2373-98-0

Basic information

• Product Name: 3,3'-Dihydroxybenzidine
• Synonyms: 1’-biphenyl)-3,3’-diol,4,4’-diamino-(;1’-biphenyl)-4,4’-diamine,3,3’-dihydroxy-(;3,3'-DIHYDROXY-4,4'-DIAMINO-BIPHENYL;3,3'-DIHYDROXYBENZIDINE;Dihydroxybenzidine;2-amino-5-(4-amino-3-hydroxyphenyl)phenol;3,3-DIHYDROXYBENZIDINE 98+%;4,4'-Diamino-3,3'-biphenyldiol
• CAS NO: 2373-98-0
• Molecular Formula: C₁₂H₁₂N₂O₂
• Molecular Weight: 216.24
• EINECS: 1312995-182-4
• Product Categories: Biphenyl & Diphenyl ether;Biphenyls (for High-Performance Polymer Research);Functional Materials;Reagent for High-Performance Polymer Research;Thiophen
• Mol File: 2373-98-0.mol
• Article Data: 2

Chemical Properties

• Melting Point: 292 °C
• Boiling Point: 356.65°C (rough estimate)
• Flash Point: 220.3°C
• Appearance: /
• Density: 1.1710 (rough estimate)
• Refractive Index: 1.6660 (estimate)
• Storage Temp.: Keep in dark place,Inert atmosphere,Room temperature
• PKA: 9.15±0.10(Predicted)
• Water Solubility: Practically insoluble in water
• CAS DataBase Reference: 3,3'-Dihydroxybenzidine(CAS DataBase Reference)
• NIST Chemistry Reference: 3,3'-Dihydroxybenzidine(2373-98-0)
• EPA Substance Registry System: 3,3'-Dihydroxybenzidine(2373-98-0)

Safety Data

• Hazard Codes: T
• Statements: 40-45-48-36/37/38
• Safety Statements: 22-53-45-36/37/39-26-6
• RTECS: DV4900000
• Hazardous Substances Data: 2373-98-0(Hazardous Substances Data)

Usage

Chemical Properties

A pale brown solid

Uses

Different sources of media describe the Uses of 2373-98-0 differently. You can refer to the following data:
1. 4,4'-diaminobiphenyl-3,3'-diol is used as organic intermediates.
2. 3,3''-Dihydroxybenzidine is used in preparation method of covalent organic framework-based metamaterial for optical device.

General Description

Colorless crystals.

Air & Water Reactions

Keep well closed. Protect from air and light.

Reactivity Profile

3,3'-Dihydroxybenzidine is an aminoalcohol. Amines are chemical bases. They neutralize acids to form salts plus water. These acid-base reactions are exothermic. The amount of heat that is evolved per mole of amine in a neutralization is largely independent of the strength of the amine as a base. Amines may be incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides. Flammable gaseous hydrogen is generated by amines in combination with strong reducing agents, such as hydrides.

Health Hazard

ACUTE/CHRONIC HAZARDS: When heated to decomposition 3,3'-Dihydroxybenzidine emits toxic fumes.

Safety Profile

Suspected carcinogen with experimental carcinogenic, neoplastigenic, and tumorigenic data. Mutation data reported. When heated to decomposition it emits toxic fumes of Nox

Synthetic route

3,3’-dihydroxy-4,4’-dinitrobiphenyl → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions	Yield
With sodium tetrahydroborate; nickel(II) chloride hexahydrate In tetrahydrofuran for 2h; Cooling with ice;	97.4%

C14H8N2O4 → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions	Yield
Stage #1: C14H8N2O4 With ammonium hydroxide at 100 - 110℃; under 750.075 - 2250.23 Torr; Large scale; Stage #2: With sulfuric acid at 20 - 70℃; pH=3-4; Large scale;	89.9%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions	Yield
With hydrogen iodide at 138℃;
With potassium hydroxide at 230 - 240℃; under 22065.2 - 29420.3 Torr;

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) → 3,3'-dihydroxybenzidine (2373-98-0) + 4,4'-diamino-3'-methoxy-biphenyl-3-ol (87084-62-6)

Conditions	Yield
With sulfuric acid

4,4'-diamino-3,3'-diethoxybiphenyl (6264-77-3) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions	Yield
With sodium hydroxide at 230 - 240℃; under 22065.2 - 29420.3 Torr;

3,3'-bis-sulfooxy-benzidine (738545-25-0) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions	Yield
With hydrogenchloride
With hydrogenchloride
With sulfuric acid

hydrogenchloride (7647-01-0) + 2,2'-dimethyl-[6,6']bibenzoxazolyl (6309-66-6) → 3,3'-dihydroxybenzidine (2373-98-0)

hydrogenchloride (7647-01-0) + 3,3'-bis-sulfooxy-benzidine (738545-25-0) → 3,3'-dihydroxybenzidine (2373-98-0)

sulfuric acid (7664-93-9) + 3,3'-bis-sulfooxy-benzidine (738545-25-0) → 3,3'-dihydroxybenzidine (2373-98-0)

2-amino-6-nitrophenol (603-87-2) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions

Yield

Multi-step reaction with 6 steps 1.1: triethylamine / 1,2-dichloro-ethane / 65 - 75 °C / Large scale 2.1: hydrogen; platinum on activated charcoal / 1,2-dichloro-ethane / 55 - 65 °C / 4500.45 - 6000.6 Torr / Large scale 3.1: sulfuric acid; sodium nitrite; copper(II) sulfate / isopropyl alcohol; ethyl acetate / Heating; Large scale 4.1: sulfuric acid; sodium iodide; dihydrogen peroxide / methanol / 34 - 38 °C / Large scale 5.1: palladium on activated charcoal; triethylamine / toluene / Heating; Large scale 6.1: ammonium hydroxide / 100 - 110 °C / 750.08 - 2250.23 Torr / Large scale 6.2: 20 - 70 °C / pH 3-4 / Large scale View Scheme

2,6-dinitrophenol (573-56-8) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions

Yield

Multi-step reaction with 7 steps 1.1: palladium on activated charcoal; hydrogen / 1,2-dichloro-ethane / 35 - 40 °C / 1500.15 - 4500.45 Torr / Large scale 2.1: triethylamine / 1,2-dichloro-ethane / 65 - 75 °C / Large scale 3.1: hydrogen; platinum on activated charcoal / 1,2-dichloro-ethane / 55 - 65 °C / 4500.45 - 6000.6 Torr / Large scale 4.1: sulfuric acid; sodium nitrite; copper(II) sulfate / isopropyl alcohol; ethyl acetate / Heating; Large scale 5.1: sulfuric acid; sodium iodide; dihydrogen peroxide / methanol / 34 - 38 °C / Large scale 6.1: palladium on activated charcoal; triethylamine / toluene / Heating; Large scale 7.1: ammonium hydroxide / 100 - 110 °C / 750.08 - 2250.23 Torr / Large scale 7.2: 20 - 70 °C / pH 3-4 / Large scale View Scheme

4-nitrobenzo[d]oxazol-2(3H)-one (28955-71-7) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions

Yield

Multi-step reaction with 5 steps 1.1: hydrogen; platinum on activated charcoal / 1,2-dichloro-ethane / 55 - 65 °C / 4500.45 - 6000.6 Torr / Large scale 2.1: sulfuric acid; sodium nitrite; copper(II) sulfate / isopropyl alcohol; ethyl acetate / Heating; Large scale 3.1: sulfuric acid; sodium iodide; dihydrogen peroxide / methanol / 34 - 38 °C / Large scale 4.1: palladium on activated charcoal; triethylamine / toluene / Heating; Large scale 5.1: ammonium hydroxide / 100 - 110 °C / 750.08 - 2250.23 Torr / Large scale 5.2: 20 - 70 °C / pH 3-4 / Large scale View Scheme

4-amino-2-benzoxazolone (81900-93-8) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions

Yield

Multi-step reaction with 4 steps 1.1: sulfuric acid; sodium nitrite; copper(II) sulfate / isopropyl alcohol; ethyl acetate / Heating; Large scale 2.1: sulfuric acid; sodium iodide; dihydrogen peroxide / methanol / 34 - 38 °C / Large scale 3.1: palladium on activated charcoal; triethylamine / toluene / Heating; Large scale 4.1: ammonium hydroxide / 100 - 110 °C / 750.08 - 2250.23 Torr / Large scale 4.2: 20 - 70 °C / pH 3-4 / Large scale View Scheme

2-Benzoxazolinone (59-49-4) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: sulfuric acid; sodium iodide; dihydrogen peroxide / methanol / 34 - 38 °C / Large scale 2.1: palladium on activated charcoal; triethylamine / toluene / Heating; Large scale 3.1: ammonium hydroxide / 100 - 110 °C / 750.08 - 2250.23 Torr / Large scale 3.2: 20 - 70 °C / pH 3-4 / Large scale View Scheme

1-chloro-2,6-dinitrobenzene (606-21-3) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions

Yield

Multi-step reaction with 8 steps 1.1: water / 50 - 85 °C / Alkaline conditions; Large scale 1.2: pH 1 / Large scale 2.1: palladium on activated charcoal; hydrogen / 1,2-dichloro-ethane / 35 - 40 °C / 1500.15 - 4500.45 Torr / Large scale 3.1: triethylamine / 1,2-dichloro-ethane / 65 - 75 °C / Large scale 4.1: hydrogen; platinum on activated charcoal / 1,2-dichloro-ethane / 55 - 65 °C / 4500.45 - 6000.6 Torr / Large scale 5.1: sulfuric acid; sodium nitrite; copper(II) sulfate / isopropyl alcohol; ethyl acetate / Heating; Large scale 6.1: sulfuric acid; sodium iodide; dihydrogen peroxide / methanol / 34 - 38 °C / Large scale 7.1: palladium on activated charcoal; triethylamine / toluene / Heating; Large scale 8.1: ammonium hydroxide / 100 - 110 °C / 750.08 - 2250.23 Torr / Large scale 8.2: 20 - 70 °C / pH 3-4 / Large scale View Scheme

3,3'-dihydroxybenzidine (2373-98-0) + Gold's reagent (20353-93-9) → 6,6'-bisbenzoxazole (31139-60-3)

Conditions	Yield
In 1,4-dioxane for 17h; Heating;	100%

3,3'-dihydroxybenzidine (2373-98-0) + orthoformic acid triethyl ester (122-51-0) → 6,6'-bisbenzoxazole (31139-60-3)

Conditions	Yield
for 48h; Heating;	100%

3,3'-dihydroxybenzidine (2373-98-0) + C19H21BrN2O8 → C51H54N6O19

Conditions	Yield
With calcium hydride In tetrahydrofuran for 48h; Inert atmosphere; Reflux;	98.2%

3,3'-dihydroxybenzidine (2373-98-0) + C48H79BrN2O8 → C108H168N6O18

Conditions	Yield
With calcium hydride In tetrahydrofuran for 48h; Inert atmosphere; Reflux;	98.2%

3,3'-dihydroxybenzidine (2373-98-0) + C22H27ClN2O8 → C57H66N6O19

Conditions	Yield
With sodium hydride In tetrahydrofuran for 48h; Inert atmosphere; Reflux;	98.2%

maleic anhydride (108-31-6) + 3,3'-dihydroxybenzidine (2373-98-0) → C20H16N2O8

Conditions	Yield
In acetone for 12h; Inert atmosphere;	96.5%

phthalic anhydride (85-44-9) + 3,3'-dihydroxybenzidine (2373-98-0) → 2,2'-(3,3'-dihydroxy-[1,1'-biphenyl]-4,4'-diyl)bis(isoindoline-1,3-dione)

Conditions	Yield
With isoquinoline In 1-methyl-pyrrolidin-2-one at 170℃; for 2h;	96%
With isoquinoline In 1-methyl-pyrrolidin-2-one at 170℃; for 2h;	91.4%
Stage #1: phthalic anhydride; 3,3'-dihydroxybenzidine In 1-methyl-pyrrolidin-2-one Inert atmosphere; Stage #2: With isoquinoline In 1-methyl-pyrrolidin-2-one at 170℃; for 2h;	86%
With isoquinoline In 1-methyl-pyrrolidin-2-one at 170℃; for 2h; Inert atmosphere; Schlenk technique;
With isoquinoline In 1-methyl-pyrrolidin-2-one at 120℃; for 6h;

3,3'-dihydroxybenzidine (2373-98-0) + N-bis-(methylsulfanylmethylene)benzenesulfonamide (13068-20-7) → 2,2'-bis(phenylsulfonylamino)-6,6'-bibenzoxazole (127933-42-0)

Conditions	Yield
With sodium hydroxide In N,N-dimethyl-formamide	95%
Stage #1: 3,3'-dihydroxybenzidine With sodium hydroxide In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: N-bis-(methylsulfanylmethylene)benzenesulfonamide In N,N-dimethyl-formamide for 8h; Reflux; Inert atmosphere;	80%

3,3'-dihydroxybenzidine (2373-98-0) + C22H27IN2O8 → C57H66N6O19

Conditions	Yield
With sodium carbonate In tetrahydrofuran for 8h; Inert atmosphere; Reflux;	93.8%

3,3'-dihydroxybenzidine (2373-98-0) + C22H27BrN2O8 → C57H66N6O19

Conditions	Yield
With potassium carbonate In tetrahydrofuran for 24h; Inert atmosphere; Reflux;	93.7%

3,3'-dihydroxybenzidine (2373-98-0) + 1-naphthaldehyde (66-77-3) → C34H24N2O2

Conditions	Yield
In ethanol at 78℃; for 6h;	93%

tert-butylisonitrile (119072-55-8, 7188-38-7) + 3,3'-dihydroxybenzidine (2373-98-0) → N3,N3'-di-tert-butyl-2,2'-bis(tert-butylimino)-2H,2'H-[7,7'-bibenzo[b][1,4]oxazine]-3,3'-diamine (1427468-99-2)

Conditions	Yield
With palladium dichloride In 1,4-dioxane at 50℃; for 2h;	89%

C18H12F12N2O3 (883747-51-1) + 3,3'-dihydroxybenzidine (2373-98-0) + benzene-1,3-dicarbonyl dichloride (99-63-8) → Reaxys ID: 18370081

Conditions	Yield
In N,N-dimethyl acetamide at 20℃; for 5h;	87%

3,3’-dihydroxy-4,4’-dinitrobiphenyl → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions	Yield
With sodium tetrahydroborate; nickel(II) chloride hexahydrate In tetrahydrofuran for 2h; Cooling with ice;	97.4%

C14H8N2O4 → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions	Yield
Stage #1: C14H8N2O4 With ammonium hydroxide at 100 - 110℃; under 750.075 - 2250.23 Torr; Large scale; Stage #2: With sulfuric acid at 20 - 70℃; pH=3-4; Large scale;	89.9%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions	Yield
With hydrogen iodide at 138℃;
With potassium hydroxide at 230 - 240℃; under 22065.2 - 29420.3 Torr;

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) → 3,3'-dihydroxybenzidine (2373-98-0) + 4,4'-diamino-3'-methoxy-biphenyl-3-ol (87084-62-6)

Conditions	Yield
With sulfuric acid

4,4'-diamino-3,3'-diethoxybiphenyl (6264-77-3) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions	Yield
With sodium hydroxide at 230 - 240℃; under 22065.2 - 29420.3 Torr;

3,3'-bis-sulfooxy-benzidine (738545-25-0) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions	Yield
With hydrogenchloride
With hydrogenchloride
With sulfuric acid

hydrogenchloride (7647-01-0) + 2,2'-dimethyl-[6,6']bibenzoxazolyl (6309-66-6) → 3,3'-dihydroxybenzidine (2373-98-0)

hydrogenchloride (7647-01-0) + 3,3'-bis-sulfooxy-benzidine (738545-25-0) → 3,3'-dihydroxybenzidine (2373-98-0)

sulfuric acid (7664-93-9) + 3,3'-bis-sulfooxy-benzidine (738545-25-0) → 3,3'-dihydroxybenzidine (2373-98-0)

2-amino-6-nitrophenol (603-87-2) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions

Yield

Multi-step reaction with 6 steps 1.1: triethylamine / 1,2-dichloro-ethane / 65 - 75 °C / Large scale 2.1: hydrogen; platinum on activated charcoal / 1,2-dichloro-ethane / 55 - 65 °C / 4500.45 - 6000.6 Torr / Large scale 3.1: sulfuric acid; sodium nitrite; copper(II) sulfate / isopropyl alcohol; ethyl acetate / Heating; Large scale 4.1: sulfuric acid; sodium iodide; dihydrogen peroxide / methanol / 34 - 38 °C / Large scale 5.1: palladium on activated charcoal; triethylamine / toluene / Heating; Large scale 6.1: ammonium hydroxide / 100 - 110 °C / 750.08 - 2250.23 Torr / Large scale 6.2: 20 - 70 °C / pH 3-4 / Large scale View Scheme

2,6-dinitrophenol (573-56-8) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions

Yield

Multi-step reaction with 7 steps 1.1: palladium on activated charcoal; hydrogen / 1,2-dichloro-ethane / 35 - 40 °C / 1500.15 - 4500.45 Torr / Large scale 2.1: triethylamine / 1,2-dichloro-ethane / 65 - 75 °C / Large scale 3.1: hydrogen; platinum on activated charcoal / 1,2-dichloro-ethane / 55 - 65 °C / 4500.45 - 6000.6 Torr / Large scale 4.1: sulfuric acid; sodium nitrite; copper(II) sulfate / isopropyl alcohol; ethyl acetate / Heating; Large scale 5.1: sulfuric acid; sodium iodide; dihydrogen peroxide / methanol / 34 - 38 °C / Large scale 6.1: palladium on activated charcoal; triethylamine / toluene / Heating; Large scale 7.1: ammonium hydroxide / 100 - 110 °C / 750.08 - 2250.23 Torr / Large scale 7.2: 20 - 70 °C / pH 3-4 / Large scale View Scheme

4-nitrobenzo[d]oxazol-2(3H)-one (28955-71-7) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions

Yield

Multi-step reaction with 5 steps 1.1: hydrogen; platinum on activated charcoal / 1,2-dichloro-ethane / 55 - 65 °C / 4500.45 - 6000.6 Torr / Large scale 2.1: sulfuric acid; sodium nitrite; copper(II) sulfate / isopropyl alcohol; ethyl acetate / Heating; Large scale 3.1: sulfuric acid; sodium iodide; dihydrogen peroxide / methanol / 34 - 38 °C / Large scale 4.1: palladium on activated charcoal; triethylamine / toluene / Heating; Large scale 5.1: ammonium hydroxide / 100 - 110 °C / 750.08 - 2250.23 Torr / Large scale 5.2: 20 - 70 °C / pH 3-4 / Large scale View Scheme

4-amino-2-benzoxazolone (81900-93-8) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions

Yield

Multi-step reaction with 4 steps 1.1: sulfuric acid; sodium nitrite; copper(II) sulfate / isopropyl alcohol; ethyl acetate / Heating; Large scale 2.1: sulfuric acid; sodium iodide; dihydrogen peroxide / methanol / 34 - 38 °C / Large scale 3.1: palladium on activated charcoal; triethylamine / toluene / Heating; Large scale 4.1: ammonium hydroxide / 100 - 110 °C / 750.08 - 2250.23 Torr / Large scale 4.2: 20 - 70 °C / pH 3-4 / Large scale View Scheme

2-Benzoxazolinone (59-49-4) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: sulfuric acid; sodium iodide; dihydrogen peroxide / methanol / 34 - 38 °C / Large scale 2.1: palladium on activated charcoal; triethylamine / toluene / Heating; Large scale 3.1: ammonium hydroxide / 100 - 110 °C / 750.08 - 2250.23 Torr / Large scale 3.2: 20 - 70 °C / pH 3-4 / Large scale View Scheme

1-chloro-2,6-dinitrobenzene (606-21-3) → 3,3'-dihydroxybenzidine (2373-98-0)

Conditions

Yield

Multi-step reaction with 8 steps 1.1: water / 50 - 85 °C / Alkaline conditions; Large scale 1.2: pH 1 / Large scale 2.1: palladium on activated charcoal; hydrogen / 1,2-dichloro-ethane / 35 - 40 °C / 1500.15 - 4500.45 Torr / Large scale 3.1: triethylamine / 1,2-dichloro-ethane / 65 - 75 °C / Large scale 4.1: hydrogen; platinum on activated charcoal / 1,2-dichloro-ethane / 55 - 65 °C / 4500.45 - 6000.6 Torr / Large scale 5.1: sulfuric acid; sodium nitrite; copper(II) sulfate / isopropyl alcohol; ethyl acetate / Heating; Large scale 6.1: sulfuric acid; sodium iodide; dihydrogen peroxide / methanol / 34 - 38 °C / Large scale 7.1: palladium on activated charcoal; triethylamine / toluene / Heating; Large scale 8.1: ammonium hydroxide / 100 - 110 °C / 750.08 - 2250.23 Torr / Large scale 8.2: 20 - 70 °C / pH 3-4 / Large scale View Scheme

3,3'-dihydroxybenzidine (2373-98-0) + acrolein (107-02-8) → [6,6'-biquinoline]-8,8'-diol

Conditions	Yield
With hydrogenchloride; sodium hydroxide In water for 2h; Skraup, Doebner-Miller Synthesis; Reflux;	34%

3,3'-dihydroxybenzidine (2373-98-0) + 2-(4-(dibutylamino)phenyl)-6-hydroxybenzofuran-5-carbaldehyde → C58H58N4O6

Conditions	Yield
With potassium cyanide; phenylboronic acid In methanol at 20℃; Inert atmosphere;	43%

3,3'-dihydroxybenzidine (2373-98-0) + methyl N-phenyldithiocarbamate (701-73-5) → 2,2'-bis(phenylamino)-6,6'-bibenzoxazole (127933-19-1)

Conditions	Yield
With mercury(II) oxide In N,N-dimethyl-formamide for 8h; Heating;	48%

3,3'-dihydroxybenzidine (2373-98-0) + methyl N-(4-methoxyphenyl)dithiocarbamate (34956-06-4) → 2,2'-bis(4-methoxyphenylamino)-6,6'-bibenzoxazole (127933-22-6)

Conditions	Yield
With mercury(II) oxide In N,N-dimethyl-formamide	50%

3,3'-dihydroxybenzidine (2373-98-0) + C12H14N2S3 (103588-18-7) → 2,2'-bis(5,6-dimethyl-2-benzothiazolylamino)-6,6'-bibenzoxazole

Conditions	Yield
With sodium hydroxide In N,N-dimethyl-formamide	58%

3,3'-dihydroxybenzidine (2373-98-0) + N-(4-chlorophenyl)-S-methyldithiocarbamate (705-69-1) → 2,2'-bis(4-chlorophenylamino)-6,6'-bibenzoxazole (127933-21-5)

Conditions	Yield
With mercury(II) oxide In N,N-dimethyl-formamide	60%

3,3'-dihydroxybenzidine (2373-98-0) + methyl (N-(4-methylphenyl))dithiocarbamate (13037-22-4) → 2,2'-bis(4-tolylamino)-6,6'-bibenzoxazole (127933-20-4)

Conditions	Yield
With mercury(II) oxide In N,N-dimethyl-formamide	63%

3,3'-dihydroxybenzidine (2373-98-0) + benzoyl chloride (98-88-4) → 2,2'-diphenyl-6,6'-bibenzoxazole (1724-54-5)

Conditions	Yield
Stage #1: 3,3'-dihydroxybenzidine; benzoyl chloride In 1-methyl-pyrrolidin-2-one at 0℃; for 1h; Inert atmosphere; Stage #2: With pyridine In 1-methyl-pyrrolidin-2-one for 2h; Inert atmosphere; Reflux;	65%

3,3'-dihydroxybenzidine (2373-98-0) + 4-fluorobenzenesulfonic acid sodium salt (651-07-0) → 3,3'-bis(4-sulfophenoxy)benzidine (860615-75-4)

Conditions	Yield
With potassium carbonate In 1-methyl-pyrrolidin-2-one; toluene at 20 - 170℃; for 28.5h; Inert atmosphere;	65%

3,3'-dihydroxybenzidine (2373-98-0) + dimethyl N-(1,3-benzothiazol-2-yl) dithio imidocarbonate (76423-99-9) → 2,2'-bis(2-benzothiazolylamino)-6,6'-bibenzoxazole (127933-31-7)

Conditions	Yield
With sodium hydroxide In N,N-dimethyl-formamide for 9h; Heating;	68%

3,3'-dihydroxybenzidine (2373-98-0) + N-p-Bromphenylsulfonyliminodithiokohlensaeuredimethylester (32323-85-6) → C26H16Br2N4O6S2 (1342307-99-6)

Conditions	Yield
Stage #1: 3,3'-dihydroxybenzidine With sodium hydroxide In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: N-p-Bromphenylsulfonyliminodithiokohlensaeuredimethylester In N,N-dimethyl-formamide for 8h; Reflux; Inert atmosphere;	70%

3,3'-dihydroxybenzidine (2373-98-0) + dimethyl N-<(2-chlorophenyl)sulfonyl>dithiocarbonimidate (84346-43-0) → C26H16Cl2N4O6S2 (1342307-95-2)

Conditions	Yield
Stage #1: 3,3'-dihydroxybenzidine With sodium hydroxide In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: dimethyl N-<(2-chlorophenyl)sulfonyl>dithiocarbonimidate In N,N-dimethyl-formamide for 8h; Reflux; Inert atmosphere;	72%

3,3'-dihydroxybenzidine (2373-98-0) + 4-methyl-benzoyl chloride (874-60-2) → 2,2'-di-p-tolyl-6,6'-bibenzoxazole (16155-59-2)

Conditions	Yield
Stage #1: 3,3'-dihydroxybenzidine; 4-methyl-benzoyl chloride In 1-methyl-pyrrolidin-2-one at 0℃; for 1h; Inert atmosphere; Stage #2: With pyridine In 1-methyl-pyrrolidin-2-one for 2h; Inert atmosphere; Reflux;	72%

3,3'-dihydroxybenzidine (2373-98-0) + N-[bis(methylthio)methylene]-p-toluenesulfonamide (2651-15-2) → 2,2'-bis(tosylamino)-6,6'-bibenzoxazole (127933-43-1)

Conditions	Yield
With sodium hydroxide In N,N-dimethyl-formamide	73%
Stage #1: 3,3'-dihydroxybenzidine With sodium hydroxide In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: N-[bis(methylthio)methylene]-p-toluenesulfonamide In N,N-dimethyl-formamide for 8h; Reflux; Inert atmosphere;	70%

N--4-chlorobenzenesulfonamide (13068-12-7) + 3,3'-dihydroxybenzidine (2373-98-0) → 2,2'-bis(4-chlorophenylsulfonylamino)-6,6'-bibenzoxazole (127933-44-2)

Conditions	Yield
Stage #1: 3,3'-dihydroxybenzidine With sodium hydroxide In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: N--4-chlorobenzenesulfonamide In N,N-dimethyl-formamide for 8h; Reflux; Inert atmosphere;	75%
With sodium hydroxide In N,N-dimethyl-formamide	73%

3,3'-dihydroxybenzidine (2373-98-0) + C10H9N3O2S3 (71156-12-2) → 2,2'-bis(6-nitro-2-benzothiazolylamino)-6,6'-bibenzoxazole (127933-34-0)

Conditions	Yield
With sodium hydroxide In N,N-dimethyl-formamide	75%

3,3'-dihydroxybenzidine (2373-98-0) + N--2-methylbenzenesulfonamide (32323-87-8) → C28H22N4O6S2 (1342307-93-0)

Conditions	Yield
Stage #1: 3,3'-dihydroxybenzidine With sodium hydroxide In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: N--2-methylbenzenesulfonamide In N,N-dimethyl-formamide for 8h; Reflux; Inert atmosphere;	75%

Upstream product

• 119-90-4 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine 
• 606-21-3 1-chloro-2,6-dinitrobenzene 
• 59-49-4 2-Benzoxazolinone 
• 81900-93-8 4-amino-2-benzoxazolone 
• 28955-71-7 4-nitrobenzo[d]oxazol-2(3H)-one 
• 573-56-8 2,6-dinitrophenol 
• 603-87-2 2-amino-6-nitrophenol 
• 7664-93-9 sulfuric acid 
• 738545-25-0 3,3'-bis-sulfooxy-benzidine 
• 7647-01-0 hydrogenchloride 
• 6309-66-6 2,2'-dimethyl-[6,6']bibenzoxazolyl 
• 6264-77-3 4,4'-diamino-3,3'-diethoxybiphenyl 

Downstream Products

• 17201-26-2 3,3'-([6,6']bi[benzooxazolyl]-2,2'-diyl)-bis-aniline 
• 17201-27-3 4,4'-([6,6']bi[benzooxazolyl]-2,2'-diyl)-bis-aniline 
• 142109-82-8 C₂₆H₁₆N₂O₄ 
• 1067889-45-5 C₄₆H₆₀N₂O₆ 
• 1151760-19-8 4,4'-bis[(3,4,5-tridodecyloxybenzylidene)amino]biphenyl-3,3'-diol 
• 860615-75-4 3,3'-bis(4-sulfophenoxy)benzidine 
• 1342307-99-6 C₂₆H₁₆Br₂N₄O₆S₂ 
• 1342307-98-5 C₂₆H₁₆Br₂N₄O₆S₂ 
• 1342307-97-4 C₂₆H₁₆Br₂N₄O₆S₂ 
• 1342307-96-3 C₂₆H₁₆Cl₂N₄O₆S₂ 

Relevant articles and documents

-

-

Method for synthesizing benzoxazole compound by using nitration by-products of aromatic hydrocarbon and application of benzoxazole compound

The invention discloses a method for synthesizing a benzoxazole compound by using nitration by-products of aromatic hydrocarbon and application of the benzoxazole compound. The method comprises the main process: performing step-by-step crystallization on nitration products of a 2,4-dinitrochlorobenzene production enterprise so as to obtain 2,4-dinitrochlorobenzene, 2,6-dinitrochlorobenzene (I) anda small amount of residues, adopting the obtained 2,6-dinitrochlorobenzene (I) as the main starting material, and performing hydrolysis, selective catalytic hydrogenation reduction, cyclization, halogenation, carbon-carbon coupling and other processes so as to synthesize the benzoxazole compound, wherein the obtained compound can be used as a main raw material to synthesize a series of chemical intermediates with important application, and the chemical intermediates include o-aminophenol, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol and hydrochloride of o-aminophenol, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol. Through the method, the industrial by-products are converted into high value-added aromatic aminophenol products, industrial hazardous waste of the 2,4-dinitrochlorobenzene production enterprise is reduced, the scope of products of the enterprise is widened, and the economic benefits of enterprise are increased.