Name: 81-64-1|1,4-Dihydroxyanthracene-9,10-dione|95%
Brand: Ambeed
SKU: A138561
Price: 7.0 USD
Availability: InStock
Rating: 94 (40 reviews)

1
[ 85-44-9 ]
[ 106-48-9 ]
[ 81-54-9 ]
[ 81-64-1 ]

Reference： [1]Chemische Berichte,1877,vol. 10,p. 608

2
[ 85-44-9 ]
[ 123-31-9 ]
[ 81-64-1 ]

Yield	Reaction Conditions	Operation in experiment
96%	With boron trioxide; sulfuric acid at 125 - 160℃; for 16h;	1; 2 Example 2: In a dry 500nl four-necked flask, 145 g (1.45 mol) of 98% sulfuric acid was added, 50.5 g (0.726 mol) of boric anhydride was added under stirring, and after the addition, stirred for 15 minutes to make it fully dissolved. Then 59.1 g of phthalic anhydride (molecular weight 148.1, 0.399 mol) and 40 g of hydroquinone (molecular weight 110.1, 0.363 mol) were added, and stirred for 15 minutes to fully dissolve. Begin to heat up with a heat-conducting oil furnace, heat up to 125°C, and keep it at 125-130°C for 8 hours. Then continue to heat up to 155°C, and keep it at 155-160°C for 8 hours. After the heat preservation, the temperature is lowered to 50-60°C, and the reaction materials are transferred to a four-neck flask filled with 730g of clear water. After the material transfer is completed, the temperature is controlled at 100-110°C, and the isolation is about 2 hours. Then the temperature is lowered to 60-80°C, filtered, washed with water, and dried to obtain the product. 85.20 g of 1,4-dihydroxyanthraquinone was obtained, the chromatographic content was 98.25%, and the yield was 96.0%.
80%	With aluminium trichloride; sodium chloride at 165℃; for 4h;
55%	With sulfuric acid; boric acid at 200℃; for 3.5h;

44%	With aluminum (III) chloride; sodium chloride at 165 - 170℃; for 0.75h;
40%	With aluminum (III) chloride; sodium chloride at 150 - 170℃; for 0.75h;	2.3. Synthesis of Anthraquinones General procedure: A series of anthraquinone derivatives was prepared as described by Singh and Geetanjali [25] with slight modification.In a dry two-necked round bottom flask was placed 45g aluminum chloride (308 mmol) and 9 g of sodium chloride (155 mmol). The mixture was heated on an oil bath until melted (external temperature, 150-170oC). Phthalic anhydride(1 g, 6.75 mmol) and hydroxyl-substituted benzene (15mmol) were slowly introduced into the molten aluminum chloride and sodium chloride and heated with stirring for 45 min. Upon the completion of the reaction, the deep redmelt was carefully poured onto 500 ml ice water. About 15 ml of concentrated hydrochloric acid was added to the mixture and it was allowed to stand overnight for product precipitation. The precipitate was collected using vacuum filtration and washed with saturated sodium bicarbonate solutionto remove acidic impurities. The sample was premixed with acid-treated silica and subjected to open column chromatography or medium pressure liquid chromatography eluted with composition of n-hex: CH2Cl2 or n-hex: EtOAc to give yellow to red coloured products. The o-alkylation reactionwas accomplished using method as described earlier [26]. Ina dry round bottom flask was placed hydroxyanthraquinone(1 mmol), methyl iodide (2 mmol) and potassium carbonate(1 mmol) in 30 ml acetone. The mixture was refluxed for8-120 h. The completion of the reaction was monitored using analytical TLC. Upon the completion of the reaction, the mixture was dried. The crude product was redissolved in dichloromethane and extracted with distilled water to remove potassium carbonate residues. The organic layer was dried over sodium sulfate anhydrous and premixed with silicaprior to purification using open column chromatography or medium pressure liquid chromatography and/or preparative thin layer chromatography. Combination of n-hex: EtoAcand n-hex: CH2Cl2 were used as eluting solvents.
	With aluminium trichloride; sodium chloride at 200℃; und nachfolgenden Erhitzen auf 230-240grad;
	at 180 - 200℃;
	With Japanese acid earth at 260 - 270℃;
	With oxalic acid at 220℃;
	With sulfuric acid; boric acid Darstellung;
	With sulfuric acid; boric acid

Reference： [1]Current Patent Assignee: JIANGSU HUAER CHEMICAL - CN113072439, 2021, A Location in patent: Paragraph 0020-0023
[2]Dhananjeyan, Mugunthu R.; Milev, Youli P.; Kron, Michael A.; Nair, Muraleedharan G. [Journal of Medicinal Chemistry, 2005, vol. 48, # 8, p. 2822 - 2830]
[3]Location in patent: experimental part Bhatti, Khalid Pervez; Zuber, Muhammad [Journal of the Chemical Society of Pakistan, 2011, vol. 33, # 5, p. 758 - 763]
[4]Saha, Koushik; Lam, Kok Wai; Abas, Faridah; Sazali Hamzah; Stanslas, Johnson; Hui, Lim Siang; Lajis, Nordin H. [Medicinal Chemistry Research, 2013, vol. 22, # 5, p. 2093 - 2104]
[5]Osman, Che Puteh; Ismail, Nor Hadiani; Widyawaruyanti, Aty; Imran, Syahrul; Tumewu, Lidya; Choo, Chee Yan; Ideris, Sharinah [Letters in drug design and discovery, 2019, vol. 16, # 3, p. 353 - 363]
[6]Raudnitz [Chemische Berichte, 1929, vol. 62, p. 512]
[7]Boeeseken [Recueil des Travaux Chimiques des Pays-Bas, 1922, vol. 41, p. 780]
[8]Tanaka; Watanabe [Bulletin of the Chemical Society of Japan, 1928, vol. 3, p. 288][Chemisches Zentralblatt, 1929, vol. 100, # I, p. 752]
[9]Nakanishi [Yakugaku Zasshi/Journal of the Pharmaceutical Society of Japan, 1931, vol. 51, p. 31,33; dtsch.Ref.S.10][Chemisches Zentralblatt, 1931, vol. 102, # I, p. 2600]
[10]Fierz-David,H.E.; Blangey,L. [Grundlegende Operationen der Farbenchemie,5.Aufl.<Wien 1943>,S.226]
[11]Borisov; Maizlish; Shaposhnikov; Korzhenevskii; Shikova; Sokolova; Koifman [Russian Journal of General Chemistry, 2012, vol. 82, # 10, p. 1740 - 1747][Zh. Obshch. Khim., 2012, vol. 82, # 10, p. 1740 - 1747,8]

3
[ 605-32-3 ]
[ 81-64-1 ]

Reference： [1]Patent: DE86630,
Fortschr. Teerfarbenfabr. Verw. Industriezweige,vol. 4,p. 301

4
[ 81-54-9 ]
[ 81-64-1 ]

Reference： [1]Chemische Berichte,1877,vol. 10,p. 554
[2]Chemische Berichte,1877,vol. 10,p. 554
[3]Journal of the Chemical Society,1952,p. 2759,2765
Journal of the Chemical Society,1955,p. 1089,1095

5
[ 81-64-1 ]
[ 17648-03-2 ]
[ 4623-24-9 ]
[3-(4-hydroxy-9,10-dioxo-9,10-dihydro-[1]anthrylamino)-phenyl]-acetonitrile [ No CAS ]

Reference： [1]Patent: US2419405,1943,

6
[ 81-64-1 ]
[ 635-12-1 ]

Yield	Reaction Conditions	Operation in experiment
98%	With sodium tetrahydroborate In methanol for 24h; Heating;
98%	With methanol; sodium tetrahydroborate at 0℃;	2.1 Quinizarin (10 g, 0.04163 mol) dissolved in methanol (190 mL) was placed in a 500 mL two-neck flask. NaBH4 (6.4 g, 0.169 mol) was slowly added to the mixed solution at 0°C and the mixed solution was stirred overnight. 6M HCl (100 mL) was slowly added to the solution, and then the crude product was extracted with ethyl acetate (EA) and recrystallized to obtain solid intermediate C-1 (8.5 g, yield: 98.0%).
97%	With sodium tetrahydroborate In methanol at 0℃; for 1h; Inert atmosphere;

95%	With sodium tetrahydroborate In methanol at 0℃; for 1h;
93%	With methanol; sodium tetrahydroborate at 0℃; for 1.5h;
92%	With sodium tetrahydroborate In methanol for 24h; Heating;
92%	With sodium tetrahydroborate In methanol at 0℃; for 1.5h;
90%	With sodium tetrahydroborate In methanol at 20℃; for 0.5h; Inert atmosphere;	3.2. Reduction General procedure: 1,4-Dihydroxyanthraquinone (1, 1 equiv.) was dissolved in methanol (3 mL) and stirred homogenously under a nitrogen atmosphere. Sodium borohydride (1, 3 or 15 equiv.) was added slowly to the reaction mixture and stirred for 30 min. Water (0.5 mL) was added to the reaction mixture and the pH was adjusted to 5-6 with 1 M HCl. Methanol was evaporated and the residue of aqueous layer was extracted with CH2Cl2 (3 × 10 mL). The combined organic layer were dried, filtered and evaporated under vacuum. The crude product was purified by column chromatography (CH2Cl2-petroleum ether, 3:2) to obtain compounds 2 (NaBH4: 1 equiv.) and 3 (NaBH4: 1, 3 and 15 equiv.).
90%	With methanol; sodium tetrahydroborate for 1h; Cooling with ice;	3.1 100 ml of a two-necked flask was charged with 960 mg (4 mmol) of 1,4-dihydroxy-9,10-anthraquinone and 40 ml of methanol,Then, 608 mg of sodium borohydride was added slowly under ice-water bath,Since this step reaction is accompanied by a large amount of gas generation,So sodium borohydride must be added slowly.After the addition of sodium borohydride, the mixture was stirred for 1 hour in an ice-A dilute salt of 10.6 ml (concentration: 6 mol.L-1) was slowly added to the reaction flask,Continue stirring in an ice-water bath for 0.5 hours,After the reaction is filtered,To give 749 mg of brown solid M-3 (yield: 90%),The molecular weight of the product was determined to be 208.15 (theory: 208.05)Proved as the target intermediate can be used for the next step reaction.The synthesis of compound M-4 was the same as that of compound M-2, and the product was mass spectrometry at a molecular weight of 266.30 (theoretical: 266.01) and could be used in the next step.
89%	With sodium tetrahydroborate In methanol at 0 - 20℃; Inert atmosphere;
82%	With sodium tetrahydroborate In methanol at 0℃; for 1h;	2.2 General procedure for the synthesis of substrates of 2b-2c To a stirred solution of 1,4-benzoquinone (8.77 g, 81 mmol) and BF3•OEt2 (1.0 mL, 8.1 mmol) in toluene was added 2,3-dimethyl-1,3-butadiene (111 mL, 97 mmol) dropwise at -20 °C over 10 min. After the addition was completed, the reaction was allowed to warm to 0 °C over 30 min. Upon completion the mixture was washed twice with brine and the organic layer was dried over Na2SO4, filtered and condensed under reduced pressure. The crude product was used directly in the next step without further purification. To the solution of 2-S1 in toluene (140 mL) was added MnO2 (17.4 g, 200 mmol) portion-wise and run at 60 °C for 12 h. The reaction mixture was cooled and filtered through Celite by washing with EtOAc. The solvent was condensed under reduced pressure and the crude material purified by column chromatography (PE/EtOAc = 10:1) to yield a yellow solid 2b (7.39 g, 49% yield for 2 steps).5 To the solution of quinizarin (2.00 g, 8.4 mmol) in methanol (20 mL) was added sodium borohydride (1.28 g, 33.6 mmol) dropwise at 0 °C. The mixture was stirred at 0 °C for 1 h until the TLC shows that the starting material was consumed. Then 20 mL of 6 M HCl was added dropwise to the mixture at 0 °C over 10 min. The solid was filtered and washed three times with water, then dried and recrystallized from acetone/n-hexane to give 1, 4-anthracenedione 2c (1.4 g, 82%) as yellow crystals.6
70%	Stage #1: 1,4-dihydroxy-9,10-anthracenedione With sodium tetrahydroborate Stage #2: With hydrogenchloride
	With methanol; sodium tetrahydroborate anschliessendes Behandeln mit wss. Essigsaeure;
	With methanol; borane-THF 2) CHCl₃; Multistep reaction;
	Multi-step reaction with 2 steps 1: NaBH₄ / ethanol 2: glacial acetic acid / ethanol
	With sodium tetrahydroborate at 25℃; for 2h; Inert atmosphere;
	With sodium tetrahydroborate

Reference： [1]Gupta, Dharmendra N.; Hodge, Philip; Khan, Naeem [Journal of the Chemical Society. Perkin transactions I, 1981, p. 689 - 696]
[2]Current Patent Assignee: LG DISPLAY CO.,LTD.; KOREA UNIVERSITY - CN112300084, 2021, A Location in patent: Paragraph 0258-0262
[3]Murkli, Steven; Klemm, Jared; King, David; Zavalij, Peter Y.; Isaacs, Lyle [Chemistry - A European Journal, 2020, vol. 26, # 66, p. 15249 - 15258]
[4]Hua, Duy H.; Tamura, Masafumi; Huang, Xiaodong; Stephany, Heidi A.; Helfrich, Brian A.; Perchellet, Elisabeth M.; Sperfslage, Bonnie J.; Perchellet, Jean-Pierre; Jiang, Suping; Kyle, Dennis E.; Chiang, Peter K. [Journal of Organic Chemistry, 2002, vol. 67, # 9, p. 2907 - 2912]
[5]Yamakado, Takuya; Takahashi, Shota; Watanabe, Kazuya; Matsumoto, Yoshiyasu; Osuka, Atsuhiro; Saito, Shohei [Angewandte Chemie - International Edition, 2018, vol. 57, # 19, p. 5438 - 5443][Angew. Chem., 2018, vol. 130, # 19, p. 5536 - 5541,6]
[6]Flock, Markus; Nieger, Martin; Breitmaier, Eberhard [Liebigs Annalen der Chemie, 1993, # 4, p. 451 - 456]
[7]da Silva Júnior, Eufrânio N.; de Carvalho, Renato L.; Almeida, Renata G.; Rosa, Luisa G.; Fantuzzi, Felipe; Rogge, Torben; Costa, Pedro M. S.; Pessoa, Claudia; Jacob, Claus; Ackermann, Lutz [Chemistry - A European Journal, 2020, vol. 26, # 48, p. 10981 - 10986]
[8]Nor, Siti Mariam Mohd; Sukari, Mohd Aspollah Hj Md; Azziz, Saripah Salbiah Syed Abdul; Fah, Wong Chee; Alimon, Hasimah; Juhan, Siti Fadilah [Molecules, 2013, vol. 18, # 7, p. 8046 - 8062]
[9]Current Patent Assignee: JILIN UNIVERSITY - CN103896966, 2016, B Location in patent: Paragraph 0034-0036
[10]Aster, Alexander; Zinna, Francesco; Rumble, Christopher; Lacour, Jérôme; Vauthey, Eric [Journal of the American Chemical Society, 2021, vol. 143, # 5, p. 2361 - 2371]
[11]Zhang, Lin-Lin; Da, Bing-Chao; Xiang, Shao-Hua; Zhu, Shuai; Yuan, Zi-Yun; Guo, Zhen; Tan, Bin [Tetrahedron, 2019, vol. 75, # 12, p. 1689 - 1696]
[12]Filatov, Mikhail A.; Etzold, Fabian; Gehrig, Dominik; Laquai, Frédéric; Busko, Dmitri; Landfester, Katharina; Baluschev, Stanislav [Dalton Transactions, 2015, vol. 44, # 44, p. 19207 - 19217]
[13]Lepage [Annales de Chimie (Cachan, France), 1959, vol. <13> 4, p. 1137,1176]
[14]Lang, Andreas; Noeth, Heinrich; Thomann-Albach, Martina [Chemische Berichte, 1997, vol. 130, # 3, p. 363 - 369]
[15]Kallmayer; Seyfang [Archiv der Pharmazie, 1985, vol. 318, # 7, p. 607 - 614]
[16]Kuninobu, Yoichiro; Seiki, Takayuki; Kanamaru, Shunsuke; Nishina, Yuta; Takai, Kazuhiko [Organic Letters, 2010, vol. 12, # 22, p. 5287 - 5289]
[17]Mlostoń, Grzegorz; Urbaniak, Katarzyna; Urbaniak, Paweł; Marko, Anna; Linden, Anthony; Heimgartner, Heinz [Beilstein Journal of Organic Chemistry, 2018, vol. 14, p. 1834 - 1839]

7
[ 81-64-1 ]
[ 81-54-9 ]

Reference： [1]Chemische Berichte,1875,vol. 8,p. 152
[2]Justus Liebigs Annalen der Chemie,1916,vol. 411,p. 349

8
[ 81-64-1 ]
[ 116-85-8 ]

Reference： [1]Synthetic Communications,1993,vol. 23,p. 3211 - 3222
[2]Patent: DE94396,

9
[ 81-64-1 ]
[ 23743-40-0 ]

Yield	Reaction Conditions	Operation in experiment
73%	With nitric acid In acetic acid at 55℃; for 3.5h;
69%	With nitric acid; acetic acid at 60℃; for 3.5h;	1 1. Synthesis of 4,11-dihydroxy anthra [2,3-d]imidazole-5,11-dione 5 8g of compound 1, ie 1,4-dihydroxy-9,10-Anthraquinone in a 250ml round bottom flask, added 100ml glacial acetic acid, stirred and mixed well, then , 5 mL of concentrated nitric acid was added, and the reaction was stirred and heated at 60 ° C for 3.5 h. The reaction solution was filtered, and the filter cake was washed with 15 mL of glacial acetic acid, then washed with a large amount of water to neutral, and dried in vacuo to give compound 2 in a yield of 69%.
62%	With nitric acid; acetic acid at 60℃; for 3.5h;	1.S1 Step S1: 6g of compound 1 is added to 90.0mL of glacial acetic acid, and then 5.0mL of concentrated nitric acid is added, and the reaction is heated and stirred at 60 ° C for 3.5 hours, the reaction solution is filtered, and the filter cake is washed with AcOH and water, respectively, and then dried to obtain compound 2 , the yield is 62%;

62%	With nitric acid; acetic acid at 60℃; for 3.5h;	1 Glycosylation4,11-dihydroxyindolo[2,3-d][1,2,3]triazole-5,10-dione 5Synthesis 6g of compound 1 was added to 90.0mL of glacial acetic acid, and then 5.0mL of concentrated nitric acid was added.The reaction was stirred with heating at 60 ° C for 3.5 h, and the reaction solution was filtered.The filter cake is washed with AcOH and water, respectively, and then dried to give compound 2,The yield was 62%.
	With nitric acid; acetic acid at 40 - 50℃;
	With nitric acid; nitrobenzene at 40 - 50℃;
	With nitric acid In acetic acid Ambient temperature; Yield given;

Reference： [1]Shchekotikhin; Makarov; Buyanov; Preobrazhenskaya [Chemistry of Heterocyclic Compounds, 2005, vol. 41, # 7, p. 914 - 920]
[2]Current Patent Assignee: HENAN NORMAL UNIVERSITY - CN108822170, 2018, A Location in patent: Paragraph 0022; 0047; 0048
[3]Current Patent Assignee: HENAN NORMAL UNIVERSITY - CN108822171, 2018, A Location in patent: Paragraph 0043-0045
[4]Current Patent Assignee: HENAN NORMAL UNIVERSITY - CN109180596, 2019, A Location in patent: Paragraph 0040; 0041; 0042; 0043
[5]Current Patent Assignee: Bayer & Co. - DE272299, 1800, C [Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 11, p. 590][Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 11, p. 590]
[6]Current Patent Assignee: Bayer & Co. - DE272299, 1800, C [Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 11, p. 590][Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 11, p. 590]
[7]Antonello; Uriarte; Palumbo [Archiv der Pharmazie, 1989, vol. 322, # 9, p. 541 - 544]

10
[ 116-85-8 ]
[ 81-64-1 ]

Reference： [1]Chemische Berichte,1928,vol. 61,p. 988

11
[ 81-64-1 ]
[ 108-24-7 ]
[ 2289-36-3 ]

Yield	Reaction Conditions	Operation in experiment
90%	With sodium acetate at 100℃; for 9h;	3.4. Acylation General procedure: A mixture of compound 1 (1 equiv.), Ac2O (33 equiv.), and NaOAc (1 equiv) was stirred at 100 °C for 2 h. The reaction mixture were added to ice cold water and extracted with CH2Cl2 (3 × 25 mL). The combined organic layers was dried and evaporated under vacuum. The crude product was purified by column chromatography (CH2Cl2-petroleum ether, 3:1) to produce compounds 6 and 7.
	With sulfuric acid

Reference： [1]Nor, Siti Mariam Mohd; Sukari, Mohd Aspollah Hj Md; Azziz, Saripah Salbiah Syed Abdul; Fah, Wong Chee; Alimon, Hasimah; Juhan, Siti Fadilah [Molecules, 2013, vol. 18, # 7, p. 8046 - 8062]
[2]Green [Journal of the Chemical Society, 1926, p. 1434]

12
[ 81-64-1 ]
[ 106-49-0 ]
[ 81-48-1 ]

Yield	Reaction Conditions	Operation in experiment
84.7%	Stage #1: 1,4-dihydroxy-9,10-anthracenedione; <i>p</i>-toluidine With hydrogenchloride; benzoic acid; zinc In methanol; water at 60 - 116℃; for 19h; Stage #2: With oxygen In methanol; water at 60℃;	In a 500 mL pressure vessel equipped with a mechanical stirrer and a thermometer, 40 g of soft water was added,Hydrochloric acid 15 g,, 40 g of 4-dihydroxyanthraquinone, 25 g of p-toluidine (purchased), 160 ml of methanol, 11 g of benzoic acid,6 g of polyethylene glycol,Slowly heated to 60 ° C, the slow addition of zinc powder 5g,The temperature at 70 ° C for 2 hours, and then heated to 90 ° C for 8 hours, then continue to constant temperature to 110 ° C for 6 hours,Continue heating to 116 ° C for 3 hours.After completion of the reaction, the temperature was lowered to 60 ° C. After passing the air, the intermediate was rapidly oxidized and filtered. The filter cake was washed successively with methanol and hot water, and 50 g of solvent violet 13 was obtained. The purity was 93%, the yield was 84.7%, DC was -0.5, DH was -0.3 and the intensity was 99.50
	With acetic acid
	With boric acid; sodium hydroxide In water at 115℃; Autoclave;	1-3 Example 1: Put 120ml water, 10g solid sodium hydroxide, 30g 1,4-dihydroxyanthraquinone, 4.6g 1,4-dihydroxyanthraquinone leuco in a 500ml autoclave, 7.2g p-toluidine, 2g boric acid, 0.5g of phase transfer catalyst, after stirring for 0.5h, the temperature is slowly raised to 115°C after sealing, after 3h, sampling is followed for detection, and the temperature is stopped after being kept for 6.5h. At this time, the content of 1,4-di-p-tolueneaminoanthraquinone is 0.67%, and the main content of the product is 53.8%. Cool down to 80, release the pressure, filter at this temperature, Then add 20ml of 70 hot water to wash, after finishing collecting the mother liquor and this washing water, The filter cake was continuously washed with water until it was neutral and then dried to obtain 24.1 g of a finished product of solvent violet 13 with a main content of 97.83%. Put the last batch of mother liquor + first wash water into a 500ml autoclave at once, 1,4-dihydroxyanthraquinone 14g, 1,4-dihydroxyanthraquinone leuco 4.6g, flake base 2g, and p-toluidine 7.2g. 0.2g of boric acid, 0.05g of phase transfer catalyst. After stirring for 0.5h, the temperature is slowly raised to 115 in a sealed seal. After 3h of heat preservation, the tracking detection starts, and the temperature is stopped at 6h. At this time, the content of 1,4-di-p-tolylaminoanthraquinone is 0.58 %, the main content of the product is 57.2%, and the temperature is reduced to 80°C,Relieve the pressure, filter at this temperature, then add 20ml of 70 hot water to wash, After the mother liquor and the washing water were collected, the filter cake was washed until it was neutral and dried to obtain 24.9 g of the finished product of purple 13 with a main content of 98.44% and a single batch yield of 97.3%. Comparing the product with Solvent Violet 13 standard sample, DE is 0.95, DC is 0.29, DC is 0.88, and intensity is 100.15. After continuous application of this series of batches, the main content is stable at 96.8% to 98.5%, and the total yield is 95.33%.

	Stage #1: 1,4-dihydroxy-9,10-anthracenedione; <i>p</i>-toluidine In butan-1-ol for 0.116667h; Stage #2: With hydrogenchloride; boric acid In butan-1-ol at 100 - 120℃; for 5h;	1-3; 1-8 (1) Condensation Inhale butanol, 1.4-dihydroxyanthraquinone, and p-toluidine into the condensation reaction kettle at a stirring speed of 55r/min, stirring time 7min, then add hydrochloric acid, boric acid and catalyst, stirring speed 85r/min, stirring time 7min, reaction kettle Adjust the internal slightly positive pressure to 0.04MPa, increase the temperature to 100-120°C, keep it for 5 hours (the insulation stage is divided into three stages, first increase the temperature to 100, keep it for 1 hour, then increase the temperature to 105, keep it for 1 hour, then increase the temperature To 120°C, keep for 3 hours), make the condensation reaction of 1.4-dihydroxyanthraquinone and p-toluidine to the end;(2) Filter press, water washingAfter the condensation reaction is completed, the materials in the reactor are cooled to 35°C for plate-and-frame pressure filtration, and the solid-liquid separation of the materials in the reaction kettle is carried out. After pressure filtration, the solid materials are washed with 80°C water to neutrality, and purple is obtained. B crude product.(3) Refined and washedPut the crude purple B product and methanol into the refining kettle, raise the temperature to 60°C, keep it for 2 hours, and perform pressure filtration to obtain a filter cake, and the filter cake is washed with water at 80°C until it is neutral.(4) Drying and mixingStep (3) The washed product contains a small amount of water, and the product is dried in a vacuum drying oven to obtain the plastic colorant violet B
	In acetonitrile for 16h; Reflux;	2.3. Preparation method and characterization of 1-hydroxy-4-(pentylamino)anthracene-9,10-dione (2b) General procedure: A mixture of quinizarin (1) and amyl amine were dissolved inacetonitrile (ACN) and refluxed. After 15 h, the acetonitrile solvent wasevaporated under reduced pressure. In column chromatography thepure compound (2b) was eluted in ethyl acetate: n-hexane (1:4 v/v). Redsolid; Yield: 48% (3.09 g),

Reference： [1]Current Patent Assignee: JIANGSU DAOBO CHEMICAL - CN105237417, 2016, A Location in patent: Paragraph 0059-0060
[2]Current Patent Assignee: I.G. FARBENINDUSTRIE AG (historic) - DE569069, 1931, C [Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 19, p. 1956][Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 19, p. 1956]
[3]Current Patent Assignee: JIANGSU DAOBO CHEMICAL - CN111675917, 2020, A Location in patent: Paragraph 0026-0037
[4]- CN112322067, 2021, A Location in patent: Paragraph 0022-0080
[5]Ko, Eun Hee; Lee, In Yeol; Oh, Hyeon; Park, Si Hyeong; Penthala, Raju; Son, Young-A [Dyes and Pigments, 2022, vol. 198]

13
[ 81-64-1 ]
[ 106-49-0 ]
[ 128-80-3 ]

Yield	Reaction Conditions	Operation in experiment
97%	With leucoquinizarin; boric acid; sodium hydrogensulfite; In ethanol; benzene; at 62 - 66℃; for 12.0h;	With a mechanical stir,Thermometer in a 500 mL four-necked flask,120 g of ethanol, 60 g of benzene,Boric acid 2 g,1,4-dihydroxyanthraquinone 40 g,Sodium bisulfite 2 g,1,4-dihydroxyanthraquinone, 8g,After stirring, 24 g of p-toluidine was added,Heating to 64 ± 2 for dehydration reaction,Reaction time of 12 hours.After completion of the reaction, the temperature was lowered to 20 C,Filtered, washed and dried to give the desired product 82.32 g solvent green 3,Purity of 98.5%,The yield was 97% (based on the sum of 1,4-dihydroxyanthraquinone and 1,4-dihydroxyanthraquinone)Shade (DC0.0, DH0.2, intensity 100.0), the filter value of 0.02.
95.9%	With 1-butyl-3-ethyl-1H-imidazolium tetrafluoroborate; at 85 - 125℃;Green chemistry; Large scale;	General procedure: (b) heating the ionic liquid to 85 C,900 kg of 1,4-dihydroxyanthraquinone was added to the ionic liquid,300 kg of 1,4-dihydroxyanthraquinone leuco, 1800 kg of p-methylaniline,The temperature was raised to 125 C with stirring to carry out the condensation reaction. The end point of the reaction was determined by HPLC.Obtaining a first mixed solution;(c) The first mixed solution is cooled to 45 C and suction filtered to obtain a filter cake and a filtrate. The filter cake is washed with 600 kg of hot water at 85 C to obtain a foaming solution. The foaming solution and the filtrate are combined and distilled. A second mixed solution is obtained; the washed filter cake is post-processed, and the filter cake is washed with hot water at 90 C to neutrality, dried, pulverized, and packaged to obtain 2000 kg of solvent green 3. The yield is 95.7% HPLC content was 98.82%, ? E 0.273, ? C 0.15 was bright, and the pressure value was 0.17.

Reference： [1]Patent: CN106675080,2017,A .Location in patent: Paragraph 0025; 0026; 0027; 0028; 0029; 0030; 0031; 0032
[2]Patent: CN110615741,2019,A .Location in patent: Paragraph 0020; 0029; 0032-0053
[3]Grundlegende Operationen der Farbenchemie, 5. Aufl. <Wien 1943>, S. 300,
[4]Fiat Final Report Nr. 1313, Bd. II <London 1948>, S. 215,
[5]Chemisches Zentralblatt,1926,vol. 97,p. 1188
[6]Patent: DE86150,
Fortschr. Teerfarbenfabr. Verw. Industriezweige,vol. 4,p. 310
[7]Patent: DE462352,
Fortschr. Teerfarbenfabr. Verw. Industriezweige,vol. 16,p. 1223

14
[ 81-64-1 ]
[ 80-48-8 ]
[ 6119-74-0 ]

Yield	Reaction Conditions	Operation in experiment
81.3%	With potassium hydroxide; In tetrahydrofuran; for 24h;Reflux;	In a 500 mL round bottom flask, 1,4-dihydroxyanthraquinone (24.0 g, 100 mmol), KOH (14.0 g, 250 mmol), methyl p-toluenesulfonate (39.1 g, 210 mmol) and THF (300 mL) were added. The reaction mixture was stirred at reflux for 24 hours. The reaction mixture was then poured into 500 mL water, and the precipitate was filtrated as the crude product which was recrystallized with CH3CN to give 21.8 g (81.3% yield) of 1,4-dimethoxyanthraquinone as an orange solid. 1H NMR spectrum of 1,4-dimethoxyanthraquinone is shown in Fig. S1. 1H NMR (400 MHz, CDCl3, 298 K) delta (ppm): 8.16 (s, 2H ), 7.17 (s, 2H), 7.34 (s, 2H), 4.00 (s, 2H); 13C NMR spectrum of 1,4-dimethoxyanthraquinone is shown in Fig. S2. 13C NMR (100 MHz, CDCl3, 298 K) delta (ppm): 183.5, 154.1, 134.2, 133.3, 126.4, 123.0, 120.2, 57.0.

Reference： [1]Journal of the Chemical Society. Perkin transactions I,1983,p. 1439 - 1441
[2]Bulletin of the Chemical Society of Japan,2004,vol. 77,p. 1385 - 1393
[3]Tetrahedron Letters,2018,vol. 59,p. 3477 - 3480
[4]Svensk Kemisk Tidskrift,1938,vol. 50,p. 274,276
[5]Svensk Kemisk Tidskrift,1938,vol. 50,p. 274,276
[6]Justus Liebigs Annalen der Chemie,1928,vol. 462,p. 88
[7]Journal of Organic Chemistry,1974,vol. 39,p. 770 - 774
[8]Journal of the Chemical Society. Chemical communications,1983,p. 89 - 90

15
[ 81-64-1 ]
[ 74-89-5 ]
[ 2475-44-7 ]

Reference： [1]Patent: US2128307,1936,
[2]Patent: US2183652,1938,

16
[ 81-64-1 ]
[ 17648-03-2 ]

Yield	Reaction Conditions	Operation in experiment
96.1%	Stage #1: 1,4-dihydroxy-9,10-anthracenedione With sodium carbonate In water at 85℃; Inert atmosphere; Stage #2: With sodium dithionite In water Inert atmosphere;	2.1 2.2.1 Synthesis of 1,4-bis((4-aminophenyl)amino)anthrancene-9,10-dione (3) A mixture of 2.48 g 1,4-dihydroxyanthraquinone (0.01 mol, 97%), 2.33 g sodium carbonate (0.022 mol) and 50 mL water was heated at 85 °C under nitrogen protection and then 4.26 g (0.022 mol, 90%) of sodium hydrosulfite was added. Thin layer chromatography (TLC) was used to monitor the completion of the reaction (mobile phase: PhMe:EtOAc, 14:3, v/v, Rf = 0.81). After stirring for 2 h, the reaction mixture was filtrated and washed with 2 * 500 mL of hot water (40-50 °C). The brown powder was dried in vacuum and 1,4-dihydroxyanthraquinone Leuco product was obtained (Yield: 96.1%).
93%	With sodium disulfite; potassium carbonate
78%	With acetic acid; aluminium In ethanol; water at 90℃; for 11h;

	With sodium dithionite; sodium carbonate
	With zinc In acetic acid at 90 - 100℃;
	With sodium dithionite
	With sodium hydroxide; sodium dithionite In methanol for 0.166667h;
	With hydrogenchloride; tin(ll) chloride
	Multi-step reaction with 3 steps 1: water / anschliessendes Behandeln mit Ammoniumperoxodisulfat 2: aqueous sulfuric acid / 150 °C 3: Na₂CO₃; Na₂S₂O₄; NaOH; water
	Multi-step reaction with 4 steps 1: water / anschliessendes Behandeln mit Ammoniumperoxodisulfat 2: sulfuric acid; boric acid / 140 °C 3: aqueous sulfuric acid / 60 °C 4: Na₂CO₃; Na₂S₂O₄; NaOH; water
	With sodium dithionite; sodium hydroxide In water

Reference： [1]Shan, Bin; Tong, Xing; Xiong, Wei; Qiu, Wenzhu; Tang, Bingtao; Lu, Rongwen; Ma, Wei; Luo, Yi; Zhang, Shufen [Dyes and Pigments, 2015, vol. 123, p. 44 - 54]
[2]Zagotto; Supino; Favini; Moro; Palumbo [Il Farmaco, 2000, vol. 55, # 1, p. 1 - 5]
[3]Wang, Chunyan; Wan, Jieping; Zheng, Zhiguo; Pan, Yuanjiang [Tetrahedron, 2007, vol. 63, # 23, p. 5071 - 5075]
[4]Clar,E.; McAndrew,B.A. [Tetrahedron, 1972, vol. 28, p. 1237 - 1240]
[5]Laatsch [Liebigs Annalen der Chemie, 1980, vol. NO. 5, # 5, p. 814 - 818]
[6]Heyer, Thomas; Niclas, Hans-Joachim; Dietzel, Stephan [Zeitschrift fur Chemie, 1989, vol. 29, # 4, p. 139 - 140]
[7]Bingham, Steve J.; Tyman, John H. P.; Malik, K. M. A.; Hibbs, David E.; Hursthouse, Michael B. [Journal of Chemical Research, Miniprint, 1998, # 9, p. 2465 - 2496]
[8]Maskey, Rajendra P.; Helmke, Elisabeth; Fiebig, Heinz-Herbert; Laatsch, Hartmut [Journal of Antibiotics, 2002, vol. 55, # 12, p. 1031 - 1035]
[9]Marschalk [Bulletin de la Societe Chimique de France, 1935, vol. <5> 2, p. 1809,1819]
[10]Marschalk [Bulletin de la Societe Chimique de France, 1935, vol. <5> 2, p. 1809,1819]
[11]Correa, Tais Arthur; Alves, Caio C. S.; Castro, Sandra B. R.; Oliveira, Erick E.; Franco, Lucas S.; Ferreira, Ana P.; De Almeida, Mauro V. [Chemical Biology and Drug Design, 2013, vol. 82, # 4, p. 463 - 467]

17
[ 81-64-1 ]
[ 476-60-8 ]
[ 17648-03-2 ]

Reference： [1]Journal of Applied Spectroscopy,1990,vol. 53,p. 835 - 840
Zhurnal Prikladnoi Spektroskopii,1990,vol. 53,p. 242 - 247

18
[ 84-65-1 ]
[ 605-32-3 ]
[ 90-44-8 ]
[ 129-43-1 ]
[ 81-64-1 ]
[ 72-48-0 ]
[ 434-84-4 ]

Reference： [1]Canadian Journal of Chemistry,1983,vol. 61,p. 1965 - 1969

19
[ 84-65-1 ]
[ 605-32-3 ]
[ 129-43-1 ]
[ 81-64-1 ]

Reference： [1]Journal of Organic Chemistry USSR (English Translation),1982,vol. 18,p. 1666 - 1673
Zhurnal Organicheskoi Khimii,1982,vol. 18,p. 1904 - 1912
[2]Journal of Organic Chemistry USSR (English Translation),1982,vol. 18,p. 1666 - 1673
Zhurnal Organicheskoi Khimii,1982,vol. 18,p. 1904 - 1912

20
[ 84-65-1 ]
[ 605-32-3 ]
[ 81-64-1 ]

Reference： [1]Journal of Organic Chemistry USSR (English Translation),1982,vol. 18,p. 1666 - 1673
Zhurnal Organicheskoi Khimii,1982,vol. 18,p. 1904 - 1912

21
[ 81-64-1 ]
[ 98-59-9 ]
[ 96701-06-3 ]

Yield	Reaction Conditions	Operation in experiment
94%	With triethylamine In acetonitrile for 2h; Reflux;	1.1 1.1 Synthesis of the first intermediate (240 g / mol, 0.0416 mol) of 1,4-dihydroxyanthraquinone dissolved in 200 mL of acetonitrile was heated to reflux. To the solution was added 30 mL (101 g / mol, 0.2 mol) of triethylamine and 19.2 g (190 g / mol, 0.1 mol) of p-toluenesulfonyl chloride. The reaction was for 2h. After the reaction was finished, the reaction solution was poured into 300 mL of water to precipitate a brown product obtained as the first intermediate. The yield was 94%.
90%	With N-ethyl-N,N-diisopropylamine In acetonitrile for 3h; Heating;
90.4%	With triethylamine Heating; a) CH₃CN, 3 h, b) CH₃CN, CHCl₃, 1 h;

87%	With triethylamine In acetonitrile for 5h; Heating;
86%	With triethylamine In acetonitrile for 5h; Reflux;	2.4. Synthetic procedure for the synthesis of 9,10-dioxo-9,10-dihydroanthracene-1,4-diyl bis(4-methylbenzenesulfonate) (V) A solution of 1,4-dihydroxyanthracene-9,10-dione (III) (10 g,41.66 mmol) in acetonitrile (300 mL) was treated with Et3N (30 mL,214 mmol) followed by p-toluene sulfonyl chloride (IV) (19.2 g,100 mmol), and the reaction mixture was stirred at reflux temperature for 5 h. After completion of the reaction, acetonitrile was removed by a rotary evaporator, and the resulting crude material was dissolved inDCM (500 mL). This mixture was washed with water (2×300 mL), and the organic layer was dried over Na2SO4 and filtered. The resulting solution was concentrated to give (V) a yellow brown solid. This crude material was triturated with diethyl ether and n-hexane to afford 9,10-dioxo-9,10-dihydroanthracene-1,4-diyl bis(4-methylbenzenesulfonate)(V) as a bright yellow solid. Yield: 86% (19.6 g); 1H NMR (CDCl3,600 MHz): δ 8.05 (dd, J=5.6, 4.3 Hz, 2H), 7.89-7.84 (m, 4H), 7.75(dd, J = 5.6, 3.3 Hz, 2H), 7.52 (s, 2H), 7.37-7.31 (m, 4H); ESI-MS: 549[M+H]+.
78%	With triethylamine In tetrachloromethane; dichloromethane	I EXAMPLE I EXAMPLE I For preparation of 1,4-ditosylanthraquinone, to quinizarin (10.0 g, 41.7 mmole, Aldrich Chem. Co.) dissolved in methylene chloride (400 ml) was added triethylamine (24 ml, 170 mmole) and p-toluenesulfonyl chloride (16 g, 84 mmole). The solution was stirred for 24 hours at room temperature, washed with water and dried over anhydrous magnesium sulfate. The course of the reaction could be followed by TLC (silica gel, CH2 Cl2). The methylene chloride was evaporated and the residue stirred with carbon tetrachloride (300 ml) at room temperature for 3 hours. Filtration of the slurry gave a bright yellow solid. The dried yellow solid (17.8 g) represented a yield of 78% and had m.p. 221°-225° C. (d). Material recrystallized from chloroform-petroleum ether had m.p. 225°-226° C. (d). Mass spectrum, m/e 548 (M+), 394 (M-C7 H7 SO2 +H), 239 (M-2C7 H7 SO2 +H), 155 (C 7 H7 SO2), 91 (C7 H7); 1 H-NMR (CD2 Cl2) δ8.02-7.94 (m, 2H), 7.91-7.69 (m, 6H), 7.45 (s, 2H), 7.33-7.24 (m, 4H), 2.35 (s, 6H); IR (Nujol) 1335 cm-1 1310 (asymmetric SO2 stretch), 1175 cm-1, 1190 (symmetric SO2 stretch), 920 cm-1, 895, 860, 810, 795, 780, 745, (S--O--C stretch); UV/VIS max (CH2 Cl2) 331 nm (ε4820). Anal. Calcd. for C28 H20 S2 O8: C,61.31; H, 3.65; S, 11.68. Found: C, 61.10; H, 3.81; S, 11.54.
	With triethylamine In dichloromethane for 6h; Inert atmosphere; Reflux;	General procedure for the synthesis of anthraquinone derivatives. General procedure: 1, 4-Hydroxy anthraquinone (2.41 g, 10.00 mmol) was dissolved in 10 mL drydichloromethane under nitrogen and then triethylamine (2.05 g, 23.0 mmol) was added. The reaction mixture was refluxed, 2,4-diamino toluene hydrochloride (3.83 g, 20.1 mM) was added and stirred for 6 h. After cooling down to room temperature (RT), the excess p-tosyl chloride was successfully removed by sequentially washing with 2 volumes of 3 N HCl and water and then extracted 3 times each with 2 volumes of dichloromethane (CH2Cl2). The combined organic layers were dried over anhydrous sodium sulfate and the solvent evaporated to dryness. The residue was dissolved in a minimum amount of CH2Cl2 and methanol was added to give compound 1 as a yellow solid as described in the previous report, 1H of 1,4-bis(tosyloxy)anthraquinone were recorded in CDCl3 solution on a Varian Mercury Plus 400 spectrometer.
4.215 g	With triethylamine In acetonitrile Reflux;	3.4. General procedure for the tosylation of 1,4-dihydroxy-9,10-anthraquinone(10 ) and 1,4-dihydroxy-2-alkyl-9,10-anthraquinones (2a' -c’)(reaction IIb) General procedure: anthraquinone(1) and its 2-alkyl derivatives (2a-2c), tosylation of the 1,4-dihydroxy-9,10-anthraquinone counterparts (1, 2a-2c' ) did neitherrequire a phase catalyst nor column chromatography to obtain 1H NMRpure compounds. Typically, 1,4-dihydroxy-9,10-anthraquinone (1') or1,4-dihydroxy-2-alkyl-9,10-anthraquinone (2a-c’) (1 mmol) was dissolvedin acetonitrile (ACN) (9 mL) that contained triethylamine (Et3N)(1.5 mL, 11.1 mmol). After adding p-toluenesulfonyl chloride (TsCl)(2.5 mmol) the mixture was refluxed under stirring for 5h (1' ) or overnight(2a-c’). Monitoring of the reaction was accomplished by TLC (SiO2, CH2Cl2). After evaporation of the solvent, the solid product wasre-dissolved in dichloromethane. The obtained organic phase waswashed with deionized water several times and dried over anhydrousNa2SO4. Following removal of solvent, the obtained product wasrecrystallized (CHCl3/hexane), washed with hexane and dried.
	With triethylamine In acetonitrile for 5h; Reflux;	1 Preparation of compound a 1,4-dihydroxyanthracene-9,10-dione (1,4-dihydroxyanthracene-9,10-dione, 10 g, 41.66 mmol) was dissolved in acetonitrile (300 mL), and then Et3N (30 mL, 214 mmol) and p-toluene sulfonyl chloride (19.2 g, 100 mmol) were added, followed by reflux stirring for 5 hours. After completion of the reaction, acetonitrile was removed with a rotary evaporator, and the resulting crude product was dissolved in DCM (Dichloromethane, 500 mL) and washed with water (2 × 300 mL). The obtained organic layer was dried over anhydrous Na2SO4, and then the filtrate obtained by filtration was concentrated to obtain a yellow-brown solid. The obtained solid was triturated with diethyl ether and n-hexane as a light yellow solid. 9,10-dioxo-9,10-dihydroanthracene-1,4-diyl bis(4-methylbenzenesulfonate) (Compound a) was obtained.

Reference： [1]Current Patent Assignee: SHENZHEN GUOHUA PHOTOELECTRIC RESEARCH INSTITUTE; SHENZHEN GUOHUA PHOTOELECTRIC TECHNOLOGY CO LTD - CN105670332, 2016, A Location in patent: Paragraph 0036; 0037; 0038
[2]Showalter, H.D. Hollis; Berman, Ellen M.; Johnson, Judith L.; Atwood, Jerry L.; Hunter, William E. [Tetrahedron Letters, 1985, vol. 26, # 2, p. 157 - 160]
[3]Sokolyuk, N. T.; Pisulina, L. P.; Kozhevnikova, E. I. [Journal of Organic Chemistry USSR (English Translation), 1992, vol. 28, # 10.2, p. 1761 - 1768][Zhurnal Organicheskoi Khimii, 1992, vol. 28, # 10, p. 2193 - 2200]
[4]Zielske, Alfred G. [Journal of Organic Chemistry, 1987, vol. 52, # 7, p. 1305 - 1309]
[5]Penthala, Raju; Kumar, Rangaraju Satish; Heo, Gisu; Kim, Hyorim; Lee, In Yeol; Ko, Eun Hee; Son, Young-A. [Dyes and Pigments, 2019, vol. 166, p. 330 - 339]
[6]Current Patent Assignee: CLOROX CO - US4661293, 1987, A
[7]Sangthong, Supranee; Ha, Helen; Teerawattananon, Thapong; Ngamrojanavanich, Nattaya; Neamati, Nouri; Muangsin, Nongnuj [Bioorganic and Medicinal Chemistry Letters, 2013, vol. 23, # 22, p. 6156 - 6160]
[8]Jaxel, Julien; Amer, Hassan; Bacher, Markus; Roller, Alexander; Guggenberger, Matthias; Zwirchmayr, Nele Sophie; Hansmann, Christian; Liebner, Falk [Dyes and Pigments, 2020, vol. 173]
[9]Current Patent Assignee: CHUNGNAM NATIONAL UNIVERSITY - KR2020/112124, 2020, A Location in patent: Paragraph 0108-0112

22
[ 81-64-1 ]
[ 77-78-1 ]
[ 6119-74-0 ]

Yield	Reaction Conditions	Operation in experiment
99%	With sodium hydride In tetrahydrofuran for 480h; Ambient temperature;
96%	With potassium carbonate In acetone for 4h; Reflux;	3.3. Methylation General procedure: A mixture of 1 (1 equiv.), K2CO3 (11 equiv.) and (CH3)2SO4 (14 equiv.) in acetone (5 mL) was refluxed for 3 h. The reaction mixture was added to 25 mL of 2 M HCl and extracted with EtOAc (3 × 25 mL). The combined organic layers were dried, filtered and evaporated under vacuum. The crude product was purified by column chromatography (CH2Cl2-petroleum ether, 4:1) to produce compounds 4 and 5.
95%	With potassium carbonate In acetone for 72h; Heating;

93%	With potassium carbonate In acetone for 24h; Heating;
74%	With potassium carbonate In butanone for 18h; Heating;
	With sodium hydroxide 1.) DMF, overnight, 2.) DMF, 60 deg C, 2 h; Yield given. Multistep reaction;
	With potassium carbonate In acetone for 24h;
	With potassium carbonate In acetone
	With potassium carbonate In butanone for 18h; Reflux;

Reference： [1]Quast, Helmut; Fuchsbauer, Hans-Lothar [Chemische Berichte, 1986, vol. 119, # 3, p. 1016 - 1038]
[2]Nor, Siti Mariam Mohd; Sukari, Mohd Aspollah Hj Md; Azziz, Saripah Salbiah Syed Abdul; Fah, Wong Chee; Alimon, Hasimah; Juhan, Siti Fadilah [Molecules, 2013, vol. 18, # 7, p. 8046 - 8062]
[3]Winters; Sercel; Showalter [Synthesis, 1988, # 9, p. 712 - 714]
[4]Ayyangar, N R; Argade, A B; Mehendale, A R; Deshpande, V H [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1991, vol. 30, # 4, p. 377 - 384]
[5]Krapcho; Shaw; Landi Jr.; Phinney [Journal of Organic Chemistry, 1984, vol. 49, # 26, p. 5253 - 5255]
[6]Hanhela, Peter J.; Paul, Brenton D. [Australian Journal of Chemistry, 1981, vol. 34, # 8, p. 1701 - 1717]
[7]Sharghi, Hashem; Tamaddon, Fatemeh [Tetrahedron, 1996, vol. 52, # 43, p. 13623 - 13640]
[8]Lu, Lingang; Chen, Qiyin; Zhu, Xiaozhang; Chen, Chuanfeng [Synthesis, 2003, # 16, p. 2464 - 2466]
[9]Correa, Tais Arthur; Alves, Caio C. S.; Castro, Sandra B. R.; Oliveira, Erick E.; Franco, Lucas S.; Ferreira, Ana P.; De Almeida, Mauro V. [Chemical Biology and Drug Design, 2013, vol. 82, # 4, p. 463 - 467]

23
[ 81-64-1 ]
[ 74-88-4 ]
[ 7336-64-3 ]

Yield	Reaction Conditions	Operation in experiment
63%	With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 12h;
63%	With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 12h; Inert atmosphere;	Synthesis of 1-hydroxy-4-methoxyanthraquinone (1a): To a stirred suspension of 1,4-dihydroanthraquinone (3.00 g, 12.5 mmol) and K2CO3 (2.45 g, 25 mmol) in 100 mL DMF, a solution of methyl iodide (1.17 mL, 18.75 mmol) in 10 mL DMF was added dropwise at room temperature over a period of 10 min. The resulting mixture was stirred at room temperature for 12 h and then 10 % aqueous HCl was added in portion to quench the reaction at pH to 5. The aqueous phase was exacted with CH2Cl2 (2 50 mL), and the extract was washed with 30 mL of saturated aqueous NaCl solution, dried over anhydrous MgSO4, filtered, and all the volatiles were removed under reduced pressure. The residue was purified by flash silica gel colum chromatography with petroleum ether (60-90 °C)/ethyl acetate, v/v 2:1) as the eluent to give 1a as a brick-red solid (2.00 g, 63 %).
	With silver(l) oxide In chloroform

Reference： [1]Gao, Liming; Guan, Jing; Lyu, Lili; Ma, Mingliang; Shan, Bin; Tan, Weiqiang; Xia, Yan; Yang, Qipeng; Zhan, Xiuzhi; Zheng, Jifang [Journal of Heterocyclic Chemistry, 2020]
[2]Tan, Weiqiang; Zheng, Jifang; Chen, Le; Chai, Huining; Guan, Jing [Tetrahedron, 2021, vol. 89]
[3]Cameron, Donald W.; Feutrill, Geoffrey I.; McKay, Peter G. [Australian Journal of Chemistry, 1982, vol. 35, # 10, p. 2095 - 2109]

24
[ 59637-76-2 ]
[ 476-60-8 ]
[ 81-64-1 ]

Reference： [1]Journal of the Chemical Society - Faraday Transactions,1996,vol. 92,p. 4965 - 4968

25
[ 81-64-1 ]
[ 476-60-8 ]

Yield	Reaction Conditions	Operation in experiment
92.7%		In a 500ml high pressure reactor, 1,4-dihydroxy anthraquinone sequentially 100g, methanol 380ml, boric acid catalyst 10g, after stirring at room temperature for 5 minutes, replaced with nitrogen 5 times, at the same time, observe whether the autoclave is leaking. Warming up, hydrogen intake valve opening, The reaction temperature is at 65 C. the pressure in the kettle was kept at 0.45 MPa for 5 h. adjust the hydrogen intake valve, Keep the pressure in the kettle up to 0.79 MPa for 1 h.Cool down to 40 C, replaced with nitrogen three times, discharge filtration, After the reaction is over, filtration, washing, drying gave 93.45 g of the desired product. The yield was 92.7% and the purity was 95.60%.

Reference： [1]Patent: CN108440250,2018,A .Location in patent: Paragraph 0015-0020
[2]Tetrahedron,2008,vol. 64,p. 3168 - 3175
[3]Pharmaceutical Sciences,1996,vol. 2,p. 49 - 53
[4]Pharmacy and Pharmacology Communications,1999,vol. 5,p. 669 - 671

26
[ 7664-93-9 ]
[ 13460-50-9 ]
[ 84-65-1 ]
[ 81-54-9 ]
[ 81-64-1 ]

Reference： [1]Patent: DE81960,
Fortschr. Teerfarbenfabr. Verw. Industriezweige,vol. 4,p. 274

27
[ 85-44-9 ]
[ 7664-93-9 ]
[ 106-48-9 ]
[ 81-54-9 ]
[ 81-64-1 ]

Reference： [1]Chemische Berichte,1875,vol. 8,p. 152

28
[ 7664-93-9 ]
[ 84-65-1 ]
ammonium persulfate (6-7 parts ) [ No CAS ]
[ 81-54-9 ]
[ 81-64-1 ]
[ 72-48-0 ]

Reference： [1]Journal fur praktische Chemie (Leipzig 1954),1896,vol. <2>54,p. 88,90
Frdl.,vol. 4,p. 278,279

29
[ 81-64-1 ]
[ 17648-03-2 ]
[ 13460-50-9 ]
[ 106-49-0 ]
[ 128-80-3 ]

Reference： [1]Chemisches Zentralblatt,1904,p. II, 339
[2]Patent: DE91150,
Fortschr. Teerfarbenfabr. Verw. Industriezweige,vol. 4,p. 316

30
[ 605-32-3 ]
[ 7664-93-9 ]
[ 13460-50-9 ]
[ 7782-77-6 ]
[ 81-64-1 ]

Reference： [1]Patent: DE86630,
Fortschr. Teerfarbenfabr. Verw. Industriezweige,vol. 4,p. 301

31
[ 81-64-1 ]
[ 7664-93-9 ]
manganese dioxide [ No CAS ]
[ 81-54-9 ]

Reference： [1]Chemische Berichte,1875,vol. 8,p. 152

32
[ 7647-01-0 ]
[ 116-85-8 ]
[ 81-64-1 ]

Reference： [1]Chemische Berichte,1925,vol. 58,p. 762

33
[ 81-64-1 ]
[ 7664-41-7 ]
[ 116-85-8 ]

Reference： [1]Patent: US2128307,1936,

34
[ 81-64-1 ]
[ 106-94-5 ]
[ 847901-15-9 ]

Yield	Reaction Conditions	Operation in experiment
97%	With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 6h; Heating;
89%	With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 6h; Inert atmosphere;	1,4-Dipropoxy-9,10-anthraquinone (1) This compound was synthesized using the procedure reported already. S1 A mixture of 1,4-dihydroxy-9,10-anthraquinone (3) (2.00 g, 8.34 mmol), 1-bromopropane (4 mL, 44.2 mmol), potassium carbonate (3.46 g, 25.0 mmol) in DMF (6 mL) was heated at 100 °C for 6 h under N2. After cooling to room temperature, water (60 mL) was added to the reaction mixture. Then the resulting solid was extracted with chloroform. The organic layer was washed with water and dried over Na2SO4. After evaporation of the solvents under reduced pressure, recrystallization from hexane, gave 1 (2.40 g, 89%) as a yellow solid (immediately after preparation).

Reference： [1]Kitamura, Chitoshi; Hasegawa, Munehiro; Ishikawa, Hiroshi; Fujimoto, Jun; Ouchi, Mikio; Yoneda, Akio [Bulletin of the Chemical Society of Japan, 2004, vol. 77, # 7, p. 1385 - 1393]
[2]Kitamura, Chitoshi; Li, Sining; Takehara, Munenori; Inoue, Yoshinori; Ono, Katsuhiko; Kawase, Takeshi; Fujimoto, Kazuhiro J. [Bulletin of the Chemical Society of Japan, 2015, vol. 88, # 5, p. 713 - 715]

35
[ 110-52-1 ]
[ 81-64-1 ]
1,4-bis-(4-bromobutyloxy)anthracene-9,10-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With potassium carbonate In acetone for 24h; Heating;
81%	With potassium carbonate In acetone for 24h; Heating / reflux;	2 To a solution of 1 ,4-dihydroxy anthraquinone (480 mg, 2 mmol) in acetone (30 mL) were added anhydrous potassium carbonate (1.1 g, 8 mmol) and 1 ,3 dibromobutane (1.29 g, 6 mmol) and the mixture was refluxed for 24 h. The progress of the reaction was monitored by TLC. After completion of the reaction, potassium carbonate was removed by filtration and the solvent was evaporated under reduced pressure to get the crude product. This was further purified by column chromatography (30% EtOAc-hexane) to afford the compound lib as a yellow solid (826mg, 81%). 1H NMR (CDCI3, 200 MHz) 1.25-1.40 (m, 6H), 1.72-2.42 (m, 6H), 2.70-2.8 (m, 4H), 3.15-3.30 (m, 2H), 3.60 (t, 2H, J = 6.20 Hz), 3.95 (s, 3H), 4.20 (t, 2H, J = 4.96 Hz), 4.60-4.75 (m, 1 H), 4.82 (d, 1 H, J=4.33 Hz), 6.78 (s, 1 H), 7.68 (s, 1 H).
81%	With potassium carbonate In acetone for 24h; Heating / reflux;	2 To a solution of 1,4-dihydroxy anthraquinone (480 mg, 2 mmol) in acetone (30 mL) were added anhydrous potassium carbonate (1.1 g, 8 mmol) and 1,3 dibromobutane (1.29 g, 6 mmol) and the mixture was refluxed for 24 h. The progress of the reaction was monitored by TLC. After completion of the reaction, potassium carbonate was removed by filtration and the solvent was evaporated under reduced pressure to get the crude product. This was further purified by column chromatography (30% EtOAc-hexane) to afford the compound lib as a yellow solid (826mg, 81%). 1H NMR (CDCl3, 200 MHz) 1.25-1.40 (m, 6H), 1.72-2.42 (m, 6H), 2.70-2.8 (m, 4H), 3.15-3.30 (m, 2H), 3.60 (t, 2H, J=6.20 Hz), 3.95 (s, 3H), 4.20 (t, 2H, J=4.96 Hz), 4.60-4.75 (m, 1H), 4.82 (d, 1H, J=4.33 Hz), 6.78 (s, 1H), 7.68 (s, 1H).

Reference： [1]Kamal, Ahmed; Ramu; Tekumalla, Venkatesh; Khanna, G.B.Ramesh; Barkume, Madan S.; Juvekar, Aarti S.; Zingde, Surekha M. [Bioorganic and Medicinal Chemistry, 2007, vol. 15, # 22, p. 6868 - 6875]
[2]Current Patent Assignee: COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH (IN) - WO2007/93873, 2007, A1 Location in patent: Page/Page column 13
[3]Current Patent Assignee: COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH (IN) - US2007/259858, 2007, A1 Location in patent: Page/Page column 7

36
[ 111-24-0 ]
[ 81-64-1 ]
1,4-bis-(5-bromopentyloxy)anthracene-9,10-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84%	With potassium carbonate In acetone for 24h; Heating;
84%	With potassium carbonate In acetone for 24h; Heating / reflux;	3 To a solution of 1 ,4-dihydroxy anthraquinone (480 mg, 2 mmol) in acetone (30 mL) were added anhydrous potassium carbonate (1.1 g, 8 mmol) and 1,3 dibromopentane (1.38 mg, 6 mmol) and the mixture was refluxed for 24 h. The progress of the reaction was monitored by TLC. After completion of the reaction, potassium carbonate was removed by filtration and the solvent was evaporated under reduced pressure to get the crude product. This was further purified by column chromatography (30% EtOAc-hexane) to afford the compound Mc as a yellow solid (904 mg, 84%).1H NMR (CDCI3): 5 1.75-2.07 (m, 12H), 3.49 (t, 4H, J = 6.59 Hz), 4.08 (t, 4H, J = 6.13 Hz), 7.25 (s, 2H), 7.69-7.75 (m, 2H), 8.13-8.20 (m, 2H).FABMS: 538 [M]+'
84%	With potassium carbonate In acetone for 24h; Heating / reflux;	3 To a solution of 1,4-dihydroxy anthraquinone (480 mg, 2 mmol) in acetone (30 mL) were added anhydrous potassium carbonate (1.1 g, 8 mmol) and 1,3 dibromopentane (1.38 mg, 6 mmol) and the mixture was refluxed for 24 h. The progress of the reaction was monitored by TLC. After completion of the reaction, potassium carbonate was removed by filtration and the solvent was evaporated under reduced pressure to get the crude product. This was further purified by column chromatography (30% EtOAc-hexane) to afford the compound IIc as a yellow solid (904 mg, 84%). 1H NMR (CDCl3): δ 1.75-2.07 (m, 12H), 3.49 (t, 4H, J=6.59 Hz), 4.08 (t, 4H, J=6.13 Hz), 7.25 (s, 2H), 7.69-7.75 (m, 2H), 8.13-8.20 (m, 2H). FABMS: 538 [M]+

Reference： [1]Kamal, Ahmed; Ramu; Tekumalla, Venkatesh; Khanna, G.B.Ramesh; Barkume, Madan S.; Juvekar, Aarti S.; Zingde, Surekha M. [Bioorganic and Medicinal Chemistry, 2007, vol. 15, # 22, p. 6868 - 6875]
[2]Current Patent Assignee: COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH (IN) - WO2007/93873, 2007, A1 Location in patent: Page/Page column 14-15
[3]Current Patent Assignee: COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH (IN) - US2007/259858, 2007, A1 Location in patent: Page/Page column 7

37
[ 81-64-1 ]
[ 109-64-8 ]
1,4-bis-(3-bromopropyloxy)anthracene-9,10-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	Stage #1: 1,4-dihydroxy-9,10-anthracenedione With potassium carbonate In acetone at 60℃; for 0.5h; Stage #2: 1,3-dibromo-propane In acetone at 60℃; for 72h;
82%	With potassium carbonate In acetone for 24h; Heating;
82%	With potassium carbonate In acetone for 24h; Heating / reflux;	1 To a solution of 1 ,4-dihydroxy anthraquinone (480 mg, 2 mmol) in acetone (30 ml_) were added anhydrous potassium carbonate (1.1 g, 8 mmol) and 1 ,3 dibromopropane (1.21 g, 6 mmol) and the mixture was refluxed for 24 h. The progress of the reaction was monitored by TLC. After completion of the reaction, potassium carbonate was removed by filtration and the solvent was evaporated under reduced pressure to get the crude product. This was further purified by column chromatography (30% EtOAc-hexane) to afford the compound Ha as a yellow solid (791 mg, 82%).1H NMR (CDCI3): δ 2.40-2.52 (m, 4H), 3.85-3.91 (t, 4H, J = 6.51 Hz), 4.22-4.28 (t, 4H, J = 5.53 Hz), 7.34 (s, 2H), 7.71-7.77 (m, 2H), 8.15-8.18 (m, 2H). FABMS: 482 (M+).

82%	With potassium carbonate In acetone for 24h; Heating / reflux;	1 To a solution of 1,4-dihydroxy anthraquinone (480 mg, 2 mmol) in acetone (30 mL) were added anhydrous potassium carbonate (1.1 g, 8 mmol) and 1,3 dibromopropane (1.21 g, 6 mmol) and the mixture was refluxed for 24 h. The progress of the reaction was monitored by TLC. After completion of the reaction, potassium carbonate was removed by filtration and the solvent was evaporated under reduced pressure to get the crude product. This was further purified by column chromatography (30% EtOAc-hexane) to afford the compound IIa as a yellow solid (791 mg, 82%). 1H NMR (CDCl3): δ 2.40-2.52 (m, 4H), 3.85-3.91 (t, 4H, J=6.51 Hz), 4.22-4.28 (t, 4H), J=5.53 Hz), 7.34 (s, 2H), 7.71-7.77 (m, 2H), 8.15-8.18 (m, 2H). FABMS: 482 (M+).
80%	Stage #1: 1,4-dihydroxy-9,10-anthracenedione With potassium carbonate In acetone at 60℃; for 0.5h; Stage #2: 1,3-dibromo-propane In acetone at 60℃; for 72h;	1 A mixture of 1,4-dihydroxyanthraquinone (2.000 g, 8.2 mmol) was addedK2CO3 (6.790 g, 49.2 mmol)Dissolved in acetone solution,The mixture was stirred at 60 ° C for 30 minutes,Followed by dropwise addition to the solution1,3-dibromopropane (15.400 g, 82.0 mmol),Stirring was continued at 60 ° C for 72 hours.After the reaction, the solution was filtered, and the solvent was suspended in vacuo.A brown solid was obtained.The solid was recrystallized from ethyl acetate,An orange needle-shaped solid was obtained. Yield: 2.978 g (80%).

Reference： [1]Liu, Qing-Xiang; Wei, Deng-Che; Zhao, Dong-Xue; Sun, Xiao-Feng; Zhao, Zhi-Xiang; Yan, Jing [New Journal of Chemistry, 2017, vol. 41, # 12, p. 4843 - 4852]
[2]Kamal, Ahmed; Ramu; Tekumalla, Venkatesh; Khanna, G.B.Ramesh; Barkume, Madan S.; Juvekar, Aarti S.; Zingde, Surekha M. [Bioorganic and Medicinal Chemistry, 2007, vol. 15, # 22, p. 6868 - 6875]
[3]Current Patent Assignee: COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH (IN) - WO2007/93873, 2007, A1 Location in patent: Page/Page column 11
[4]Current Patent Assignee: COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH (IN) - US2007/259858, 2007, A1 Location in patent: Page/Page column 6
[5]Current Patent Assignee: TIANJIN UNIVERSITY - CN105541876, 2016, A Location in patent: Paragraph 0024

38
[ 81-64-1 ]
[ 13076-29-4 ]

Yield	Reaction Conditions	Operation in experiment
95%	With hydrogenchloride; sodium borohydrid In methanol	1,4-Dimethoxyanthracene (2). 1,4-Dimethoxyanthracene (2). To a cold (0° C.) methanol (20 mL) solution of 1.00 g (0.0042 mol) of quinizarin under argon was added 0.638 g (0.0168 mol) of sodium borohydride. The resulting mixture was stirred at 0° C. for 1 h. To it, 11 mL of 6 N HCl was added dropwise at 0° C. over a period of 10 min. The precipitated orange solids were collected, washed several times with distilled water, dried under vacuum, and recrystallized from acetone-ether to give 0.83 g (95% yield) of anthracene-1,4-dione17 as yellow crystals, mp 204-206° C. 1H NMR d 8.60 (s, 2 H, C 9,10 Hs), 8.10 (dd, J=6.4, 3.2 Hz, 2 H, C 5,8 Hs), 7.70 (dd, J=6.4, 3.2 Hz, 2 H, C 6,7 Hs), 7.10 (s, 2 H, C 2,3 Hs); 13C NMR d 184.7 (s, C=O), 140.1 (d), 134.8 (s), 130.2 (d), 129.6 (d), 128.9 (d), 128.4 (s).
	Multi-step reaction with 3 steps 1: 83 percent / K₂CO₃ / 1,2-dichloro-benzene / 1 h / Heating 2: 100 percent / NaBH₄ / methanol; tetrahydrofuran / 0.5 h / 0 °C 3: 40 percent / HCl / tetrahydrofuran / 2 h / 40 °C
	Multi-step reaction with 2 steps 1: K₂CO₃ / acetone 2: 62 percent / Zn; glacial acetic acid / 15 h / Heating

Multi-step reaction with 2 steps 1: potassium hydroxide / tetrahydrofuran / 24 h / Reflux 2: zinc; acetic acid / 96 h / Reflux

Reference： [1]Current Patent Assignee: KANSAS STATE UNIVERSITY - US2002/91163, 2002, A1
[2]Kitamura, Chitoshi; Hasegawa, Munehiro; Ishikawa, Hiroshi; Fujimoto, Jun; Ouchi, Mikio; Yoneda, Akio [Bulletin of the Chemical Society of Japan, 2004, vol. 77, # 7, p. 1385 - 1393]
[3]Lu, Lingang; Chen, Qiyin; Zhu, Xiaozhang; Chen, Chuanfeng [Synthesis, 2003, # 16, p. 2464 - 2466]
[4]Shi, Bingbing; Li, Zhengtao; Liu, Yuezhou; Shangguan, Liqing; Zhu, Huangtianzhi; Ju, Huaqiang; Huang, Feihe [Tetrahedron Letters, 2018, vol. 59, # 38, p. 3477 - 3480]

39
[ 81-64-1 ]
<i>O</i>-<4-amino-phenyl>>-triethylene glycol [ No CAS ]
[ 81-54-9 ]

Reference： [1]Journal of Chemical Research, Miniprint,1998,p. 2465 - 2496

40
[ 81-64-1 ]
[ 40498-13-3 ]
[ 106-49-0 ]
C₂₈H₂₄N₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93.1%	Stage #1: 1,4-dihydroxy-9,10-anthracenedione; <i>p</i>-toluidine With boric acid In butan-1-ol for 0.166667h; Heating / reflux; Stage #2: 2,3-dihydro-1,4-dihydroxyanthraquinone In 1-methyl-pyrrolidin-2-one; butan-1-ol for 12h; Heating / reflux;	1 Example 1 [0043] 165 ml of n-butanol are metered into a 500 ml 4-necked flask. With stirring, 50.5 g of p-toluidine, 15.5 g of boric acid and 42 g of 99.5% quinizarine are introduced. The mixture is heated at reflux with a water trap. After 10 minutes of reflux, 7.5 g of 93.5% dihydroquinizarine in solution in 22.5 ml of N-methyl-2-pyrrolidone are added dropwise over the course of 3 hours. After a further 9 hours at reflux the mixture is cooled and filtered and the filter product is washed with 80 ml of hot n-butanol at 60 C., then in portions with 200 ml of hot methanol at 60 C., thereafter with 2000 ml of hot water at 60 C., and is finally dried in vacuo. [0044] Yield: 79 g (93.1% of theory)
93.7%	With boric acid In 1-methyl-pyrrolidin-2-one; butan-1-ol for 5h; Heating / reflux;	2 Example 2 Example 2 [0046] 330 ml of n-butanol and 45 ml of N-methyl-2-pyrrolidone are metered into a 1000 ml sulphation vessel. With stirring, 101 g of p-toluidine, 31 g of boric acid and 84 g of 99.5% quinizarine and 15 g of 93.5% dihydroquinizarine are introduced. The mixture is heated at reflux with a water trap. After 5 hours at reflux the mixture is cooled and filtered and the filter product is washed with 160 ml of hot n-butanol at 60 C., then in portions with 400 ml of hot methanol at 60 C., thereafter with 4000 ml of hot water at 60 C., and finally is dried in vacuo. [0047] Yield: 159 g (93.7% of theory) [0048] In the mass coloration of polystyrene the product gives a very clear bluish green.
93.7%	With boric acid In Caprolactame; butan-1-ol for 5h; Heating / reflux;	3 Example 3 Example 3 [0049] 330 ml of n-butanol are metered into a 1000 ml sulphation vessel. With stirring, 45 g of caprolactam, 101 g of p-toluidine, 31 g of boric acid and 84 g of 99.5% quinizarine and 15 g of 93.5% dihydroquinizarine are introduced. The mixture is heated at reflux with a water trap. After 5 hours at reflux the mixture is cooled and filtered and the filter product is washed with 160 ml of hot n-butanol at 60 C., then in portions with 400 ml of hot methanol at 60 C., thereafter with 4000 ml of hot water at 60 C., and finally is dried in vacuo. [0050] Yield: 159 g (93.7% of theory) [0051] In the mass coloration of polystyrene the product gives a clear bluish green.

90.7%	With boric acid; toluene-4-sulfonic acid In 1-methyl-pyrrolidin-2-one; butan-1-ol for 5h; Heating / reflux;	4 Example 4 Example 4 [0052] 330 ml of n-butanol and 45 ml of N-methyl-2-pyrrolidone are metered into a 1000 ml sulphation vessel. With stirring, 101 g of p-toluidine, 31 g of boric acid, 1 g of p-toluenesulphonlc acid and 84 g of 99.5% quinizarine and 15 g of 93.5% dihydroquinizarine are introduced. The mixture is heated at reflux with a water trap. After 5 hours at reflux the mixture is cooled and filtered and the filter product is washed with 160 ml of hot n-butanol at 60 C., then in portions with 400 ml of hot methanol at 60 C., thereafter with 4000 ml of hot water at 60 C., and finally is dried in vacuo. [0053] Yield: 154 g (90.7% of theory) [0054] In the mass coloration of polystyrene the product gives a clear bluish green.
90.2%	With boric acid In Caprolactame; butan-1-ol for 5h; Heating / reflux;	5 Example 5 Example 5 [0055] 320 ml of n-butanol are metered into a 1000 ml sulphation vessel. With stirring, 80 g of caprolactam, 101 g of p-toluidine, 31 g of boric acid and 84 g of 99.5% quinizarine and 15 g of 93.5% dihydroquinizarine are introduced. The mixture is heated at reflux with a water trap. After 5 hours at reflux the mixture is cooled and filtered and the filter product is washed with 160 ml of hot n-butanol at 60 C., then in portions with 400 ml of hot methanol at 60 C., thereafter with 4000 ml of hot water at 60 C., and finally is dried in vacuo. [0056] Yield: 153 g (90.2% of theory) [0057] In the mass coloration of polystyrene the product gives a very clear bluish green.
89%	With boric acid In Caprolactame; butan-1-ol for 6h; Heating / reflux;	6 Example 6 Example 6 [0058] 240 ml of n-butanol are metered into a 1000 ml sulphation vessel. With stirring, 160 g of caprolactam, 101 g of p-toluidine, 31 g of boric acid and 84 g of 99.5% quinizarine and 15 g of 93.5% dihydroquinizarine are introduced. The mixture is heated at reflux with a water trap. After 6 hours at reflux the mixture is cooled and filtered and the filter product is washed with 160 ml of hot n-butanol at 60 C., then in portions with 400 ml of hot methanol at 60 C., thereafter with 4000 ml of hot water at 60 C., and finally is dried in vacuo. [0059] Yield: 151 g (89.0% of theory) [0060] In the mass coloration of polystyrene the product gives a very clear bluish green.
74.8%	With LACTIC ACID; boric acid In Caprolactame; toluene for 5h; Heating / reflux;	7 Example 7 Example 7 [0061] 240 ml of toluene are metered into a 1000 ml sulphation vessel. With stirring, 360 g of caprolactam, 101 g of p-toluidine, 20 g of boric acid, 10 g of lactic acid and 84 g of 99.5% quinizarine and 15 g of 93.5% dihydroquinizarine are introduced. The mixture is heated at reflux with a water trap. After 5 hours at reflux the mixture is cooled and filtered and the filter product is washed in portions with 400 ml of hot methanol at 60 C., thereafter with 4000 ml of hot water at 60 C., and finally is dried in vacuo. [0062] Yield: 127 g (74.8% of theory) [0063] In the mass coloration of polystyrene the product gives a bluish green.
71.3%	With LACTIC ACID; boric acid In Caprolactame at 110℃; for 5h;	8 Example 8 Example 8 [0064] In a 1000 ml sulphation vessel, 400 g of caprolactam, 101 g of p-toluidine, 20 g of boric acid, 10 g of lactic acid and 84 g of 99.5% quinizarine and 15 g of 93.5% dihydroquinizarine are introduced. The mixture is heated at 110 C. After 5 hours the mixture is cooled and filtered, and the filter product is then washed in portions with 400 ml of hot methanol at 60 C and then with 4000 ml of hot water at 60 C., and finally is dried in vacuo. [0065] Yield: 121 g (71.3% of theory) [0066] In the mass coloration of polystyrene the product gives a bluish green.

Reference： [1]Current Patent Assignee: LANXESS AG - US2003/225294, 2003, A1 Location in patent: Page 3
[2]Current Patent Assignee: LANXESS AG - US2003/225294, 2003, A1 Location in patent: Page 3
[3]Current Patent Assignee: LANXESS AG - US2003/225294, 2003, A1 Location in patent: Page 3
[4]Current Patent Assignee: LANXESS AG - US2003/225294, 2003, A1 Location in patent: Page 3
[5]Current Patent Assignee: LANXESS AG - US2003/225294, 2003, A1 Location in patent: Page 3
[6]Current Patent Assignee: LANXESS AG - US2003/225294, 2003, A1 Location in patent: Page 4
[7]Current Patent Assignee: LANXESS AG - US2003/225294, 2003, A1 Location in patent: Page 4
[8]Current Patent Assignee: LANXESS AG - US2003/225294, 2003, A1 Location in patent: Page 4

41
[ 81-64-1 ]
[ 17648-03-2 ]
[ 52273-77-5 ]
[ 676246-12-1 ]

Yield	Reaction Conditions	Operation in experiment
	boric acid; In methanol; at 66℃; for 16h;Heating / reflux;	In a glass reaction flask are combined 73 grams of sublimed quinizarin (available from Aceto Corp., Lake Success, N.Y.), 49 grams of leucoquinizarin (available from Aceto Corp.), 66 grams of 3-aminobenzene ethanol (available from Frinton Labs, Vineland, N.J.), 31 grams of boric acid (available from Aldrich Chemical Co., Milwaukee, Wis.), and 780 grams of methanol (available from J T Baker, Phillipsburg, N.J.). The materials are mixed and heated until the solvent refluxes at about 66 C. After about 16 hours of reflux, it is believed that the reaction will be complete, having generated an alcohol-substituted colorant of the formula [CHEMMOL-00109] [0194] The reaction mixture is cooled and filtered. The product filter cake is dried in air at ambient temperature. The spectral strength of the alcohol-substituted colorant is determined using a spectrophotographic procedure based on the measurement of the colorant in solution by dissolving the colorant in toluene and measuring the absorbance using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer. The spectral strength of the alcohol-substituted colorant is believed to be measured as about 21,000 mL Absorbance Units per gram at absorption lambdamax.

Reference： [1]Patent: US2004/82801,2004,A1 .Location in patent: Page 33; 34

42
[ 14285-68-8 ]
[ 81-64-1 ]
[ 7128-64-5 ]
[ 918153-35-2 ]

Reference： [1]Inorganic Chemistry,2006,vol. 45,p. 10052 - 10054

43
[ 81-64-1 ]
[ 106-49-0 ]
[ 81-48-1 ]
[ 128-80-3 ]

Yield	Reaction Conditions	Operation in experiment
	With LACTIC ACID; Trimethyl borate; 2,3-dihydro-1,4-dihydroxyanthraquinone; In 4-butanolide; at 100℃; for 13.0h;Product distribution / selectivity;	67.8 g of quinizarin, 4.27 g of dihydroquinizarin (contains 0.28 g of quinizarin), 39.7 g of p-toluedine, 2.52 g of trimethyl borate and 7.50 g of 90% by weight lactic acid were introduced into 120 ml of gamma-butyrolactone under nitrogen. The temperature was raised to 100 C. over 1 h and the mixture was maintained at 100 C. for 12 h, the degree of conversion being policed via thin layer chromatography. The residual level of quinizarin had dropped to below 10% after just 8 h. At that point, the mixture was cooled down to room temperature, filtered off with suction, and the filter residue was washed with 250 ml of hot methanol (at 60 C.) and 11 of hot water (at 80 C.) in portions. Drying at 50 C. under reduced pressure left 91.46 g (92.6% of theory) of a violet crystalline powder of the formula The product contained 5.31% of the compound of the formula and also 0.93% of quinizarin. Heating time: 1 h Condensation time: 12 h
	With LACTIC ACID; 2,3-dihydro-1,4-dihydroxyanthraquinone; boric acid; In 4-butanolide; at 100 - 125℃; for 19.0h;Product distribution / selectivity;	67.8 g of quinizarin, 4.27 g of dihydroquinizarin (contains 0.28 g of quinizarin), 39.7 g of p-toluedine, 1.00 g of boric acid and 7.50 g of 90% by weight lactic acid were introduced into 100 ml of gamma-butyrolactone under nitrogen. The mixture was heated to 100 C. over 1 h and maintained at 100 C. for 8 h. Since a thin layer chromatogram showed that about 30% of the quinizarin had still not reacted, 20 g of p-toluedine were added and stirring was continued at 100 C. for 6 h: remaining quinizarin about 20%. This was followed by heating to 125 C. and stirring at that temperature for a further 4 h. Since the residual level of quinizarin had now dropped to below 10%, the mixture was cooled to room temperature, and filtered with suction, and the filter residue was washed with 250 ml of hot methanol (at 60 C.) and 11 of hot water (at 80 C.) in portions. Drying at 50 C. under reduced pressure left 90.11 g (91.2% of theory) of a violet crystalline powder of the formula of Example 5.The product contained 6.98% of the compound of the formula and also 1.22% of quinizarin. Heating time: 1 h Condensation time: 18 h

Reference： [1]Patent: US2008/139830,2008,A1 .Location in patent: Page/Page column 5
[2]Patent: US2008/139830,2008,A1 .Location in patent: Page/Page column 5-6

44
[ 81-64-1 ]
[ 24544-08-9 ]
[ 32724-62-2 ]

Yield	Reaction Conditions	Operation in experiment
82.0%	With LACTIC ACID; Trimethyl borate; 2,3-dihydro-1,4-dihydroxyanthraquinone; at 115 - 145℃; for 11.5h;	20.35 g of quinizarin, 20.38 g of dihydroquinizarin (contains 0.47 g of quinizarin), 10.8 g of trimethyl borate and 8.71 g of 90% by weight lactic acid were introduced into 159.7 g of <strong>[24544-08-9]2,6-diethyl-<strong>[24544-08-9]4-methylaniline</strong></strong> under nitrogen. The mixture was heated to 115 C. over 1 h, in the course of which the resulting methanol was distilled off. Without delay, the temperature was then raised to 145 C. over 2.5 h, and the mixture was stirred at 145 C. for 8 h, during which resulting water was distilled off. Completeness of reaction was checked via a thin layer chromatogram. The mixture was then cooled down to 125 C. and air was passed into it for 3 h. After cooling to 80 C., 20.6 g of potassium hydroxide powder were added and air was again passed into it at 80 C. for 4 h. 290 ml of methanol were added dropwise in the course of 2 h at 70 C., followed by 1 h of stirring under gentle boiling. Finally, the suspension was cooled down to room temperature, filtered off with suction, washed with 200 ml of cold methanol and then with 11 of hot water (at 80 C.) in portions. Vacuum drying at 80 C. left 72.9 g (82.0% of theory) of a blue crystalline powder of the formula Heating time: 3.5 h Condensation time: 8 h

Reference： [1]Patent: US2008/139830,2008,A1 .Location in patent: Page/Page column 6-7

45
[ 14285-68-8 ]
[ 81-64-1 ]
[ 7128-64-5 ]
C₇₆H₃₃N₄O₂₄Re₄S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In 1,3,5-trimethyl-benzene;Heating / reflux;	Herein we report on a new orthogonal-bonding approach for assembling functional molecules. This approach, which is an offshoot of the directional-bonding approach, involves the simultaneous introduction of a bis(chelating) dianion to coordinate to two equatorial sites of two fac-(CO)3Re cores and a ditopic nitrogen-donor ligand to the remaining orthogonal axial site, leading to the generation of a new, hitherto unexplored class of metallacycles (FIG. 3).2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene (tpbb) and 1,4-dihydroxy-9,10-anthraquinone (H2-dhaq) or 1,2,4-trishydroxy-9,10-anthraquinone (H2-thaq) were chosen for use as basic building units. The presence of two nitrogen donors should permit the tpbb ligand to act as a neutral bifunctional molecular clip. We rationalized that the use of the bischelating ligands H2-dhaq and H2-thaq would result in a macrocycle host with a large internal cavity. Although both ligands are important in dye chemistry, electroluminescent devices, biology, and pharmaceutical chemistry, their use as building units in the construction of supramolecular assemblies has not been previously investigated. The combination of the above-mentioned new building blocks and the novel orthogonal-bonding approach permits the preparation of unique gondola-shaped structures with crown-ether-like recognition sites, highly fluorescent properties, and selective binding capabilities. This approach is so effective that the products can be prepared in near quantitative yield.The assembly of compounds 3 and 4 was achieved by reacting equimolar amounts of Re2(CO)10, tpbb, and H2-dhaq or H2-thaq in refluxing mesitylene. The resulting dark-green products were air and moisture stable and are slightly soluble in polar solvents. The IR spectrum of 3 in acetone exhibited strong bands at 2014 and 1900 cm-1, characteristic of fac-Re(CO)3. The 1H NMR spectrum of 3 showed well-resolved signals for each of the protons. Compared to the free ligands, the signals corresponding to the tpbb protons remained nearly unchanged, while those of the dhaq proton of H2 was shifted upfield by 0.16 ppm after complexation with the Re(I) centers. A similar pattern was observed for 4 with an additional singlet at 10.99 ppm corresponding to the uncoordinated hydroxyl hydrogen (C2-OH) atoms. The ESI-MS spectrum of 3 showed a molecular ion peak at m/z 2418.1.A single-crystal X-ray diffraction analysis shows that compound 3 adopts an unusual gondola-shaped structure (FIG. 4). The structure can be regarded as a special type of grid. The two tpbb ligands serve as molecular clips, utilizing the benzoxazoline N atoms to bridge two doubly bridged dirhenium units. The bishydroxy anthraquinone (dhaq) acts as a doubly bridging unit using the adjacent phenolate and quinone oxygens. Interestingly, the hydrophobic internal cavity of the metallacycle is sufficiently large (size: 5.6 ×7.0 ×17.8 ) to accommodate four MeOH molecules. Compound 4 is isostructural with respect to 3 but contains two additional uncoordinated hydroxyl groups. It is noteworthy that compounds 3 and 4 possess multiple-recognition sites. The arrangement of heteroatoms may be considered as the structural framework of 1,10-dithio-(18crown-6) (see Supporting Information).Compound 3 in CH2Cl2 displayed intense absorption bands in the 230-395 nm region, which are assigned to ?-?* transitions of the dhaq and tpbb (357, 378, 397 nm) ligands, and a weak shoulder at 420 nm, assigned to the MLCT transition (Re?tpbb). In addition, weak absorption bands appeared at 585 and 632 nm, attributed to an intraligand transition of the dhaq unit. Compounds 3 and 4 show a high luminescence at room temperature with a quantum yield of 0.179 for 3 and 0.397 for 4 relative to Ru(bpy)32+. Upon excitation at lambdamax=378 nm, compound 3 emits a set of structured bands centered at 438 nm with a lifetime of 1.4 ns. These emission bands are similar to that of the tpbb ligand. The small Stokes shift and very short lifetime of 3 indicate that the emission originates from the singlet ?-?* excited state. In the solid state, compound 3 exhibits two emission maxima at 448 and 518 nm when excited at 335 nm. The emission band at 448 nm is due to the decay of the ?-?* excited state of tpbb, while the band at 518 nm may be attributed to the decay of the d-?*Re tpbb excited state.

Reference： [1]Patent: US2009/82574,2009,A1 .Location in patent: Page/Page column 10-11

46
[ 81-64-1 ]
[ 106-96-7 ]
[ 1045-75-6 ]

Yield	Reaction Conditions	Operation in experiment
98%	With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 18h;	2.2 Synthesis and characterization of alkyne 1 The treatment of 1,4-dihydroxyanthraquinone (1.0g, 4.16mmol) with propargyl bromide (1.24ml, 8.33mmol) in DMF (15ml) using dried Potassium carbonate (2.87g, 20.76mmol) as base resulted into alkyne 1 upon stirring at room temperature for 18h [30]. Yield: 98%; Colour/Texture: mustard yellow colored solid; M.pt: 160-162°C; MF: C20H12O4; Elem. Anal. Calculated(%): C=75.94, H=3.82, O=20.24, Found(%): C=75.90, H=3.84, O=20.26; IR (neat, cm-1): 3288, 3020, 2160, 2017, 1666, 1599, 1448, 1317, 1271, 1230, 1192, 1037, 961, 642; 1H NMR (500MHz, CDCl3) δ=8.16 (dd, J=5.7, 3.3Hz, 2H), 7.72 (dd, J=5.8, 3.3Hz, 2H), 7.52 (s, 2H), 7.26 (s, 1H), 4.90 (d, J=2.3Hz, 4H), 2.57 (s, 2H). 13C NMR (126MHz, CDCl3) δ=182.99 (s), 152.86 (s), 134.09 (s), 133.52 (s), 126.56 (s), 124.74 (s), 123.74 (s), 78.19 (s), 77.28-76.77 (t), 76.69 (s), 58.28 (s).
98%	With potassium carbonate In N,N-dimethyl-formamide; toluene at 20℃; for 18h;	2.2 Synthesis and characterization of alkyne 1 The treatment of 1,4-dihydroxyanthraquinone (1.0g, 4.16mmol) with propargyl bromide (1.24ml, 8.33mmol) in DMF (15ml) using dried Potassium carbonate (2.87g, 20.76mmol) as base resulted into alkyne 1 upon stirring at room temperature for 18h [30]. Yield: 98%; Colour/Texture: mustard yellow colored solid; M.pt: 160-162°C; MF: C20H12O4; Elem. Anal. Calculated(%): C=75.94, H=3.82, O=20.24, Found(%): C=75.90, H=3.84, O=20.26; IR (neat, cm-1): 3288, 3020, 2160, 2017, 1666, 1599, 1448, 1317, 1271, 1230, 1192, 1037, 961, 642; 1H NMR (500MHz, CDCl3) δ=8.16 (dd, J=5.7, 3.3Hz, 2H), 7.72 (dd, J=5.8, 3.3Hz, 2H), 7.52 (s, 2H), 7.26 (s, 1H), 4.90 (d, J=2.3Hz, 4H), 2.57 (s, 2H). 13C NMR (126MHz, CDCl3) δ=182.99 (s), 152.86 (s), 134.09 (s), 133.52 (s), 126.56 (s), 124.74 (s), 123.74 (s), 78.19 (s), 77.28-76.77 (t), 76.69 (s), 58.28 (s).
96%	With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 24h;

23%

With potassium carbonate In propan-2-one for 120h; Schlenk technique; Reflux;

Reference： [1]Saini, Parveen; Sushma; Singh, Gurjaspreet; Kaur, Gurpreet; Singh, Jandeep; Singh, Harminder [Inorganic Chemistry Communications, 2022, vol. 141]
[2]Saini, Parveen; Sushma; Singh, Gurjaspreet; Kaur, Gurpreet; Singh, Jandeep; Singh, Harminder [Inorganic Chemistry Communications, 2022, vol. 141]
[3]Location in patent: experimental part Sharghi, Hashem; Khoshnood, Abbas; Doroodmand, Mohammad Mahdi; Khalifeh, Reza [Journal of the Iranian Chemical Society, 2012, vol. 9, # 2, p. 231 - 250]
[4]Balasingham, Rebeca G.; Williams, Catrin F.; Mottram, Huw J.; Coogan, Michael P.; Pope, Simon J. A. [Organometallics, 2012, vol. 31, # 16, p. 5835 - 5843]

47
[ 81-64-1 ]
[ 635-12-1 ]
[ 860733-22-8 ]

Yield	Reaction Conditions	Operation in experiment
1: 69% 2: 21%	With sodium tetrahydroborate In methanol at 20℃; for 0.5h; Inert atmosphere;	3.2. Reduction General procedure: 1,4-Dihydroxyanthraquinone (1, 1 equiv.) was dissolved in methanol (3 mL) and stirred homogenously under a nitrogen atmosphere. Sodium borohydride (1, 3 or 15 equiv.) was added slowly to the reaction mixture and stirred for 30 min. Water (0.5 mL) was added to the reaction mixture and the pH was adjusted to 5-6 with 1 M HCl. Methanol was evaporated and the residue of aqueous layer was extracted with CH2Cl2 (3 × 10 mL). The combined organic layer were dried, filtered and evaporated under vacuum. The crude product was purified by column chromatography (CH2Cl2-petroleum ether, 3:2) to obtain compounds 2 (NaBH4: 1 equiv.) and 3 (NaBH4: 1, 3 and 15 equiv.).

Reference： [1]Nor, Siti Mariam Mohd; Sukari, Mohd Aspollah Hj Md; Azziz, Saripah Salbiah Syed Abdul; Fah, Wong Chee; Alimon, Hasimah; Juhan, Siti Fadilah [Molecules, 2013, vol. 18, # 7, p. 8046 - 8062]

48
[ 81-64-1 ]
[ 109-73-9 ]
[ 13217-65-7 ]

Yield	Reaction Conditions	Operation in experiment
90%	With [bis(acetoxy)iodo]benzene at 20℃; for 0.25h;	3.5. Amination-General Procedure General procedure: Butylamine (112, 225 or 450 equiv.) was added dropwise to a mixture of 1, 3, 5, or 7 (1 equiv.) and PhI(OAc)2 (0.41 mmol, or without catalyst) at RT (or heated at 80 °C) and stirred for 15 min to 3 d. The reaction mixture, 25 mL 10 M HCl and NaHCO3 (84 mL) were added to ice cold water (84 mL) successively. The resulting solution was extracted with EtOAc (3 × 25 mL). The organic layer was washed with H2O (3 × 25 mL), dried and evaporated. The crude product was then chromatographed on silica gel (DCM-petroleum ether, 4:1) to give a mixture of amine derivatives of anthraquinone 1a, 1b, 3a, 5a-d.

Reference： [1]Nor, Siti Mariam Mohd; Sukari, Mohd Aspollah Hj Md; Azziz, Saripah Salbiah Syed Abdul; Fah, Wong Chee; Alimon, Hasimah; Juhan, Siti Fadilah [Molecules, 2013, vol. 18, # 7, p. 8046 - 8062]

49
[ 81-64-1 ]
[ 109-70-6 ]
1,4-bis(3-chloropropoxy)anthra-9,10-quinone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: 1,4-dihydroxy-9,10-anthracenedione With potassium carbonate In butanone at 20℃; for 0.5h; Stage #2: 1.3-chlorobromopropane In butanone for 48h; Reflux;	Preparation of Halogenated and Nitrogenated Anthraquinone Derivatives 1,4-bis(3-Chloropropoxy)Anthra-9,10-Quinone (7)Anhydrous potassium carbonate (Vetec, PA) (10.4 g, 75mmol) was added to a solution of 1,4-dihydroxyanthraquinone 1 (5.95 g, 25 mmol) in butanone(200 mL). The mixture was stirred at room temperature for 30 min. and 1-bromo-3-chloropropane (Sigma-Aldrich 99%)(23.6 g, 150 mmol) was added. The reaction mixture was then stirred under reflux for 2 days, concentrated under reduced pressure and partitioned between dichloromethane andwater. The organic layer was concentrated under reducedpressure and the residue was purified by column chromatographyon silica gel (dichloromethane/methanol 8:2), affordingcompound 7 in 70% yield (6.76 g, 17 mmol). Yellowcrystals, mp 119-122 °C. 1H NMR (300 MHz, CDCl3) δ (ppm): 2.35 (m, 4H, J 6.1, 11.8 Hz, H2’=H2’’); 3.98 (t, 4H, J6.1 Hz, H3’=H3’’); 4.25 (t, 4H, J 5.7 Hz, H1’=H1’’); 7.33 (s,2H, H2=H3); 7.70 (dd, 2H, J 3.3, 5.7 Hz, H6= H7); 8.14 (dd,2H, J 3.3, 5.7 Hz, H5=H8). 13C NMR (75 MHz, CDCl3) δ (ppm): 32.4, 42.0, 66.7, 122.2, 123,6, 126.5, 133.5, 134.3,153.8, 183.2. IR (ν, cm-1, KBr): 3068, 2935, 2881, 1664,1240, 648.

Reference： [1]Alves, Caio Cesar S.; Da Costa, Cristiane F.; De Castro, Sandra B.R.; Correa, Tais A.; Santiago, Gabriele O.; Diniz, Renata; Ferreira, Ana Paula; De Almeida, Mauro V. [Medicinal Chemistry, 2013, vol. 9, # 6, p. 812 - 818]

50
[ 112-16-3 ]
[ 81-64-1 ]
[ 26131-27-1 ]

Yield	Reaction Conditions	Operation in experiment
90%	With pyridine In N,N-dimethyl acetamide at 0 - 20℃; for 24h;	Preparation of Lipophilic Anthraquinone Derivatives 2.2.3. 4-(Dodecanoyloxy)-9,10-Dioxo-9,10-Dihydro-1-Anthracenyl Dodecanoate (5)Dodecanoyl chloride (Sigma-Aldrich, 98%) (1.31 g, 6mmol) was added to a cold solution of 1,4-dihydroxyanthraquinone 1 (0.53 g, 2.25 mmol) in dimethylacetamide(20 mL) and pyridine (0.3 mL). The reaction mixture was stirred at room temperature for 24 hour. The light yellow precipitate was removed by filtration and washed with hexane, affording the ester 5 in 90% yield (1.22 g, 2 mmol). Light yellow crystals, mp 78-81 °C. 1H NMR (300 MHz, CDCl3) δ (ppm): 0.88 (t, 6H, J 6.9 Hz,H12’=H12”); 1.29 (m, 28H, H5’-H11’= H5”-H11”); 1.48(m, 4H, H4’=H4”); 1.84 (m, 4H, H3’=H3”); 2.79 (t, 4H, J7.4 Hz, H2’=H2”); 7.41 (s, 2H, H2=H3); 7.74 (dd, 2H, J 3.3,5.5 Hz, H6=H7); 8.16 (dd, 2H, J 3.3, 5.5 Hz, H5=H8). 13CNMR (75 MHz, CDCl3) δ (ppm): 14.3, 21.7, 22.9, 24.7,29.4, 29.5, 29.7, 29.8, 32.1, 34.5, 126.4, 127.1, 131.1, 133.6,134.2, 148.5, 172.4, 181.8. IR (ν, cm-1, KBr): 3157, 2916,2848, 1774, 1678, 1136.

Reference： [1]Alves, Caio Cesar S.; Da Costa, Cristiane F.; De Castro, Sandra B.R.; Correa, Tais A.; Santiago, Gabriele O.; Diniz, Renata; Ferreira, Ana Paula; De Almeida, Mauro V. [Medicinal Chemistry, 2013, vol. 9, # 6, p. 812 - 818]

51
[ 98-03-3 ]
[ 81-64-1 ]
1,4-dihydroxy-2-(hydroxy(thiophen-2-yl)methyl)anthracene-9,10-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	Stage #1: 1,4-dihydroxy-9,10-anthracenedione With potassium hydroxide In methanol; water for 0.5h; Inert atmosphere; Cooling with ice; Stage #2: thiophene-2-carbaldehyde With sodium dithionite In methanol; water	1.9; 2.9; 3.9 (9) 2-((2-Thienyl)hydroxymethyl)-1,4 dihydroxy-9,10anthraquinonePreparation of (LYH09): Add 0.5 kg of 1,4-dihydroxyanthraquinone and 1 kg of potassium hydroxide in the glass-lined reaction tank.Add 50L of methanol and 10L of water as solvent.Protected by nitrogen and reacted under ice bath conditions.After 30 minutes, 1.5 kg of sodium dithionite was dissolved in 5 L of water to be added dropwise to the reaction system.After the solution changes color, 1 kg of excess reaction material 2-thiophenecarboxaldehyde is slowly added, and the reaction is completed.Add 20 L of 3% hydrogen peroxide solution diluted 5 times, and continue stirring for 120 min.Finally, 10 L of a 1 mol/L hydrochloric acid solution was added for acidification, and the solid powder product was obtained after filtration.The solid yield was 89%.
69%	Stage #1: 1,4-dihydroxy-9,10-anthracenedione With sodium dithionite; sodium hydroxide In methanol; water at 0℃; for 0.166667h; Inert atmosphere; Stage #2: thiophene-2-carbaldehyde In methanol; water at 0℃; for 3h; Inert atmosphere; Stage #3: With dihydrogen peroxide In methanol; water for 0.166667h; Cooling;
44%	Stage #1: 1,4-dihydroxy-9,10-anthracenedione With sodium dithionite; potassium hydroxide In methanol; water for 0.25h; Inert atmosphere; Cooling with ice; Stage #2: thiophene-2-carbaldehyde In methanol; water at 0℃; for 4h; Inert atmosphere; Stage #3: With dihydrogen peroxide In water for 0.333333h;	2.1 General procedures for the synthesis of compounds A1-A14. General procedure: In an ice bath,the solution of quinizarin (1 mmol) in MeOH (20 ml) and aqueous KOH (1 N, 6 ml) was added a solution of Na2S2O4 (1.0 mmol) in water under N2. After 15 min, the aldehyde (4 mmol) was added via syringe. The reaction mixture was stirred for 4 h at 0 °C. The solution was poured into 20 ml of cold water, which contained 4 ml of 30% H2O2 and stirred for 20 min. The mixture was acidified by addition of HCl (3 N, 2 ml) and extracted with CH2Cl2, dried and concentrated. The residue was purified by flash column chromatography to afford A1-14 as an orange solid. The yields of the derivatives (A1-A14) were 20-80%.

Reference： [1]Current Patent Assignee: GUANGXI UNIVERSITY - CN109608374, 2019, A Location in patent: Paragraph 0049; 0066; 0067; 0090; 0107; 0108; 0131; 0148
[2]Zhao, Li-Ming; Ma, Feng-Yan; Jin, Hai-Shan; Ma, Jiao; Wang, Huan; Fu, Chuan-Zhao [European Journal of Organic Chemistry, 2013, # 31, p. 7193 - 7199]
[3]Liu, Yanghou; Liang, Yuehui; Jiang, Jun; Qin, Qing; Wang, Lisheng; Liu, Xu [Bioorganic and Medicinal Chemistry Letters, 2019, vol. 29, # 9, p. 1120 - 1126]

52
[ 475-38-7 ]
[ 123-73-9 ]
[ 81-64-1 ]

Yield	Reaction Conditions	Operation in experiment
82%	With benzoic acid; <i>L</i>-proline In toluene at 50℃; for 5h; Inert atmosphere; Enzymatic reaction;

Reference： [1]Somai Magar, Krishna Bahadur; Xia, Likai; Lee, Yong Rok [Chemical Communications, 2015, vol. 51, # 41, p. 8592 - 8595]

53
[ 81-64-1 ]
[ 36831-84-2 ]

Yield	Reaction Conditions	Operation in experiment
95%	With sodium tetrahydroborate; hydrazine In methanol at 0℃; for 1h; Cooling with ice; Inert atmosphere;	1 1,4-anthracene synthesis: With a thermometer,Mechanically stirred three-necked flask,Under nitrogen atmosphere,Adding a solution of hydrazine (1 eq) in methanol,In an ice bath environment,When the temperature of the reaction system drops to 0 ° C,Sodium borohydride (4 eq) was added in portions;After the reaction was reacted at 0 ° C for 1 hour,Add 6N hydrochloric acid,Obtaining an orange solid precipitate,Filtering,Washed twice with double distilled water,Vacuum drying,Recrystallized from acetone/diethyl ether,Get an orange solid,The output is 95%.Mp: 203 to 205 °C.
86%	With sodium tetrahydroborate In methanol at 0℃; for 1h; Inert atmosphere;

Reference： [1]Current Patent Assignee: SICHUAN ZHONGKE MICRO NANO TECH - CN109232394, 2019, A Location in patent: Paragraph 0078; 0082; 0083
[2]Kato, Daiki; Sakai, Hayato; Tkachenko, Nikolai V.; Hasobe, Taku [Angewandte Chemie - International Edition, 2016, vol. 55, # 17, p. 5230 - 5234][Angew. Chem., 2016, vol. 128, # 17, p. 5316 - 5320,5]

54
[ 81-64-1 ]
[ 6005-76-1 ]
1,4-dihydroxy-2-((E)-1-hydroxy-4-phenylbut-3-enyl)anthracene-9,10-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	Stage #1: 1,4-dihydroxy-9,10-anthracenedione With sodium dithionite; sodium hydroxide In methanol; water at 0℃; for 0.166667h; Inert atmosphere; Stage #2: 4-phenylbut-3-enal In methanol; water at 0℃; for 3h; Inert atmosphere; Stage #3: With dihydrogen peroxide In methanol; water for 0.166667h; Cooling;	1.1. General procedure for the synthesis of 3. General procedure: To a 0 °Csolution of quinizarin (0.5 mmol) in MeOH (10 ml) and aqueous NaOH (1 N, 2.5ml) was added a solution of Na2S2O4 (1.0 mmol)in water under N2. After 10 min, the aldehyde (1.0 mmol) was addedvia syringe. The reaction mixture was stirred for 3 h at 0 °C. The solution was poured into 10 ml ofcold water, which contained 2 ml of 30% H2O2 and stirredfor 10 min. The mixture was acidified by addition of HCl (3 N, 1 ml) andextracted with CH2Cl2, dried and concentrated. Theresidue was purified by flash column chromatography to afford 3 as an orange solid. 1.1.1. 1,4-Dihydroxy-2-((E)-1-hydroxy-4-phenylbut-3-enyl)anthracene-9,10-dione(3a). Yield 80%; mp 130-132C; 1H NMR (400 MHz, CDCl3) δ 13.48 (s,1H), 12.91 (s, 1H), 8.33-8.35 (m, 2H), 7.82-7.84 (m, 2H), 7.51 (s, 1H),7.36-7.38 (m, 2H), 7.29-7.32 (m, 2H), 7.21-7.24 (m, 1H), 6.55 (d, J = 16.0 Hz, 1H), 6.28 (dt, J = 16.0, 8.0 Hz, 1H), 5.19 (dt, J = 8.0, 4.0 Hz, 1H), 2.88-2.95 (m, 1H),2.57-2.65 (m, 1H), 2.53 (d, J = 4.0Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 187.4,186.4, 157.9, 155.2, 145.1, 136.9, 134.6, 134.4, 134.1, 133.5, 133.4, 128.6,127.5, 127.0, 126.2, 125.8, 125.1, 112.5, 111.8, 68.5, 40.6. HRMS (ESI): m/zcaclcd for C24H17O5 [(M-H+)-], 385.1076; found, 385.1075.