dried to obtain 25.5 parts of the same 1-amino-2 -bromo-4-hydroxyanthraquinone cake as in Example 1. |
With sulfur trioxide; bromine; boric acid In water | 1 EXAMPLE 1 EXAMPLE 1 100 parts of 1-aminoanthraquinone are introduced into 625 parts of 75 percent strength sulfuric acid at room temperature, whilst stirring, and 150 parts of bromine are added. The mixture is stirred for 2 hours at from 100° to 110° C., and 1,750 parts of oleum (containing 24% of SO3) are then added over 10 minutes. 67 parts of boric acid are then introduced and the mixture is stirred for 4 hours at 125° C. Thereafter it is poured out into 3,000 parts of water and the suspension is stirred for 1/2 hour. It is then filtered and the filter residue is washed neutral and dried. Yield: 140 parts of 1-amino-2-bromo-4-hydroxyanthraquinone; purity 97%. | |
With sulfuric acid; sulfur trioxide; bromine; boric acid | 2 EXAMPLE 2 EXAMPLE 2 100 parts of 1-aminoanthraquinone and 630 parts of 85 percent strength sulfuric acid are mixed at room temperature. 135 parts of bromine are then added and the mixture is stirred for 2 hours at 100°-110° C. After adding 760 parts of oleum containing 24% of SO3, over 10 minutes, 67 parts of boric acid are added and the mixture is stirred for 4 hours at 125° C. It is then worked up as described in Example 1. Yield: 142 parts of 1-amino-2-bromo-4-hydroxyanthraquinone; purity 95%. | |
With sulfuric acid; bromine; boric acid In water | 2 EXAMPLE 2 EXAMPLE 2 87 g (0.39 moles) 1-aminoanthraquinone are added to 306 g of 98% sulfuric acid at 30°-45° C. 140 g (0.88 moles) bromine are added and the reaction mixture is heated to 60° C. with stirring and held at 60° C. for 5 hours. The reaction mixture is then heated to 70°-75° C. and held at this temperature for 15 hours. The reaction mixture is cooled to 50° C., then 778 g of 24% oleum and 50 g (1.14 moles) boric acid are added while the temperature is kept between 30°-50° C. The reaction mixture is reheated to 115° C. and held at this temperature for 6 hours. The reaction mixture is then cooled to 30° C. and drowned into 400 g of 57% sulfuric acid. The sulfuric acid concentration is then adjusted to 57% by the addition of 904 g of water. The 1-amino-2-bromo-4-hydroxyanthraquinone is isolated by filtration through a glass fiber filter and the precipitate is washed with hot water until the pH of the filtrate is 3-4, which indicates that the precipitate is essentially free of sulfuric acid. After drying at 80° C., 118 g of product are obtained. This material has a purity of 95% and thus the yield is 86% of theory. |
Yield | Reaction Conditions | Operation in experiment |
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Then 100 parts of water are added and the reaction mixture is stirred for about 1/2 to 1 hour at 80 C., diluted with 500 parts of water and filtered. The filter cake is washed neutral with water and dried, affording 7.4 parts of end product. 1-aminoanthraquinone is also obtained in high yield by repeating the above procedure using 5.5 parts of 1-amino-2,4-dibromoanthraquinone instead of 10 parts of 1-amino-2,4-dichloroanthraquinone. |
Yield | Reaction Conditions | Operation in experiment |
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6 EXAMPLE 6 The thus obtained 5-nitrotetrahydroanthraquinone was subjected to oxidation and reduction in accordance with the standard method to obtain 1-aminoanthraquinone having a purity above 98 wt% and a 2-aminoanthraquinone content of 0.5 wt%. | ||
10 EXAMPLE 10 The thus obtained 5-nitrotetrahydroanthraquinone was subjected to oxidation and reduction in accordance with the standard method to obtain 1-aminoanthraquinone having a purity above 98.0 wt% and a 2-aminoanthraquinone content of 0.5 wt%. | ||
C.2 COMPARATIVE EXAMPLE 2 The thus obtained 5-nitrotetrahydroanthraquinone was subjected to oxidation and reduction in accordance with the standard method to obtain 1-aminoanthraquinone having a purity above 98 wt% and a 2-aminoanthraquinone content of 0.9%. |
With sodium hydroxide; hydrogen In cyclohexanol | 9 EXAMPLE 9 EXAMPLE 9 To a mixture of 12.8 grams of 5-nitrotetrahydroanthraquinone and 170 grams of cyclohexanol was added 0.3 gram of a Raney-nickel catalyst. Then, hydrogen was fed into the mixture while agitating at 100° C. for hydrogenation. After hydrogen was absorbed in an amount of 2 mols per mol of the nitro compound, the catalyst was separated by filtration. To the resultant filtrate was added 10 grams of a 20% aqueous sodium hydroxide solution, followed by agitating at 100° C. for 1 hour. Then, the reaction solution was cooled to 10° C. to precipitate crystals which were separated by filtration, washed with water and dried to obtain 9.2 grams of 1-aminoanthraquinone having a purity of 98%. | |
With sodium hydroxide In cyclohexanol | 18 EXAMPLE 18 EXAMPLE 18 3 Grams of a Raney nickel catalyst and 100 grams of a 20% aqueous sodium hydroxide solution were added to a mixture of 128 grams of 5-nitrotetrahydroanthraquinone and 1,700 grams of cyclohexanol, into which was fed hydrogen while agitating at 100° C. for having hydrogen absorbed in the starting 5-nitro compound in an amount of 2 mols per mol of the 5-nitro compound. After completion of hydrogenation, the catalyst was separated by filtration and air was passed into the resultant filtrate at 30° C. for 1 hour. The resultant solution was cooled to 10° C. to precipitate crystals, which were then separated by filtration, washed with water and dried to obtain 92 grams of 1-aminoanthraquinone having a purity of 98.2%. |
Yield | Reaction Conditions | Operation in experiment |
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93% | With sodium hydroxide In methanol; nitrogen; hydrogen | 7 EXAMPLE 7 EXAMPLE 7 A 500 ml. electromagnetically stirred autoclave was charged with 10 g of 1-nitroanthraquinone having a purity of 91.5% and containing 7.0% of 1,5-dinitroanthraquinone, 0.5% of 1,8-dinitroanthroquinone and 1.0% of anthraquinone as impurities, 120 g of a 3% aqueous solution of sodium hydroxide (0.01 mole as sodium hydroxide), 80 g of methanol, and 200 mg of 5% palladium-carbon (2% based on the 1-nitroanthraquinone). The 1-nitroanthraquinone was hydrogenated at a temperature of 50° C. and a pressure of 40 to 30 Kg/cm2.G. In 60 minutes, 0.16 mole of hydrogen was absorbed, whereupon the reaction was stopped. The inside of the autoclave was purged with nitrogen, and 80 g of a 3% aqueous solution of sodium hydroxide was added. Methanol was distilled off at reduced pressure (60 to 70 mmHg abs.) and 40 to 50° C. Then, the reaction mixture was suction-filtered in a stream of nitrogen to remove the catalyst and the diaminoanthraquinones. The filtrate was oxidized with air at 20 to 30° C. for 2 hours with stirring to afford 7.65 g of 1-aminoanthraquinone having a purity of 98% in a yield of 93% of theory. |
Yield | Reaction Conditions | Operation in experiment |
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67% | In sulfolane at 130℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
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38% | With copper(II) bis(trifluoromethanesulfonate); copper(l) chloride In toluene at 120℃; for 24h; Inert atmosphere; | 19 Typical experimental procedure General procedure: A mixture of N-methylisatin 1a (161 mg, 1 mmol, 1 equiv), phenylacetylene 2a (0.12 mL, 1 mmol, 1.2 equiv), 1-aminoanthraquinone (0.266 g, 1 mmol, 1.2 equiv) 3a, cuprous chloride (9.9 mg, 10 mol %), and copper(II) triflate (36.1 mg, 10 mol %) in dry toluene (4 mL) was refluxed at 120 °C for 24 h under nitrogen atmosphere. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature, filtered through a pad of neutral alumina using ethyl acetate as a solvent. The solvent was evaporated in vacuo and the residue was chromatographed on neutral alumina using gradient elution of hexane/ethyl acetate as solvent to yield compounds 4a as pink powder, 183 mg, 39% yield and 5a as violet powder, 197 mg, 42% yield. |
Yield | Reaction Conditions | Operation in experiment |
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38%; 45% | With copper(II) bis(trifluoromethanesulfonate); copper(l) chloride; In toluene; at 120℃; for 24h;Inert atmosphere; | General procedure: A mixture of N-methylisatin 1a (161 mg, 1 mmol, 1 equiv), phenylacetylene 2a (0.12 mL, 1 mmol, 1.2 equiv), 1-aminoanthraquinone (0.266 g, 1 mmol, 1.2 equiv) 3a, cuprous chloride (9.9 mg, 10 mol %), and copper(II) triflate (36.1 mg, 10 mol %) in dry toluene (4 mL) was refluxed at 120 C for 24 h under nitrogen atmosphere. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature, filtered through a pad of neutral alumina using ethyl acetate as a solvent. The solvent was evaporated in vacuo and the residue was chromatographed on neutral alumina using gradient elution of hexane/ethyl acetate as solvent to yield compounds 4a as pink powder, 183 mg, 39% yield and 5a as violet powder, 197 mg, 42% yield. |
Yield | Reaction Conditions | Operation in experiment |
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87% | With dodecatungstosilic acid; phosphorus pentoxide In neat (no solvent, solid phase) at 20℃; for 0.0166667h; Green chemistry; | General method for the synthesis of Schiff bases 1-25 General procedure: A mixture of 1-aminoanthraquinone (1 mmol), a substituted aromatic aldehyde or ketone (1 mmol) and dodecatungstosilicic acid/P2O5 (0.2 g, 1 mol % of 1-aminoanthraquinone/P2O5) as a catalyst was ground in a mortar with a pestle under solvent-free conditions at room temperature for 1-3 min, Scheme 1. The reaction mixture turned to a pasty material that indicated the completion of the reaction. Crushed ice was added to afford precipitates of the Schiff bases. In order to remove the catalyst, the product was washed several times with ice-cold water. The solid products were obtained in excellent yield. |
Yield | Reaction Conditions | Operation in experiment |
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65% | With sodium dithionite; sodium hydroxide In ethanol; water at 60℃; for 0.0111111h; Inert atmosphere; | 1-Amino-2-hydroxymethyl-9,10-dioxo-9,10-dihydroanthracene (5) Sodium dithionite (2.26 g, 13 mmol) was added under argon to a suspension of finely powdered 1-amino-9,10-dioxo-9,10-dihydroanthracene (3) (2.20 g, 10 mmol) in 75 mL of a mixture of ethanol:water:1N NaOH (5:1:1.5, v/v/v). The mixture was then heated at 60 °C until a clear light orange solution was obtained, then it was cooled down to rt followed by the addition of 37 % formaldehyde (8 mL, 100 mmol) under argon with vigorous stirring. The reaction was stopped after 40 s and a stream of air was introduced to the reaction mixture from an air-line. The resulting precipitate was collected by filtration, washed with water and dried under vacuum. Column chromatography of the crude product on silica gel using a gradient of acetone/dichloromethane from 1 % up to 5 % gave compound 5 (1.65 g, 65.0 %) as a red solid; m.p. 197 - 199 °C (lit. m.p. 200 - 201 °C) [1]. HPLC-UV (254 nm) ESI-MS, purity: 96.0 %. LC-MS (m/z): 252 [M - H]-, 254 [M + H]+. 1H NMR (500 MHz, DMSO-d6): δ 4.56 (d, 2H, -CH2, 3J 5.45 Hz), 5.47 (t, 1H, -OH, 3J 5.45 Hz), 7.48 (d, 1H, 4-H, 3J3,4 7.5 Hz), 7.63 (d, 1H, 3-H, 3J3,4 7.5 Hz), 7.84 (td, 1H, 6-H or 7-H, 3J5,6 = 3J6,7 = 3J7,8 7.6 Hz, 4J5,7 = 4J6,8 1.4 Hz), 7.89 (td, 1H, 6-H or 7-H, 3J5,6 = 3J6,7 = 3J7,8 7.6 Hz, 4J5,7 = 4J6,8 1.4 Hz), 8.14 (ddd, 1H, 5-H or 8-H, 3J5,6 = 3J7,8 7.6 Hz, 4J5,7 = 4J6,8 1.4 Hz, 5J5,8 0.45 Hz), 8.22 (ddd, 1H, 5-H or 8-H, 3J5,6 = 3J7,8 7.6 Hz, 4J5,7 = 4J6,8 1.4 Hz, 5J5,8 0.45 Hz). 13C NMR (126 MHz, DMSO): δ 60.3 (CH2), 111.6 (C-9a), 115.5 (C-4), 126.2, 126.4 (C-5, C-8), 132.1 (C-3), 132.4, 132.6, 134.5 (C-8a, C-10a, C-4a), 133.4, 134.3 (C-6, C-7), 134.9, 149.6 (C-1, C-2), 182.7 (C-10), 184.4 (C-9). HRMS (ESI-TOF) m/z: [M - H]- calcd. for C15H10NO3 252.0661, found 252.0681. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With potassium carbonate; potassium iodide; Chloroacetamide In N,N-dimethyl-formamide at 90 - 150℃; for 25h; | |
With potassium carbonate; potassium iodide; Chloroacetamide In N,N-dimethyl-formamide at 90℃; for 24h; | FIGURE 84 shows the synthesis of soluble uPAR binding bifunctional molecule UPAR-GN3. | |
With potassium carbonate; potassium iodide; Chloroacetamide In N,N-dimethyl-formamide at 90℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
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79.6% | Stage #1: 1,3,5-trichloro-2,4,6-triazine; 1-amino-9,10-anthracenedione With sodium carbonate In water; acetone at 0 - 5℃; for 2h; Cooling with ice; Stage #2: N-(2-Aminoethyl)pyridinium chloride With sodium carbonate In water; acetone at 35 - 40℃; for 2h; Stage #3: 1-amino-3-(dimethylamino)propane; epichlorohydrin Further stages; | 1 Example 1 2.25 parts of 1-aminoanthraquinone were dissolved in 3 parts of acetone and 5 parts of a mixed solution of water in an ice salt bath and stirred for 0-5 deg.] C, was slowly added 1.84 parts of trichloro-s-triazine, washed with 10% Na2CO3Solution was adjusted to pH 5-6, the reaction solution was stirred for 2 hours until pH = 5-6 is kept unchanged.Add warmed up to 35-40 deg.] C, stirring 1.58 parts of N- (2- aminoethyl) pyridinium chloride, washed with 10% Na2CO3Adjusted pH = 5-6.The reaction was stirred for 2 hours until the pH of the solution was kept constant 5-6.Continue to heat up to 85 , was added under stirring 1.02 parts of N, N- dimethyl-propanediamine, with 15% dilute hydrochloric acid to adjust pH = 4, stirred for 4 hours.Cooled to 45-50 , 0.95 parts of epichlorohydrin was slowly added dropwise, maintaining the reaction temperature until the reaction was completed four hours, and finally salting was added, removed by filtration, to give the compound (P-1) 6.08 parts yield 79.6%. |
Yield | Reaction Conditions | Operation in experiment |
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1) condensation of poaching: the 1,5-dichloro ethyltetrahydroanthraquinone 120 kg, 1-amino-anthraquinone 180 kg, copper powder 7 kg and anhydrous sodium carbonate 105 kg mix, 105 C dehydration 1h, 2h temperature to 260 C, to carry on the solid phase condensation reaction, thermal insulation 8h, natural cooling 0.5h, cold water cooling 4h, crushing, generating three anthraquinone imine crude, the three anthraquinone imine crude product into the 3000 kg in water, stirring, the temperature is increased to 92 C, thermal insulation 1h, water cooling to 60 C the following, filtering, washing with water to neutral, drying, ? 1% to the moisture content, generating three refined anthraquinone imine. 2) closed-loop reaction: for 50 C lower, adding urea to the solid phase in the reactor 90 kg, sodium fluoride 40 kg, anhydrous sodium acetate 4.5 kg, alchlor 200 kg and adding three refined anthraquinone imine 90 kg-mixing materials, then heating, 50 min in the outer to 190 C, for 190-245 C to the foaming reaction, to the temperature in the treats the solid phase 185-245 C time, thermal insulation 30 min, natural cooling 0.5h, the cold water spray cooling 4h, cooling to 45 C, crushing, to be closed-loop material. 3) segregation alkali cleaning: stirring, the closed-loop material 350 kg to 2200 kg in water, then adding 95% sulfuric acid of 90 kg, heating to 92 C, thermal insulation 1h, then water 800 kg diluting and lowering the temperature to 60 C the following, filtering, washing with water to neutral, then adding the concentration 35% liquid alkali 350 kg and alkali cleaning of the bottom water 3500 kg of preparation 65 C for washing, alkali cleaning, re-water to neutral, drying, be reducing dye clethrionomys GG, sampling detection, a dark brown powder, purity of 98.6%. |
Yield | Reaction Conditions | Operation in experiment |
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90% | Stage #1: 1-amino-9,10-anthracenedione With sulfuric acid; sodium nitrite Stage #2: Diethyldithiocarbamic acid In water at 5 - 10℃; for 0.5h; | General method of obtaining of dithiocarbamates10-30 General procedure: To 13.44 mmol of carbon disulfide in 15 cm3 of water atconstant stirring and cooling 0-5 C, 6.72 mmol of diethylamine/morpholine/piperidine/pyrrolidine was added. The reaction mixture was kept at stirring 15 min. Solution ofdithiocarbaminic acid is ready for the synthesis of dithiocarbamates10-30.Diazonium salt 10-90 was obtained without isolation from2.24 mmol of appropriate aminoanthracenedione 1-9 and0.201 g of sodium nitrite (2.91 mmol) (or 0.402 g,5.81 mmol in case of diamine 7) in 20 cm3 of concentratedsulfuric acid. The obtained solution was neutralized with10 % aqueous solution of sodium carbonate (up to pH = 7).To the neutralized solution of diazonium sulfate at constantstirring and temperature 5-10 C, solution of previouslyin situ generated dithiocarbaminic acid of diethylamine/morpholine/piperidine or pyrrolidine was added. Thereaction mixture was stirred for 30 min; the precipitate wasfiltered, washed with water (2 9 40 cm3), and dried on air. 9,10-Dihydro-9,10-dioxoanthracen-1-yl diethylcarbamodithioate(10, C19H17NO2S2)Yield 0.71 g (90 %); m.p.:[100 C (decomp.); 1H NMR(400 MHz, DMSO-d6): d = 1.21 (t, 3H, J = 6.8 Hz, CH3),1.37 (t, 3H, J = 7.2 Hz, CH3), 3.96 (m, 4H, CH2), 7.88-8.23 (m, 7H, CHAr) ppm; 13C NMR (125 MHz, DMSOd6):d = 11.68, 13.76 (CH3), 48.97, 49.61 (CH2), 126.89,127.29, 128.05, 132.44, 133.17, 133.87, 134.28, 134.67,135.01, 135.19, 135.62, 141.55 (CAr), 182.46, 182.67(C=O), 192.43 (C=S) ppm; and IR (KBr): v = 1680, 1631(C=O), 1261, 1207 (-S-C(S)-) cm-1. |
Yield | Reaction Conditions | Operation in experiment |
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82% | Stage #1: 1-amino-9,10-anthracenedione With sulfuric acid; sodium nitrite Stage #2: morpholine-4-carbodithioic acid In water at 5 - 10℃; for 0.5h; | General method of obtaining of dithiocarbamates10-30 General procedure: To 13.44 mmol of carbon disulfide in 15 cm3 of water atconstant stirring and cooling 0-5 C, 6.72 mmol of diethylamine/morpholine/piperidine/pyrrolidine was added. The reaction mixture was kept at stirring 15 min. Solution ofdithiocarbaminic acid is ready for the synthesis of dithiocarbamates10-30.Diazonium salt 10-90 was obtained without isolation from2.24 mmol of appropriate aminoanthracenedione 1-9 and0.201 g of sodium nitrite (2.91 mmol) (or 0.402 g,5.81 mmol in case of diamine 7) in 20 cm3 of concentratedsulfuric acid. The obtained solution was neutralized with10 % aqueous solution of sodium carbonate (up to pH = 7).To the neutralized solution of diazonium sulfate at constantstirring and temperature 5-10 C, solution of previouslyin situ generated dithiocarbaminic acid of diethylamine/morpholine/piperidine or pyrrolidine was added. Thereaction mixture was stirred for 30 min; the precipitate wasfiltered, washed with water (2 9 40 cm3), and dried on air. |
Yield | Reaction Conditions | Operation in experiment |
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95% | Stage #1: 1-amino-9,10-anthracenedione With sulfuric acid; sodium nitrite Stage #2: piperidine-1-carbodithioic acid In water at 5 - 10℃; for 0.5h; | General method of obtaining of dithiocarbamates10-30 General procedure: To 13.44 mmol of carbon disulfide in 15 cm3 of water atconstant stirring and cooling 0-5 C, 6.72 mmol of diethylamine/morpholine/piperidine/pyrrolidine was added. The reaction mixture was kept at stirring 15 min. Solution ofdithiocarbaminic acid is ready for the synthesis of dithiocarbamates10-30.Diazonium salt 10-90 was obtained without isolation from2.24 mmol of appropriate aminoanthracenedione 1-9 and0.201 g of sodium nitrite (2.91 mmol) (or 0.402 g,5.81 mmol in case of diamine 7) in 20 cm3 of concentratedsulfuric acid. The obtained solution was neutralized with10 % aqueous solution of sodium carbonate (up to pH = 7).To the neutralized solution of diazonium sulfate at constantstirring and temperature 5-10 C, solution of previouslyin situ generated dithiocarbaminic acid of diethylamine/morpholine/piperidine or pyrrolidine was added. Thereaction mixture was stirred for 30 min; the precipitate wasfiltered, washed with water (2 9 40 cm3), and dried on air. |
Yield | Reaction Conditions | Operation in experiment |
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91% | Stage #1: 1-amino-9,10-anthracenedione With sulfuric acid; sodium nitrite Stage #2: pyrrolidinedithiocarbamate In water at 5 - 10℃; for 0.5h; | General method of obtaining of dithiocarbamates10-30 General procedure: To 13.44 mmol of carbon disulfide in 15 cm3 of water atconstant stirring and cooling 0-5 C, 6.72 mmol of diethylamine/morpholine/piperidine/pyrrolidine was added. The reaction mixture was kept at stirring 15 min. Solution ofdithiocarbaminic acid is ready for the synthesis of dithiocarbamates10-30.Diazonium salt 10-90 was obtained without isolation from2.24 mmol of appropriate aminoanthracenedione 1-9 and0.201 g of sodium nitrite (2.91 mmol) (or 0.402 g,5.81 mmol in case of diamine 7) in 20 cm3 of concentratedsulfuric acid. The obtained solution was neutralized with10 % aqueous solution of sodium carbonate (up to pH = 7).To the neutralized solution of diazonium sulfate at constantstirring and temperature 5-10 C, solution of previouslyin situ generated dithiocarbaminic acid of diethylamine/morpholine/piperidine or pyrrolidine was added. Thereaction mixture was stirred for 30 min; the precipitate wasfiltered, washed with water (2 9 40 cm3), and dried on air. |
Yield | Reaction Conditions | Operation in experiment |
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1, 12 kg of copper oxide, 100 kg of sodium carbonate,200 kg 1-aminoanthraquinone,300kg3-Bromobenzene anthroneIn turn into the drum reactor,The equipment was evacuated and 2000 kg of nitrobenzene was evacuated into the reactor. 2, turn the reactor, open the furnace heating. Heated to 110-120 ° C dehydration for 30 minutes, Continue to warm up to 210 ° C and incubate for 2 hours. 3, after the insulation reaction, open vacuum evaporated nitrobenzene, condensed by the condenser recovery. Nitrobenzene evaporated, cool to 80 ° C, vacuum discharge to the boiled pot. 4, in the boiled pot with 70 ° C hot water beating 1 hour, filtered by filter press, washed to neutral,Compressed air is dry and unloaded. 1, will be prepared 500kg anthraquinone imine and by 300kg triethylene glycol,800 kg of sodium hydroxide,400 kg of potassium hydroxide and 1500 kg of water is added to the solution and stirred evenly.2, heat up to 150 ± 2 ° C and heat for 4 hours.3, after the insulation, add water to 80 ° C, into the oxidation pot, adjust the volume of 8000L.4, open the compressed air, oxidized at 75 ° C for 2 hours.5, filtered through the filter press, the filtrate recovered to the distillation of concentrated pot, triethylene glycol alkaline solution distillation concentrated to alkalinity45-50percent, triethylene glycol content of 5-10percent. After passing, return to the next batch of materials.6, filter press filter cake, with 70-80 ° C hot water washed to neutral, compressed air dry, unloading dryTo restore the olive green B original dye |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With iodine In water; N,N-dimethyl-formamide at 120℃; for 3h; | General procedure: Method II. 2,5-Dimethoxytetrahydrofuran (0.35 ml,2.688 mmol or 0.70 ml, 5.376 mmol (for compound 2f))and iodine (0.034 g, 0.134 mmol or 0.068 g, 0.268 mmol(for compound 2f)) were added to aminoanthracene-9,10-dione 1a-g (1.344 mmol) in DMF (30 ml) and 2(1.2 ml). The reaction mixture was stirred at 120° for 3 h.The mixture was cooled, diluted with water (100 ml). Theprecipitate was filtered off, washed with water, and dried. |
92% | With water; iodine In N,N-dimethyl-formamide at 120℃; for 3h; | Synthesis of compounds 2a-g 2,5-Dimethoxytetrahydrofuran (0.35 ml,2.688 mmol or 0.70 ml, 5.376 mmol (for compound 2f)) and iodine (0.034 g, 0.134 mmol or 0.068 g, 0.268 mmol (for compound 2f)) were added to aminoanthracene-9,10-dione 1a-g (1.344 mmol) in DMF (30 ml) and 2 (1.2 ml). The reaction mixture was stirred at 120° for 3 h. The mixture was cooled, diluted with water (100 ml). The precipitate was filtered off, washed with water, and dried. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With sodium hydride In N,N-dimethyl-formamide at 150℃; for 72h; Inert atmosphere; | First, at room temperature,A solution of 53 mM sodium hydride (NaH)And 50 ml of N, N-dimethylformamide (DMF) were placed in the reaction flask and stirred. then,1-amino anthraquinone (1-amino anthraquinone)And 1 mmol-1-fluoro-4-mitrobenzene,And the resulting mixture was heated to 150 ° C under a nitrogen atmosphere and stirring was continued for 72 hours.After cooling to room temperature, the resulting mixture was slowly poured into 500 ml of water,And then rinsed with methanol after filtration to obtain a red powder. after that,The red powder was filtered again, recrystallized using DMF,Thereby obtaining a dinitro compound represented by the formula (I) in a red solid in a yield of 57%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97.1% | Stage #1: 3,9-dibromo-7h-benz(de)anthracen-7-one; 1-amino-9,10-anthracenedione With sodium carbonate; copper(II) oxide at 265℃; for 6h; Stage #2: With pyridine; aluminum (III) chloride at 140℃; for 6h; | 3 [0034] 1) Condensation reaction: 3,9-dibromo-7h-benz(de)anthracen-7-one 220kg, 1-amino anthraquinone 230kg, Sodium carbonate 110kg and 6kg of copper oxide were mixed evenly then raised temperature to 265 ° C for 6h and incubated for heat 6h. it was cooled naturally for 0.5h, then crushed, and at the same time cooling the material to the internal temperature of 100 ° C. The material added to the mass ration of 19 times of the water, insulation boiled at 90 ~ 100 ° C for 1 hour and dilute the discharge. Then carried out filtration, drying to obtain condensate brown RP imine, Moisture content ≤ 1%, spare. [0035] 2) Closed loop reaction: into the reactor added anhydrous aluminum chloride 400kg start stirring for leveling the material then added 150kg of Pyridine then raise the temperature to 140 °C and incubated for 6h at 30 ~ 160 ° C. After the end of the incubation, cooled to 100 ° C, then added 50Kg of brown RP imine, while feeding control temperature to 90 ± 10 ° C and then raised to 120 ° C and incubated for 3h at between 120 ~ 160 ° Cand prepared vat brown RP crude. [0036] 3) Oxidation to remove copper: while stirring, the vat brown RP crude product prepared in step 2 added to 250kg of Bottom water then carried out beating for 1h and after the end of beating the 380kg water was added. then use sulfuric acid to adjust the material to neutral , after adding add sulfuric acid 30kg it was stirred for 15min. the sampling analysis of acidity, at control acidity at 3 ~ 15%, then added sodium chlorate 3.5kg and raised temperature to 85 ° C and and incubated for heat 7h at 85 ~ 95 ° C . then cool to 60 ° C, carried out filtration , washed to neutral with 70 ° C hot water and dried to obtain vat brown RP. Sampling detection, purity of 99.1%, closed loop rate of 99.8%, calculated the total yield of 97.1%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With potassium carbonate; potassium iodide In N,N-dimethyl-formamide at 90 - 150℃; for 25h; | The anthroquinone (0.180g, 0.8mmol) was dissolved in 10ml anhydrous DMF to which KI (13mg, 0.08mmol), potassium carbonate (221mg,1.6mmol), and chloroacetamide (93mg,1.0mmol) were added. The solution was heated to 90°C for lhr followed by 150°C for 24 hours followed by extraction with IN HCL and EtOAc. The organic fractions were dried using sodium sulfate, concentrated in vacuo, and the remaining red residue purified by ISCO silica chromatography using a Hex/EtOAc gradient (10% EtOAc to 50% over 30min) resulting in the isolation of anilinoanthroquinone intermediate ii (156mg, 0.7mmol) in 87 % yield as a red solid H NMR (600 MHz, Chloroform-i 8.29 (d, J= 7.7 Hz, 1H), 8.25 (d, J= 7.6 Hz, 1H), 7.77 (t, J= 7.5 Hz, 1H), 7.72 (t, J= 7.5 Hz, 1H), 7.65 (d, J= 7.3 Hz, 1H), 7.46 (t, J= 7.8 Hz, 1H), 6.97 (d, J= 8.3 Hz, 1H), 6.84 (brm, 2H). 13C NMR (151 MHz, CDC13) 185.24, 183.60, 150.99, 134.73, 134.40, 133.94, 133.17, 129.64, 128.31, 126.79, 123.08, 117.29, 113.65. HRMS (ES+) calc'd for C14H9N02 (M+H) m/z 224.0633, Found. 224.0623 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With [2,2]bipyridinyl; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper diacetate In toluene at 120℃; for 36h; Inert atmosphere; Sealed tube; | 33 Example 33 To a 15 mL reaction tube was added 4 (0.5 mmol, 111.5 mg), toluene (3 mL)Cu (OAc) 2 (0.05 mmol,9.1 mg),2,2'-bipyridine (0.25 mmol, 39.0 mg), TEMPO (1 mmol, 156.2 mg) and 2a (0.6 mmol, 80.0 μL). After the vacuum was purged with nitrogen, the reaction tube was sealed and placed in an oil bath at 120 ° C for 36 h. The reaction was stopped, 15 mL of dichloromethane was added, followed by washing with water and saturated NaCl solution successively, and the organic phase was dried over anhydrous MgSO4. Filtration, spin drying, silica gel column separation (petroleum ether / ethyl acetate = 5/1)The target product 5a (77.3 mg, 46%) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With indium(III) bromide In chlorobenzene at 130℃; for 24h; Inert atmosphere; Schlenk technique; | I. Indium-Catalyzed Annulation of o-Acylanilines with Alkoxyheteroarenes: A GeneralProcedure for Tables 3-5 General procedure: InBr3 [(4.43 mg, 12.5 μmol), (13.3 mg, 37.5 μmol) or (39.0 mg, 110 μmol)] or InI3 (6.19mg, 12.5 μmol) was placed in a 20 mL Schlenk tube, which was heated at 80 °C in vacuo for 15min. The tube was cooled down to room temperature and filled with argon or air. PhCl (0.20,0.30, 0.40, 0.50 or 1.7 mL) or o-C6H4Cl2 (0.20 mL) was added to the tube, and the mixture wasthen stirred at room temperature for 3 min. To this were added alkoxyheteroarenes 3 (0.250,0.300, 0.500, 0.625 or 5.50 mmol) and o-acylanilines 2 (0.250, 0.300 or 2.20 mmol) in the order,and the mixture was stirred at 70, 100, 110, 120, 130 or 170 °C. After stirring for 3, 24 or 36 h,a saturated NaHCO3 aqueous solution (0.5 mL) was added at room temperature, and theresulting mixture was stirred for 20 min. The aqueous phase was extracted with EtOAc (5 mL× 3). The combined organic layer was washed with brine (1 mL) and then dried overanhydrous sodium sulfate (Na2SO4). Filtration and evaporation of the solvent followed bypurification gave product 4. Unless otherwise noted, the annulation reaction was performedaccording to the above procedure, and products 4 synthesized here were fully characterized by1H and 13C NMR spectroscopy and HRMS. Products 4 with fluorine atoms were characterizedadditionally by 19F NMR spectroscopy. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98.2% | With ammonium nitrate In aq. phosphate buffer at 50℃; for 5h; | 1-5 Example 4 In a 500 ml four-necked flask with mechanical stirring and a thermometer,Add 180 ml of propanol,1-amino anthraquinone25g,Ammonium nitrate 6g,Disodium hydrogen phosphate-sodium dihydrogen phosphate buffer 200g,After stirring evenly,Warming up to 50 ° C,Slowly pass 5.8g of methyl chloride gas,Ventilation time 5 hours,After the end of the aeration, the temperature was kept at 50 ° C for 2 hours, and after the end of the heat preservation, water was added.Filter and dry to obtain the target product g1-methylaminopurine 26.3g,The purity was 99.2%, and the yield was 98.2%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With platinum; hydrogen In N,N-dimethyl-formamide at 140℃; for 4h; Autoclave; | 2.4. Evaluation of Catalytic Performance Catalytic hydrogenation of 1-nitroanthraquinone with H2was performed in a 500 mL stainless steel autoclave andstirred with a magnetic driven stirrer. The autoclave wascharged with 3 g of 1-nitroanthraquinone in 150 mL ofDMF solution and appointed amount of CuPtx nanoparticles.The autoclave was purged with N2 for 10 minto replace air inside. And then, pure H2 was pressurizedinto the autoclave and the reaction solution washeated to specified reaction temperatures. When the reactiontemperature reached the specified value, the stirringrate was increased to 400 rpm. After reacting for a periodof time, the reaction was quenched by running coolingwater through a cooling coil in the autoclave. The productswere analyzed using high performance liquid chromatography(HPLC). A reverse-phase column (Innoval ASB C18,5 mm, 4.6 mm×250 mm) and a UV detector (λ=254 nm)were used for analysis at 30 °C. A mixture of water andmethanol of chromatographic grade (v/v, 20/80) was usedas a mobile phase at a flow rate of 1.0 mL min-1. The concentrationsof the products and 1-nitroanthraquinone wereanalyzed by the external standard method. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | Stage #1: 1-amino-9,10-anthracenedione; suberoyl chloride In toluene Reflux; Stage #2: With acetic acid | 2 Synthesis of 1- [N- (8-carboxyheptyl)] aminoanthraquinone 3.48 g of suberic acid (0.02 mol) and 15 mL of dichlorosulfoxide were mixed and dissolved in 35 mL of toluene, and 0.01 g of pyridine was added as a catalyst. The temperature was raised to 60 ° C and the reaction was refluxed. When the solvent was pale yellow (12h-24h), the reaction was stopped. Dichlorosulfoxide and toluene were distilled off under reduced pressure, and toluene (20 mL × 2) was added for distillation. The residue was used in the following reaction.To the above residue were sequentially added 40 mL of toluene and 0.89 g of 1-aminoanthraquinone, and the temperature was slowly raised to reflux. With the progress of the reaction, the reaction solution gradually changed from red to orange-yellow. The progress of the reaction was monitored by TLC, and stopped when the reaction was almost complete (15h-20h). The solvent toluene was distilled off under reduced pressure (to be completely distilled off as much as possible). The obtained mixture was dissolved in 200 mL of potassium carbonate solution (concentration: 12%), and the unreacted 1-aminoanthraquinone was removed by filtration; acetic acid was added dropwise to the filtrate. A pale yellow precipitate formed. After the precipitation was completed, the precipitate was suction filtered, and the precipitate was washed with alcohol to remove excess 1,8-suberic acid. The product was dried in a vacuum drying cabinet with a yield of 85%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With bromine In N,N-dimethyl-formamide at 40℃; for 1h; | 1.1 (1) Synthesis of Compound A-1 Dissolve 1-amino anthraquinone (10 g, 44.83 mmol) in dimethylformamide (200 ml),Bromine (Br2 7.5 g, 47.07 mmol) was added and stirred at about 40 ° C for 1 hour.After the reaction was completed, the mixture was cooled to room temperature, 300 ml of distilled water was added, stirred, and filtered.After filtration, the filtrate was dried, and compound A-1 (8.5 g, 85%) was obtained. |
85% | With bromine In N,N-dimethyl-formamide at 40℃; for 1h; | 1.4 (4) Synthesis of Compound A-4 1-Aminoanthraquinone (10 g, 44.83 mmol) was dissolved in dimethylformamide (200 ml), bromine (Br2 7.5 g, 47.07 mmol) was added, and the mixture was stirred at about 40 ° C for 1 hour. After the reaction was completed, the mixture was cooled to room temperature, 300 ml of distilled water was added, stirred, and filtered. After filtration, the filtrate was dried to give compound A-4 (8.5g, 85%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | In neat (no solvent) at 20℃; for 0.0666667h; Microwave irradiation; | General procedure General procedure: In a small-scale experiment 4-hydroxypyridinium chlorochromate functionalized silica gel (3.95 g, contain 10 mmol of 4-hydroxypyridinium chlorochromate) an alcohol (10 mmol) was rapidly added at room temperature and the resulting mixture stirred vigorously for the appropriate time. The mixture was irradiated for the time indicated in the table by microwave radiation (Table 2). The progresses of the reactions were monitored by TLC. After cooling to room temperature the product was extracted with diethyl ether (2 × 10 mL) and filtered. Evaporation of solvent gave a crude product which was passed through a short silica gel column by ethyl acetate: pet.ether (1:7) as eluent to afford the pure product. The structures of the products were confirmed by their melting point, IR and /or NMR spectral data and comparison with commercially available authentic samples.36-38 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With copper(II) chloride dihydrate; copper(II) oxide In methanol at 20℃; | 2.3. General synthesis of targeted co-crystal (G 1 -G 4 ) General procedure: Anthraquinone derivative (0.2g), pyrimidine derivative (0.2g), methanol (10ml), a catalytic amount of copper chloride and cupric oxide was collectively added in a 100ml one neck round bottom flask. The reaction mixture was allowed to stir for 20-30 minutes at ambient temperature. The reaction progress was monitored reg- ularly by TLC. After the completion of the reaction, the mixture was left till it turns completely in a dry powder form. The for- mulated compound ( Fig. 3 , G 1 -G 4 ) was washed with cold water and dried. The newly synthesized compound was solubilized in hot methanol, filtered offand slowly recrystallized to afford the pure compound. The general schematic representation of reactions is shown in Fig. 3 . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With copper(II) chloride dihydrate; copper(II) oxide In methanol at 20℃; | 2.3. General synthesis of targeted co-crystal (G 1 -G 4 ) General procedure: Anthraquinone derivative (0.2g), pyrimidine derivative (0.2g), methanol (10ml), a catalytic amount of copper chloride and cupric oxide was collectively added in a 100ml one neck round bottom flask. The reaction mixture was allowed to stir for 20-30 minutes at ambient temperature. The reaction progress was monitored reg- ularly by TLC. After the completion of the reaction, the mixture was left till it turns completely in a dry powder form. The for- mulated compound ( Fig. 3 , G 1 -G 4 ) was washed with cold water and dried. The newly synthesized compound was solubilized in hot methanol, filtered offand slowly recrystallized to afford the pure compound. The general schematic representation of reactions is shown in Fig. 3 . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With triethylamine In dichloromethane at 0 - 60℃; for 15.5h; | 2.1.2. Synthesis of Asp-X3 The synthesis scheme for Asp-X3 is shown in Fig. 1. First, 6.51 g 1-amino-anthraquinone and 6 ml triethylamine were dispersed in 20 mlCH2Cl2 inside a 100-ml three-neck flask, and the reaction mixture wascooled to 0 °C in an ice bath followed by the dropwise addition of acetylsalicylrylchloride (obtained above) over a 15-min interval whilestirring. After that, the mixture was continuously stirred for another 30min, and then incubated at 60 °C for 15 h while stirring. Next, the reactionwas allowed to cool to 40 °C and then filtered through a Buchnerfunnel, and the filtrate was collected, and the excess solvent wasremoved by rotary evaporation. The residue was dissolved in 5 mlCH2Cl2 and washed three times with 5% NaHCO3 saturated aqueoussolution in a separating funnel. The bottom (organic) phase wascollected and anhydrous MgSO4 was added to absorb the extra waterand then removed by filtration. CH2Cl2 in the filtrate was removed byrotary evaporation. The residue was redissolved in 5 ml CH2Cl2 andsubjected to column chromatography (silica gel, CH2Cl2/MeOH = 200:1to 40:1), followed by recrystallization in Methylene Chloride-PetroleumEther. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | In ethanol at 75℃; for 10h; | 4 Example 4: Preparation of anthraquinone aminopropyl ethyl maleimide (IIb) Add 19.5 g (0.1 mol) of the maleimido ethyl acrylate prepared in Preparation Example 2 into a 250 mL three-necked flask,Add 100mL ethanol and stir,After it is completely dissolved, add 22.3g (0.1mol) 1-aminoanthraquinone,The temperature was raised to 75°C and reacted for 10 hours. Spin the reaction solution to dryness,The crude product was separated and purified by column chromatography to obtain 35.9 light yellow solid with a yield of 86%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | In neat (no solvent) at 50℃; for 0.266667h; Green chemistry; | General procedure forthesynthesis ofaminoanthraquinone derivatives A mixture of 1- or 2-amino anthraquinone (1.0 mmol), triethyl orthoformate (1.0mmol) and CH-acid compounds (1.0mmol) was stirred in an oil bath at 50°C for the time mentioned in Table2. After fnalizing the reaction (monitored by TLC (n-hexane: ethyl acetate 1:1), the obtained solid products were collected to give desired products. The structures of the synthesized products described by their physical and spectral data (1 H NMR, 13C NMR, and FT-IR spectra and mass). 5-(((9,10-Dioxo-9,10-dihydroanthracen-1-yl)amino)methylene) pyrimidine-2,4,6(1H,3H,5H)-trione (5a) Yield: 96%; in the form of yellow solid; mp>360°C; FT-IR (cm-1) 3171, 3030, 2992, 2833, 1734, 1689, 1653, 1592, 1561, 1498, 1445, 1426, 1361, 1302, 1260, 1163, 1048, 1000, 859, 803, 781, 733, 705, 608, 524, 511, 492, 448, 408; Table 3 The comparison of our method with other approaches for the synthesis of product 5g a Isolated yields b Minutes Entry Product Conditions Temp. (°C) Time (h) Yield (%)a Reference 1 Acetic acid r.t 24 93 [56] 2 Formic acid refux 30 94 [57] 3 Solvent-free 50 14b 94 This work1 3 A.Sardashti-Birjandi et al. 1 H NMR (300MHz, DMSO-d6): 7.92-7.97 (m, 3H, 3CH arom), 8.07 (d, J=6.9, 1H, CH arom), 8.19 (d, J=9, 1H, CH arom), 8.23-8.28 (m, 2H, 2CH arom), 8.75 (d, J=13.5, 1H, CHNH), 11.01-11.10 (2S, 2H, 2 CONHCO), 14.11 (d, J=13.5, CHNH); 13C NMR (300MHz, DMSO-d6): 96.02, 119.94, 122.99, 124.19, 126.95, 127.41, 132.72, 134.17, 134.76, 135.08, 135.27, 136.13, 140.73, 150.34 (CHNH), 151.18 (HNCONH), 164.05 (CCONH), 165.32 (CCONH), 182.45, 185.28; Mass (MALDI-TOF) m/z calcd for C19H11N3O5 [M] 361.07 found: 361.2 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | In neat (no solvent) at 50℃; for 0.383333h; Green chemistry; | General procedure forthesynthesis ofaminoanthraquinone derivatives A mixture of 1- or 2-amino anthraquinone (1.0 mmol), triethyl orthoformate (1.0mmol) and CH-acid compounds (1.0mmol) was stirred in an oil bath at 50°C for the time mentioned in Table2. After fnalizing the reaction (monitored by TLC (n-hexane: ethyl acetate 1:1), the obtained solid products were collected to give desired products. The structures of the synthesized products described by their physical and spectral data (1 H NMR, 13C NMR, and FT-IR spectra and mass) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In neat (no solvent) at 50℃; for 0.416667h; Green chemistry; | General procedure forthesynthesis ofaminoanthraquinone derivatives A mixture of 1- or 2-amino anthraquinone (1.0 mmol), triethyl orthoformate (1.0mmol) and CH-acid compounds (1.0mmol) was stirred in an oil bath at 50°C for the time mentioned in Table2. After fnalizing the reaction (monitored by TLC (n-hexane: ethyl acetate 1:1), the obtained solid products were collected to give desired products. The structures of the synthesized products described by their physical and spectral data (1 H NMR, 13C NMR, and FT-IR spectra and mass) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | In neat (no solvent) at 50℃; for 0.4h; Green chemistry; | General procedure forthesynthesis ofaminoanthraquinone derivatives A mixture of 1- or 2-amino anthraquinone (1.0 mmol), triethyl orthoformate (1.0mmol) and CH-acid compounds (1.0mmol) was stirred in an oil bath at 50°C for the time mentioned in Table2. After fnalizing the reaction (monitored by TLC (n-hexane: ethyl acetate 1:1), the obtained solid products were collected to give desired products. The structures of the synthesized products described by their physical and spectral data (1 H NMR, 13C NMR, and FT-IR spectra and mass) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In neat (no solvent) at 50℃; for 0.833333h; Green chemistry; | General procedure forthesynthesis ofaminoanthraquinone derivatives A mixture of 1- or 2-amino anthraquinone (1.0 mmol), triethyl orthoformate (1.0mmol) and CH-acid compounds (1.0mmol) was stirred in an oil bath at 50°C for the time mentioned in Table2. After fnalizing the reaction (monitored by TLC (n-hexane: ethyl acetate 1:1), the obtained solid products were collected to give desired products. The structures of the synthesized products described by their physical and spectral data (1 H NMR, 13C NMR, and FT-IR spectra and mass) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In neat (no solvent) at 50℃; for 0.233333h; Green chemistry; | General procedure forthesynthesis ofaminoanthraquinone derivatives A mixture of 1- or 2-amino anthraquinone (1.0 mmol), triethyl orthoformate (1.0mmol) and CH-acid compounds (1.0mmol) was stirred in an oil bath at 50°C for the time mentioned in Table2. After fnalizing the reaction (monitored by TLC (n-hexane: ethyl acetate 1:1), the obtained solid products were collected to give desired products. The structures of the synthesized products described by their physical and spectral data (1 H NMR, 13C NMR, and FT-IR spectra and mass) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | In neat (no solvent) at 50℃; for 0.233333h; Green chemistry; | General procedure forthesynthesis ofaminoanthraquinone derivatives A mixture of 1- or 2-amino anthraquinone (1.0 mmol), triethyl orthoformate (1.0mmol) and CH-acid compounds (1.0mmol) was stirred in an oil bath at 50°C for the time mentioned in Table2. After fnalizing the reaction (monitored by TLC (n-hexane: ethyl acetate 1:1), the obtained solid products were collected to give desired products. The structures of the synthesized products described by their physical and spectral data (1 H NMR, 13C NMR, and FT-IR spectra and mass) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 92% 2: 6% | Stage #1: 1-amino-9,10-anthracenedione With chlorosulfonic acid In 1,2-dichloro-benzene at 75 - 130℃; for 11h; Stage #2: With sulfuric acid In 1,2-dichloro-benzene at 130℃; for 4h; | (1) Add 11 times the weight of 1-aminoanthraquinone to o-dichlorobenzene in the sulfonation reactor, stir and raise the temperature to 85°C to dissolve all the 1-aminoanthraquinone.(2) Turn on the vacuum system of the sulfonation reactor and continue to heat up to 100°C with a vacuum of -0.008Mpa to complete dehydration;(3) The temperature of the sulfonation reactor was cooled to 75°C, and the chlorosulfonic acid of 1.35 times the moles of 1-aminoanthraquinone was added slowly and uniformly in 7 hours, and the temperature was increased to 85°C, and the temperature was kept for 2 hours;(4) The sulfonation reactor continues to heat up to 130°C, and keep it warm for 2 hours after the temperature rises;(5) Add 1-aminoanthraquinone 3.15 moles of 98% concentrated sulfuric acid at 130°C and complete it in 4 hours at an average speed;(6) Cool down to 75°C, keep warm after cooling, stand still and separate into layers. The upper o-dichlorobenzene is returned to the system for reuse, and the lower sulfonation reaction sulfuric acid liquid debromine chemical section. During the stratification and separation, 98% sulfuric acid is used as the extractant to make the sulfonation reactant enter the concentrated sulfuric acid, and the o-dichlorobenzene is removed from the upper layer. 98% concentrated sulfuric acid has four functions as desulfurizing agent, working medium, chlorosulfonic acid decomposing agent, and extracting agent. |
Tags: 82-45-1 synthesis path| 82-45-1 SDS| 82-45-1 COA| 82-45-1 purity| 82-45-1 application| 82-45-1 NMR| 82-45-1 COA| 82-45-1 structure
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P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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