87-64-9

Basic information

• Product Name: 2-CHLORO-6-METHYLPHENOL
• Synonyms: 6-CHLORO-O-CRESOL;2-CHLORO-6-METHYLPHENOL;2-Methyl-6-chlorophenol;6-chloro-o-creso;o-Cresol, 6-chloro-;2-Chloro-6-methylphenol,98%;2-Chloro-6-methylphenol, tech;6-CHLORO-ORTHO-CRESOL
• CAS NO: 87-64-9
• Molecular Formula: C₇H₇ClO
• Molecular Weight: 142.58
• EINECS: 201-760-8
• Product Categories: Phenol&Thiophenol&Mercaptan;Chlorine Compounds;Phenols
• Mol File: 87-64-9.mol
• Article Data: 18

Chemical Properties

• Melting Point: 130 °C
• Boiling Point: 86 °C
• Flash Point: 72°C
• Appearance: Coloroless to yellow liquid
• Density: 1,201 g/cm3
• Vapor Pressure: 0.229mmHg at 25°C
• Refractive Index: 1.5450
• Storage Temp.: Sealed in dry,Room Temperature
• PKA: 8.84±0.10(Predicted)
• Water Solubility: Soluble in water (24 mg/ml at 25°C).
• BRN: 774623
• CAS DataBase Reference: 2-CHLORO-6-METHYLPHENOL(CAS DataBase Reference)
• NIST Chemistry Reference: 2-CHLORO-6-METHYLPHENOL(87-64-9)
• EPA Substance Registry System: 2-CHLORO-6-METHYLPHENOL(87-64-9)

Safety Data

• Hazard Codes: Xi,Xn
• Statements: 21/22-36/38-36/37/38-22-38
• Safety Statements: 26-28-36/37/39-23
• RIDADR: 3437
• RTECS: GO7120100
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 87-64-9(Hazardous Substances Data)

Usage

Chemical Properties

Coloroless to yellow liquid

Uses

2-Chloro-6-methylphenol is s an important raw material and intermediate used in Organic Synthesis, Pharmaceuticals, Agrochemicals and Dyestuffs.

InChI:InChI=1/C7H7ClO/c1-5-3-2-4-6(8)7(5)9/h2-4,9H,1H3

Synthetic route

ortho-cresol (95-48-7) → 2-methyl-4-chlorophenol (1570-64-5) + 2-chloro-6-methylphenol (87-64-9)

Conditions	Yield
With oxone; potassium chloride In acetonitrile at 20℃; for 15h;	A 77% B 5%
With hydrogenchloride; dihydrogen peroxide; acetic acid In Petroleum ether for 12h; Reflux;	A 47% B 41%
With 2,3,4,4,5,6-hexachlorocyclohexa-2,5-dien-1-one In N,N-dimethyl-formamide Product distribution;	A 89.5 (unit not given) B n/a

2-methylchlorobenzene (95-49-8) → 4-Chloro-3-methylphenol (59-50-7) + 2-Chlorobenzyl alcohol (17849-38-6) + 3-chloro-o-cresol (3260-87-5) + 3-chloro-4-methylphenol (615-62-3) + 2-chloro-m-cresol (608-26-4) + 2-chloro-6-methylphenol (87-64-9)

Conditions	Yield
With wild type cytochrome P450 CYP102A1 variants RLYF/A330P; oxygen; NADPH Enzymatic reaction;	A 22% B 15% C 22% D n/a E 10% F 28%
With wild type cytochrome P450 CYP102A1(P450Bm3); oxygen; NADPH Enzymatic reaction;	A 24% B 25% C 28% D n/a E 7% F 13%

4-bromo-2-chloro-6-methyl-phenol (7530-27-0) → 2-chloro-6-methylphenol (87-64-9)

Conditions	Yield
With palladium on activated charcoal; cyclohexane; benzene Hydrogenolyse unter Zusatz von Natriumacetat;

toluene-4-sulfonic acid-(2-chloro-6-methyl-phenyl ester) → 2-chloro-6-methylphenol (87-64-9)

Conditions	Yield
With sodium hydroxide

ortho-cresol (95-48-7) → 2-chloro-6-methylphenol (87-64-9)

Conditions	Yield
With chlorine at 50 - 55℃;
With chlorine at 50 - 55℃;

ortho-cresol (95-48-7) → 4,6-dichloro-2-methylphenol (1570-65-6) + 2-chloro-6-methylphenol (87-64-9)

Conditions	Yield
With sulfuric acid Reaktion ueber mehrere Stufen;

1-chloro-3-methylbenzene (108-41-8) → 2-methyl-4-chlorophenol (1570-64-5) + 2-chloro-p-cresol (6640-27-3) + m-chlorobenzyl alcohol (873-63-2) + 2-chloro-6-methylphenol (87-64-9)

Conditions	Yield
With dinitrogen monoxide In water Rate constant; Product distribution; Mechanism; Ambient temperature; Irradiation; reaction with OH or SO4(2-) radicals;

barium-<4-hydroxy-3-methyl-benzenesulfonate > → 2-chloro-6-methylphenol (87-64-9)

Conditions	Yield
With water; chlorine Erhitzen des Reaktionsprodukts mit wss. H2SO4;

potassium salt of/the/ 3-chloro-2-oxy-toluene-sulfonic acid-(5) → 2-chloro-6-methylphenol (87-64-9)

Conditions	Yield
With sulfuric acid at 130℃;

sulfuric acid (7664-93-9) + ortho-cresol (95-48-7) → 4,6-dichloro-2-methylphenol (1570-65-6) + 2-chloro-6-methylphenol (87-64-9)

Conditions	Yield
anschl. Versetzen mit Nitrobenzol und mit rauchender H2SO4, Einleiten von Chlor bei 55grad und Behandeln der wss. Schicht bei 115-180grad;

chlorine (7782-50-5) + ortho-cresol (95-48-7) + natrium carbonate → 2-methyl-4-chlorophenol (1570-64-5) + 2-chloro-6-methylphenol (87-64-9)

MCPA (94-74-6) → 4,6-dichloro-2-methylphenol (1570-65-6) + 2-methyl-4-chlorophenol (1570-64-5) + 2-methylbenzene-1,4-diol (95-71-6) + 2-methylbenzene-1,3-diol (608-25-3) + 2,5-dihydroxy-3-methylbenzoaldehyde (108372-60-7) + 2-Methyl-1,4-benzoquinone (553-97-9) + ortho-cresol (95-48-7) + 3-methylbenzene-1,2-diol (488-17-5) + 2-chloro-6-methylphenol (87-64-9) + 5-chloro-7-methyl-3H-benzofuran-2-one

Conditions	Yield
With water UV-irradiation;

...Expand

methanol (67-56-1) + C8H6ClF3O3S → 1-chloro-2-methoxy-3-methylbenzene (3438-15-1) + 2-chloro-6-methylphenol (87-64-9)

Conditions	Yield
With carbon monoxide under 30003 Torr; Inert atmosphere; Autoclave; Heating;

(S)-isopropyl 2-(5-(2-bromoethoxy)-4'-(4,4-dimethylpiperidin-1-yl)-6'-methyl-[2,3'-bipyridin]-5'-yl)-2-(tert-butoxy)acetate + 2-chloro-6-methylphenol (87-64-9) → (S)-isopropyl 2-(tert-butoxy)-2-(5-(2-(2-chloro-6-methylphenoxy)ethoxy)-4'-(4,4-dimethylpiperidin-1-yl)-6'-methyl-[2,3'-bipyridin]-5'-yl)acetate

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 80℃;	98%

5-bromo-6-chloro-3-pyridinecarboxylic acid methyl ester (78686-77-8) + 2-chloro-6-methylphenol (87-64-9) → methyl 5-bromo-6-(2-chloro-6-methylphenoxy)nicotinate

Conditions	Yield
With caesium carbonate In dimethyl sulfoxide at 80℃; for 1.5h;	91%

9-acridinecarbonyl chloride (66074-67-7) + 2-chloro-6-methylphenol (87-64-9) → 2'-methyl-6'-chlorophenyl acridine-9-carboxylate (158749-40-7)

Conditions	Yield
With dmap; triethylamine In dichloromethane for 1h; Ambient temperature;	85%

N-ethyl-4-(5-(ethylsulfonyl)-2-fluorophenyl)-6-methyl-7-oxo-6,7-dihydro-1H-pyrrolo[2,3-c]pyridine-2-carboxamide + 2-chloro-6-methylphenol (87-64-9) → N-ethyl-4-[5-ethylsulfonyl-2-(2-fluoro-6-methylphenoxy)phenyl]-6-methyl-7-oxo-1H-pyrrolo[2,3-c]pyridine-2-carboxamide

Conditions	Yield
With caesium carbonate In dimethyl sulfoxide at 110℃; for 16h;	82%

methyl glycidate (4538-50-5) + 2-chloro-6-methylphenol (87-64-9) → (2R)-3-(2-chloro-6-methylphenoxy)-2-hydroxypropionic acid methyl ester (1612884-59-9)

Conditions	Yield
In acetonitrile at 23℃; for 24h; enantioselective reaction;	80%

formaldehyd (50-00-0) + dimethyl amine (124-40-3) + 2-chloro-6-methylphenol (87-64-9) → 2-chloro-4-dimethylaminomethyl-6-methylphenol (82965-44-4)

Conditions	Yield
In ethanol; water for 24h; Heating / reflux;	66%
In ethanol; water for 24h; Reflux;	66%

2-chloro-6-methylphenol (87-64-9) + methyl 3-bromo-4-fluorobenzoate (82702-31-6) → methyl 3-bromo-4-(2-chloro-6-methylphenoxy)benzoate

Conditions	Yield
With caesium carbonate In dimethyl sulfoxide at 100℃; for 1h; Inert atmosphere;	65.5%

hexamethylenetetramine (100-97-0) + 2-chloro-6-methylphenol (87-64-9) → 3-Chloro-4-hydroxy-5-methylbenzaldehyde (107356-10-5)

Conditions	Yield
With trifluoroacetic acid Heating;	62%
With trifluoroacetic acid at 60℃; for 0.5h; Inert atmosphere;	40%
In trifluoroacetic acid at 20 - 70℃; for 90h;

2-chloro-6-methylphenol (87-64-9) → 2-chloro-4,4-difluoro-6-methyl-cyclohexa-2,5-dienone

Conditions	Yield
With triethylamine pentahydrogen fluoride salt; carbonic acid dimethyl ester at 20℃; for 6h; Electrochemical reaction;	62%

2-(tert-butoxycarbonylamino)ethyl methanesulfonate (96628-67-0) + 2-chloro-6-methylphenol (87-64-9) → tert-butyl (2-(2-chloro-6-methylphenoxy)ethyl)carbamate

Conditions	Yield
Stage #1: 2-chloro-6-methylphenol With caesium carbonate In N,N-dimethyl-formamide at 20℃; for 0.25h; Stage #2: 2-(tert-butoxycarbonylamino)ethyl methanesulfonate In N,N-dimethyl-formamide at 100℃; for 16h;	61%

formaldehyd (50-00-0) + 2-chloro-6-methylphenol (87-64-9) → 3-Chlor-4-hydroxy-5-methylbenzylalkohol (60211-27-0)

Conditions	Yield
With sodium hydroxide In water for 72h; Ambient temperature;	60%

2-chloro-6-methylphenol (87-64-9) + phenylboronic acid (98-80-6) → 2-methyl-6-phenylphenol (17755-10-1)

Conditions	Yield
With potassium fluoride; 2’-(dimethylamino)-2-biphenylyl-palladium(II)chloride dinorbornylphosphine complex In 1,4-dioxane at 110℃; Suzuki cross-coupling reaction;	60%

ethyl 2-chloronicotinate (1452-94-4) + 2-chloro-6-methylphenol (87-64-9) → 2-(2-chloro-6-methylphenoxy)nicotinic acid (1239340-23-8)

Conditions	Yield
Stage #1: ethyl 2-chloronicotinate; 2-chloro-6-methylphenol With caesium carbonate In ISOPROPYLAMIDE at 130℃; for 6h; Stage #2: With water In ISOPROPYLAMIDE at 110℃; for 4h; Stage #3: With hydrogenchloride In water pH=3;	55%

fullerene-C60 (99685-96-8, 161105-99-3, 161106-00-9, 111138-12-6, 133318-63-5, 134053-11-5, 134931-35-4, 134931-36-5, 139703-76-7, 145633-27-8, 175414-73-0, 175414-74-1, 175414-75-2, 175519-12-7, 175519-13-8, 175519-14-9, 175519-15-0, 136376-46-0, 144906-37-6, 144906-38-7, 151767-00-9, 152882-97-8, 152882-98-9, 152882-99-0, 153062-34-1, 154171-74-1, 154171-75-2, 154333-99-0, 154334-00-6, 154397-63-4, 154460-59-0, 199456-56-9, 108739-25-9, 120329-57-9, 120329-58-0) + 2-chloro-6-methylphenol (87-64-9) → C67H7ClO

Conditions	Yield
Stage #1: fullerene-C60; 2-chloro-6-methylphenol With potassium tert-butylate In N,N-dimethyl-formamide at 60℃; for 1h; Inert atmosphere; Schlenk technique; Stage #2: With trifluoroacetic acid In N,N-dimethyl-formamide at 60℃; for 0.166667h; Inert atmosphere; Schlenk technique; regioselective reaction;	54%

2-chloro-6-methylphenol (87-64-9) → 4-bromo-2-chloro-6-methyl-phenol (7530-27-0)

Conditions	Yield
With N-Bromosuccinimide; acetic acid at 20℃; for 12h;	52%
With benzyltrimethylazanium tribroman-2-uide In methanol; dichloromethane for 5h; Ambient temperature;
With N-Bromosuccinimide In acetic acid at 20℃;
With N-Bromosuccinimide; acetic acid at 20℃; for 12h;
With N-Bromosuccinimide In acetic acid at 20℃;

2-chloro-6-methylphenol (87-64-9) + 4,6-dichloro-2-(methylsulfonyl)pyrimidine (4489-34-3) → 4,6-dichloro-2-(2-chloro-6-methylphenoxy)pyrimidine

Conditions	Yield
Stage #1: 2-chloro-6-methylphenol With sodium hydride In tetrahydrofuran at -50℃; for 0.5h; Inert atmosphere; Stage #2: 4,6-dichloro-2-(methylsulfonyl)pyrimidine In tetrahydrofuran at -50℃; for 30h; Inert atmosphere;	52%

benzyl bromide (100-39-0) + fullerene-C60 (99685-96-8, 161105-99-3, 161106-00-9, 111138-12-6, 133318-63-5, 134053-11-5, 134931-35-4, 134931-36-5, 139703-76-7, 145633-27-8, 175414-73-0, 175414-74-1, 175414-75-2, 175519-12-7, 175519-13-8, 175519-14-9, 175519-15-0, 136376-46-0, 144906-37-6, 144906-38-7, 151767-00-9, 152882-97-8, 152882-98-9, 152882-99-0, 153062-34-1, 154171-74-1, 154171-75-2, 154333-99-0, 154334-00-6, 154397-63-4, 154460-59-0, 199456-56-9, 108739-25-9, 120329-57-9, 120329-58-0) + 2-chloro-6-methylphenol (87-64-9) → C81H19ClO

Conditions	Yield
Stage #1: fullerene-C60; 2-chloro-6-methylphenol With potassium tert-butylate In N,N-dimethyl-formamide at 20℃; for 1h; Schlenk technique; Inert atmosphere; Stage #2: benzyl bromide In N,N-dimethyl-formamide at 150℃; for 1h; Schlenk technique; Inert atmosphere; regioselective reaction;	51%

ethyl bromoacetate (105-36-2) + fullerene-C60 (99685-96-8, 161105-99-3, 161106-00-9, 111138-12-6, 133318-63-5, 134053-11-5, 134931-35-4, 134931-36-5, 139703-76-7, 145633-27-8, 175414-73-0, 175414-74-1, 175414-75-2, 175519-12-7, 175519-13-8, 175519-14-9, 175519-15-0, 136376-46-0, 144906-37-6, 144906-38-7, 151767-00-9, 152882-97-8, 152882-98-9, 152882-99-0, 153062-34-1, 154171-74-1, 154171-75-2, 154333-99-0, 154334-00-6, 154397-63-4, 154460-59-0, 199456-56-9, 108739-25-9, 120329-57-9, 120329-58-0) + 2-chloro-6-methylphenol (87-64-9) → C75H19ClO5

Conditions	Yield
Stage #1: fullerene-C60; 2-chloro-6-methylphenol With potassium tert-butylate In N,N-dimethyl-formamide at 20℃; for 1h; Schlenk technique; Inert atmosphere; Stage #2: ethyl bromoacetate In N,N-dimethyl-formamide at 150℃; for 1h; Schlenk technique; Inert atmosphere; regioselective reaction;	48%

furan-3-boronic acid (55552-70-0) + 2-chloro-6-methylphenol (87-64-9) → 2-(furan-3-yl)-6-methylphenol

Conditions	Yield
With potassium fluoride; 2’-(dimethylamino)-2-biphenylyl-palladium(II)chloride dinorbornylphosphine complex In 1,4-dioxane at 110℃; Suzuki cross-coupling reaction;	41%

2-chloro-6-methylphenol (87-64-9) + 2-bromoethanol (540-51-2) → 2-(2-chloro-6-methylphenoxy)ethanol

Conditions	Yield
With sodium hydroxide In water at 90℃; for 16h;	36.3%

2-chloro-6-methylphenol (87-64-9) → 3-Chloro-4-hydroxy-5-methylbenzaldehyde (107356-10-5)

Conditions	Yield
With hexamethylenetetramine; sodium hydrogencarbonate In ice-water; diethyl ether; hexane; trifluoroacetic acid	35%
With sodium bicarbonate; hexamethylenetetramine In ice-water; hexane; trifluoroacetic acid	35%

4-[2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]-2,5-difluorobenzonitrile + 2-chloro-6-methylphenol (87-64-9) → 2-(2-chloro-6-methylphenoxy)-4-[2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]-5-fluorobenzonitrile

Conditions	Yield
With potassium carbonate In dimethyl sulfoxide at 110℃; for 17h;	17%

N-ethyl-4-(5-(ethylsulfonyl)-2-fluorophenyl)-6-methyl-7-oxo-6,7-dihydro-1H-pyrrolo[2,3-c]pyridine-2-carboxamide + 2-chloro-6-methylphenol (87-64-9) → 4-[2-(2-chloro-6-methylphenoxy)-5-ethylsulfonylphenyl]-N-ethyl-6-methyl-7-oxo-1H-pyrrolo[2,3-c]pyridine-2-carboxamide

Conditions	Yield
With caesium carbonate In dimethyl sulfoxide at 110℃; for 16h;	11%

2-chloromethyl-5-methoxy-4H-pyran-4-one (40838-34-4) + 2-chloro-6-methylphenol (87-64-9) → 2-(2-chloro-6-methyl-phenoxymethyl)-5-methoxy-pyran-4-one (107775-78-0)

Conditions	Yield
With ethanol; potassium ethoxide

acetic anhydride (108-24-7) + 2-chloro-6-methylphenol (87-64-9) → acetic acid-(2-chloro-6-methyl-phenyl ester) (6341-98-6)

Conditions	Yield
With sulfuric acid

diethyl phosphorochloridothioate (2524-04-1) + 2-chloro-6-methylphenol (87-64-9) → thiophosphoric acid O,O'-diethyl ester-O''-(2-chloro-6-methyl-phenyl ester) (3279-61-6)

Conditions	Yield
With sodium carbonate; butanone

Upstream product

• 7664-93-9 sulfuric acid 
• 95-48-7 ortho-cresol 
• 7782-50-5 chlorine 
• 95-49-8 2-methylchlorobenzene 
• 67-56-1 methanol 
• 94-74-6 MCPA 
• 108-41-8 1-chloro-3-methylbenzene 
• 7530-27-0 4-bromo-2-chloro-6-methyl-phenol 

Downstream Products

• 19094-75-8 2-methyl-6-chlorophenoxyacetic acid 
• 1440-83-1 chloro-acetic acid-(2-chloro-6-methyl-phenyl ester) 
• 56949-52-1 1-(2-chloro-6-methyl-phenoxy)-propan-2-ol 
• 58656-17-0 2-Chlor-6-methylphenyl-2-nitrophenylether 
• 1440-84-2 (+/-)-2-Brom-propionsaeure-(2-chlor-6-methylphenylester) 
• 158749-40-7 2'-methyl-6'-chlorophenyl acridine-9-carboxylate 
• 73791-20-5 2-Chlor-6-methyl-p-nitroso-phenol 
• 77691-31-7 6-Chlor-4-chlormethyl-o-kresol 
• 1239340-23-8 2-(2-chloro-6-methylphenoxy)nicotinic acid 
• 91506-05-7 5-bromo-1-chloro-2-methoxy-3-methylbenzene 
• 29093-41-2 2,6-dimethoxy-3-methylcarbazole 
• 603-86-1 2-chloro-6-nitrophenol 
• 855301-45-0 (Z)-2-Benzoylamino-3-[4-(2-chloro-6-methyl-phenoxy)-phenyl]-acrylic acid 
• 944327-00-8 3-chloro-4,N-dihydroxy-5-methylbenzamidine 

Relevant articles and documents

para-Selective chlorination of cresols and m-xylenol using sulfuryl chloride in the presence of poly(alkylene sulfide)s

Chlorination of o-cresol, m-cresol, and m-xylenol using sulfuryl chloride in the presence of a range of poly(alkylene sulfide)s and a Lewis acid (aluminum or ferric chloride) has been studied. The sulfur containing catalysts used led to the production of para-chlorophenols in high yields and higher para/ortho ratios than for reactions in the absence of such poly(alkylene sulfide)s. The effectiveness of the polymers was found to be dependent on the length of the spacer groups between the sulfur atoms. For example, polymers with shorter spacers provided high yields of 4-chloro-o-cresol (ca. 97%), while polymers with at least one longer spacer provided high yields of both 4-chloro-m-cresol (up to 94.6%) and 4-chloro-m-xylenol (up to 97.6%).

Regioselective synthesis of important chlorophenols in the presence of methylthioalkanes with remote SMe, OMe or OH substituents

Various methylthio alcohols, methoxy(methylthio)alkanes and bis(methylthio)alkanes have been used as regioselectivity modifiers in the chlorination reactions of various phenols at room temperature. The process involves the use of a slight excess of sulfuryl chloride in the presence of aluminum or ferric chloride as an activator. Methylthio alcohols, methoxy(methylthio)alkanes and bis(methylthio)alkanes having 2 and 3 methylene groups as a spacer were found to be good for the para-selective chlorination of o-cresol and phenol. On the other hand, methylthio alcohols, methoxy(methylthio)alkanes and bis(methylthio)alkanes having 6 and 9 methylene groups were found to be good for the selective para-chlorination of m-xylenol and m-cresol. Calculations using density functional theory on bis(methylthio)alkanes have suggested two different types of stable chlorinated intermediates depending on the number of methylene units as a spacer.

Comparison of cyclic and polymeric disulfides as catalysts for the regioselective chlorination of phenols

Two cyclic and two polymeric disulfides have been synthesized and established to be useful catalysts for the chlorination of m-xylenol, o-cresol, m-cresol and phenol using freshly distilled sulfuryl chloride in the presence of aluminum or ferric chloride as a co-catalyst at room temperature. The yields of p-isomers and para/ortho ratios were higher compared to cases where no catalyst was used with most catalysts for most phenols even when a very low concentration of disulfide was used.