88-05-1

Basic information

• Product Name: 2,4,6-Trimethylaniline
• Synonyms: 2,4,6-Trimethylanyline;2,4,6-Trimethylaniline,97%;2,4,6-trimethylaniline98%;2,4,6-Trimethylanili;2,4,6-TriMethylaniline, 97% 100GR;Aminomesitylene 2-Amino-1,3,5-trimethylbenzene Mesidine Mesitylamine;2,4,6-TRIMETHYLANILINE FOR SYNTHESIS;2 Minus 2-3 Methylaniline
• CAS NO: 88-05-1
• Molecular Formula: C₉H₁₃N
• Molecular Weight: 135.21
• EINECS: 201-794-3
• Product Categories: Intermediates of Dyes and Pigments;API intermediates
• Mol File: 88-05-1.mol
• Article Data: 77

Chemical Properties

• Melting Point: -5 °C
• Boiling Point: 108-110 °C11 mm Hg(lit.)
• Flash Point: 205 °F
• Appearance: clear brown/liquid (clear)
• Density: 0.963 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.0627mmHg at 25°C
• Refractive Index: n20/D 1.551(lit.)
• Storage Temp.: Store below +30°C.
• PKA: pK1:4.38(+1) (25°C)
• Water Solubility: IMMISCIBLE
• BRN: 636559
• CAS DataBase Reference: 2,4,6-Trimethylaniline(CAS DataBase Reference)
• NIST Chemistry Reference: 2,4,6-Trimethylaniline(88-05-1)
• EPA Substance Registry System: 2,4,6-Trimethylaniline(88-05-1)

Safety Data

• Hazard Codes: T+,T
• Statements: 21/22-26-36/38-33-23/24/25
• Safety Statements: 26-28-36/37-45-28A
• RIDADR: UN 2810 6.1/PG 2
• WGK Germany: 3
• RTECS: BZ0700000
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: III
• Hazardous Substances Data: 88-05-1(Hazardous Substances Data)

Usage

Chemical Properties

clear yellow to brown liquid. Insoluble in water, soluble in organic solvents such as ethanol and ether.

Uses

2,4,6-Trimethylaniline is useful for the preparation of Grubbs' catalyst. It is used as a precursor to dyes. It undergoes condensation reaction with glyoxal to prepare glyoxal-bis(mesitylimine). It is also involved in the preparation of 1,3-diketimines ligands by condensation with 1,3-diketones. Further, it is used for the production of Acid Blue 129 dye, which is useful in histochemistry studies. In addition to this, it serves as a building block to various bulky ligands.

Preparation

2,4,6-Trimethylaniline is prepared by selective mononitration of mesitylene, avoiding oxidation of the methyl groups.Mix sulfuric acid and nitric acid into mixed acid, nitrify with mesitylene at atmospheric pressure below 10°C for 4 hours, stand for stratification, and let off the waste acid. The obtained 2,4,6-trimethylnitrobenzene, iron powder, hydrochloric acid and water were prepared in a ratio of 1:3.74:0.9:2.22 (mol ratio) for reduction reaction at 100-105°C for 8h. Crude 2,4,6-Trimethylaniline was then distilled off from the reduced material and purified by distillation.

General Description

2,4,6-Trimethylaniline is a clear liquid. easily turns light brown when exposed to air and light. It is an intermediate for dyes, organic pigments and pesticides.

Reactivity Profile

2,4,6-Trimethylaniline 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.

Health Hazard

2,4,6-Trimethylaniline is moderately toxic orally. It is also considered highly toxic by unspecified routes. It is a skin and eye irritant. Suspect occupational carcinogen. (Non-Specific -- Aromatic Amines) The danger of acute poisoning is represented by methemoglobinemia leading to adverse effects on the red cells. A number of the amines may act as skin sensitizers.

Fire Hazard

When heated to decomposition, 2,4,6-Trimethylaniline emits toxic fumes of nitrogen oxides. Avoid decomposing heat.

Safety Profile

Poison by inhalation. Moderately toxic by ingestion. A skin and severe eye irritant. Questionable carcinogen with experimental carcinogenic data. Mutation data reported. When heated to decomposition it emits toxic fumes of NOx.

Potential Exposure

Used on small scale in organic synthesis.

Shipping

UN2810 Toxic liquids, organic, n.o.s., Hazard Class: 6.1; Labels: 6.1-Poisonous materials, Technical Name Required.

InChI:InChI=1/C9H13N/c1-6-4-7(2)9(10)8(3)5-6/h4-5H,10H2,1-3H3

Synthetic route

1-Benzyl-1,4-dihydronicotinamide (952-92-1) → 1-benzyl-3-carbamoylpyridinium ion (16183-83-8) + 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
In acetonitrile at 25℃; Kinetics;	A 100% B 85%

N-methyl-2,4,6-trimethylaniline (13021-14-2) → 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With dichloro(dimethylglyoxime)(dimethylglyoximato)cobalt(III); (4,4'-di-tert-butyl-2,2'-dipyridyl)-bis-(2-phenylpyridine(-1H))-iridium(III) hexafluorophosphate; triethylamine In acetonitrile at -78℃; for 24h; Reagent/catalyst; Sealed tube; Inert atmosphere; Irradiation;	100%

nitromesitylene (603-71-4) → 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With palladium 10% on activated carbon; hydrogen In tetrahydrofuran for 12h;	99%
With titanium tetrachloride; di-isobutyl telluride In dichloromethane for 0.5h; Ambient temperature;	98%
With hydrogen In tetrahydrofuran; water at 120℃; under 37503.8 Torr; for 24h; chemoselective reaction;	96%

2,4,6-trimethylphenyl bromide (576-83-0) → 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With 2-((dicyclohexylphosphino)methyl)-1,3-bis(2,6-diisopropylphenyl)-4,5-dimethyl-1H-imidazol-3-ium iodide; ammonia; palladium diacetate; sodium t-butanolate In 1,4-dioxane at 120℃; under 7500.75 Torr; for 24h; Autoclave; Inert atmosphere;	99%
With copper(l) iodide; sodium azide; N,N`-dimethylethylenediamine In dimethyl sulfoxide at 100℃; for 10h; Inert atmosphere;	72%
Stage #1: 2,4,6-trimethylphenyl bromide With magnesium In tetrahydrofuran Inert atmosphere; Stage #2: With 3-tert-butyl-3-phenyloxaziridine In tetrahydrofuran; toluene at -45℃; for 2h; Inert atmosphere; Stage #3: With ammonium chloride In tetrahydrofuran; water; toluene Reagent/catalyst; Inert atmosphere;	31%

2,4,6-Trimethylacetophenone (1667-01-2) → 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With methanol; O-benzenesulfonyl-acetohydroxamic acid ethyl ester; toluene-4-sulfonic acid at 23℃; for 24h; Inert atmosphere;	96%
With ethanol; hydroxylamine hydrochloride at 160℃; und Erhitzen mit Salzsaeure im Druckrohr;

anti-2,2',4,4',6,6'-Hexamethylazobenzene (20488-59-9) → 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With sodium dithionite In methanol; dichloromethane; water for 3h; Heating;	96%

nitromesitylene (603-71-4) → 2,4,6-trimethylaniline (88-05-1) + tellurium

Conditions	Yield
With disodium telluride In 1,4-dioxane; water at 50℃; for 2h;	A 95% B n/a

N,N-dibenzyl-2,4,6-trimethylaniline (137129-03-4) → 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With formic acid; potassium hydroxide In ethanol at 70℃; for 1h;	95%

carbon monoxide (201230-82-2) + nitromesitylene (603-71-4) → mesityl isocyanate (2958-62-5) + 1,3-bis(2,4,6-trimethylphenyl)urea (6095-81-4) + anti-2,2',4,4',6,6'-Hexamethylazobenzene (20488-59-9) + 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
Vanadium (III) chloride-(tris-tetrahydrofuran); (Bu4N) In various solvent(s) at 120℃; for 0.5h; Product distribution; further catalysts, other reaction times;	A 94% B n/a C n/a D n/a
Vanadium (III) chloride-(tris-tetrahydrofuran); (Bu4N) In various solvent(s) at 120℃; for 0.5h;	A 94% B n/a C n/a D n/a

2,3,5,6-tetrafluoro-4-(2,4,6-trimethylphenylazo)pyridine (86249-71-0) → 2,3,5,6-tetrafluoropyridin-4-amine (1682-20-8) + 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With sodium disulfite; hydrogen iodide for 1h; Heating;	A 31% B 93%

10-Methyl-4a,9,9a,10-tetrahydro-acridine → acridinium + 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
In acetonitrile at 25℃; Kinetics;	A 93% B 78%

mesitylboronic acid (5980-97-2) → 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With copper(I) oxide; ammonium hydroxide; air In methanol at 20℃; for 12h;	92%
With caesium carbonate; O-(2,4-dinitrophenyl)hydroxylamine In 1,2-dichloro-ethane at 25℃; for 48h; Inert atmosphere;	42%

1,3,5-trimethyl-benzene (108-67-8) → 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With tert-butyl N-tosyloxycarbamate at 20℃; for 36h; Solvent; Reagent/catalyst; Temperature; Concentration; chemoselective reaction;	89%
With 16-crown-6; 1-aminoquinolinium perchlorate In trifluoroacetic acid for 4h; Irradiation;	80%
With hydrogenchloride; aluminium trichloride; sodium azide In various solvent(s) at 20℃;	76%

N-(diphenyl methylene)-2,4,6-trimethylaniline (67565-93-9) → 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
Acid hydrolysis;	87%

2,4,6-trimethylphenyl p-toluenesulfonate (356031-47-5) → 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With bis(tri-ortho-tolylphosphine)palladium(0); (R)-(-)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyl-di-tert-butylphosphine; ammonia; sodium t-butanolate In 1,4-dioxane at 50℃; for 24h; Inert atmosphere;	86%

(2,4,6-trimethyl-phenyl)-carbamic acid tert-butyl ester (56700-69-7) → 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With methanol; oxalyl dichloride at 20℃; for 2h;	83%

1-fluoro-2,4,6-trimethylbenzene (392-69-8) + potassium enolate of acetone (128190-66-9, 25088-58-8) → 1-(2,4,6-trimethylphenyl)-2-propanone (42797-68-2) + 1-(2,4,6-Trimethylphenyl)-2-propanol (27645-30-3) + 2,4,6-trimethylaniline (88-05-1) + 1,3,5-trimethyl-benzene (108-67-8)

Conditions	Yield
With ammonia; potassium amide at -33℃; Product distribution; Rate constant;	A 2.8% B 5.6% C 11.7% D 80%
With ammonia; potassium amide at -33℃;	A 1.8 % Chromat. B 3.1 % Chromat. C 18.2 % Chromat. D 77 % Chromat.
With ammonia; potassium amide at -33℃;	A 2.8 % Chromat. B 5.6 % Chromat. C 11.7 % Chromat. D 80 % Chromat.

dimesityl-1,3-tetraphenylcyclodigermazane (122422-41-7) + 3,5-di-tert-butyl-o-benzoquinone (3383-21-9) → 2,2-diphenyl(6,8-di-t-butyl)-4,5-benzo-2-germa-1,3-dioxolane (110577-23-6) + ditertiobutyl-2,4 (trimethyl-2,4,6 phenylimino)-6 cyclohexadiene-2,4 one-1 (112079-83-1) + 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
In benzene-d6 inert atmosphere (Ar or N2); 100°C, 12 h; not isolated; (1)H-NMR;	A n/a B <1 C 80%

(C6H5)2ClGeNHC6H2(CH3)3 (122422-42-8) + 3,5-di-tert-butyl-o-benzoquinone (3383-21-9) → 2,2-diphenyl(6,8-di-t-butyl)-4,5-benzo-2-germa-1,3-dioxolane (110577-23-6) + ditertiobutyl-2,4 (trimethyl-2,4,6 phenylimino)-6 cyclohexadiene-2,4 one-1 (112079-83-1) + 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In benzene-d6 byproducts: DBU*HCl; inert atmosphere (Ar or N2); 20°C, 17 h; (1)H-NMR; evapn., pentane addn., filtn.;	A 67% B <1 C 80%

2-bromomesitylene (1667-04-5) → 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With ammonium sulfate; bis(1,5-cyclooctadiene)nickel (0); sodium t-butanolate at 100 - 110℃; for 12h;	72%

mesitylenecarboxylic acid (480-63-7) → 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
Stage #1: mesitylenecarboxylic acid With trifluorormethanesulfonic acid; trimethylsilylazide In chloroform at 90℃; for 0.06h; Schmidt Reaction; Flow reactor; Stage #2: With water In methanol; chloroform at 20℃; Schmidt Reaction; Flow reactor;	71%

2,4,6-trimethylphenyl bromide (576-83-0) → 2,4,6-trimethylaniline (88-05-1) + 1,3,5-trimethyl-benzene (108-67-8)

Conditions	Yield
With sodium amide In diethyl ether; ammonia for 2h; Irradiation;	A 70% B 6%
With sodium amide In diethyl ether; ammonia for 2h; Product distribution; Irradiation; variation of reaction conditions;	A 70% B 6%

N-(tert-butoxycarbonyl)-O-(mesitylsulfonyl)hydroxylamine (36016-39-4) + 1,3,5-trimethyl-benzene (108-67-8) → 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With bis{rhodium[3,3'-(1,3-phenylene)bis(2,2-dimethylpropanoic acid)]}; trifluoroacetic acid In 2,2,2-trifluoroethanol at 0℃; for 25h; regioselective reaction;	70%
With Rh2(esp)2; trifluoroacetic acid In 2,2,2-trifluoroethanol at 0 - 20℃; for 25h; Inert atmosphere;	70%

18-crown-6 ether (17455-13-9) + potassium graphite + C52H58Br2N8Ni2 → C12H24O6*2C17H19N3(1-)*K(1+)*Ni(1+) + 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
In benzene at 20℃; for 12h; Inert atmosphere;	A 70% B n/a

iodomesitylene (4028-63-1) → 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With ammonium hydroxide; potassium phosphate; 1-(5,6,7,8-tetrahydroquinolin-8-yl)-2-methylpropan-1-one; copper(I) bromide In dimethyl sulfoxide at 80℃; for 24h; Inert atmosphere; Sealed tube;	60%

cyclohexa-1,4-diene (1165952-92-0) → 2,4,6-trimethylaniline (88-05-1) + benzene (71-43-2)

Conditions	Yield
In acetonitrile at 25℃; Kinetics;	A 26% B 60%

2,4-di-tert-Butylphenol (96-76-4) + C28H33MnN5O4 → 3,3',5,5'-tetra(tert-butyl)biphenyl-2,2'-diol (6390-69-8) + [MnIII(3,4,8,9-tetrahydro-3,3,6,6,9-hexamethyl-1H-1,4,8,11-benzotetraazocyclotridecane-2,5,7,10-(6H,11H)-tetrone)]- + 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
In acetonitrile at 20℃; Inert atmosphere;	A 25% B n/a C 56%

N,N'-bis(2,4,6-trimethylphenyl)ethanediimine (56222-36-7) + 1,2-phenylenediacetonitrile (613-73-0) → naphthalene-1,4-dicarbonitrile (3029-30-9) + 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With potassium hydroxide In N,N-dimethyl-formamide at 100℃; for 15h;	A 54% B n/a

azidotri-2,4,6-trimethylphenylgermane (124862-47-1) → diethoxybis(2,4,6-trimethylphenyl)germane (124862-49-3) + Ge(C6H2(CH3)3)2NHCH2(C6H2(CH3)2) (124862-48-2) + 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With ethanol In ethanol; cyclohexane	A 14% B 50% C 11%

mesitylenesulfonylhydroxylamine (36016-40-7) + 1,3,5-trimethyl-benzene (108-67-8) → 2,4,6-trimethylaniline (88-05-1)

Conditions	Yield
With bis{rhodium[3,3'-(1,3-phenylene)bis(2,2-dimethylpropanoic acid)]}; trifluoroacetic acid In 2,2,2-trifluoroethanol at 0℃; for 0.5h; regioselective reaction;	49%
With Rh2(esp)2 In 2,2,2-trifluoroethanol at 0℃; for 0.5h; Inert atmosphere;	49%

phthalic anhydride (85-44-9) + 2,4,6-trimethylaniline (88-05-1) → 1-(N-phthalimido)-2,4,6-trimethylbenzene (93315-97-0)

Conditions	Yield
With acetic acid at 150℃; for 2h; Inert atmosphere;	100%
With acetic acid at 140℃; for 12h;	90%
With 1H-imidazole at 140℃; for 3h; Inert atmosphere; Schlenk technique;	22%

acetic anhydride (108-24-7) + 2,4,6-trimethylaniline (88-05-1) → N-mesitylacetamide (5096-21-9)

Conditions	Yield
at 0 - 20℃; for 2.5h; Inert atmosphere; Schlenk technique;	100%
With sulfonic acid-functionalized hyper-cross-linked poly(2-naphthol) In neat (no solvent) at 25℃; for 0.166667h; Green chemistry; chemoselective reaction;	93%
With N,N,N-trimethyl-2-(sulfooxy)ethanaminium chloride In neat (no solvent) at 20℃; for 0.216667h; Milling; Green chemistry;	90%

Ethyl oxalyl chloride (4755-77-5) + 2,4,6-trimethylaniline (88-05-1) → 2-(2,4,6-trimethylphenylamino)-2-oxoacetic acid ethyl ester (79354-30-6)

Conditions	Yield
With pyridine at 20℃; for 1.5h; Inert atmosphere;	100%
With triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;	97%
In tetrahydrofuran at 70℃; for 1h;	96%

p-Toluic acid (99-94-5) + 2,4,6-trimethylaniline (88-05-1) → N-(2,4,6-trimethylphenyl)-4-methylbenzamide (86489-65-8)

Conditions	Yield
With diphosphorus tetraiodide In tetrachloromethane; dichloromethane Heating;	100%

triphenylbismuth(V) diacetate (28899-97-0) + 2,4,6-trimethylaniline (88-05-1) → N-mesitylaniline (23592-67-8)

Conditions	Yield
With copper(II) dipivaloate In dichloromethane for 0.0833333h; Product distribution; Ambient temperature; other BiV reagents; copper-catalyzed phenylation of amines by BiV reagents;	100%
copper In dichloromethane for 24h; Ambient temperature;	92%
With copper(II) dipivaloate In dichloromethane for 0.0833333h; Ambient temperature;	100 % Chromat.

di-tert-butyl dicarbonate (24424-99-5) + 2,4,6-trimethylaniline (88-05-1) → (2,4,6-trimethyl-phenyl)-carbamic acid tert-butyl ester (56700-69-7)

Conditions	Yield
With indium(III) bromide at 30 - 35℃; for 0.5h;	100%
Stage #1: 2,4,6-trimethylaniline With triethylamine In tetrahydrofuran; water at 20℃; for 0.0833333h; Stage #2: di-tert-butyl dicarbonate In tetrahydrofuran; water at 0 - 20℃; for 6h;	100%
In tetrahydrofuran for 168h; Heating;	98%

2,4,6-trimethylaniline (88-05-1) + trifluoromethyl dihydro-1,4-dioxin-3-carbonyl chloride → 5,6-dihydro-2-trifluoromethyl-N-(2,4,6-trimethyl)phenyl-1,4-dioxin-3-carboxamide

Conditions	Yield
Stage #1: trifluoromethyl dihydro-1,4-dioxin-3-carbonyl chloride With pyridine; polystyrene-bound 4-hydroxy-3-nitrobenzophenone In dichloromethane at 20℃; for 24h; Acylation; Stage #2: 2,4,6-trimethylaniline With triethylamine In acetonitrile for 14h; Acylation; Heating;	100%

phenylacetylene (536-74-3) + 2,4,6-trimethylaniline (88-05-1) → N-(1-phenylethylidene)-2,4,6-trimethylaniline (75472-71-8, 17432-52-9)

Conditions	Yield
With [Zn2Cp*3]+[B(3,5-(CF3)2C6H3)4]- at 20℃; for 72h; Reagent/catalyst; Inert atmosphere; Schlenk technique; regioselective reaction;	100%
With C18H5AlF36O4Zn In benzene-d6 at 60℃; for 1h; Inert atmosphere; regioselective reaction;	100%
With C30H36FeP2*2Au(1+)*Cl(1-)*C32H12BF24(1-) In (2)H8-toluene at 120℃; for 6h; Reagent/catalyst; Inert atmosphere; Schlenk technique; Sealed tube; Glovebox;	100%

2,4,6-trimethylaniline (88-05-1) + (Z)-4-[2,4,6-Tris-(bis-trimethylsilanyl-methyl)-phenylamino]-pent-3-en-2-one (926625-25-4) → C41H78N2Si6 (926625-28-7)

Conditions	Yield
With titanium tetrachloride In toluene for 16h; Heating;	100%
With titanium tetrachloride In toluene for 16h; Heating;	94%

2,4,6-trimethylaniline (88-05-1) + 1,2-dibromobenzene (583-53-9) → N1,N2-bis(2,4,6-trimethylphenyl)-1,2-benzenediamine (852414-57-4)

Conditions	Yield
With ammonium chloride; sodium t-butanolate; palladium diacetate In water; argon; toluene	100%
With tri-tert-butylphosphonium tetrafluoroborate; palladium diacetate; sodium t-butanolate In toluene at 60 - 135℃; Inert atmosphere;	87%
With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; palladium diacetate In toluene for 12h; Heating;	86%

2,4,6-trimethylaniline (88-05-1) → 2,4,6-trimethylaniline hydrochloric acid salt (6334-11-8)

Conditions	Yield
With hydrogenchloride In diethyl ether at 0 - 20℃; for 0.5h;	100%

3-nitrophenyl isothiocyanate (3529-82-6) + 2,4,6-trimethylaniline (88-05-1) → 1-(mesityl)-3-(3-nitrophenyl)thiourea (851886-25-4)

Conditions	Yield
In methanol at 20℃; for 2h;	100%
In methanol at 20℃; for 2h;

2-(2,3,4,5-tetramethylcyclopentadienyl)-benzaldehyde + 2,4,6-trimethylaniline (88-05-1) → N-[2-(2,3,4,5-tetramethylcyclopentadienyl)phenylmethylene]-N-(2,4,6-trimethylphenyl)amine

Conditions	Yield
acetic acid In ethanol at 20℃;	100%

2-bromoisobutyric acid bromide (20769-85-1) + 2,4,6-trimethylaniline (88-05-1) → 2-bromo-N-mesityl-2-methylpropanamide (101263-21-2)

Conditions	Yield
With triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;	100%
With triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;	100%
With triethylamine In dichloromethane at 0 - 20℃; for 3h; Inert atmosphere;	94%

orthoformic acid triethyl ester (122-51-0) + 2,4,6-trimethylaniline (88-05-1) → N,N'-dimesitylformamidine (75105-48-5)

Conditions	Yield
With acetic acid In neat (no solvent) at 160℃; for 3h;	100%
With acetic acid In neat (no solvent) at 120 - 160℃; for 4h;	98%
With acetic acid at 90 - 120℃; for 4 - 6h; Product distribution / selectivity;	92%

2-cyclohexylacetylene (931-48-6) + 2,4,6-trimethylaniline (88-05-1) → N-(1-(cyclohexyl)ethylidene)-2,4,6-trimethylaniline

Conditions	Yield
With C18H5AlF36O4Zn In benzene-d6 at 60℃; for 8h; Inert atmosphere; regioselective reaction;	100%
With AuC34H47N(1+)*B(C6F5)4(1-)=(AuC34H47N)(B(C6F5)4) In benzyl methyl ether; benzene-d6 at 90℃; for 24h; Inert atmosphere;	82 %Spectr.
(C4HN(adamantyl)Me2(2,6-diisopropylphenyl))AuCl; potassium tetrakis(pentafluorophenyl)borate In benzyl methyl ether; benzene-d6 at 90℃; for 24h; Product distribution / selectivity; Inert atmosphere;	82 %Spectr.

2,4,6-trimethylaniline (88-05-1) + 4-n-methylphenylacetylene (766-97-2) → 2,4,6-trimethyl-N-(1-(p-tolyl)ethylidene)aniline (1227637-88-8)

Conditions	Yield
With C18H5AlF36O4Zn In benzene-d6 at 60℃; for 1h; Inert atmosphere; regioselective reaction;	100%
With silver tetrafluoroborate; {(2,6-bis(1-isopropyl-2,3-dihydro-1H-imidazole-2-thione)pyridine)12Cu8}(PF6)8 In acetonitrile at 70℃; Reagent/catalyst; Schlenk technique; Inert atmosphere; regioselective reaction;	98%
With silver tetrafluoroborate; [1-(3,3-dimethyl-2-oxobutyl)-4-benzyl-1,2,4-triazol-5-ylidene]AuCl; acetonitrile at 90℃; for 12h; regioselective reaction;	93 %Chromat.

4-bromo-1-ethynylbenzene (766-96-1) + 2,4,6-trimethylaniline (88-05-1) → N-[1-(4-bromophenyl)ethylidene]-2,4,6-trimethylaniline (1318024-67-7)

Conditions	Yield
With C18H5AlF36O4Zn In benzene-d6 at 60℃; for 0.5h; Inert atmosphere; regioselective reaction;	100%
With decamethyldizincocene; N,N'-dimethylaniliniumtetrakis(pentafluorophenyl)borate In benzene-d6 at 20℃; for 21.66h; regioselective reaction;	95 %Spectr.
With (η1,η5)bis(pentamethylcyclopentadienyl)zinc; N,N'-dimethylaniliniumtetrakis(pentafluorophenyl)borate In benzene-d6 at 60℃; for 0.5h; Inert atmosphere; regioselective reaction;

2,4,6-trimethylaniline (88-05-1) + 4-ethynyl-N,N-dimethylaniline (17573-94-3) → N-[1-(4-(dimethylamino)phenyl)ethylidene]-2,4,6-trimethylaniline (1318024-68-8)

Conditions	Yield
With C18H5AlF36O4Zn In benzene-d6 at 60℃; for 2h; Inert atmosphere; regioselective reaction;	100%
With decamethyldizincocene; N,N'-dimethylaniliniumtetrakis(pentafluorophenyl)borate In benzene-d6 at 20℃; for 21.75h; regioselective reaction;	96 %Spectr.
With bis(pentamethylcyclopentadienyl)dizinc; N,N'-dimethylaniliniumtetrakis(pentafluorophenyl)borate In benzene-d6 at 20℃; for 21.75h; Inert atmosphere; regioselective reaction;

3-hydroxy-1(3H)-isobenzofuranone (16859-59-9) + 2,4,6-trimethylaniline (88-05-1) → 3-(2,4,6-trimethylphenylamino)phthalide (1332980-69-4)

Conditions	Yield
In isopropyl alcohol Reflux;	100%

C20H23NO2 + 2,4,6-trimethylaniline (88-05-1) → C29H34N2O (1349188-96-0)

Conditions	Yield
With acetic acid In toluene	100%

C17H26FeO2Si2 (1400792-42-8) + 2,4,6-trimethylaniline (88-05-1) → C26H37FeNOSi2 (1400792-54-2)

Conditions	Yield
With toluene-4-sulfonic acid In toluene at 125℃; for 4.5h; Inert atmosphere; Schlenk technique;	100%

n-octyne (629-05-0) + 2,4,6-trimethylaniline (88-05-1) → 2,4,6-trimethyl-N-(octan-2-ylidene)aniline (914388-61-7)

Conditions	Yield
With C18H5AlF36O4Zn In benzene-d6 at 60℃; for 2h; Inert atmosphere; regioselective reaction;	100%
With C33H49Cl2N2PPd; silver trifluoromethanesulfonate In acetonitrile at 80℃; for 25h; Inert atmosphere; Schlenk technique;	59%
With silver hexafluoroantimonate; C25H28Au2Br2N4 In neat (no solvent) at 40℃; for 4h; Inert atmosphere; Schlenk technique;	76 %Spectr.
With (η1,η5)bis(pentamethylcyclopentadienyl)zinc; N,N'-dimethylaniliniumtetrakis(pentafluorophenyl)borate In benzene-d6 at 20℃; for 4h; Inert atmosphere; regioselective reaction;

chloroform (67-66-3) + 2,4,6-trimethylaniline (88-05-1) → 2-mesityl isocyanide (57116-96-8)

Conditions	Yield
Stage #1: 2,4,6-trimethylaniline With 15-crown-5; sodium hydride In benzene at 40 - 50℃; for 0.25h; Stage #2: chloroform In benzene at 40℃; for 1h;	100%
With benzyltriethylammonium chloride; sodium hydroxide In dichloromethane; water for 22h;	53%

2,4,6-trimethylaniline (88-05-1) + 4-methoxyphenylacetylen (768-60-5) → N-(1-(4-methoxyphenyl)ethylidene)-2,4,6-trimethylaniline (1609074-94-3)

Conditions	Yield
With C18H5AlF36O4Zn In benzene-d6 at 60℃; for 6h; Inert atmosphere; regioselective reaction;	100%
With silver hexafluoroantimonate; AuBr(8-Mes) In acetonitrile at 90℃; for 14h; Schlenk technique; Sealed tube;	98%
With (THT)Au(P(C3H7)2CB11Cl11) In neat (no solvent) at 50℃; for 24h; Catalytic behavior;	93%

6-(2,6-diisopropoxyphenyl)-2-pyridinecarboxaldehyde + 2,4,6-trimethylaniline (88-05-1) → C27H32N2O2

Conditions	Yield
In methanol at 20℃; for 12h;	100%
With air In ethanol at 20℃; for 4h;

ferrocenecarboxaldehyde (12093-10-6) + 2,4,6-trimethylaniline (88-05-1) → N-ferrocenylmethylidene-2,4,6-trimethylaniline

Conditions	Yield
In chloroform soln. of Fe-complex and ligand in CHCl3 was heated under reflux, cooled to room temp.; solvent was evapd., dried under vac.; elem. anal.;	99.62%
With toluene-4-sulfonic acid In toluene Reflux; Dean-Stark;	90%
In chloroform refluxing (6 h); removal of solvent, trituration with hexane;	82%
In ethanol boiling;
In toluene for 8h; Inert atmosphere; Reflux; Molecular sieve;

Upstream product

• 20488-57-7 1-(2,4,6-trimethylphenyl)-2-phenyldiazene 
• 4028-63-1 iodomesitylene 
• 5980-97-2 mesitylboronic acid 
• 87-62-7 2,6-dimethylaniline 
• 576-83-0 2,4,6-trimethylphenyl bromide 
• 108-67-8 1,3,5-trimethyl-benzene 
• 938-18-1 mesitylene-2-carboxylic acid chloride 
• 67565-93-9 N-(diphenyl methylene)-2,4,6-trimethylaniline 
• 603-71-4 nitromesitylene 
• 7647-01-0 hydrogenchloride 
• 13021-15-3 2,4,6-trimethyl-N,N-dimethylaniline 
• 1196-12-9 2-nitrosomesitylene 
• 7732-18-5 water 
• 67-56-1 methanol 

Downstream Products

• 29555-12-2 N,N'-bis(2,4,6-trimethylphenyl)thiourea 
• 2958-62-5 mesityl isocyanate 
• 6629-72-7 2,4,6-trimethyl-N-[(2,4,6-trimethyl-phenylsulfanyl)-methyl]-aniline 
• 13021-15-3 2,4,6-trimethyl-N,N-dimethylaniline 
• 6784-26-5 2-isocyanato-1,3,5-trimethylbenzene 
• 6095-82-5 2,4,6-trimethylphenyl isothiocyanate 
• 867133-41-3 N,N'-dimesityl-4,6-dinitro-m-phenylenediamine 
• 20632-31-9 2,4,6-trimethyl-phenylurea 
• 114188-00-0 2-(3-mesityl-triazenyl)-benzoic acid methyl ester 
• 118660-57-4 methyl-succinic acid bis-(2,4,6-trimethyl-anilide) 
• 116-75-6 C_.I_. Solvent Blue 104 
• 29418-30-2 mesityl-o-tolyl-diazene 
• 14033-86-4 2,6-dimethyl-1,4-benzoquinone-4-(2,4,6-trimethil anil) 
• 6095-81-4 N,N'-di(2,4,6-trimethylphenyl)urea 

Relevant articles and documents

Solvent Effects in the Electrophilic Amination of Mesitylene with the System NaN3-AlCl3-HCl

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Transformation of Formazanate at Nickel(II) Centers to Give a Singly Reduced Nickel Complex with Azoiminate Radical Ligands and Its Reactivity toward Dioxygen

The heteroleptic (formazanato)nickel bromide complex LNi(μ-Br)2NiL [LH = Mes-NH-N═C(p-tol)-N═N-Mes] has been prepared by deprotonation of LH with NaH followed by reaction with NiBr2(dme). Treatment of this complex with KC8led to transformation of the formazanate into azoiminate ligands via N-N bond cleavage and the simultaneous release of aniline. At the same time, the potentially resulting intermediate complex L′2Ni [L′ = HN═C(p-tol)-N═N-Mes] was reduced by one additional electron, which is delocalized across the π system and the metal center. The resulting reduced complex [L′2Ni]K(18-c-6) has aS=1/2ground state and a square-planar structure. It reacts with dioxygen via one-electron oxidation to give the complex L′2Ni, and the formation of superoxide was detected spectroscopically. If oxidizable substrates are present during this process, these are oxygenated/oxidized. Triphenylphosphine is converted to phosphine oxide, and hydrogen atoms are abstracted from TEMPO-H and phenols. In the case of cyclohexene, autoxidations are triggered, leading to the typical radical-chain-derived products of cyclohexene.

Iron-Catalyzed Alkyne Carboamination via an Isolable Iron Imide Complex

Transition metal imide-mediated C-N bond formation is a powerful strategy for the introduction of nitrogen into organic compounds. We have discovered that the reaction ofN-mesityl(β-diketiminato)iron imide complextBuLFeNMes (tBuL = 3,5-bis(2,6-diisopropylphenylimino)-2,2,6,6-tetramethylheptyl and Mes = 2,4,6-trimethylphenyl) with a terminal alkyne substrate gives a β-alkynyl enamine product by a novel alkyne carboamination process. Stoichiometric experiments revealed a catalyst deactivation pathway involving generation of the acetylide complex,tBuLFeCCPh, and mesityl amine (MesNH2) from the acetylene complex,tBuLFe(HCCPh), and mesityl azide (MesN3). This reactivity is suppressed in the presence of coordinating additive 4-tert-butylpyridine (tBuPy), likely through formation of the four-coordinate complextBuLFe(HCCPh)(tBuPy). These insights were instrumental in identifying reaction conditions that allow for turnover of the iron catalyst.

Minimization of Back-Electron Transfer Enables the Elusive sp3 C?H Functionalization of Secondary Anilines

Anilines are some of the most used class of substrates for application in photoinduced electron transfer. N,N-Dialkyl-derivatives enable radical generation α to the N-atom by oxidation followed by deprotonation. This approach is however elusive to monosubstituted anilines owing to fast back-electron transfer (BET). Here we demonstrate that BET can be minimised by using photoredox catalysis in the presence of an exogenous alkylamine. This approach synergistically aids aniline SET oxidation and then accelerates the following deprotonation. In this way, the generation of α-anilinoalkyl radicals is now possible and these species can be used in a general sense to achieve divergent sp3 C?H functionalization.