81-64-1

Basic information

• Product Name: 1,4-Dihydroxyanthraquinone
• Synonyms: DSD ACID;CI NO 58050;CI 58050;LABOTEST-BB LT00052844;PIGMENT VIOLET 12;QUINAZARIN;QUINIZARINE;QUINIZARIN
• CAS NO: 81-64-1
• Molecular Formula: C₁₄H₈O₄
• Molecular Weight: 240.21
• EINECS: 201-368-7
• Product Categories: Intermediates of Dyes and Pigments;Anthraquinones, Hydroquinones and Quinones;Anthraquinones;Hydroxyanthraquinones;Solvent Dyestuff
• Mol File: 81-64-1.mol
• Article Data: 57

Chemical Properties

• Melting Point: 198-199 °C(lit.)
• Boiling Point: 450 °C
• Flash Point: 222 °C
• Appearance: red-brown/powder
• Density: 1.3032 (rough estimate)
• Vapor Density: 8.3 (vs air)
• Vapor Pressure: 1 mm Hg ( 196.7 °C)
• Refractive Index: 1.5430 (estimate)
• Storage Temp.: Store below +30°C.
• Solubility: <1g/l
• PKA: pK (18°) 9.51
• Water Solubility: <1 g/L (20℃)
• Merck: 14,8064
• BRN: 1914036
• CAS DataBase Reference: 1,4-Dihydroxyanthraquinone(CAS DataBase Reference)
• NIST Chemistry Reference: 1,4-Dihydroxyanthraquinone(81-64-1)
• EPA Substance Registry System: 1,4-Dihydroxyanthraquinone(81-64-1)

Safety Data

• Hazard Codes: Xi,N
• Statements: 36/37/38-43-50/53
• Safety Statements: 22-24/25-36/37-26-61-60
• RIDADR: UN 3077 9 / PGIII
• WGK Germany: 2
• RTECS: CB6600000
• TSCA: Yes
• PackingGroup: III
• Hazardous Substances Data: 81-64-1(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 81-64-1 differently. You can refer to the following data:
1. Antioxidant in synthetic lubricants, dyes.
2. 1,4-Dihydroxyanthraquinone, also known as quinizarin, is of great importance in manufacturing disperse, acid, and vat dyes.
3. 1,4-Dihydroxyanthraquinone is used to color gasoline and some heating oils. It is used as an intermediate for the synthesis of indanthrene- and alizarin-derived dyes. It is also used to form lake pigments with calcium, barium and lead. It may be used in the synthesis of cyclopentanoids by cyclization of α,β-unsaturated aldehyde with 1, 4 1,4-Dihydroxyanthraquinone. It has been studied as a long range emissive ratiometric fluorescent probe for live cell imaging.

Preparation

commonly known as Quinizarin. (a) Boric acid, boric acid and mercury, boric acid and nitrous acid or nitrous acid and mercury in the presence of Anthracene-9,10-dione with sulfuric acid; (b) In the presence of boric acid and nitrous acid, treated with sulfuric acid ?1-Hydroxyanthracene-9,10-dione or 2-Hydroxyanthracene-9,10-dione, (c)In the presence of boric acid, treated with sulfuric acid 1-Hydroxy-4-nitroanthracene-9,10-dione?or?1,4-Dichloroanthracene-9,10-dione?; (d) in the Boric acid and where did in the presence of sulfuric acid, Phthalic anhydride and 4-Chlorophenol?or Hydroquinone condensation, closed loop.

Definition

ChEBI: A dihydroxyanthraquinone having the two hydroxy substituents at the 1- and 4-positions; formally derived from anthraquinone by replacement of two hydrogen atoms by hydroxy groups

Synthesis Reference(s)

Synthesis, p. 633, 1974 DOI: 10.1055/s-1974-23387Tetrahedron Letters, 28, p. 1533, 1987 DOI: 10.1016/S0040-4039(01)81035-2

General Description

1,4-Dihydroxyanthraquinone is an organic dye molecule with an aromatic structure. It is a derivative of anthraquinone bearing hydroxyl moieties. They may find uses in pharmacological, biochemical and dye industries. Anthraquinone dye are resistant to degradation.

Flammability and Explosibility

Nonflammable

Safety Profile

Poison by intravenous route. Moderately toxic by intraperitoneal route. Mutation data reported. An eye irritant. A weak allergen. When heated todecomposition it emits acrid smoke and irritating fumes.

Purification Methods

Crystallise quinizarin from glacial acetic acid. [Beilstein 8 H 450, 8 IV 3260.]

Properties and Applications

orange. Orange red powder. Insoluble in water, soluble in ether, in strong base in certain solubility, but soluble in organic solvent oil, etc. In concentrated sulfuric acid in green yellow fluorescence. Mainly used for oil coloring. Also used in all kinds of plastic and resin, light industry products coloring.

InChI:InChI=1/C14H8O4/c15-9-5-6-10(16)12-11(9)13(17)7-3-1-2-4-8(7)14(12)18/h1-6,15-16H

Synthetic route

N-(p-tolyl)-1,4-dihydroxy-9,10-anthraquinone 9-imine (100073-85-6) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With sulfuric acid at 20℃; for 1h;	100%

9a-chloro-5,8-dihydroxy-1-trimethylsilyloxy-1,4,4a,9a-tetrahydro-9,10-anthraquinone → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With pyridine In chloroform for 48h; Ambient temperature;	100%

9,10-Dihydroxy-2,3-dihydro-anthracene-1,4-dione (17648-03-2) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With nitric acid; bentonite for 0.166667h; Product distribution; Further Variations:; Reagents; reaction times; types of irradiation; Oxidation; Irradiation;	100%
With sodium hydroxide; oxygen

1,4-dimethoxyanthraquinone (6119-74-0) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With boron tribromide In dichloromethane at -78℃; for 0.166667h;	100%

1,4-dibenzoyloxy-9,10-anthraquinone (33266-08-9) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With water; trifluoroacetic acid at 72℃; for 0.0833333h;	99%

1,4-diacetoxy-9,10-anthraquinone (2289-36-3) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With water; trifluoroacetic acid at 72℃; for 0.0833333h;	96%
Multi-step reaction with 2 steps 1: 4 percent / alkali-metal alcoholate / 70 °C 2: 91 percent / conc. aq. HCl / ethanol / 1 h / Heating View Scheme
Multi-step reaction with 2 steps 1: sodium isopropoxide / propan-2-ol / 0.5 h / 70 °C 2: 100 percent / conc. H2SO4 / 1 h / 20 °C View Scheme
With lipase supported in poly(methylmethacrylate) beads; water In cyclohexane at 24.84℃; Enzymatic reaction;

phthalic anhydride (85-44-9) + 4-chloro-phenol (106-48-9) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With sulfuric acid; boric acid at 190 - 225℃; for 5h;	94%
With fuming sulphuric acid; boric acid at 25℃; for 11h; Temperature; Solvent; Concentration; Reagent/catalyst;	90%
With sulfuric acid; boric acid at 200℃; for 3.5h;	85%

9,10-di(p-tolylamino)-1,4-anthraquinone (98771-41-6) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With hydrogenchloride In ethanol for 1h; Heating;	91%

anthracene-1,4,9,10-tetraone (1709-63-3) + ethylenediamine (107-15-3) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1) + 6-hydroxy-1,2,3,4-tetrahydronaphtho<2,3-f>quinoxaline-7,12-dione (20269-39-0)

Conditions	Yield
In pyridine Ambient temperature;	A 1.2% B 90.7%
In pyridine at 30℃; for 6h;	A 1.2% B 90.7%

anthracene-1,4,9,10-tetraone (1709-63-3) + 2-acetoxy-1,3-butadiene (24454-89-5) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1) + 2-acetoxy-1,4,4a,12a-tetrahydronaphthacene-5,6,11,12-tetrone (63229-39-0) + Acetic acid 9,10,11,14-tetraoxo-1,4,9,10-tetrahydro-4a,9a-[2]buteno-anthracen-2-yl ester

Conditions	Yield
In benzene at 55℃; for 96h;	A n/a B 83% C n/a
In benzene at 55℃; for 96h; Title compound not separated from byproducts;

5,8-Dihydroxy-1,4-naphthoquinone (475-38-7) + crotonaldehyde (123-73-9) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With benzoic acid; L-proline In toluene at 50℃; for 5h; Inert atmosphere; Enzymatic reaction;	82%

1-hydroxyanthraquinone (129-43-1) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With sulfuric acid; boric acid for 5h; Irradiation;	81%
With air; sulfuric acid Product distribution; Mechanism; Irradiation; without air (argon);

9,10-phenanthrenequinone (84-65-1) → 2-hydroxy-9,10-anthraquinone (605-32-3) + 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With sulfuric acid; boric acid for 5h; Product distribution; Mechanism; Irradiation; other time;	A n/a B 81%

phthalic anhydride (85-44-9) + hydroquinone (123-31-9) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With aluminium trichloride; sodium chloride at 165℃; for 4h; Fridel-Crafts acylation;	80%
With sulfuric acid; boric acid at 200℃; for 3.5h;	55%
With aluminum (III) chloride; sodium chloride at 165 - 170℃; for 0.75h; Friedel-Crafts Acylation;	44%

1-hydroxy-4-fluoro-anthracene-9,10-dione → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With sodium trimethylsilanolate In tetrahydrofuran Substitution; stirring f the mixture at room temperature under a nitrogen atmosphere for 18 h;	80%

1,4-difluoroanthracene-9,10-dione (28736-42-7) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With methyl propargyl alcohol; potassium tert-butylate In dimethyl sulfoxide at 125℃; for 0.0333333h; microwave irradiation;	78%
Multi-step reaction with 2 steps 1: 90 percent / NaOSi(CH3)3 / tetrahydrofuran / stirring f the mixture at room temperature under a nitrogen atmosphere for 18 h 2: 80 percent / NaOSi(CH3)3 / tetrahydrofuran / stirring f the mixture at room temperature under a nitrogen atmosphere for 18 h View Scheme

Phthaloyl dichloride (88-95-9) + 1,4-dimethoxybezene (150-78-7) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With aluminium trichloride In nitrobenzene at 80℃; for 0.5h;	72%

2,3-dichloro-1,4-dihydroxyanthracene-9,10-dione (29525-00-6) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
Stage #1: 2,3-dichloro-1,4-dihydroxyanthracene-9,10-dione With iron In acetic acid for 0.75h; Dehalogenation; reduction; Heating; Stage #2: With oxygen In sodium hydroxide pH=8 - 9; Oxidation;	72%

9,10-phenanthrenequinone (84-65-1) → 2-hydroxy-9,10-anthraquinone (605-32-3) + 1-hydroxyanthraquinone (129-43-1) + 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With sulfuric acid at 25℃; Irradiation;	A 70% B n/a C n/a
With sulfuric acid at 25℃; Irradiation; prolonged irradiation;	A n/a B 55% C 6%

4-chloro-phenol (106-48-9) + benzene-1,2-dicarboxylic acid (88-99-3) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With sulfuric acid; boric acid at 230℃; for 0.166667h; Product distribution; Further Variations:; Temperatures; Reagents; reaction times; microwave powers; microwave irradiation;	68.3%

hydroquinone (123-31-9) + Phthaloyl dichloride (88-95-9) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
With aluminium trichloride In nitrobenzene at 100℃; for 0.5h;	65%
With aluminium trichloride; C6H4NO2 at 165℃; for 4h; Fridel-Crafts acylation;

3-(phenylsulfanyl)isobenzofuran-1(3H)-one (51287-54-8) + p-benzoquinone (106-51-4) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
Stage #1: 3-(phenylsulfanyl)isobenzofuran-1(3H)-one With lithium tert-butoxide In tetrahydrofuran at -60℃; for 0.416667h; Stage #2: p-benzoquinone In tetrahydrofuran at -60 - 20℃; Hauser annulation; Further stages.;	56%

1-nitroanthraquinone (82-34-8) → 1-hydroxyanthraquinone (129-43-1) + 1,4-dihydroxy-9,10-anthracenedione (81-64-1) + 1,2-dihydroxy-9,10-anthracenedione (72-48-0)

Conditions	Yield
With potassium hydroxide; Cumene hydroperoxide In dimethyl sulfoxide at 15 - 25℃; for 10h;	A 55% B 13% C 32%
With Cumene hydroperoxide; potassium tert-butylate In N,N,N,N,N,N-hexamethylphosphoric triamide at 15 - 20℃; for 3h;	A 45% B 8% C 35%

3-oxo-1,3-dihydroisobenzofuran-1-carbonitrile (27613-27-0) + p-benzoquinone (106-51-4) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1)

Conditions	Yield
Stage #1: 3-oxo-1,3-dihydroisobenzofuran-1-carbonitrile With lithium tert-butoxide In tetrahydrofuran at -60℃; for 0.416667h; Stage #2: p-benzoquinone In tetrahydrofuran at -60 - 20℃; Hauser annulation; Further stages.;	52%

methanol (67-56-1) + 2,10-hydroxy-9-chloro-1,4-anthraquinone (41099-45-0) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1) + 1-hydroxy-4-methoxyanthracene-9,10-dione (7336-64-3)

Conditions	Yield
With perchloric acid for 12h; Heating;	A 36% B 49%

leuco-1,4-dihydroxyanthraquinone (38399-72-3) + 2,3-isopropylidene-glyceraldehyde (15186-48-8) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1) + dihydroxy-1,4 (hydroxy-3 propyl)-2 anthraquinone-9,10 (128885-71-2) + (-)-(S)<(dimethyl-2,2 dioxolanne-1,3 yl-4) methyl>-2 dihydroxy-1,4 anthraquinone-9,10 (111301-39-4) + <(dimethyl-2,2 dioxolanne-1,3 yl-4) hydroxymethyl>-2 dihydroxy-1,4 anthraquinone-9,10 (111301-40-7, 111331-26-1)

Conditions	Yield
With potassium hydroxide; sodium hydrogensulfite Product distribution; 1.) MeOH, 15 min, 20 deg C, 2.) MeOH, 12 h, 20 deg C, further temperatures;	A 33% B 4% C 22% D 37%

1,4-bis(prop-2'-enyloxy)-9,10-anthraquinone (79207-97-9) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1) + 1,4-dihydroxy-2-(prop-2'-enyl)-9,10-anthraquinone (79208-09-6) + 2,3-diallyl-1,4-dihydroxyanthraquinone (79208-01-8) + 1-hydroxy-4-propanoyl-2-(prop-2'-enyl)anthraquinone (79208-08-5)

Conditions	Yield
In 1,2-dichloro-benzene for 25h; Heating;	A 5% B 32% C 14% D 18%

5,8-diacetoxy-1,4-naphthoquinone (14569-45-0) + (E,E)-1-(N,N-dimethylamino)-4-nitro-1,3-butadiene (108030-46-2) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1) + 5-nitro-1,4-dihydroxy-9,10-anthracenedione (27573-16-6) + Acetic acid 4-hydroxy-5-nitro-9,10-dioxo-9,10-dihydro-anthracen-1-yl ester (117554-15-1) + Acetic acid 4-hydroxy-8-nitro-9,10-dioxo-9,10-dihydro-anthracen-1-yl ester (117554-14-0)

Conditions	Yield
In xylene for 24h; Ambient temperature;	A 4.2% B 30.2% C n/a D n/a
In xylene for 24h; Ambient temperature; Title compound not separated from byproducts;	A 4.2% B 30.2% C n/a D n/a

(E,E)-1-(N,N-dimethylamino)-4-nitro-1,3-butadiene (108030-46-2) + 5,8-Dihydroxy-1,4-naphthoquinone (475-38-7) → 1,4-dihydroxy-9,10-anthracenedione (81-64-1) + 5-nitro-1,4-dihydroxy-9,10-anthracenedione (27573-16-6) + 2-(dimethylamino)-5,8-dihydroxynaphthalene-1,4-dione (117554-13-9)

Conditions	Yield
In xylene for 12h; Ambient temperature;	A 9.2% B 14.1% C 24.9%

1,4-dihydroxy-9,10-anthracenedione (81-64-1) + allyl bromide (106-95-6) → 1,4-bis(prop-2'-enyloxy)-9,10-anthraquinone (79207-97-9)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 55℃; for 16h;	100%
With potassium carbonate In acetone for 48h; Reflux;	89%
With tetraethylammonium bromide; potassium carbonate; sodium hydroxide at 85℃; for 0.5h; Microwave irradiation; Sealed tube;	85%
With potassium carbonate In acetone Heating;	81%
With potassium carbonate In acetone Reflux;

1,4-dihydroxy-9,10-anthracenedione (81-64-1) + dimethyl sulfate (77-78-1) → 1,4-dimethoxyanthraquinone (6119-74-0)

Conditions	Yield
With sodium hydride In tetrahydrofuran for 480h; Ambient temperature;	99%
With potassium carbonate In acetone for 4h; Reflux;	96%
With potassium carbonate In acetone for 72h; Heating;	95%

1,4-dihydroxy-9,10-anthracenedione (81-64-1) + ethylenediamine (107-15-3) → 6-hydroxy-1,2,3,4-tetrahydronaphtho[2,3-f]-quinoxaline-7,12-dione (15077-66-4)

Conditions	Yield
With [bmim]PF6; copper dichloride at 20℃; for 2h; Product distribution; Further Variations:; Reagents;	99%

decacarbonyldirhenium(0) (14285-68-8) + 1,4-dihydroxy-9,10-anthracenedione (81-64-1) + Uvitex OB (7128-64-5) → [(Re(CO)3)4(2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene)2(1,4-dihydroxy-9,10-anthraquinone(-2H))2] (918153-35-2)

Conditions	Yield
In 1,2,5-trimethyl-benzene under reflux;	99%

3-bromo-4-methoxybenzylaldehyde (34841-06-0) + 1,4-dihydroxy-9,10-anthracenedione (81-64-1) → 2-((3-bromo-4-methoxyphenyl)(hydroxy)methyl)-1,4-dihydroxyanthracene-9,10-dione

Conditions	Yield
Stage #1: 1,4-dihydroxy-9,10-anthracenedione With potassium hydroxide In methanol; water for 0.5h; Inert atmosphere; Cooling with ice; Stage #2: 3-bromo-4-methoxybenzylaldehyde With sodium dithionite In methanol; water Time;	99%
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: 3-bromo-4-methoxybenzylaldehyde In methanol; water at 0℃; for 4h; Inert atmosphere; Stage #3: With dihydrogen peroxide In water for 0.333333h;	76%

1,4-dihydroxy-9,10-anthracenedione (81-64-1) → 1,4-anthraquinone (635-12-1)

Conditions	Yield
With sodium tetrahydroborate In methanol for 24h; Heating;	98%
With methanol; sodium tetrahydroborate at 0℃;	98%
With sodium tetrahydroborate In methanol at 0℃; for 1h; Inert atmosphere;	97%

2,3-Dichloroprop-1-ene (78-88-6) + 1,4-dihydroxy-9,10-anthracenedione (81-64-1) → 1,4-Bis-(2-chloro-allyloxy)-anthraquinone (72183-81-4)

Conditions	Yield
With potassium carbonate; potassium iodide In acetone for 344h; Heating;	98%
With potassium carbonate In N,N-dimethyl-formamide at 70℃;

1,4-dihydroxy-9,10-anthracenedione (81-64-1) + ethylenediamine (107-15-3) → 6-hydroxy-1,2,3,4-tetrahydronaphtho<2,3-f>quinoxaline-7,12-dione (20269-39-0)

Conditions	Yield
copper dichloride In pyridine at 30℃; for 24h; Product distribution; Mechanism; further copper chloride catalyst, effect of oxygen without catalyst, further amine;	98%
With copper dichloride In pyridine at 30℃; for 6h; Product distribution; other diamines, also in the absence of a copper salts;	98%
copper dichloride In pyridine at 30℃; for 24h;	98%
With oxygen; copper dichloride In pyridine at 30℃; for 6h;	98%
With copper dichloride Ambient temperature;	33%

leucoquinizarin (476-60-8) + 1,4-dihydroxy-9,10-anthracenedione (81-64-1) + N-acetyl-p-phenylenediamine (122-80-5) → C22H16N2O4

Conditions	Yield
Stage #1: N-acetyl-p-phenylenediamine With hydrogenchloride In water at 40 - 50℃; for 0.5h; Stage #2: leucoquinizarin; 1,4-dihydroxy-9,10-anthracenedione In water at 85 - 90℃; Solvent; Temperature;	97.13%

1,4-dihydroxy-9,10-anthracenedione (81-64-1) + p-toluidine (106-49-0) → D and C green 6 (128-80-3)

Conditions	Yield
With leucoquinizarin; boric acid; sodium hydrogensulfite In ethanol; benzene at 62 - 66℃; for 12h; Temperature; Solvent;	97%
With 1-butyl-3-ethyl-1H-imidazolium tetrafluoroborate at 85 - 125℃; Reagent/catalyst; Temperature; Green chemistry; Large scale;	95.9%
With boric acid; calcium carbonate; tin(ll) chloride at 110 - 130℃;

trifluoromethane sulfonyl chloride (421-83-0) + 1,4-dihydroxy-9,10-anthracenedione (81-64-1) → 1,4-Bis-(trifluoromethanesulfonyloxy)-9,10-anthracenedione (96701-08-5)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine; 0,2,4-dichlorophenyl-0-methylisopropylamidothiophosphate In dichloromethane at 5 - 10℃; for 0.5h;	97%

1,4-dihydroxy-9,10-anthracenedione (81-64-1) + allyl bromide (106-95-6) → 10-[1-(prop-2-enyl)]-1,4,10-trihydroxy-9(10H)-anthracenone

Conditions	Yield
With indium; water In tetrahydrofuran; methanol at 30℃; Barbier allylation;	97%

1,4-dihydroxy-9,10-anthracenedione (81-64-1) + propyl bromide (106-94-5) → 1,4-dipropoxy-9,10-anthraquinone (847901-15-9)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 6h; Heating;	97%
With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 6h; Williamson Ether Synthesis; Inert atmosphere;	89%

1,4-dihydroxy-9,10-anthracenedione (81-64-1) + leuco-1,4-dihydroxyanthraquinone (38399-72-3) + 1,4-phenylenediamine (106-50-3) → C20H14N2O3

Conditions	Yield
With boric acid In butan-1-ol for 16h; Reagent/catalyst; Reflux;	97%

1,4-dihydroxy-9,10-anthracenedione (81-64-1) → 9,10-Dihydroxy-2,3-dihydro-anthracene-1,4-dione (17648-03-2)

Conditions	Yield
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;	96.1%
With sodium disulfite; potassium carbonate Hydrogenation;	93%
With acetic acid; aluminium; indium(III) chloride In ethanol; water at 90℃; for 11h;	78%

1,4-dihydroxy-9,10-anthracenedione (81-64-1) + silver nitrate → C14H6(O)2(OAg)2 (620591-70-0)

Conditions	Yield
With triethylamine In ethanol; triethylamine; acetonitrile byproducts: NEt3*HNO3; a soln. of quinone in Et3N and EtOH were added dropwise under N2 to a soln. of AgNO3 in MeCN-EtOH in the dark at 25°C, the mixt. was stirred for 2 h; filtd., ppt. was washed with cold EtOH, filtrate evapd. under vac.; elem. anal.;	96%

1,4-dihydroxy-9,10-anthracenedione (81-64-1) + propargyl bromide (106-96-7) → 1,4-bis(prop-2-ynyloxy)anthracene-9,10-dione (1045-75-6)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 24h;	96%
With potassium carbonate In acetone for 120h; Schlenk technique; Reflux;	23%

1,4-dihydroxy-9,10-anthracenedione (81-64-1) → leuco-1,4-dihydroxyanthraquinone

Conditions	Yield
Stage #1: 1,4-dihydroxy-9,10-anthracenedione With sodium hydroxide In water at 70 - 75℃; for 0.5h; Stage #2: With thiourea In water at 88℃; for 2h; Reagent/catalyst;	96%

1,4-dihydroxy-9,10-anthracenedione (81-64-1) + N-butylamine (109-73-9) → solvent blue 35 (17354-14-2)

Conditions	Yield
With acetic acid; sodium sulfate In ethanol for 4h; Reflux;	95.3%
With sodium dithionite; ethanol

1,4-dihydroxy-9,10-anthracenedione (81-64-1) + methylamine (74-89-5) → disperse blue 14 (2475-44-7)

Conditions	Yield
With 1-methyl-1H-imidazole; tetrafluoroboric acid; bromobutyric acid In methanol at 50 - 55℃; Temperature; Large scale;	95.1%
With ethanol; sodium carbonate; copper(II) sulfate at 140℃;
With sodium hydroxide; copper(II) sulfate at 140℃;

1,4-dihydroxy-9,10-anthracenedione (81-64-1) + Trimethylenediamine (109-76-2) → 2-(3'-aminopropylamino)-1,4-dihydroxyanthraquinone

Conditions	Yield
copper dichloride In pyridine at 30℃; for 24h;	95%
With oxygen; copper dichloride In pyridine at 30℃; for 6h;	95%

1,4-dihydroxy-9,10-anthracenedione (81-64-1) + malononitrile (109-77-3) → 2-amino-3-cyano-5-hydroxyanthra<1,2-b>furan-6,11-dione (86092-18-4)

Conditions	Yield
With triethylamine In dimethyl sulfoxide Ambient temperature;	95%

1,4-dihydroxy-9,10-anthracenedione (81-64-1) + methyl iodide (74-88-4) → 1,4-dimethoxyanthraquinone (6119-74-0)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 40℃;	95%
With aluminum oxide; potassium fluoride In dimethyl sulfoxide at 35℃; for 10h;	58.5%
With potassium carbonate In acetone Reflux;	31.5%

1,4-dihydroxy-9,10-anthracenedione (81-64-1) → 1,4-dimethoxyanthracene (13076-29-4)

Conditions	Yield
With hydrogenchloride; sodium borohydrid In methanol	95%
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 View Scheme
Multi-step reaction with 2 steps 1: K2CO3 / acetone 2: 62 percent / Zn; glacial acetic acid / 15 h / Heating View Scheme
Multi-step reaction with 2 steps 1: potassium hydroxide / tetrahydrofuran / 24 h / Reflux 2: zinc; acetic acid / 96 h / Reflux View Scheme

Upstream product

• 85-44-9 phthalic anhydride 
• 106-48-9 4-chloro-phenol 
• 123-31-9 hydroquinone 
• 82-34-8 1-nitroanthraquinone 
• 14569-45-0 5,8-diacetoxy-1,4-naphthoquinone 
• 108030-46-2 (E,E)-1-(N,N-dimethylamino)-4-nitro-1,3-butadiene 
• 87021-32-7 2-(5'-bromo-2'-hydroxybenzoyl)benzoic acid 
• 111422-40-3 3-(2,5-Dimethoxy-phenyl)-3-(4-methoxy-phenoxy)-3H-isobenzofuran-1-one 
• 84-65-1 9,10-phenanthrenequinone 
• 100073-85-6 N-(p-tolyl)-1,4-dihydroxy-9,10-anthraquinone 9-imine 
• 475-38-7 5,8-Dihydroxy-1,4-naphthoquinone 
• 128-95-0 1,4-diamino-9,10-anthraquinone 
• 7664-93-9 sulfuric acid 
• 13460-50-9 metaboric acid 

Downstream Products

• 75300-11-7 1,4-bis-(3-hydroxymethyl-anilino)-anthraquinone 
• 81-47-0 1-hydroxy-4-(3-hydroxymethyl-anilino)-anthraquinone 
• 74440-71-4 1-hydroxy-4-(2,4,5-trimethyl-anilino)-anthraquinone 
• 58979-45-6 1-hydroxy-4-[4-(2-hydroxy-ethoxy)-anilino]-anthraquinone 
• 70714-75-9 1,4-bis-(4-cyclohexyl-anilino)-anthraquinone 
• 119560-60-0 [4-(4-hydroxy-9,10-dioxo-9,10-dihydro-[1]anthrylamino)-phenyl]-acetonitrile 
• 81-48-1 1-hydroxy-4-(4-methylphenylamino)-9,10-anthraquinone 
• 5470-98-4 1,4-dihydroxy-9,10-dioxo-9,10-dihydro-anthracene-2,3-dicarbonitrile 
• 122924-85-0 9,10-diphenyl-9,10-dihydro-anthracene-1,4,9,10-tetraol 
• 60058-19-7 4,4'-(9,10-dioxo-9,10-dihydro-anthracene-1,4-diyldiamino)-bis-toluene-2-sulfonic acid 
• 1709-63-3 anthracene-1,4,9,10-tetraone 
• 635-12-1 1,4-anthraquinone 
• 81-54-9 1,2,4-trihydroxy-9,10-anthraquinone 
• 81-61-8 1,2,5,8-tetrahydroxy-anthraquinone 

Relevant articles and documents

Clean process for synthesizing 1, 4-dihydroxy anthraquinone

The invention relates to the technical field of dye intermediates, and especially relates to a clean process for synthesizing 1, 4-dihydroxy anthraquinone. The process comprises the following steps: sequentially adding 98% sulfuric acid, boric anhydride, phthalic anhydride and hydroquinone into a dry reaction container according to a stoichiometric ratio, uniformly stirring, heating to 100-180 DEG C, and carrying out heat preservation reaction for 2-24 hours; after the heat preservation reaction is finished, cooling the materials, and transferring the materials into another reaction container for hydrolysis; and after hydrolysis is completed, cooling, filtering and washing to obtain the 1, 4-dihydroxy anthraquinone. According to the clean process for synthesizing the 1, 4-dihydroxy anthraquinone, provided by the invention, the dosage of the raw material phthalic anhydride can be reduced, the wastewater treatment difficulty is greatly reduced, and the production cost is also reduced; and meanwhile, the yield of the 1, 4-dihydroxy anthraquinone is also improved to a certain extent.

Evaluation of a series of 9,10-anthraquinones as antiplasmodial agents

Background: A phytochemical study on medicinal plants used for the treatment of fever and malaria in Africa yielded metabolites with potential antiplasmodial activity, many of which are Anthraquinones (AQ). AQs have similar sub-structure as naphthoquinones and xanthones, which were previously reported as novel antiplasmodial agents. Objective: The present study aimed to investigate the structural requirements of 9,10-anthraquinones with hydroxy, methoxy and methyl substituents to exert strong antiplasmodial activity and to investigate their possible mode of action. Methods: Thirty-one AQs were synthesized through Friedel-Crafts reaction and assayed for antiplasmodial activity in vitro against Plasmodium falciparum (3D7). The selected compounds were tested for toxicity and probed for their mode of action against β-hematin dimerization through HRP2 and lipid catalyses. The most active compounds were subjected to a docking study using AutoDock 4.2. Results: The active AQs have similar common structural characteristics. However, it is difficult to establish a structure-activity relationship as certain compounds are active despite the absence of the structural features exhibited by other active AQs. They have either ortho- or meta-arranged substituents and one free hydroxyl and/or carbonyl groups. When C-6 is substituted with a methyl group, the activity of AQs generally increased. 1,3-DihydroxyAQ (15) showed good antiplasmodial activity with an IC50 value of 1.08 μM, and when C-6 was substituted with a methyl group, 1,3-dihydroxy-6-methylAQ (24) showed stronger antiplasmodial activity with an IC50 value of 0.02μM, with better selectivity index. Compounds 15 and 24 showed strong HRP2 activity and mild toxicity against hepatocyte cells. Molecular docking studies showed that the hydroxyl groups at the ortho (23) and meta (24) positions are able to form hydrogen bonds with heme, of 3.49 A and 3.02 A, respectively. Conclusion: The activity of 1,3-dihydroxy-6-methylAQ (24) could be due to their inhibition against the free heme dimerization by inhibiting the HRP2 protein. It was further observed that the anthraquinone moiety of compound 24 bind in parallel to the heme ring through hydrophobic interactions, thus preventing crystallization of heme into hemozoin.

Monitoring the activity of immobilized lipase with quinizarin diester fluoro-chromogenic probe

Ouinizarin diester is used as a fluoro-chromogenic substrate of the activity of lipase supported in poly(methylmetacrylate) beads (CALB, Novozymfi 435) dispersed in organic solvents. The monoester and diester of quinizarin are both non-fluorescent species contrasting with the enzymatic product quinizarin that shows optical absorption in the visible region and strong fluorescence signal. The enzymatic conversion is accomplished by spectroscopic measurements and it follows a sigmoid curve from which the mean reaction time of the enzymatic process can be determined. This parameter indicates the enzyme activity of the immobilized lipase. Its dependency with the amount of lipase allowed the determination of the ratio of the catalytic rate and the Michaelis constant (kc/Km) and the experimental value found was (1.0 ± 0.1) × 10?2 mg?1/min in the case of quinizarin diacetate.