* 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.
Reference:
[1] Patent: US2278987, 1940, ,
[2] Promysl.org.Chim., 1936, vol. 2, p. 576[3] Chem. Zentralbl., 1937, vol. 108, # I, p. 2871
[4] Patent: US2278987, 1940, ,
[5] Promysl.org.Chim., 1936, vol. 2, p. 576[6] Chem. Zentralbl., 1937, vol. 108, # I, p. 2871
[7] Patent: US2278987, 1940, ,
[8] Promysl.org.Chim., 1936, vol. 2, p. 576[9] Chem. Zentralbl., 1937, vol. 108, # I, p. 2871
[10] Patent: US2278987, 1940, ,
[11] Promysl.org.Chim., 1936, vol. 2, p. 576[12] Chem. Zentralbl., 1937, vol. 108, # I, p. 2871
[13] Patent: US2278987, 1940, ,
[14] Promysl.org.Chim., 1936, vol. 2, p. 576[15] Chem. Zentralbl., 1937, vol. 108, # I, p. 2871
[16] Patent: US2278987, 1940, ,
[17] Promysl.org.Chim., 1936, vol. 2, p. 576[18] Chem. Zentralbl., 1937, vol. 108, # I, p. 2871
[19] Patent: US2278987, 1940, ,
[20] Promysl.org.Chim., 1936, vol. 2, p. 576[21] Chem. Zentralbl., 1937, vol. 108, # I, p. 2871
[22] Patent: US2278987, 1940, ,
[23] Promysl.org.Chim., 1936, vol. 2, p. 576[24] Chem. Zentralbl., 1937, vol. 108, # I, p. 2871
[25] Patent: US2278987, 1940, ,
[26] Promysl.org.Chim., 1936, vol. 2, p. 576[27] Chem. Zentralbl., 1937, vol. 108, # I, p. 2871
[28] Patent: US2278987, 1940, ,
[29] Promysl.org.Chim., 1936, vol. 2, p. 576[30] Chem. Zentralbl., 1937, vol. 108, # I, p. 2871
[31] Patent: US2278987, 1940, ,
[32] Promysl.org.Chim., 1936, vol. 2, p. 576[33] Chem. Zentralbl., 1937, vol. 108, # I, p. 2871
[34] Patent: US2278987, 1940, ,
[35] Promysl.org.Chim., 1936, vol. 2, p. 576[36] Chem. Zentralbl., 1937, vol. 108, # I, p. 2871
[37] Patent: US2278987, 1940, ,
[38] Promysl.org.Chim., 1936, vol. 2, p. 576[39] Chem. Zentralbl., 1937, vol. 108, # I, p. 2871
[40] Patent: US2278987, 1940, ,
[41] Promysl.org.Chim., 1936, vol. 2, p. 576[42] Chem. Zentralbl., 1937, vol. 108, # I, p. 2871
[43] Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 11, p. 698
[44] Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 11, p. 698
[45] J.Soc.chem.Ind.Japan Spl., vol. 38, p. 640 B[46] Chem. Zentralbl., 1936, vol. 107, # II, p. 469
[47] Dyes and Pigments, 2012, vol. 95, # 2, p. 377 - 383
[48] Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 11, p. 698
[49] Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 11, p. 698
4
[ 82-05-3 ]
[ 128-59-6 ]
Reference:
[1] Patent: US1967617, 1932, ,
5
[ 116-90-5 ]
[ 128-59-6 ]
Reference:
[1] Kogyo Kagaku Zasshi, 1943, vol. 46, p. 1256[2] Chem.Abstr., 1948, p. 6119
6
[ 111-83-1 ]
[ 128-59-6 ]
[ 85652-50-2 ]
Yield
Reaction Conditions
Operation in experiment
72%
With 18-crown-6 ether; potassium carbonate In 1-methyl-pyrrolidin-2-one at 100℃; for 8 h;
Taking 1.21g (2.48mmol) 16, 17-dihydroxy Anthracyclinone purple puts in 100 ml flask, add 50mLN-methyl pyrrolidone, heating 10 min to 100 °C the 16, 17-dihydroxy Anthracyclinone purple disperse as much as possible. Then add 1.00g (7.2mmol) no water K2CO3, 0.98g (5.08mmol) 1-polybromide octane, and presence of 18-crown -6. Maintain reaction temperature 100 °C, reaction 8 hours the reaction is stopped.The reaction solution is poured into 100 ml water, fully mixing, filtering, drying to obtain the crude product. Dichloromethane is used for dissolving the crude product, filtering to remove undissolved components. turns on lathe does dichloromethane, to obtain the solid, dried to obtain 1.26g grams of product, yield is 72percent. The silica gel chromatographic column, to CH2Cl2: CH3OH=20 1 as eluant, further elution separation and purification.
Reference:
[1] Patent: CN103804163, 2016, B, . Location in patent: Paragraph 0036; 0037; 0038
[2] Frontiers of Chemistry in China, 2010, vol. 5, # 2, p. 200 - 207
[3] Dyes and Pigments, 2012, vol. 95, # 2, p. 377 - 383
With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 12h;
With 18-crown-6 ether; potassium carbonate In N,N-dimethyl-formamide at 80℃; for 12h;
4 Implementing example four , 16, 17-b f propoxycyclohexyl Anthracyclinone purple preparation
Taking 2.00g (4.10mmol) 16, 17-dihydroxy Anthracyclinone purple, is added to the 100 ml round-bottom flask, add 20 ml of N, N-dimethyl formamide, stirred and heated up to 80 °C enabling their disperse, adding 1.60g (11.6mmol) no water K2CO3, adding 1.35g (8.2mmol) of 1- hexyl bromide and presence of 18-crown -6. Maintain 80 °C reaction, 12h rear stop the reaction. Is filtered, the filtrate for rotary evaporimeter turns on lathe does , N remove the solvent, N-dimethyl formamide and unreacted end of the 1-bromo-hexane. Adding 200 ml water, fully mixing, filtering, drying, to obtain black powdery solid substances 1.51g, yield 65%. Crude product using petroleum ether: ethyl acetate = 2 the [...] 1 as leaching agent gradient elution, to make pure product.
With 18-crown-6 ether; potassium carbonate; In 1-methyl-pyrrolidin-2-one; at 100℃; for 8.0h;
Taking 1.21g (2.48mmol) 16, 17-dihydroxy Anthracyclinone purple puts in 100 ml flask, add 50mLN-methyl pyrrolidone, heating 10 min to 100 C the 16, 17-dihydroxy Anthracyclinone purple disperse as much as possible. Then add 1.00g (7.2mmol) no water K2CO3, 0.98g (5.08mmol) 1-polybromide octane, and presence of 18-crown -6. Maintain reaction temperature 100 C, reaction 8 hours the reaction is stopped.The reaction solution is poured into 100 ml water, fully mixing, filtering, drying to obtain the crude product. Dichloromethane is used for dissolving the crude product, filtering to remove undissolved components. turns on lathe does dichloromethane, to obtain the solid, dried to obtain 1.26g grams of product, yield is 72%. The silica gel chromatographic column, to CH2Cl2: CH3OH=20 1 as eluant, further elution separation and purification.
With 18-crown-6 ether; potassium carbonate In dimethyl sulfoxide at 100℃; for 5h;
5 Implementing example five , 16, 17-bis (dodecyloxy) purple Anthracenone preparation of
Taking 1.08g (2.1mmol) 16, 17-dihydroxy Anthracyclinone purple into the 100 ml round-bottom flask, add 20 ml of dimethyl sulfoxide, as reaction solvent. Adding 0.90g (6.50mmol) no water K2CO3and 1.12g (4.50mmol) 1-bromo-dodecane and catalytic amount 18-crown -6, temperature control 100 °C reaction 5 hours, the remaining experimental procedure is the same as the above. The finally obtained 1.25g product, yield 69%.
16, 17-dihydroxy Anthracyclinone violet synthesis adopts the 16, 17-dimethoxy Anthracyclinone purple as raw materials, in dichloromethane as solvent BBr3to escapes the methylation reagent, to obtain a target compound.The 250 ml round-bottom flask by adding 8.03g (15.5mmol) of the 16, 17-dimethoxy anthrone purple and 100 ml dichloromethane, for stirring the mixture at room temperature for 1 hour, giving full dispersed. Under stirring condition, under the condition of the ice, and then adding 7.80g (31mmol) of boron tribromide. After dropping, stirring at room temperature for 8 hours. Re-heating reflux reaction 8 hours. TLC tracking, the almost complete reaction of raw materials, to stop the reaction. When the system temperature is dropped to the room temperature. The reaction the fluid leansto entering 500 ml about 2mol/L of in HCl solution, mechanical stirring 30 minutes, to obtain a two-phase system. Filtering, the filter cake washed with water, drying filter cake to be 16, 17-dihydroxy Anthracyclinone purple thick 7.16g, the yield is 94%.Because the 16, 17-dihydroxy Anthracyclinone of poor solubility, is not easy to purification, the resulting product therefore directly in the next step reaction.
With 18-crown-6 ether; potassium carbonate In N,N-dimethyl-formamide at 80℃; for 5h;
2 Implementation of the example two, 16, 17- two last of the ten Heavenly Stems oxygen radicals Anthracyclinone purple synthesis of
Taking 1.98g (4.10mmol) 16, 17-dihydroxy Anthracyclinone purple by adding 100 ml round-bottom flask, add 20 ml of N, N-dimethyl formamide, stirred and heated up to 80 °C make it fully into the reaction system, adding 1.60g (11.5mmol) no water K2CO3, plus 1.81g (8.2mmol) of 1-bromo decane, then adding 0.1 g 18-crown -6 as catalyst, in the 80 °C to continue reaction 5 hours. The filtering, filtering the insoluble impurities and inorganic salt. Under the condition of stirring, the reaction solution is added to the 100 ml water, the product precipitated. Filtering, drying, are blueblack toner powdery solid. Recrystallization with ethyl acetate to obtain 16, 17- two last of the ten Heavenly Stems oxygen radicals Anthracyclinone purple. After dry 2.36g grams of product, yield is 74%.