84-67-3

Basic information

• Product Name: M-TOLIDINE
• Synonyms: 2,2'-DIMETHYL-4,4'-DIAMINOBIPHENYL;APB-144;M-TOLIDINE;1’-Biphenyl]-4,4’-diamine,2,2’-dimethyl-[1;2,2’-dimethylbenzidine;2,2'-dimethyl[1,1'-biphenyl]-4,4'-diamine;4-(4-amino-2-methylphenyl)-3-methylbenzenamine;4,4'-Diamino-2,2'-dimethylbiphenyl
• CAS NO: 84-67-3
• Molecular Formula: C₁₄H₁₆N₂
• Molecular Weight: 212.29
• EINECS: 201-551-1
• Product Categories: Intermediates of Dyes and Pigments;fine chemicals, specialty chemicals, intermediates, electronic chemical, organic synthesis;fine chemicals, specialty chemicals, intermediates, electronic chemical, organic synthesis, functional materials
• Mol File: 84-67-3.mol
• Article Data: 6

Chemical Properties

• Melting Point: 105-106℃
• Boiling Point: 344.4 °C at 760 mmHg
• Flash Point: 192.9 °C
• Appearance: /
• Density: 1.106
• Vapor Pressure: 6.61E-05mmHg at 25°C
• Refractive Index: 1.638
• Storage Temp.: Keep in dark place,Sealed in dry,Room Temperature
• Solubility: Chloroform (Slightly), Methanol (Slightly)
• PKA: 4.89±0.10(Predicted)
• CAS DataBase Reference: M-TOLIDINE(CAS DataBase Reference)
• NIST Chemistry Reference: M-TOLIDINE(84-67-3)
• EPA Substance Registry System: M-TOLIDINE(84-67-3)

Safety Data

• Safety Statements: 24/25
• Hazardous Substances Data: 84-67-3(Hazardous Substances Data)

Usage

Chemical Properties

Pink particles

Uses

Different sources of media describe the Uses of 84-67-3 differently. You can refer to the following data:
1. 2,2''-Dimethyl-[1,1''-biphenyl]-4,4''-diamine (cas# 84-67-3) is a useful reagent for manufacturing cured films and semiconductor devices.
2. M-TOLIDINE is used for preparation polyimide and epoxy resin material.

Preparation

M-Tolidine is made by the reduction of m-nitrotoluene with zinc dust and sodium hydroxide solution. The subsequent rearrangement is carried out with hydrochloric acid or sulfuric acid and gives rise to m-tolidine dihydrochloride or m-tolidine sulfate, which are isolated as salts. The free base is diffificult to isolate and is therefore not a commercial product.

Chemical Reactivity

M-Tolidine gives no color in the presence of iron(III) chloride. It is tetrazotized with nitrite and acid and couples to form dyes.

InChI:InChI=1/C14H16N2/c1-9-7-11(15)3-5-13(9)14-6-4-12(16)8-10(14)2/h3-8H,15-16H2,1-2H3

Synthetic route

1-methyl-3-nitrobenzene (99-08-1) → 2,2'-dimethylbenzidine (84-67-3)

Conditions	Yield
With 1,4-dihydroxy-9,10-anthracenedione; platinum on activated charcoal; hydrogen; sodium hydroxide In 5,5-dimethyl-1,3-cyclohexadiene; water at 65 - 75℃; under 6750.68 Torr; for 8h; Solvent; Reagent/catalyst; Pressure; Temperature; Autoclave;	79.2%
With sodium hydroxide; ethanol; zinc man gibt weitere 150 g Zinkstaub hinzu und kocht dann mit Salzsaeure; das ausgeschiedene Tolidinhydrochlorid bringt man durch Wasser in Loesung und faellt es durch konz.Salzsaeure wieder aus;
(i) Zn, aq. NaOH, (ii) aq. HCl, Et2O; Multistep reaction;
Multi-step reaction with 3 steps 1: alcoholic potash 2: alcoholic ammonium sulfide 3: diluted alcohol; diluted sulfuric acid View Scheme
Multi-step reaction with 2 steps 1: zinc; sodium hydroxide / water; ethanol / 4 h / Reflux; Inert atmosphere 2: hydrogenchloride / water / 5 h / Inert atmosphere; Reflux View Scheme

2,2'-dimethyl-4,4'-dinitro-biphenyl (59517-20-3) → 2,2'-dimethylbenzidine (84-67-3)

Conditions	Yield
With 3% Pd/C; hydrazine In ethanol at 100℃; for 12h;	76%
With ethanol; nickel Hydrogenation;
With hydrogenchloride; zinc

3,3'-dimethylazobenzene (588-04-5) → 2,2'-dimethylbenzidine (84-67-3)

Conditions	Yield
With hydrogenchloride; ethanol; tin(ll) chloride
With hydrogen sulfide; ammonia Durch Ansaeuern des Reaktionsproduktes mit Salzsaeure;
Multi-step reaction with 2 steps 1: alcoholic ammonium sulfide 2: diluted alcohol; diluted sulfuric acid View Scheme
With hydrogenchloride; sulfur dioxide; potassium iodide

3,3'-dimethylhydrazobenzene (621-26-1) → 2,2'-dimethylbenzidine (84-67-3)

Conditions	Yield
With ethanol; sulfuric acid
With hydrogenchloride In water for 5h; Inert atmosphere; Reflux;

3,3'-dimethylhydrazobenzene (621-26-1) + acid → 2,2'-dimethylbenzidine (84-67-3)

ethanol (64-17-5) + 3,3'-dimethylazobenzene (588-04-5) + HCl-salt tin dichloride → 2,2'-dimethylbenzidine (84-67-3)

Conditions	Yield
durch elektrochemischen Reduktion;

hydrogenchloride (7647-01-0) + sulphurous acid (7782-99-2) + 3,3'-dimethylazobenzene (588-04-5) + potassium iodide → 2,2'-dimethylbenzidine (84-67-3)

Conditions	Yield
at 40 - 50℃;

2-iodo-5-nitrotoluene (5326-38-5) → 2,2'-dimethylbenzidine (84-67-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: copper-powder / 280 °C 2: Raney nickel; ethanol / Hydrogenation View Scheme

C40H32N2 (1221066-39-2) → 2,2'-dimethylbenzidine (84-67-3)

Conditions	Yield
With hydrogenchloride In tetrahydrofuran; water at 20℃; for 2h;

2-bromo-5-nitrotoluene (7149-70-4) → 2,2'-dimethylbenzidine (84-67-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: copper / N,N-dimethyl-formamide / 12 h / 160 °C 2: hydrazine; 3% Pd/C / ethanol / 12 h / 100 °C View Scheme

2,2'-dimethylbenzidine (84-67-3) + acetic anhydride (108-24-7) → N-{4'-acetamido-2,2'-dimethyl-[1,1'-biphenyl]-4-yl}acetamide (96000-61-2)

Conditions	Yield
at 20℃; for 24h;	97%

2,2'-dimethylbenzidine (84-67-3) + Hexafluoroacetone (684-16-2) → 5,5′-bis(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)-2,2′-dimethylbenzidine

Conditions	Yield
With 1,1,1,3',3',3'-hexafluoro-propanol at 80℃; for 7h; Reagent/catalyst; Temperature; Inert atmosphere;	96.8%
With toluene-4-sulfonic acid at 135℃; for 22h; Autoclave; Inert atmosphere;	69%

1-(tert-butoxycarbonyl)-L-proline (15761-39-4) + 2,2'-dimethylbenzidine (84-67-3) → (2S,2'S)-di-tert-butyl 2,2'-(((2,2'-dimethyl-[1,1'-biphenyl]-4,4'-diyl)bis(azanediyl))bis(carbonyl))bis(pyrrolidine-1-carboxylate)

Conditions	Yield
With N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In dichloromethane at 20℃; for 2h;	96%
With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 20℃; for 2h;	96%

citraconic acid anhydride (616-02-4) + 2,2'-dimethylbenzidine (84-67-3) → C24H20N2O4

Conditions	Yield
With acetic acid In toluene for 1h; Inert atmosphere; Reflux;	96%

maleic anhydride (108-31-6) + 2,2'-dimethylbenzidine (84-67-3) → C22H16N2O4

Conditions	Yield
Stage #1: maleic anhydride; 2,2'-dimethylbenzidine In N,N-dimethyl-formamide; toluene at 20℃; for 3h; Dean-Stark; Stage #2: With toluene-4-sulfonic acid In N,N-dimethyl-formamide; toluene for 22h;	95.8%
Stage #1: maleic anhydride; 2,2'-dimethylbenzidine In N,N-dimethyl-formamide; toluene at 20℃; for 3h; Dean-Stark; Stage #2: With toluene-4-sulfonic acid In N,N-dimethyl-formamide; toluene for 22h; Reflux;

2,2'-dimethylbenzidine (84-67-3) + 4-anilinophenol (122-37-2) → bis(4-diphenylamino)-2,2'-dimethyl-4,4'-diaminobiphenyl (1013336-06-5)

Conditions	Yield
Stage #1: With tetrabutoxytitanium; 1-acetoxy-4-methylbenzene at 60℃; for 1h; Stage #2: 2,2'-dimethylbenzidine; 4-anilinophenol In toluene at 110℃; for 48h;	88%

C12H8ClN3OS (188047-59-8) + 2,2'-dimethylbenzidine (84-67-3) → C38H32Cl2N8O2S2 (1190107-87-9)

Conditions	Yield
In acetonitrile at 20 - 25℃; for 0.75h; Sonication;	85%

2,2'-dimethylbenzidine (84-67-3) + 3-methyl-4-nitro-benzoyl chloride (35675-46-8) → C30H26N4O6

Conditions	Yield
With pyridine In N,N-dimethyl acetamide at 20℃; for 24h; Cooling with ice;	85%

2,4-dichloro-6-phenyl-1,3,5-triazine (1700-02-3) + 2,2'-dimethylbenzidine (84-67-3) → C37H35N7

Conditions	Yield
Stage #1: 2,2'-dimethylbenzidine With sodium carbonate; sodium hydroxide In 1,4-dioxane; toluene Reflux; Stage #2: 2,4-dichloro-6-phenyl-1,3,5-triazine In 1,3-dioxane; toluene for 6h; Reflux;	78.11%

C18H13N3O2S (911293-02-2) + 2,2'-dimethylbenzidine (84-67-3) → C50H42N8O4S2 (1190107-92-6)

Conditions	Yield
In acetonitrile at 20 - 25℃; for 0.75h; Sonication;	78%

4-nitrophthalic anhydride (5466-84-2) + 2,2'-dimethylbenzidine (84-67-3) → C30H18N4O8

Conditions	Yield
With propionic acid at 150℃; for 10h;	78%

2,2'-dimethylbenzidine (84-67-3) → 3,3′-dimethylbiphenyl-4,4′-dicarboxylic acid (63297-02-9) + 4,4'-diiodo-3,3'-dimethylbiphenyl (7583-27-9)

Conditions	Yield
	A n/a B 74%

2,2'-dimethylbenzidine (84-67-3) → 4,4'-diiodo-3,3'-dimethylbiphenyl (7583-27-9)

Conditions	Yield
	74%

2,2'-dimethylbenzidine (84-67-3) + C15H8INO4 → 2-(3-(4'-amino-2,2'-dimethyl-[1,1'-biphenyl]-4-yl)-6-iodo-4-oxo-3,4-dihydroquinazolin-2-yl)benzoic acid

Conditions	Yield
In ethanol Heating;	56.3%

1,5-dibromo-pentane (111-24-0) + 2,2'-dimethylbenzidine (84-67-3) → 2,2'-dimethyl-4'-(piperidin-1-yl)biphenyl-4-amine (1221066-32-5)

Conditions	Yield
With potassium carbonate In ethanol; toluene at 150℃; for 0.666667h; Microwave irradiation;	40%

2,2'-dimethylbenzidine (84-67-3) + sodium 1-amino-4-bromoanthraquinone-2-sulfonate (6258-06-6) → sodium 1,1'-((2,2'-dimethyl-[1,1'-biphenyl]-4,4'-diyl)bis(azanediyl))bis(4-amino-9,10-dioxo-9,10-dihydroanthracene-3-sulfonate)

Conditions	Yield
With copper In aq. phosphate buffer at 120℃; for 0.333333h; pH=6 - 7; Ullmann Condensation; Microwave irradiation;	15%
With disodium hydrogenphosphate; sodium dihydrogenphosphate; copper In water at 120℃; for 0.333333h; Microwave irradiation;	15%

2,2'-dimethylbenzidine (84-67-3) + potassium cyanide (151-50-8) → 2,2'-dimethylbiphenyl-4,4'-dicarbonitrile (117490-51-4)

Conditions	Yield
With sulfuric acid; water; copper(II) sulfate Diazotization;

2,2'-dimethylbenzidine (84-67-3) → 2,2'-dimethyl-1,1'-biphenyl (605-39-0)

Conditions	Yield
Diazotization.anschliessend Behandeln mit H3PO2;
Diazotization.Erwaermen mit Ca(OH)2 oder CaO in Methanol oder Aethanol;
Diazotization.Destillation des Diazoniumjodids mit Zinkstaub;

2,2'-dimethylbenzidine (84-67-3) → 4,4'-dichloro-2,2'-dimethyl-biphenyl (19482-15-6)

Conditions	Yield
With hydrogenchloride at 10℃; Diazotization.Behandlung der Diazoniumsalz-Loesung mit CuCl in konz. wss. HCl;

2,2'-dimethylbenzidine (84-67-3) + ethyl acetoacetate (141-97-9) → N,N'-(2,2'-dimethyl-biphenyl-4,4'-diyl)-bis-acetoacetamide

Conditions	Yield
With xylene

2,2'-dimethylbenzidine (84-67-3) + benzaldehyde (100-52-7) → N,N'-dibenzylidene-2,2'-dimethyl-benzidine (96968-76-2)

2,2'-dimethylbenzidine (84-67-3) + salicylaldehyde (90-02-8) → 2,2'-dimethyl-N,N'-disalicylidene-benzidine (23072-76-6)

2,2'-dimethylbenzidine (84-67-3) + acetic acid (64-19-7) → N-{4'-acetamido-2,2'-dimethyl-[1,1'-biphenyl]-4-yl}acetamide (96000-61-2)

2,2'-dimethylbenzidine (84-67-3) + m-nitrobenzoic acid chloride (121-90-4) → 2,2'-Dimethyl-4,4'-bis-(3-nitro-benzoylamino)-biphenyl (104294-86-2)

Conditions	Yield
With benzene

furfural (98-01-1) + 2,2'-dimethylbenzidine (84-67-3) + potassium cyanide (151-50-8) → {4'-[(Cyano-furan-2-yl-methyl)-amino]-2,2'-dimethyl-biphenyl-4-ylamino}-furan-2-yl-acetonitrile (139555-38-7)

Conditions	Yield
With acetic acid 1.) H2O, RT, 1.5 h, 2.) H2O, C2H5OH, RT, overnight; Yield given. Multistep reaction;

Upstream product

• 588-04-5 3,3'-dimethylazobenzene 
• 621-26-1 3,3'-dimethylhydrazobenzene 
• 64-17-5 ethanol 
• 7647-01-0 hydrogenchloride 
• 7782-99-2 sulphurous acid 
• 7149-70-4 2-bromo-5-nitrotoluene 
• 59517-20-3 2,2'-dimethyl-4,4'-dinitro-biphenyl 
• 99-08-1 1-methyl-3-nitrobenzene 
• 1221066-39-2 C₄₀H₃₂N₂ 
• 5326-38-5 2-iodo-5-nitrotoluene 

Downstream Products

• 104294-86-2 2,2'-Dimethyl-4,4'-bis-(3-nitro-benzoylamino)-biphenyl 
• 139555-31-0 (4'-{[Cyano-(4-methoxy-phenyl)-methyl]-amino}-2,2'-dimethyl-biphenyl-4-ylamino)-(4-methoxy-phenyl)-acetonitrile 
• 139555-28-5 (4'-{[Cyano-(2-hydroxy-phenyl)-methyl]-amino}-2,2'-dimethyl-biphenyl-4-ylamino)-(2-hydroxy-phenyl)-acetonitrile 
• 139555-36-5 (5-Bromo-2-hydroxy-phenyl)-(4'-{[(5-bromo-2-hydroxy-phenyl)-cyano-methyl]-amino}-2,2'-dimethyl-biphenyl-4-ylamino)-acetonitrile 
• 1013336-06-5 bis(4-diphenylamino)-2,2'-dimethyl-4,4'-diaminobiphenyl 
• 31458-17-0 4,4'-dibromo-2,2'-dimethyl-1,1′-biphenyl 
• 7583-27-9 4,4'-diiodo-3,3'-dimethylbiphenyl 
• 63297-02-9 3,3′-dimethylbiphenyl-4,4′-dicarboxylic acid 
• 1190107-92-6 C₅₀H₄₂N₈O₄S₂ 
• 1190107-87-9 C₃₈H₃₂Cl₂N₈O₂S₂ 
• 38274-14-5 2,2'-bis-(bromomethyl)-1,1'-biphenyl 
• 2764-09-2 4.4'-Di-(4-heptyloxy-benzylidenamino)-2.2'-dimethyl-biphenyl 
• 139555-30-9 (E)-2-[4'-((E)-1-Cyano-3-phenyl-allylamino)-2,2'-dimethyl-biphenyl-4-ylamino]-4-phenyl-but-3-enenitrile 

Relevant articles and documents

DIAMINE COMPOUND, POLYIMIDE PRECURSOR AND POLYIMIDE FILM PREPARED BY USING SAME

The present invention discloses a novel diamine having a structure including an intramolecular imide group while having an aromatic ring group with a rigid structure. In addition, and by comprising the novel diamine as a polymerization component, the present invention can provide a polyimide film having improved mechanical and thermal properties while maintaining optical properties of polyimide.

Production method of 2,2'-dimethyl[1,1'-biphenyl]-4,4'-diamine

The invention discloses a production method of 2,2'-dimethyl[1,1'-biphenyl]-4,4'-diamine. According to the production method of the 2,2'-dimethyl[1,1'-biphenyl]-4,4'-diamine, with 3-nitrotoluene as aninitial raw material, reduction is conducted at first to obtain 3,3'-dimethylhydrazo-benzene, and then rearrangement is conducted to obtain the 2,2'-dimethyl[1,1'-biphenyl]-4,4'-diamine; reduction isconducted with Pd/C as a main catalyst and an anthraquinone compound plus sodium di(2-ethyl-hexyl)sulfosuccinate as cocatalysts; and the anthraquinone compound is one or two of 1,4-dihydroxyanthraquinone, 2-hydroxyanthraquinone and 2,6-dihydroxyanthraquinone. According to the production method of the 2,2'-dimethyl[1,1'-biphenyl]-4,4'-diamine, through a large number of experiments, it is found that by combining the sodium di(2-ethyl-hexyl)sulfosuccinate and the anthraquinone compound as the cocatalysts, the reaction selectivity of production of the 3,3'-dimethylhydrazo-benzene through reduction of the 3-nitrotoluene can be greatly improved, and the reaction yield which is 70% or above can be obtained finally, so that conditions are created for mass application of the 2,2'-dimethyl[1,1'-biphenyl]-4,4'-diamine on the aspect of production of special materials.

Variation of the backbone conjugation in NLO model compounds: Torsion-angle-restricted, biphenyl-based push-pull-systems

Terminal piperidinyl- and nitro-functionalized biphenyls, bridged between the 2 and. 2′ positions by a variable number of methylene groups, are synthesized and fully characterized. These push-pull systems with defined and restricted torsion angles between their phenyl rings are ideal model compounds to investigate the influence of the chromophore's conjugation in nonlinear optic (NLO) responses, A general synthetic route that can be implemented to access these model compounds is reported, starting from dibromo or ditriflate biphenyls. Hartwig-Buchwald cross-coupling, a selective azacycloalkylation of diaminobiphenyls and a mild oxidation of primary amines to nitro groups in the presence of a tertiary amine summarizes the synthetic pathway towards the desired model compounds. NLO properties of the series of torsionally constrained push-pull biphenyls are collected by electric-field-induced second-harmonic generation (EFISH) experiments. The results agree qualitatively with semi-empirical simulations based on the AM1 Hamiltonian. A. linear dependence of the quadratic response on the cos2(o) of the inter-aryl dihedral angle is observed, which points to oscillator strength loss as the dominant effect of increasing backbone twist