95-49-8

Usage

Uses

Used in Chemical Synthesis:
2-Chlorotoluene is used as a precursor to synthesize aryl coupling products via palladium-catalyzed Negishi cross-coupling. It can also be used in the Buchwald-Hartwig amination to synthesize arylamines.
Used in Organic Chemicals and Dyes:
2-Chlorotoluene is used as a solvent and intermediate for organic chemicals and dyes. It is used for permanganate oxidation to give o-chlorobenzoic acid and in the preparation of 3-chloro-4-methylcatechol and 4-chloro-3-methylcatechol.
Used in Pharmaceutical and Synthetic Rubber Industries:
2-Chlorotoluene is used as a solvent and in the synthesis of dyes, pharmaceuticals, and synthetic rubber compounds.

Preparation

The solution of cuprous chloride is cooled in an ice bath 0-5° C temperature. In this cold solution, the 2-methylbenzenediazonium is poured with constant shaking and allowing the mixture to come to room temperature. After about 10 minutes, the mixture gradually warmed with a good shaking.As the temperature rises the brown addition product begins to decompose with the evolution of nitrogen and with the formation of an oily layer of 2-chlorotoluene. When the decomposition reaction is at an end, the mixture is steam distilled, continuing the process only as long as oily droplets are present in the distillate, for the product is not appreciably soluble in water. The layer of 2-chlorotoluene is carefully separated and washed twice with an equal volume of concentrated sulfuric acid, which removes both the 2-cresol and the azo compound. Then 2-chlorotoluene is washed with water in order to remove the inorganic acid. Finally, 2-chlorotoluene is dried over calcium chloride, distilled, using an air condenser and collecting the product boiling at 153-158° C. Pure 2-chlorotoluene boils at 157° C. The yield is 25-30 g.Experiments in Organic Chemistry, L. F. Fieser, 216, 1941Highly Selective Oxidative Monochlorination To Synthesize Organic Intermediates: 2-Chlorotoluene, 2-Chloroaniline, 2-Chlorophenol, and 2-Chloro-4-methylphenol

Synthesis Reference(s)

Journal of the American Chemical Society, 101, p. 768, 1979 DOI: 10.1021/ja00497a063Organic Syntheses, Coll. Vol. 1, p. 170, 1941

Reactivity Profile

2-Chlorotoluene may be incompatible with strong oxidizing and reducing agents. Also may be incompatible with amines, nitrides, azo/diazo compounds, alkali metals, and epoxides. Reacts violently with dimethyl sulfoxide .

Hazard

Toxic by inhalation. Eye, skin, and upper respiratory tract irritant.

Health Hazard

Inhalation of vapor may cause respiratory irrtation. Prolonged and repeated vapor exposures may produce systemic toxic effects.

Flammability and Explosibility

Flammable

Safety Profile

Moderately toxic by unspecified routes. Flammable when exposed to heat or flame. When heated to decomposition it emits toxic fumes of Cl-. See also TOLE CHLORIDE and CHLORINATED HYDROCARBONS, AROMATIC.

Purification Methods

Dry 2-chlorotoluene for several days with CaCl2, then distil it from Na using a glass helices-packed column. [Beilstein 5 IV 805.]

Synthetic route

3-chloro-4-methylbenzenesulfonic acid (98-34-0) → 2-methylchlorobenzene (95-49-8)

Conditions	Yield
With quinoline; sulfuric acid; copper(II) oxide at 220℃; for 3h;	95%

o-toluidine hydrochloride (636-21-5) → 2-methylchlorobenzene (95-49-8)

Conditions	Yield
Stage #1: o-toluidine hydrochloride With isopentyl nitrite In acetone at 0 - 15℃; Stage #2: With copper dichloride In ethanol; acetone at 5 - 20℃; for 2h; Reagent/catalyst; Solvent; Temperature; Sandmeyer Reaction;	87%

tri-tert-butyl phosphine (13716-12-6) + [(t-Bu)3P](o-tolyl)PdCl → 2-methylchlorobenzene (95-49-8)

Conditions	Yield
In benzene-d6 at 70℃; Equilibrium constant;	76%

carbon monoxide (201230-82-2) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → 2-methylchlorobenzene (95-49-8) + 1,2-bis(2-chlorophenyl)ethane (6639-40-3) + 1,3-bis(2-chlorophenyl)propan-2-one (85150-76-1)

Conditions	Yield
With [2,2]bipyridinyl; tetrabutylammonium tetrafluoroborate; iron(II) chloride; Fe64/Ni36 anode In N,N-dimethyl-formamide Ambient temperature; electrolysis;	A 2 % Chromat. B 10 % Chromat. C 75%

chlorine (7782-50-5) + toluene (108-88-3) → para-chlorotoluene (106-43-4) + 2-methylchlorobenzene (95-49-8)

Conditions	Yield
With iron(III) chloride In ethanol at 50 - 80℃; for 14h; Temperature; Inert atmosphere;	A 26.8% B 72.3%

toluene (108-88-3) → para-chlorotoluene (106-43-4) + 2-methylchlorobenzene (95-49-8)

Conditions	Yield
With chlorine; natural kaolinitic clay In tetrachloromethane for 2h; Heating;	A 72% B 23%
With aluminum (III) chloride; chlorine at 50℃; for 6h; Temperature; Inert atmosphere;	A 71.3% B 27.8%
With hydrogenchloride; 1-(n-butyl)-3-methylimidazolium triflate at 100℃; for 96h;	A 38% B 60%

o-toluidine (95-53-4) → 2-methylchlorobenzene (95-49-8)

Conditions	Yield
With chloro-trimethyl-silane; N-benzyl-N,N,N-triethylammonium chloride; sodium nitrite In tetrachloromethane 1.) 0 deg C, 1.5 h, 2.) r.t., 17 h;	70%
With hydrogenchloride Diazotization.Behandlung der Diazoniumsalz-Loesung mit CuCl;
Reaktion ueber mehrere Stufen;

toluene (108-88-3) → 2-methylchlorobenzene (95-49-8)

Conditions	Yield
With potassium hydrogensulfate; potassium chloride; isoquinolinium dichromate In water at 20℃; Catalytic behavior; Reagent/catalyst; Temperature; Sonication; Green chemistry; regioselective reaction;	69%
With chlorine; iron im diffusen Licht;

C32H25ClN(1+)*BF4(1-) → 2-methylchlorobenzene (95-49-8) + 1-chloro-2-(fluoromethyl)benzene (345-34-6)

Conditions	Yield
at 180℃; under 0.5 Torr; for 3h;	A 30% B 65%

Dithiopivalinsaeure-2-chlorbenzylester (137092-29-6) → 2-(tert-butyl)benzo[b]thiophene (35181-77-2) + methyl dithiopivalate (40920-16-9) + 2-methylchlorobenzene (95-49-8)

Conditions	Yield
In N,N-dimethyl-formamide Mechanism; cathodic reduction, Hg cathode;	A n/a B 63% C 62%

toluene (108-88-3) → para-chlorotoluene (106-43-4) + 2-methylchlorobenzene (95-49-8) + 2,4-dichlorotoluene (95-73-8)

Conditions	Yield
With hydrogenchloride; sodium hypochlorite In water at 20℃; Product distribution; Further Variations:; Temperatures; molar quantity of reagents; Chlorination; oxidative chlorination;	A 29% B 63% C 3.5%
With oxone; potassium chloride In acetonitrile at 20℃; for 24h; Product distribution; Further Variations:; Reagents ratio;
With sulfuric acid; [BMIM]Cl; chlorine at 70℃; for 8h;

2-methylenesuccinic acid (97-65-4) + o-toluene-diazonium chloride (2028-34-4) → 2-methylchlorobenzene (95-49-8) + 2-chloro-2-(2-methylbenzyl)butanedioic acid (1427331-00-7)

Conditions	Yield
With copper(II) choride dihydrate In [(2)H6]acetone; water at 25℃; for 2.5h; Meerwein Arylation;	A n/a B 58%

1,1-dimethoxyethylene (922-69-0) + 2-bromo-1-chlorobenzene (694-80-4) → 2-methylchlorobenzene (95-49-8) + 7,7-Dimethoxybicyclo<4.2.0>octa-1,3,5-triene (81447-53-2)

Conditions	Yield
With methyllithium In diethyl ether Heating;	A 10% B 54%

C6H4S2O4N(1-)*N2C6H5CH2(1+) → 2-methylchlorobenzene (95-49-8)

Conditions	Yield
With N-benzyl-N,N,N-triethylammonium chloride; copper In acetonitrile at 20℃; for 0.75h; Substitution;	51%

2,6-dimethylphenyl chloroformic acid ester (876-99-3) → 2-methylchlorobenzene (95-49-8) + 2,6-dimethyl-1-chlorobenzene (6781-98-2)

Conditions	Yield
With aluminum (III) chloride at 80 - 110℃; for 3h;	A n/a B 43.8%

toluene (108-88-3) → para-chlorotoluene (106-43-4) + 2-methylchlorobenzene (95-49-8) + benzyl chloride (100-44-7)

Conditions	Yield
With iron(III)porphyrinate; boron trifluoride diethyl etherate In dichloromethane	A 14% B 11% C 38%
With sulfuryl dichloride; chromium(0) hexacarbonyl at 120℃; for 20h; Product distribution; with various metal complexes at various temperatures;	A 5.6% B 3.4% C 25.6%
With chlorine for 2h; Irradiation;	A n/a B n/a C 12%

toluene (108-88-3) → para-chlorotoluene (106-43-4) + 2-methylchlorobenzene (95-49-8) + 2,2,3,3,4,4,5,5,6,6,7,7,7-Tridecafluoro-heptanoic acid p-tolyl ester (102607-12-5)

Conditions	Yield
With lead(IV) acetate; C6F13COOH; lithium chloride at 80℃; for 7h;	A n/a B n/a C 21.2%

1-(2-chlorobenzyl)-2,4,6-triphenylpyridin-1-ium tetrafluoroborate → 2-methylchlorobenzene (95-49-8) + 1-chloro-2-(fluoromethyl)benzene (345-34-6)

Conditions	Yield
at 200℃; under 2 Torr; for 3h;	A 5% B 15%

(2)H8-toluene (2037-26-5) + bis(4-chlorophenyl)(4-methylphenyl)-selenonium chloride (127356-68-7) → para-chlorotoluene (106-43-4) + 2-methylchlorobenzene (95-49-8) + C7(2)H7Cl (84344-06-9) + C7(2)H7Cl (84344-05-8)

Conditions	Yield
aluminium trichloride at 20℃; for 4h; other Lewis acids, other rct.-temp., other yields;	A 0.53% B 2.27% C 1.15% D 1.31%
aluminium trichloride at 20℃; for 4h; Product distribution; Mechanism; other lewis acids (FeCl3, SbCl5, SbCl3, SbF3), other temp. (50 deg C), other yields;	A 0.53% B 2.27% C 1.15% D 1.31%

methylmagnesium chloride (676-58-4) + 1,2-dichloro-benzene (95-50-1) → o-xylene (95-47-6) + 2-methylchlorobenzene (95-49-8)

Conditions	Yield
(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride In tetrahydrofuran at 105℃; for 1h;	A 2% B 93 % Chromat.
(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride In tetrahydrofuran at 105℃; for 1h; Product distribution; other substrates, other Grignard reagent, other catalysts, other time, other temperature;	A 2 % Chromat. B 93 % Chromat.

o-toluenesulfonic acid (88-20-0) → 2-methylchlorobenzene (95-49-8)

Conditions	Yield
With copper dichloride

3-chloro-4-methylbenzenesulfonyl chloride (42413-03-6) → 2-methylchlorobenzene (95-49-8)

Conditions	Yield
With sulfuric acid anschliessend Kochen mit H2SO4;
Multi-step reaction with 2 steps 1: aqueous alkali View Scheme

dichloro-tris-o-tolyloxy-phosphorane (77164-28-4) → 2-methylchlorobenzene (95-49-8)

Conditions	Yield
at 180℃;
at 180℃;

o-toluene-diazonium chloride (2028-34-4) → 2-methylchlorobenzene (95-49-8)

Conditions	Yield
With copper(l) chloride
With hydrogenchloride; copper hydride at 0℃;
With hydrogenchloride

2-chloro-benzaldehyde (89-98-5) → 2-methylchlorobenzene (95-49-8)

Conditions	Yield
With hydrazine hydrate; diethylene glycol Erhitzen des mit Kaliumhydroxid versetzten Reaktionsgemisches;

toluene-4-sulfonic acid (104-15-4) → 2-methylchlorobenzene (95-49-8)

Conditions	Yield
With sulfuric acid; chlorine; iron(III) chloride

acetic acid-(2,4,6,N-tetrachloro-anilide) (27876-29-5) + acetic acid (64-19-7) + toluene (108-88-3) → para-chlorotoluene (106-43-4) + 2-methylchlorobenzene (95-49-8)

Conditions	Yield
im Dunkeln;

methyl radical (2229-07-4) + chlorobenzene (108-90-7) → 1-chloro-3-methylbenzene (108-41-8) + para-chlorotoluene (106-43-4) + 2-methylchlorobenzene (95-49-8)

Conditions	Yield
at 130℃;

carbon dioxide (124-38-9) + 2,4-dichlorotoluene (95-73-8) → ortho-methylbenzoic acid (118-90-1) + 2-methylchlorobenzene (95-49-8) + 3-chloro-4-methylbenzoic acid (5162-82-3) + 5-chloro-2-methylbenzoic acid (7499-06-1)

Conditions	Yield
With tetrabutylammomium bromide In N,N-dimethyl-formamide at 5℃; electrolysis (I=0.4 A); Yield given. Further byproducts given. Yields of byproduct given;

18-crown-6/o-methylbenzenediazonium tetrafluoroborate complex (126541-37-5) → 18-crown-6 ether (17455-13-9) + 2-methylchlorobenzene (95-49-8)

Conditions	Yield
In 1,2-dichloro-ethane at 20℃; Rate constant; Kinetics; Thermodynamic data; var. crown ethers, ΔH(excit.), ΔS(excit.);

2-methylchlorobenzene (95-49-8) + phenylboronic acid (98-80-6) → 2-methylbiphenyl (643-58-3)

Conditions	Yield
With Cs2O3; PCy3 adduct of cyclopalladated ferrocenylimine In 1,4-dioxane at 100℃; for 15h; Suzuki cross-coupling reaction;	100%
With potassium phosphate; C50H63Cl2N3Pd In ethanol at 80℃; for 4h; Catalytic behavior; Reagent/catalyst; Solvent; Suzuki-Miyaura Coupling;	100%
With potassium carbonate In water; isopropyl alcohol at 100℃; for 18h; Suzuki-Miyaura Coupling; Inert atmosphere;	100%

2-methylchlorobenzene (95-49-8) + 2,6-dimethylbenzene boronic acid (100379-00-8) → 2,2',6'-trimethylbiphenyl (10273-87-7)

Conditions	Yield
With tris-(dibenzylideneacetone)dipalladium(0); caesium carbonate In 1,4-dioxane for 12h; Suzuki coupling; Inert atmosphere; Reflux;	100%
With potassium phosphate; C22H23Br2N3Pd In water; isopropyl alcohol at 20℃; for 44h; Reagent/catalyst; Suzuki-Miyaura Coupling;	98%
With potassium phosphate monohydrate; R-Phos; bis(dibenzylideneacetone)-palladium(0) In 1,4-dioxane at 100℃; for 0.666667h; Suzuki-Miyaura reaction; Inert atmosphere;	95%

2-methylchlorobenzene (95-49-8) + 2,6-diisopropylbenzenamine (24544-04-5) → N-(2,6-diisopropylphenyl)-N-(o-tolyl)amine

Conditions	Yield
With di-μ-bromobis-(tritert-butylphosphine)dipalladium(I); sodium t-butanolate In toluene at 100℃; for 0.75h; Catalytic behavior; Time; Buchwald-Hartwig Coupling;	100%
With C34H39N3O4Pd; sodium t-butanolate In 1,4-dioxane at 100℃; for 0.166667h; Buchwald-Hartwig Coupling; Schlenk technique; Inert atmosphere;	99%
With C28H29Cl2N3OPd; potassium tert-butylate In toluene at 110℃; for 15h; Buchwald-Hartwig Coupling; Schlenk technique; Inert atmosphere;	99%

2-methylchlorobenzene (95-49-8) + 2,3,3-trimethyl-4-penten-2-ol (36934-19-7) → 1-methyl-2-(3-methylbut-2-en-1-yl)benzene (1146120-91-3)

Conditions	Yield
With palladium diacetate; caesium carbonate; tricyclohexylphosphine In toluene for 17h; Inert atmosphere; Reflux;	100%

2-methylchlorobenzene (95-49-8) + phenol (108-95-2) → 1-methyl-2-phenoxybenzene (3991-61-5)

Conditions	Yield
With copper(I) oxide; caesium carbonate In tetrahydrofuran at 150℃; for 3h; Ullmann condensation;	100%
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 12h;	69%
With copper(l) iodide; potassium carbonate In N,N-dimethyl-formamide at 20 - 110℃;	33%

2,2-difluorethylamine (430-67-1) + 2-methylchlorobenzene (95-49-8) → N-(2,2-difluoro-ethyl)-o-toluidine (2366-95-2)

Conditions	Yield
With bis(η3-allyl-μ-chloropalladium(II)); 5-(di(adamantan-1-yl)phosphino)-1′,3′,5′-triphenyl-1′H-1,4′-bipyrazole; potassium phenolate In 1,4-dioxane at 100℃; for 6h; Sealed tube; Inert atmosphere;	99%
With copper(I) oxide; copper

piperidine (110-89-4) + 2-methylchlorobenzene (95-49-8) → 1-(2-methylphenyl)piperidine (7250-70-6)

Conditions	Yield
With C35H44Cl2N4Pd; potassium tert-butylate In tetrahydrofuran at 130℃; for 12h; Inert atmosphere; Sealed tube;	99%
With C36H43Cl2N3Pd; potassium tert-butylate In 1,4-dioxane at 110℃; for 12h; Buchwald-Hartwig Coupling; Inert atmosphere; Schlenk technique;	94%
With C40H44ClN3Pd; potassium tert-butylate In toluene at 110℃; for 24h; Buchwald-Hartwig Coupling; Inert atmosphere;	87%

2-methylchlorobenzene (95-49-8) + 2-Methylphenylboronic acid (16419-60-6) → 2,2'-dimethyl-1,1'-biphenyl (605-39-0)

Conditions	Yield
With PdCl2(TMes)2; caesium carbonate In ethanol at 90℃; for 15h; Suzuki coupling; Inert atmosphere; Reflux;	99%
With potassium phosphate; C22H23Br2N3Pd In water; isopropyl alcohol at 20℃; for 44h; Reagent/catalyst; Suzuki-Miyaura Coupling;	99%
With potassium fluoride; 18-crown-6 ether; bis-phenanthrylimidazolium chloride; palladium diacetate In tetrahydrofuran at 50℃; for 8h; Suzuki-Miyaura coupling;	98%

2-methylchlorobenzene (95-49-8) + acetophenone (98-86-2) → 2-(2-methylphenyl)-1-phenyl-1-ethanone (5033-67-0)

Conditions	Yield
With C41H50ClN3Pd; sodium t-butanolate In 1,4-dioxane at 100℃; for 4h;	99%
With C34H36ClN3Pd; sodium t-butanolate In 1,4-dioxane at 100℃; for 4h; Reagent/catalyst;	97%
With (C5H5)Fe(C5H3C(CH3)NC6H4CH3)PdCl(CN2(C6H3(CH(CH3)2)2)2C2H2); potassium tert-butylate In toluene for 2h; Inert atmosphere; Reflux;	96%

2-methylchlorobenzene (95-49-8) + 1-phenyl-propan-1-one (93-55-0) → 2-(2-methylphenyl)-1-phenylpropan-1-one (53423-27-1)

Conditions	Yield
With C41H50ClN3Pd; sodium t-butanolate In 1,4-dioxane at 100℃; for 4h;	99%
Stage #1: 2-methylchlorobenzene; 1-phenyl-propan-1-one With sodium t-butanolate In tetrahydrofuran at 20℃; for 0.0333333h; Glovebox; Inert atmosphere; Stage #2: With C26H42ClNPd In tetrahydrofuran at 20℃; for 4h; Glovebox; Inert atmosphere;	97%
With N-heterocyclic carbene-palladacycle; sodium t-butanolate In tetrahydrofuran at 70℃; for 2h;	94%

2-methylchlorobenzene (95-49-8) + 4-methoxyphenyl magnesium bromide (13139-86-1) → 4'-methoxy-2-methylbiphenyl (92495-54-0)

Conditions	Yield
With C35H31BrN4NiP In tetrahydrofuran at 70℃; for 17h; Schlenk technique; Inert atmosphere;	99%
Stage #1: 2-methylchlorobenzene With Ni(PPh3)(1,3-di-tert-butylimidazol-2-ylidene)Br2 In tetrahydrofuran at 0℃; for 0.0333333h; Inert atmosphere; Schlenk technique; Stage #2: 4-methoxyphenyl magnesium bromide In tetrahydrofuran at 0 - 25℃; for 4h; Inert atmosphere; Schlenk technique;	98%
With C46H55ClFeN3Pd; lithium chloride In tetrahydrofuran at 60℃; for 12h; Kumada coupling reaction; Inert atmosphere;	92%

2-methylchlorobenzene (95-49-8) + 2,6-dimethylaniline (87-62-7) → 2,6-dimethyl-N-(o-tolyl)aniline (68014-57-3)

Conditions	Yield
With potassium tert-butylate In 1,4-dioxane at 110℃; for 3h;	99%
With tris-(dibenzylideneacetone)dipalladium(0); 1-methyl-2-(2-(dicyclohexylphosphino)phenyl)-1H-benzoimidazole; sodium t-butanolate In toluene at 20 - 135℃; for 20h; Buchwald-Hartwig reaction; Inert atmosphere;	99%
With C35H44Cl2N4Pd; potassium tert-butylate In tetrahydrofuran at 110℃; for 1h; Inert atmosphere; Sealed tube;	98%

2-methylchlorobenzene (95-49-8) + N-methylaniline (100-61-8) → N-methyl-N-(2-methylphenyl)aniline (6590-44-9)

Conditions	Yield
With palladium diacetate; sodium t-butanolate; ruphos In neat (no solvent) at 110℃; for 12h; Buchwald-Hartwig Coupling; Green chemistry;	99%
With C16H34ClPPd; sodium t-butanolate In toluene at 100℃; Buchwald-Hartwig amination; Inert atmosphere;	98%
With [Pd(N,N′-bis(2,6-bis(diphenylmethyl)-4-methoxyphenyl)imidazol-2-ylidene)(acac)Cl]; potassium 2-methylbutan-2-olate In 1,4-dioxane at 110℃; for 21h; Buchwald-Hartwig Coupling; Glovebox; Inert atmosphere;	98%

morpholine (110-91-8) + 2-methylchlorobenzene (95-49-8) → N-(o-tolyl)morpholine (7178-40-7)

Conditions	Yield
With potassium tert-butylate In 1,4-dioxane at 110℃; for 3h;	99%
With (1,3-bis(2,6-diisopropylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene)Pd(cinnamyl, 3-phenylallyl)Cl; sodium t-butanolate In neat (no solvent) at 110℃; for 12h; Buchwald-Hartwig Coupling; Inert atmosphere; Green chemistry;	99%
With C28H29Cl2N3OPd; potassium tert-butylate In toluene at 110℃; for 15h; Buchwald-Hartwig Coupling; Schlenk technique; Inert atmosphere;	99%

2-methylchlorobenzene (95-49-8) + 4-methoxyphenylboronic acid (5720-07-0) → 4'-methoxy-2-methylbiphenyl (92495-54-0)

Conditions	Yield
With NHC-Pd(II)-Im; potassium tert-butylate In water at 80℃; for 24h; Suzuki-Miyaura coupling;	99%
With potassium phosphate tribasic trihydrate; PdCl2(C3H3N2(CH3))(C3H2N2(C6H3(C3H7)2)2) In tetrahydrofuran; water at 20℃; for 24h; Suzuki-Miyaura coupling reaction; Inert atmosphere;	99%
With potassium dihydrogen phosphate trihydrate; [1,3-bis(2,6-diisopropylphenyl)imidazol-2-yl-isoquinolin-2-yl]palladium dichloride In tetrahydrofuran; water at 50℃; for 6h; Inert atmosphere;	99%

2-methylchlorobenzene (95-49-8) + 4-methoxy-aniline (104-94-9) → N-(4-methoxyphenyl)-2-methylbenzenamine (85448-89-1)

Conditions	Yield
With sodium t-butanolate; tris(dibenzylideneacetone)dipalladium (0); P(i-BuNCH2CH2)3N In toluene at 100℃; for 24h; Buchwald-Hartwig amination;	99%
With sodium hydride; 1,3-bis[(2,6-diisopropyl)phenyl]imidazolinium chloride; tert-butyl alcohol; bis(acetylacetonate)nickel(II) In 1,4-dioxane at 100℃;	99%
With bis(η3-allyl-μ-chloropalladium(II)); potassium tert-butylate; 1,3-bis[(2,6-diisopropyl)phenyl]imidazolinium chloride In 1,4-dioxane at 100℃; for 1.5h; Inert atmosphere;	99%

2-methylchlorobenzene (95-49-8) + diphenylamine (122-39-4) → 2-methyl-N,N-diphenylaniline (4316-55-6)

Conditions	Yield
With sodium t-butanolate; tris(dibenzylideneacetone)dipalladium (0); P(i-BuNCH2CH2)3N In toluene at 100℃; for 20h; Buchwald-Hartwig amination;	99%
With monophosphine 1,2,3,4,5-pentaphenyl-1'-(di-tert-butylphosphino)ferrocene; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In toluene at 80℃; for 21h;	99%
With 4-di-tert-butylphosphanyl-1-phenyl-5-(2-methoxyphenyl)-1H-[1,2,3]triazole; sodium t-butanolate; bis(dibenzylideneacetone)-palladium(0) In toluene at 110℃; for 20h;	96%

2-methylchlorobenzene (95-49-8) + aniline (62-53-3) → N-phenyl-2-methylaniline (1205-39-6)

Conditions	Yield
With dichloro(3-chloropyridinyl)(1,3-(diisopropylphenyl)-4,5-bis(dimethylamino)imidazol-2-ylidene)palladium(II); caesium carbonate In 1,2-dimethoxyethane at 80℃; for 24h; Buchwald-Hartwig Coupling; Schlenk technique; Sealed tube; Inert atmosphere;	99%
With C28H29Cl2N3OPd; potassium tert-butylate In toluene at 110℃; for 15h; Buchwald-Hartwig Coupling; Schlenk technique; Inert atmosphere;	99%
With C36H45Cl2N3OPd; potassium tert-butylate In 1,4-dioxane at 90℃; for 1h; Buchwald-Hartwig Coupling; Inert atmosphere; Schlenk technique;	98%

2-methylchlorobenzene (95-49-8) + cyclohexylamine (108-91-8) → N-(2-methylphenyl)cyclohexylamine (14185-37-6)

Conditions	Yield
With potassium tert-butylate In 1,4-dioxane at 110℃; for 3h;	99%
With C35H44Cl2N4Pd; potassium tert-butylate In tetrahydrofuran at 110℃; for 3h; Inert atmosphere; Sealed tube;	98%
With C33H40ClN3O2Pd; potassium tert-butylate In toluene at 110℃; for 12h; Buchwald-Hartwig Coupling; Inert atmosphere; Schlenk technique; Sealed tube;	94%

n-Octylamine (111-86-4) + 2-methylchlorobenzene (95-49-8) → N-(2-methylphenyl)octylamine

Conditions	Yield
With C38H49N2P*C9H10ClPd In 1,4-dioxane at 20℃; for 18h; Inert atmosphere; Schlenk technique;	99%
With (R)-(-)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyl di-t-butylphosphine; sodium t-butanolate; palladium diacetate In 1,2-dimethoxyethane at 100℃; for 48h;	98%
With sodium t-butanolate; palladium diacetate; (R)-(-)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyl di-t-butylphosphine In 1,2-dimethoxyethane at 100℃; for 48h;	98%

2-methylchlorobenzene (95-49-8) + p-toluidine (106-49-0) → N-(4-methylphenyl)-2-methylaniline (34160-14-0)

Conditions	Yield
With bis(η3-allyl-μ-chloropalladium(II)); potassium tert-butylate; 1,3-bis[(2,6-diisopropyl)phenyl]imidazolinium chloride In 1,4-dioxane at 100℃; for 1.5h; Inert atmosphere;	99%
With C35H44Cl2N4Pd; potassium tert-butylate In tetrahydrofuran at 130℃; for 12h; Inert atmosphere; Sealed tube;	98%
With C33H40ClN3O2Pd; potassium tert-butylate In toluene at 110℃; for 12h; Buchwald-Hartwig Coupling; Inert atmosphere; Schlenk technique; Sealed tube;	97%

2-methylchlorobenzene (95-49-8) + 2,5-Dimethylaniline (95-78-3) → N-(2-methylphenyl)-2,5-dimethylaniline

Conditions	Yield
With potassium tert-butylate In 1,4-dioxane at 110℃; for 3h;	99%
With [PdCl{[(η5-C5H5)]Fe[(η5-C5H3)-N2C4H2-Cl]}(DCPAB)]; potassium tert-butylate at 120℃; for 12h; Buchwald-Hartwig reaction;	95%
With [PdCl(η5-C5H5)Fe((η5-C5H3)-NC5H3Br)C3H2N2(C6H4-2,6-iPr2)2]; potassium tert-butylate In poly(ethylene glycol-400) at 120℃; for 24h; Buchwald-Hartwig amination; Inert atmosphere;	92%
With C37H44ClN2O3PPd; potassium hydroxide; tert-butyl alcohol In water at 100℃; for 12h; Buchwald-Hartwig Coupling; Schlenk technique; Inert atmosphere;	91%

n-Dodecylamine (124-22-1) + 2-methylchlorobenzene (95-49-8) → N-dodecyl-2-methylaniline (20025-92-7)

Conditions	Yield
With potassium tert-butylate In 1,4-dioxane at 110℃; for 3h;	99%

ortho-tolylmagnesium bromide (932-31-0) + 2-methylchlorobenzene (95-49-8) → 2,2'-dimethyl-1,1'-biphenyl (605-39-0)

Conditions	Yield
amido pincer complex of nickel chloride catalyst In tetrahydrofuran at 20℃; for 28h; Kumada cross-coupling reaction;	99%

2-methylchlorobenzene (95-49-8) + o-toluidine (95-53-4) → 2,2'-dimethyldiphenylamine (617-00-5)

Conditions	Yield
With C28H29Cl2N3OPd; potassium tert-butylate In toluene at 110℃; for 15h; Buchwald-Hartwig Coupling; Schlenk technique; Inert atmosphere;	99%
With C35H44Cl2N4Pd; potassium tert-butylate In tetrahydrofuran at 110℃; for 1h; Inert atmosphere; Sealed tube;	98%
With C36H43Cl2N3Pd; potassium tert-butylate In 1,4-dioxane at 110℃; for 1h; Buchwald-Hartwig Coupling; Inert atmosphere; Schlenk technique;	98%

2-methylchlorobenzene (95-49-8) + 2,4,6-trimethylaniline (88-05-1) → 2,4,6-trimethyl-N-(2-methylphenyl)aniline (39267-45-3)

Conditions	Yield
With C28H29Cl2N3OPd; potassium tert-butylate In toluene at 110℃; for 15h; Buchwald-Hartwig Coupling; Schlenk technique; Inert atmosphere;	99%
With C35H44Cl2N4Pd; potassium tert-butylate In tetrahydrofuran at 110℃; for 1h; Inert atmosphere; Sealed tube;	98%
With bis{1,1’-diphenyl-3,3’-methylenediimidazoline-2,2’-diylidene}nickel(II) dibromide; potassium tert-butylate In 1,4-dioxane at 90℃; for 4h; Catalytic behavior; Reagent/catalyst; Buchwald-Hartwig Coupling; Inert atmosphere; Schlenk technique;	98%

2-methylchlorobenzene (95-49-8) + 1-Phenylethanol (98-85-1, 13323-81-4) → 2-(2-methylphenyl)-1-phenyl-1-ethanone (5033-67-0)

Conditions	Yield
Stage #1: 1-Phenylethanol With allylchloro[1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidine]palladium(II); para-chlorotoluene; potassium tert-butylate In toluene at 40℃; for 3h; Inert atmosphere; Stage #2: 2-methylchlorobenzene In toluene at 80℃; for 6h; Inert atmosphere;	99%

2-methylchlorobenzene (95-49-8) + rac-1-(4-methoxyphenyl)-ethanol (3319-15-1) → 1-(4-methoxyphenyl)-2-(2-methylphenyl)ethanone (33509-94-3)

Conditions	Yield
Stage #1: rac-1-(4-methoxyphenyl)-ethanol With allylchloro[1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidine]palladium(II); para-chlorotoluene; potassium tert-butylate In toluene at 40℃; for 3h; Inert atmosphere; Stage #2: 2-methylchlorobenzene In toluene at 80℃; for 3h; Inert atmosphere;	99%

2-methylchlorobenzene (95-49-8) + benzamide (55-21-0) → N-benzoyl-2-methylaniline (584-70-3)

Conditions	Yield
With 4-diphenylphosphino-13-dicyclohexylphosphino-[2.2]paracyclophane; water; palladium diacetate; caesium carbonate In 1,4-dioxane at 125℃; for 24h; Buchwald-Hartwig coupling;	99%
With 5-(di-tert-butylphosphino)-1′, 3′, 5′-triphenyl-1′H-[1,4′]bipyrazole; bis[chloro(1,2,3-trihapto-allylbenzene)palladium(II)]; potassium carbonate In 1,4-dioxane at 90℃; for 18h; Buchwald-Hartwig Coupling; Inert atmosphere; Glovebox;	99%
With copper(I) oxide; potassium phosphate; N1,N2-bis(thiophen-2-ylmethyl)oxalamide In tert-butyl alcohol at 130℃; for 24h; Schlenk technique;	79%
With potassium carbonate; N,N`-dimethylethylenediamine at 130℃; for 23h; Neat (no solvent);	78%
Stage #1: 2-methylchlorobenzene; benzamide With copper(l) iodide; potassium carbonate; trans-N,N'-dimethylcyclohexane-1,2-diamine In acetonitrile for 0.00277778h; Inert atmosphere; Glovebox; Stage #2: In acetonitrile at 200℃; for 1h; Microwave irradiation;	38 %Chromat.

2-methylchlorobenzene (95-49-8) + phenylpropyolic acid (637-44-5) → 1-phenylethynyltoluene (14309-60-5)

Conditions	Yield
With bis[dicyclohexyl(2,4,6-triisopropyl-[1,1':3',1''-terphenyl]-2-yl)phosphane]palladium(II) dichloride; caesium carbonate In tetrahydrofuran at 80℃; for 2.5h;	99%
With [Pd((η5-C5H5)Fe[(η5-C5H3)C(Me)=N(C6H4-4-Me)])(μ-Cl)]2; potassium carbonate; XPhos In 5,5-dimethyl-1,3-cyclohexadiene; water at 120℃; for 3h;	88%
With (R)-1-[(SP)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-tert-butylphosphine; palladium diacetate; caesium carbonate In dimethyl sulfoxide at 130℃; for 12h;	31%

Upstream product

• 88-20-0 o-toluenesulfonic acid 
• 42413-03-6 3-chloro-4-methylbenzenesulfonyl chloride 
• 77164-28-4 dichloro-tris-o-tolyloxy-phosphorane 
• 2028-34-4 o-toluene-diazonium chloride 
• 89-98-5 2-chloro-benzaldehyde 
• 104-15-4 toluene-4-sulfonic acid 
• 27876-29-5 acetic acid-(2,4,6,N-tetrachloro-anilide) 
• 64-19-7 acetic acid 
• 108-88-3 toluene 
• 2229-07-4 methyl radical 
• 108-90-7 chlorobenzene 
• 95-53-4 o-toluidine 
• 922-69-0 1,1-dimethoxyethylene 
• 694-80-4 2-bromo-1-chlorobenzene 

Downstream Products

• 7450-03-5 (2-methylphenyl)trimethylsilane 
• 56260-30-1 dibenzofuran-2-yl-o-tolyl-methanone 
• 860596-93-6 3,6-dichloro-2-(4-chloro-3-methyl-benzoyl)-benzoic acid 
• 108-39-4 3-methyl-phenol 
• 95-48-7 ortho-cresol 
• 861327-98-2 4,6-bis-(3-chloro-4-methyl-benzoyl)-isophthalic acid 
• 861562-81-4 2,5-bis-(3-chloro-4-methyl-benzoyl)-terephthalic acid 
• 37074-39-8 4-chloro-3-methylacetophenone 
• 108953-93-1 3-o-toluoyloxy-crotonic acid ethyl ester 
• 74617-45-1 2,4'-dichloro-3'-methyl-benzophenone 
• 108166-23-0 N-([1,1'-biphenyl]-4-yl)-2-methylbenzamide 
• 146448-53-5 N-<(4-Methylphenyl)sulfonyl>-2-methylbenzenecarboxamide 
• 951891-12-6 2-bromo-4'-chloro-3'-methyl-benzophenone 
• 2728-04-3 N,N-diethyl-ortho-toluamide 

Relevant academic research and scientific papers

Deep compositional understanding of TBA: AlCl3 ionic liquid for its applications

Chloroaluminate ionic liquids (ILs) have been immensely used as homogeneous catalyst in Friedel-Crafts reaction. We have recently synthesized chloroaluminate ILs by reacting aluminium chloride with a hydrophobic neutral ligand i.e. tributylamine (TBA:AlCl3). The current study elaborates on the investigations of the composition of the ionic liquids at various stages of their formation. The ionic liquids were synthesized using various mole ratios of tributyl amine and aluminium chloride in range of 1:1 to 1:2.3, in presence of an aromatic solvent in a one pot reaction. Various characterization techniques like Mass spectrometry, 27Al Nuclear Magnetic Resonance, 31P Nuclear Magnetic Resonance and Fourier Transform Infrared spectroscopy were used to elucidate the formation of various moieties of the TBA:AlCl3 Ionic Liquid. This study also elaborates on the investigations of the cationic and anionic moieties and their structure-property relationship for various applications. Various Friedel-Crafts reaction of industrial importance were performed using the ionic liquid having (Al2Cl7)?moiety to assess its performance and compared with conventional processes. The synthesized products were characterised by sophisticated analytical techniques like 1H NMR, 13C NMR, FTIR, GC–MS, GC-FID, to name a few. This class of ionic liquids also have importance in various electrochemical applications like aluminium deposition and aluminium batteries.

Rate enhancements due to ultrasound in isoquinolinium dichromate and isoquinolinium chlorochromate catalyzed chlorination of aromatic compounds in presence of KHSO4/KCl

Chlorination of aromatic compounds underwent magnificent rate accelerations in isoquinolinium dichromate and isoquinolinium chlorochromate catalyzed chlorination of aromatic hydrocarbons in the presence of KCl and KHSO4. Reaction times reduced highly significantly from 4-5 h in conventional protocol to 30-40 min under sonication, followed by high yields of monochloro derivatives as products with high regioselectivity.

Method for producing parachlorotoluene through continuous chlorination of methylbenzene

The invention discloses a method for producing parachlorotoluene through continuous chlorination of methylbenzene. The method comprises the following steps: with an active molecular sieve as a catalyst, performing continuous chlorination on methylbenzene in a static bed, wherein a ratio of parachlorotoluene to o-chlorotoluene in the chlorination products is 1.2-6.0; performing aeration and distillation separation on the chlorination product to obtain high-purity parachlorotoluene, and enabling the separated methylbenzene and raw material methylbenzene to enter the static bed together so as toperform continuous chlorination; periodically reproducing the catalyst in the static bed; and alternately using and activating two groups or more than two groups of static beds. According to the method disclosed by the invention, continuous chlorination production of methylbenzene is realized, the ratio of parachlorotoluene to o-chlorotoluene is 1.2-6.0, the catalyst can be repeatedly used, the production cost is reduced, and solid waste emission is reduced.

2 - Chloro -3 - methyl benzoic acid and intermediate preparation method (by machine translation)

The invention discloses a 2 - chloro - 3 - methyl benzoic acid and intermediate preparation method. A 2 - chloro - 3 - methyl benzoic acid and intermediate preparation method, comprising the following steps, in the oxygen pressure is 0.1 mpa - 0.8 mpa under the condition of, under the action of the catalyst and promoter, the 2, 6 - dimethyl chlorobenzene to carry out oxidation reaction, can be; wherein said 2, 6 - dimethyl chlorobenzene and the oxygen molar amount ratio of 1: 1.8 - 1: 2.2. The 2 - chloro - 3 - methyl benzoic acid, in order to industrially easily available raw materials for the reaction, after treatment is simple, high yield, purity is good, small pollution to the environment, is more suitable for industrial. (by machine translation)

A process for preparing O-toluene

The present invention provides a process for preparing dichloro toluene, relates to the field of preparation of organic intermediates. The invention relates to 2, 3 - dichloro toluene, 2, 4 - dichloro toluene and 2, 5 - dichloro toluene in more than one type of raw materials, supported palladium as the catalyst, a fixed bed continuous reaction preparation of O-toluene. This invention uses the industrial by-product 2, 3 - dichloro toluene, 2, 4 - dichloro toluene and 2, 5 - dichloro toluene as the raw materials, supported palladium catalyst good selectivity, long-time use, O-chlorotoluene high yield.

Preparation method of aryl diazonium chlorocuprate

The invention provides a preparation method of aryl diazonium chlorocuprate. Stable salt is formed by aryl diazonium salt and chlorocuprate radicals, the aryl diazonium chlorocuprate is prepared in situ, and a complex is prepared and decomposed by controlling reaction temperature. According to the method, the diazonium salt is prepared by non-aqueous solvents, the aryl diazonium chlorocuprate is then prepared in situ, finally, Sandmeyer is performed by the aid of the difference of stability of the diazonium salt, and recovery and emission reduction functions can be achieved in practical production.

Method for preparing o-chlorotoluene through methylbenzene loop chlorination

The invention discloses a method for preparing o-chlorotoluene through methylbenzene loop chlorination. The method particularly includes the steps that iron powder or ferric trichloride is added into methylbenzene to serve as catalysts, [BMTM]Cl-nZnCl2 ionic liquid serves as an assistant (n is equal to 1, 2 or 2.5), and stirring is carried out; dry chlorine is led in, a suitable temperature is controlled under the dark condition to conduct chlorination, the o-chlorotoluene is obtained in a high-selectivity manner, and alkali liquor absorption is carried out after tail gas condensation to remove excessive unreacted chlorine; and after reacting is ended, a reacting product and the ionic liquid assistant are separated, the separated ionic liquid can be repeatedly used. Compared with the prior art, the method can well improve the methylbenzene conversion rate, and the o-chlorotoluene selectivity reaches 88%; in addition, the separated and recycled [BMTM]Cl-nZnCl2 ionic liquid is repeatedly used, the production cost is reduced, and the method is suitable for o-chlorotoluene industrial production.

Zinc chloride load HY molecular sieve catalytic toluene synthesis of O-toluene

The invention relates to the technical field of preparation of o-chlorotoluene, in particular to a method for synthesizing the o-chlorotoluene by catalyzing toluene through a zinc chloride load HY molecular sieve, and belongs to the technical field of toluene orientation chlorination. According to the method, the zinc chloride load HY molecular sieve is adopted as a catalyst, Cl2 is adopted as a chlorinating agent, and a liquid phase chlorination method is adopted for carrying out selective chlorination on the toluene. According to the method for preparing the o-chlorotoluene by carrying out selective chlorination on the toluene, the reaction condition is mild and easy to control, the synthetic process is simple, the adopted ZnCl2/HY catalyst is good in catalytic activity and can be separated from a product easily, pollution to the environment is small, corrosivity to equipment is small, and the method has high industrial application value.

Room temperature C(sp2)-H oxidative chlorination: Via photoredox catalysis

Photoredox catalysis has been developed to achieve oxidative C-H chlorination of aromatic compounds using NaCl as the chlorine source and Na2S2O8 as the oxidant. The reactions occur at room temperature and exhibit exclusive selectivity for C(sp2)-H bonds over C(sp3)-H bonds. The method has been used for the chlorination of a diverse set of substrates, including the expedited synthesis of key intermediates to bioactive compounds and a drug.

Visible Light-Induced Oxidative Chlorination of Alkyl sp3 C-H Bonds with NaCl/Oxone at Room Temperature

A visible light-induced monochlorination of cyclohexane with sodium chloride (5:1) has been successfully accomplished to afford chlorocyclohexane in excellent yield by using Oxone as the oxidant in H2O/CF3CH2OH at room temperature. Other secondary and primary alkyl sp3 C-H bonds of cycloalkanes and functional branch/linear alkanes can also be chlorinated, respectively, under similar conditions. The selection of a suitable organic solvent is crucial in these efficient radical chlorinations of alkanes in two-phase solutions. It is studied further by the achievement of high chemoselectivity in the chlorination of the benzyl sp3 C-H bond or the aryl sp2 C-H bond of toluene.