496-72-0

Basic information

• Product Name: 3,4-Diaminotoluene
• Synonyms: 1,2-benzenediamine,-methyl-;1,2-Diamino-4-ethylbenzene;1,2-Diamino-4-methylbenzene;1,2-diamion-4-methylbenzene;2-Benzenediamine,4-methyl-1;3,4-Diamino-1-methylbenzene;3,4-toluenediamine(toxicliquids,organic,n.o.s.);3,4-Tolylenediamine
• CAS NO: 496-72-0
• Molecular Formula: C₇H₁₀N₂
• Molecular Weight: 122.17
• EINECS: 207-826-2
• Product Categories: Intermediates of Dyes and Pigments;Amines;Aromatics;Intermediates;Building Blocks;Chemical Synthesis;Nitrogen Compounds;Organic Building Blocks;Polyamines
• Mol File: 496-72-0.mol
• Article Data: 55

Chemical Properties

• Melting Point: 87-89 °C(lit.)
• Boiling Point: 155-156 °C18 mm Hg(lit.)
• Flash Point: 155-156°C/18mm
• Appearance: Brown to grayish-brown/Crystalline Chunks or Flakes
• Density: 1.2207 (rough estimate)
• Vapor Pressure: 0.0179mmHg at 25°C
• Refractive Index: 1.5103 (estimate)
• Storage Temp.: Keep in dark place,Inert atmosphere,Room temperature
• Solubility: Chloroform (Sparingly), Methanol (Slightly)
• PKA: 4.59±0.10(Predicted)
• Water Solubility: 16 g/L (20 ºC)
• Stability: Stable. Incompatible with strong oxidizing agents.
• BRN: 507965
• CAS DataBase Reference: 3,4-Diaminotoluene(CAS DataBase Reference)
• NIST Chemistry Reference: 3,4-Diaminotoluene(496-72-0)
• EPA Substance Registry System: 3,4-Diaminotoluene(496-72-0)

Safety Data

• Hazard Codes: Xn
• Statements: 20/21/22-36/37/38-52/53-40-36-22
• Safety Statements: 26-37/39-61-36/37/39
• RIDADR: UN 2811
• WGK Germany: 2
• RTECS: XS9820000
• TSCA: Yes
• HazardClass: 6.1(b)
• PackingGroup: III
• Hazardous Substances Data: 496-72-0(Hazardous Substances Data)

Usage

Chemical Properties

Off-white small blocks

Uses

Different sources of media describe the Uses of 496-72-0 differently. You can refer to the following data:
1. 5-Methylbenzotriazole intermediate.
2. 4-Methyl-o-phenylenediamine was employed as chromogenic reagent in the spectrophotometric determination of selenium(IV). It was used in the synthesis of an asymmetrical tetradentate Schiff base via condensation with dehydroacetic acid and salicylic aldehyde.

General Description

A colorless to brownish purple crystalline solid. Toxic by ingestion and inhalation and an irritant to skin and eyes. Soluble in water, alcohol and ether. Decomposes to emit toxic oxides of nitrogen when heated to high temperature. Used in making dyes.

Air & Water Reactions

Insoluble in water.

Reactivity Profile

3,4-Diaminotoluene neutralizes acids in exothermic reactions to form salts plus water. May be incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides. Flammable gaseous hydrogen may be generated in combination with strong reducing agents, such as hydrides.

Fire Hazard

Flash point data for 3,4-Diaminotoluene are not available. 3,4-Diaminotoluene is probably combustible.

InChI:InChI=1/C8H12N2/c9-5-7-3-1-2-4-8(7)6-10/h1-4H,5-6,9-10H2

Synthetic route

4-methyl-2-nitroaniline (89-62-3) → 4-methyl-1,2-diaminobenzene (496-72-0)

Conditions	Yield
With hydrogen; nickel In methanol at 65 - 75℃; for 1h; Autoclave; Inert atmosphere;	97%
With aluminum oxide; hydrazine hydrate; iron(III) chloride at 111℃; for 0.1h; Irradiation; microwave;	96%
With hydrazine hydrate In ethanol at 70℃; for 4h; chemoselective reaction;	94%

3,4-Dinitrotoluene (610-39-9) → 4-methyl-1,2-diaminobenzene (496-72-0)

Conditions	Yield
With 5%-palladium/activated carbon; hydrogen In ethanol at 20℃; for 48h;	96.6%
With hydrogen In methanol at 50℃; under 1500.15 Torr; for 0.25h; Inert atmosphere;	88%
With 5 wt% ruthenium/carbon; hydrogen; sodium nitrite In isopropyl alcohol at 150℃; under 62256.2 Torr; for 4h; Temperature; Autoclave;

5-methylbenzo[c][1,2,5]thiadiazole (1457-93-8) → 4-methyl-1,2-diaminobenzene (496-72-0)

Conditions	Yield
With methanol; samarium diiodide In tetrahydrofuran at 20℃; for 0.333333h;	91%
With magnesium In methanol at 45 - 60℃; for 1.83333h;	86%

2-nitro-5,5'-dimethylazobenzene → 4-methyl-1,2-diaminobenzene (496-72-0)

Conditions	Yield
With formic acid; zinc In methanol at 20℃; for 24h; Inert atmosphere;	90%

5-methyl-2-nitroaniline (578-46-1) → 4-methyl-1,2-diaminobenzene (496-72-0)

Conditions	Yield
With tetrahydroxydiboron; water at 80℃; for 8h;	86%
With tetrahydroxydiboron; 5%-palladium/activated carbon; water In acetonitrile at 50℃; for 24h;	80%
With hydrogenchloride; tin

5-methylbenzofuroxan (19164-41-1) → 4-methyl-1,2-diaminobenzene (496-72-0)

Conditions	Yield
With ammonium sulfate; magnesium In methanol Ambient temperature;	80%
With Saccharomyces cerevisiae BY In methanol at 20℃; for 6.5h; pH=7.0; aq. buffer; Enzymatic reaction;	80%

2-nitro-4,4'-dimethylazobenzene → 4-methyl-1,2-diaminobenzene (496-72-0)

Conditions	Yield
With formic acid; zinc In methanol at 20℃; for 10h; Inert atmosphere;	76%

2-amino-4-methylacetanilide (53476-34-9) → 2,5-dimethylbenzimidazole (1792-41-2) + 4-methyl-1,2-diaminobenzene (496-72-0)

Conditions	Yield
Erhitzen;

(4-amino-3-nitrophenyl)methanol (63189-97-9) → 4-methyl-1,2-diaminobenzene (496-72-0)

Conditions	Yield
With hydrogenchloride; tin

(E)-1-(4-methyl-2-nitrophenyl)-2-(p-tolyl)diazene → 4-methyl-1,2-diaminobenzene (496-72-0)

Conditions	Yield
With hydrogenchloride; tin

bis-(4-methyl-2-nitro-phenyl)-diazene → 4-methyl-1,2-diaminobenzene (496-72-0)

Conditions	Yield
With hydrogenchloride; tin

bis-(4-methyl-2-p-tolylazo-phenyl)-diazene → p-toluidine (106-49-0) + 4-methyl-1,2-diaminobenzene (496-72-0)

Conditions	Yield
bei reduktiver Spaltung;

4-methyl-2-p-tolylazo-aniline (58010-91-6) → p-toluidine (106-49-0) + 4-methyl-1,2-diaminobenzene (496-72-0)

Conditions	Yield
durch Reduktionsmittel;

4-methyl-2-p-tolylazo-aniline (58010-91-6) → 4-methyl-1,2-diaminobenzene (496-72-0)

Conditions	Yield
bei der Reduktion;

4,4'-dimethyl-2-nitro-ONN-azoxybenzene (102276-78-8) → p-toluidine (106-49-0) + 4-methyl-1,2-diaminobenzene (496-72-0) + C14H17N3

Conditions	Yield
With hydrogenchloride; acetic acid; tin(ll) chloride for 2h; Title compound not separated from byproducts;

4,4'-dimethyl-2,3'-dinitro-ONN-azoxybenzene (102276-79-9) → 4-methylbenzene-1,3-diamine (95-80-7) + 4-methyl-1,2-diaminobenzene (496-72-0) + C14H16N4O

Conditions	Yield
With hydrogenchloride; acetic acid; tin(ll) chloride for 3h; Title compound not separated from byproducts;

hydrogenchloride (7647-01-0) + 5-Methyl-benzo[1,2,5]selenadiazole (1123-91-7, 37159-63-0) + tin dichloride → 4-methyl-1,2-diaminobenzene (496-72-0) + selenium

hydrogenchloride (7647-01-0) + 5-Methyl-benzo[1,2,5]selenadiazole (1123-91-7, 37159-63-0) + tin → 4-methyl-1,2-diaminobenzene (496-72-0) + selen(o) hydrogen

anhydro-<3-nitro-4-amino-benzyl alcohol → 4-methyl-1,2-diaminobenzene (496-72-0)

Conditions	Yield
With hydrogenchloride; tin

ethanol (64-17-5) + 4-methyl-2-nitroaniline (89-62-3) + sodium amalgam → 4-methyl-1,2-diaminobenzene (496-72-0)

hydrogenchloride (7647-01-0) + 4-methyl-2-nitroaniline (89-62-3) + tin → 4-methyl-1,2-diaminobenzene (496-72-0)

4-methyl-2-nitroaniline (89-62-3) + zinc + alcoholic KOH-solution → 4-methyl-1,2-diaminobenzene (496-72-0)

ethanol (64-17-5) + acetic acid (64-19-7) + 2-(2-(4-methyl-2-nitrophenyl)hydrazono)-3-oxo-N-phenylbutanamide (26128-86-9) + zinc dust → 4-methyl-1,2-diaminobenzene (496-72-0) + 3.6-dimethyl-dihydropyrazine-dicarboxylic acid-(2.5)-dianilide

4-methyl-2-p-tolylazo-aniline (58010-91-6) → p-toluidine (106-49-0) + 4-methyl-1,2-diaminobenzene (496-72-0) + 2-p-tolyl-5-methyl-benztriazole

Conditions	Yield
at 300℃;

hydrogenchloride (7647-01-0) + (4-methyl-2-nitro-phenylhydrazono)-phenyl-acetonitrile (69864-29-5) + tin → hydrogen cyanide (74-90-8) + 4-methyl-1,2-diaminobenzene (496-72-0) + benzoic acid (65-85-0)

hydrogenchloride (7647-01-0) + 3,4-Dinitrotoluene (610-39-9) + tin (II)-chloride → 5-methyl-2-nitroaniline (578-46-1) + 4-methyl-1,2-diaminobenzene (496-72-0) + 4-methyl-2-nitroaniline (89-62-3)

Conditions	Yield
at 7℃;

hydrogenchloride (7647-01-0) + (4-amino-3-nitrophenyl)methanol (63189-97-9) + tin → 4-methyl-1,2-diaminobenzene (496-72-0)

Conditions	Yield
durch laengeres Behandeln;

hydrogenchloride (7647-01-0) + ethanol (64-17-5) + trichloro-acetic acid-(4-methyl-2-nitro-anilide) (339590-78-2) + tin → 4-methyl-1,2-diaminobenzene (496-72-0)

hydrogenchloride (7647-01-0) + bis-(4-methyl-2-nitro-phenyl)-diazene + tin → 4-methyl-1,2-diaminobenzene (496-72-0)

glycolic Acid (79-14-1) + 4-methyl-1,2-diaminobenzene (496-72-0) → (5-methyl-1H-benzimidazole-2-yl)methanol (20034-02-0)

Conditions	Yield
With hydrogenchloride In water for 3h; Reflux;	100%
With hydrogenchloride In water for 6h; Reflux;	83%
With phosphoric acid at 130℃; for 3h;	72%

4-methyl-1,2-diaminobenzene (496-72-0) + benzil (134-81-6) → 2,3-diphenyl-6-methylquinoxaline (16107-85-0)

Conditions	Yield
at 100℃; for 0.25h;	100%
With gallium(III) triflate In ethanol at 20℃; for 0.0833333h;	100%
With aluminum oxide at 20℃; for 0.166667h; neat (no solvent);	100%

4-methyl-1,2-diaminobenzene (496-72-0) + dimethylglyoxal (431-03-8) → 2,3,6-trimethylquinoxaline (17635-21-1)

Conditions	Yield
With zirconium(IV) chloride In methanol at 20℃; for 0.0833333h;	100%
With silica-supported stannous chloride In methanol at 20℃; for 0.0333333h;	99%
With zirconium oxide salicylaldehyde-(3-aminopropyl)trimethoxysilane imine complex modified SBA-15 In water for 0.1h; Reflux;	99%

4-methyl-1,2-diaminobenzene (496-72-0) + 1,2-bis(4-methoxyphenyl)-1,2-ethanedione (1226-42-2) → 2,3-bis-(4-methoxy-phenyl)-6-methyl-quinoxaline

Conditions	Yield
at 80℃; for 1h; solid-state reaction;	100%
With zirconium(IV) chloride In methanol at 20℃; for 0.5h;	100%
With aluminum oxide at 20℃; for 0.166667h; neat (no solvent);	99%

furil (492-94-4) + 4-methyl-1,2-diaminobenzene (496-72-0) → 2,3-di(furan-2-yl)-6-methyl-quinoxaline

Conditions	Yield
With gallium(III) triflate In ethanol at 20℃; for 0.166667h;	100%
With amberlyst-15 In water at 70℃; for 0.183333h;	99%
With aluminum oxide at 20℃; for 0.166667h; neat (no solvent);	99%

4-methyl-1,2-diaminobenzene (496-72-0) + orthoformic acid triethyl ester (122-51-0) → 6-methyl-1H-benzo[d]imidazole (614-97-1)

Conditions	Yield
With zirconium(IV) chloride In methanol at 20℃; for 3h;	100%
With sulfonated rice husk ash In neat (no solvent) at 60℃; for 0.116667h;	95%
With nano-Ni(II)/Y zeolite catalyst In neat (no solvent) at 60℃; for 1.33333h; Green chemistry;	83%
With silica tungstic acid at 80℃; for 0.2h; Neat (no solvent);	80%
With iron oxide In neat (no solvent) at 80℃; for 0.6h; Green chemistry;	77%

4-methyl-1,2-diaminobenzene (496-72-0) + Trichloroacetyl isocyanate (3019-71-4) → 2,2,2-trichloro-N-(5-methyl-1H-benzimidazol-2-yl)acetamide + 2,2,2-trichloro-N-(6-methyl-1H-benzimidazol-2-yl)acetamide

Conditions	Yield
In dichloromethane at -10 - 20℃; Overall yield = 88 %;	A 100% B n/a

C12H15IO2 (1083427-54-6) + 4-methyl-1,2-diaminobenzene (496-72-0) → C31H36I2N2O2

Conditions	Yield
In ethanol at 80℃; for 8h; Inert atmosphere;	100%

4-methyl-1,2-diaminobenzene (496-72-0) + furoin (552-86-3) → 2,3-di(furan-2-yl)-6-methyl-quinoxaline

Conditions	Yield
With [P4-VP]-PdNPs In N,N-dimethyl-formamide at 120℃; for 0.0133333h; Reflux;	99%
With morpholine; iron(III) chloride In ethanol at 80℃; for 1.5h;	94%
With 5% ruthenium on carbon; oxygen In water at 75℃; for 24h;	89%

4-methyl-1,2-diaminobenzene (496-72-0) + 1,1'-carbonyldiimidazole (530-62-1) → 5-methyl-1,3-dihydro-2H-benzimidazol-2-one (5400-75-9)

Conditions	Yield
In N,N-dimethyl-formamide at 20℃; for 15h;	99%
In tetrahydrofuran; dichloromethane at 20℃; for 8h;	89%
In tetrahydrofuran at 20℃;	82%

indan-1,2,3-trione hydrate (485-47-2) + 4-methyl-1,2-diaminobenzene (496-72-0) → 7-methyl-11H-indeno[1,2-b]quinoxalin-11-one

Conditions	Yield
In water at 30℃; for 0.00972222h; Irradiation; Sonication; Green chemistry;	99%
With bismuth(lll) trifluoromethanesulfonate In water at 20℃; for 0.1h;	91%
In ethanol for 2h; Heating;

4-nitrobenzaldehdye (555-16-8) + 4-methyl-1,2-diaminobenzene (496-72-0) → 5‐methyl‐2‐(4‐nitrophenyl)‐1H‐benzo[d]imidazole (69570-93-0)

Conditions	Yield
With hydrogenchloride; dihydrogen peroxide In acetonitrile at 20℃; for 0.833333h;	99%
With silica-bound phosphoric acid In water at 70℃; for 0.00416667h;	95%
With oxygen In water; acetonitrile at 20℃; under 760.051 Torr; for 24h; Sealed tube; Green chemistry;	94%

1,10-phenanthroline-5,6-dione (27318-90-7) + 4-methyl-1,2-diaminobenzene (496-72-0) → 7-methyldipyrido[3,2-a:2’,3’-c]phenazine (205367-28-8)

Conditions	Yield
With sulfated titania (TiO2-SO42-) In ethanol at 20℃; for 0.133333h;	99%
With sulfated TiO2-P25 (Degussa titania) for 0.0333333h; Microwave irradiation; Neat (no solvent);	99%
With sulfate loaded TiO2 for 0.0333333h; Microwave irradiation; Neat (no solvent);	99%

cyclohexanone (108-94-1) + 4-methyl-1,2-diaminobenzene (496-72-0) → 8'-methyl-1',2',3',4',10',11a'-hexahydrospiro[cyclohexane-1,11'-dibenzo[b,e][1,4]diazepine]

Conditions	Yield
With iodine In acetonitrile at 25℃; for 0.0333333h;	99%
at 26 - 30℃; for 3.5h; Ionic liquid;	95%
With salicylic acid at 20℃; for 1h;	92%

Triethyl orthoacetate (78-39-7) + 4-methyl-1,2-diaminobenzene (496-72-0) → 2,5-dimethylbenzimidazole (1792-41-2)

Conditions	Yield
With nano-Ni(II)/Y zeolite catalyst In neat (no solvent) at 60℃; for 0.766667h; Green chemistry;	99%
With [PVP-SO3H] HSO4 at 60℃; for 0.0666667h;	96%
With ammonium chloride In water Inert atmosphere; Reflux; Green chemistry;	95%

2-chloro-benzaldehyde (89-98-5) + 4-methyl-1,2-diaminobenzene (496-72-0) → 2-(2-chloro-phenyl)-5-methyl-1(3)H-benzoimidazole (14225-76-4)

Conditions	Yield
With hydrogenchloride; dihydrogen peroxide In acetonitrile at 20℃; for 0.666667h;	99%
With air In 1,4-dioxane at 100℃; for 20h;	90%
With methanesulfonic acid; silica gel In neat (no solvent) at 90℃; for 6h; Green chemistry;	82%
With TCCA In 1,4-dioxane; acetonitrile at 20℃; for 1.83333h;	80%

1,2-di(4-methylphenyl)-1,2-ethanedione (3457-48-5) + 4-methyl-1,2-diaminobenzene (496-72-0) → 6-methyl-2,3-di-p-tolylquinoxaline (16107-87-2)

Conditions	Yield
With Cs(cetyltrimethylammonium)2PW12O40 In neat (no solvent) at 80℃; for 0.166667h; Green chemistry;	99%
With zirconium tetrakis(dodecyl sulfate) In water at 20℃; for 0.583333h;	95%
at 120℃; for 0.0666667h; Microwave irradiation;	95%

4-hydroxy-benzaldehyde (123-08-0) + 4-methyl-1,2-diaminobenzene (496-72-0) → 2-(4-hydroxyphenyl)-5-methylbenzimidazole

Conditions	Yield
With sodium metabisulfite; air In N,N-dimethyl-formamide at 90℃; for 2h;	99%
With sodium metabisulfite In ethanol; water at 20℃; for 2h;	89%
With sodium disulfite for 0.0133333h; microwave irradiation;	85%
With sodium metabisulfite In N,N-dimethyl-formamide at 100℃; for 42h;	69%

di-tert-butyl dicarbonate (24424-99-5) + 4-methyl-1,2-diaminobenzene (496-72-0) → N, N'-di-(tert-butoxycarbonyl)-3,4-diaminotoluene (1282523-80-1)

Conditions	Yield
With iron oxide In ethanol at 20℃; for 0.75h; Green chemistry; chemoselective reaction;	99%
With guanidine hydrochloride In ethanol at 35 - 40℃; for 0.333333h;	94%
With [H2-cryptand 222](Br3)2 In acetonitrile at 20℃; for 8h; chemoselective reaction;	70%
Stage #1: di-tert-butyl dicarbonate With C12H24KO6(1+)*Br3H(1-) In ethanol at 20℃; for 0.0166667h; Stage #2: 4-methyl-1,2-diaminobenzene In ethanol at 20℃; for 4.25h;	65%

carbon dioxide (124-38-9) + 4-methyl-1,2-diaminobenzene (496-72-0) → 5-methyl-1,3-dihydro-2H-benzimidazol-2-one (5400-75-9)

Conditions	Yield
With tetrabutylammonium tungstate In 1-methyl-pyrrolidin-2-one at 139.84℃; under 15001.5 Torr; for 24h; Autoclave;	99%
In tetrahydrofuran; water at 20℃; under 7500.75 Torr; for 9h; UV-irradiation;	99%
With Sn(IV)-doped DFNS supported CdSnO3 nanoparticles under 11251.1 Torr; for 1h; UV-irradiation;	98%

4-methyl-1,2-diaminobenzene (496-72-0) + benzyl alcohol (100-51-6) → 5-methyl-2-phenyl-1H-1,3-benzimidazole (2963-65-7)

Conditions	Yield
With C19H35Cl2CoN2P; sodium triethylborohydride In toluene at 150℃; for 24h; Molecular sieve; Schlenk technique;	99%
With trans-bis(quinoline-2-carboxylato)bis(ethanol)cobalt(II); sodium carbonate In acetonitrile at 20℃; for 2h;	90%
With C56H86Cl3IrN2P2Ru Schlenk technique; Inert atmosphere;	89%

2-Formylphenoxyacetic acid (6280-80-4) + 4-methyl-1,2-diaminobenzene (496-72-0) + 2-CHLOROBENZYLAMINE (89-97-4) → C23H20ClN3O2

Conditions	Yield
With natural silk-supported manganese(II) tetrasulfophthalocyanine In water at 20℃; for 8h; Green chemistry;	99%

4-Methylbenzyl alcohol (589-18-4) + 4-methyl-1,2-diaminobenzene (496-72-0) → 5-methyl-2-(4-methylphenyl)-1H-benzimidazole (7118-66-3)

Conditions	Yield
With C19H35Cl2CoN2P; sodium triethylborohydride In toluene at 150℃; for 24h; Molecular sieve; Schlenk technique;	99%
Stage #1: 4-Methylbenzyl alcohol With N-hydroxyphthalimide; Mo72V30; oxygen In ethyl acetate at 70℃; for 6.5h; Stage #2: 4-methyl-1,2-diaminobenzene In ethyl acetate	87%
With N-hydroxyphthalimide at 70℃; for 3h;	79%
With C13H16MnN2O3S(1+)*Br(1-); potassium hydroxide In neat (no solvent) at 140℃; for 20h;	74%

4-methyl-1,2-diaminobenzene (496-72-0) + hexan-1-ol (111-27-3) → 5-methyl-2-pentyl-1H-benzo[d]imidazole

Conditions	Yield
With C19H35Cl2CoN2P; sodium triethylborohydride In toluene at 150℃; for 24h; Molecular sieve; Schlenk technique;	99%
With 1,10-Phenanthroline; potassium tert-butylate; nickel dichloride In toluene at 140℃; for 24h; Schlenk technique; Inert atmosphere; Sealed tube;	45%

1,2-di(thiophen-2-yl)ethyne (23975-15-7) + 4-methyl-1,2-diaminobenzene (496-72-0) → 6-methyl-2,3-di-2-thiophenylquinoxaline

Conditions	Yield
With dimethyl sulfoxide at 140℃; for 3.5h; Sealed tube;	99%

1-naphthaldehyde (66-77-3) + 4-methyl-1,2-diaminobenzene (496-72-0) → ((2-amino-5-methylphenyl)amino)(naphthalen-1-yl)methanol

Conditions	Yield
With polyamine dendrimer with glycerol initiated polyepichlorohydrin; air In ethanol at 20℃; for 0.0333333h;	99%

benzaldehyde (100-52-7) + 4-methyl-1,2-diaminobenzene (496-72-0) → 5-methyl-2-phenyl-1H-1,3-benzimidazole (2963-65-7)

Conditions	Yield
With hydrogenchloride; dihydrogen peroxide In acetonitrile at 20℃; for 0.666667h;	98%
With sodium hydrogensulfite In N,N-dimethyl acetamide at 100℃; for 2h;	98.9%
With ammonium peroxydisulfate; sodium dodecyl-sulfate In water at 25℃; for 0.3h; Micellar solution;	98%

acetic anhydride (108-24-7) + 4-methyl-1,2-diaminobenzene (496-72-0) → 3,4-diacetylaminotoluene (5433-07-8)

Conditions	Yield
With Co3O4 nanoparticles at 20℃; for 0.2h; Green chemistry;	98%
In water at 50℃; for 0.133333h;	91%

Glyoxal (131543-46-9) + 4-methyl-1,2-diaminobenzene (496-72-0) → 6-methylquinoxaline (6344-72-5)

Conditions	Yield
With 10 wtpercent sulfated polyborate In neat (no solvent) at 100℃; for 0.05h; Green chemistry;	98%
With Polystyrene-Supported AlCl3 In ethanol for 0.2h; Reflux;	94%
With potassium fluoride on basic alumina at 20℃; for 1h;	92%

4-methyl-1,2-diaminobenzene (496-72-0) + 9,10-phenanthrenequinone (84-11-7) → 11-methyl-dibenzo[a,c]phenazine (4559-60-8)

Conditions	Yield
With calcium hydrogensulfate In ethanol at 20℃; for 0.0833333h;	98%
With N,N,N’,N’-tetrabromobenzene-1,3-disulfonamide In neat (no solvent) at 80℃; for 0.133333h;	97%
With 1-(propyl-3-sulfonate) 3-methylimidazol(3H)-1-ium phosphotungstate In water at 20℃; for 0.166667h; Reagent/catalyst; Time;	97%

Upstream product

• 89-62-3 4-methyl-2-nitroaniline 
• 19164-41-1 5-methylbenzofuroxan 
• 7647-01-0 hydrogenchloride 
• 69864-29-5 (4-methyl-2-nitro-phenylhydrazono)-phenyl-acetonitrile 
• 63189-97-9 (4-amino-3-nitrophenyl)methanol 
• 588-04-5 3,3'-dimethylazobenzene 
• 82257-37-2 5-methyl-1H,3H-2,1,3-benzothiadiazole 2,2-dioxide 
• 612-45-3 4-methyl-2-nitroacetanilide 
• 106-49-0 p-toluidine 
• 103-89-9 4-Methylacetanilide 
• 610-39-9 3,4-Dinitrotoluene 
• 108-44-1 1-amino-3-methylbenzene 
• 501-60-0 1,2-di(p-tolyl)diazene 
• 955-98-6 1,2-bis(4-methylphenyl)diazene oxide 

Downstream Products

• 1034250-03-7 2-methyl-3-N-ethyl-5-methylbenzimidazole 
• 23291-66-9 2,4-dimethylbenzimidazole 
• 2963-65-7 5-methyl-2-phenyl-1H-1,3-benzimidazole 
• 100381-43-9 1,2,3,4-tetrahydro-7-methylphenazine 
• 72553-50-5 6''-methyl-5'''-phenyl-trispiro[bis-cyclohexane-1,1'';1',3''-cyclopenta[b]quinoxaline-2'',4'''-oxazol]-5'''-one 
• 95843-35-9 5-methyl-2-phenyl-2,3-dihydro-1H-benzo[1,3,2]diazaphosphole 2-oxide 
• 94784-36-8 bis-(2-chloro-ethyl)-(5-methyl-2-oxo-2,3-dihydro-1H-2λ⁵-benzo[1,3,2]diazaphosphol-2-yl)-amine 
• 66608-31-9 4-Methyl-N,N'-bis-(N-diethoxyphosphoryl-thiocarbamoyl)-1,2-phenylendiamin 
• 66608-47-7 4-Methyl-N,N'-bis-(N-diisopropoxyphosphoryl-thiocarbamoyl)-1,2-phenylendiamin 
• 33873-18-6 3-benzylidene-1,2-epoxy-7-methyl-1,3a-diphenyl-2,3,3a,4-tetrahydro-1H-cyclopenta[b]quinoxaline-2-carboxylic acid methyl ester 
• 33873-19-7 3-benzylidene-1,2-epoxy-7-methyl-1,3a-diphenyl-2,3,3a,4-tetrahydro-1H-cyclopenta[b]quinoxaline-2-carboxylic acid ethyl ester 
• 3878-24-8 5-methyl-2-(thiophen-2-yl)-1H-benzo[d]imidazole 
• 4600-16-2 5-Methyl-2-phenyl-2,3-dihydro-1H-1,3,2-benzodiazaphosphol-2-sulfid 
• 70376-38-4 N,N'-(4-methyl-1,2-phenylene)bis(4-methylbenzenesulfonamide) 

Relevant articles and documents

Differential antiproliferative activity of new benzimidazole-4,7-diones

Ten benzimidazole-4,7-diones were synthesized and tested in vitro on two tumor cell lines. Several compounds showed a significant antiproliferative activity on K562 cells, although to a different extent, whereas compound 1i showed a highly significant activity on SW620 cells, comparable to that of doxorubicin. Both the substituents in the quinone ring and the position of the nitrogen atom in the pyridine moiety play a crucial role for the biological activity.

Novel cathepsin K inhibitors block osteoclasts in vitro and increase spinal bone density in zebrafish

Cathepsin K (Cat K) is a predominant cysteine protease and highly potent collagenase expressed in osteoclasts. Cat K inhibitors are anti-resorptive agents to treat osteoporosis. A novel scaffold of cathepsin K inhibitors, exemplified by lead compound 1x, was used as the template for designing and synthesizing a total of 61 derivatives that have not been reported before. An exploratory structure-activity relationship analysis identified the potent Cat K inhibitor A22, which displayed an IC50 value of 0.44 μM against Cat K. A22 was very specific for Cat K and caused a significantly higher in vitro inhibition of the enzyme as compared to that of lead compound 1x. A surface plasmon resonance analysis confirmed in vitro binding of A22 to Cat K. Molecular docking studies indicated several favourable interaction sites for A22 within the active pocket of Cat K. Furthermore, A22 also blocked active osteoclasts in vitro and increased spinal bone density in zebrafish, in which it showed an activity that was higher than that of the marketed therapeutic bone metabolizer etidronate disodium. A22 represents a very promising lead compound for the development of novel antiresorptive agents functioning as orthosteric inhibitors of Cat K.

Green synthesis and: In situ immobilization of gold nanoparticles and their application for the reduction of p -nitrophenol in continuous-flow mode

A green and facile method has been developed for the preparation of in situ immobilized gold nanoparticles (AuNPs) using agarose as a reducing and stabilizing agent. The size of the synthesized AuNPs ranges between 10 and 100 nm, and their average size can be controlled by the concentrations of the agarose and gold salt. The agarose matrix as a mild and green reaction medium can provide a good dispersion environment for forming AuNPs, and the hydrogel can be well homogenized with polyacrylic macroporous microbeads as well, which can adsorb and stabilize the particles leading to the simultaneous synthesis and immobilization of AuNPs avoiding harmful inorganic compounds or organic solvents. The supported gold nanocatalyst was successfully applied as a catalyst in packed bed reactors for efficient NaBH4-mediated reduction of p-nitrophenol in continuous-flow mode.