3260-88-6

Basic information

• Product Name: 3-chloro-2-methoxyanisole
• Synonyms: 3-chloro-2-methylanisole,98%;2-CHLORO-6-METHOXYTOLUENE;3-CHLORO-2-METHYLANISOLE;2-Chloro-6-methoxytoluene~2-Methoxy-6-chlorotoluene;2-Methoxy-6-chlorotoluene;2-METHYL-3-CHLOROANISOLE ;1-Chloro-3-methoxy-2-methylbenzene;3-chloro-2-methoxyanisole
• CAS NO: 3260-88-6
• Molecular Formula: C₈H₉ClO
• Molecular Weight: 156.61
• EINECS: 221-862-6
• Product Categories: Anisole;Anisoles, Alkyloxy Compounds & Phenylacetates;Chlorine Compounds;Ethers;Organic Building Blocks;Oxygen Compounds
• Mol File: 3260-88-6.mol
• Article Data: 13

Chemical Properties

• Melting Point: -3°C
• Boiling Point: 213-217 °C(lit.)
• Flash Point: 140 °F
• Appearance: /
• Density: 1.16 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.427mmHg at 25°C
• Refractive Index: n20/D 1.42(lit.)
• Storage Temp.: Sealed in dry,Room Temperature
• BRN: 1862220
• CAS DataBase Reference: 3-chloro-2-methoxyanisole(CAS DataBase Reference)
• NIST Chemistry Reference: 3-chloro-2-methoxyanisole(3260-88-6)
• EPA Substance Registry System: 3-chloro-2-methoxyanisole(3260-88-6)

Safety Data

• Hazard Codes: Xi
• Safety Statements: S24/25:Avoid contact with skin and eyes.
• RIDADR: UN 1993 3/PG 3
• WGK Germany: 3
• TSCA: Yes
• HazardClass: 3
• PackingGroup: III
• Hazardous Substances Data: 3260-88-6(Hazardous Substances Data)

Usage

Uses

Arene-manganese tricarbonyl complexes are prepared using 3-Chloro-2-methylanisole.

General Description

3-Chloro-2-methylanisole can be prepared via trifluoroacetic (TFA) anhydride reaction. Enthalpy of vaporization of 3-chloro-2-methylanisole at boiling point (488.15K) is 42.747kjoule/mol.

InChI:InChI=1/C8H9ClO/c1-6-7(9)4-3-5-8(6)10-2/h3-5H,1-2H3

Synthetic route

methanol (67-56-1) + 2,6-dichlorotoluene (118-69-4) + sodium methylate (124-41-4) → 1-chloro-3-methoxy-2-methylbenzene (3260-88-6)

Conditions	Yield
Stage #1: methanol; 2,6-dichlorotoluene; sodium methylate In dimethyl sulfoxide at 160℃; for 8h; Stage #2: With polyethylene glycol 600 In dimethyl sulfoxide at 80℃; for 2h; Temperature; Reagent/catalyst; Concentration;	95.6%

3-chloro-o-cresol (3260-87-5) + dimethyl sulfate (77-78-1) → 1-chloro-3-methoxy-2-methylbenzene (3260-88-6)

Conditions	Yield
With sodium hydroxide

methanol (67-56-1) + 3-chloro-2-methylbenzenamine (87-60-5) → 1-chloro-3-methoxy-2-methylbenzene (3260-88-6)

Conditions	Yield
With tetrafluoroboric acid; sodium nitrite 1) water, 0 deg C to room temperature, 2) reflux; Yield given. Multistep reaction;

3-chloro-2-methylbenzenamine (87-60-5) → 1-chloro-3-methoxy-2-methylbenzene (3260-88-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: Diazotization 2: NaOH-solution View Scheme
Multi-step reaction with 2 steps 1: (i) (diazotization), (ii) (heating) View Scheme
Multi-step reaction with 2 steps 1: (i) (diazotization), (ii) aq. H2SO4 View Scheme

6-chloro-2-nitrotoluene (83-42-1) → 1-chloro-3-methoxy-2-methylbenzene (3260-88-6)

Conditions	Yield
Multi-step reaction with 3 steps 1: Fe, aq. HCl 2: (i) (diazotization), (ii) aq. H2SO4 View Scheme

2,6-dichlorotoluene (118-69-4) → 1-chloro-3-methoxy-2-methylbenzene (3260-88-6)

Conditions	Yield
With potassium hydroxide In methanol; water
With hydrogenchloride; sodium methylate; dimethyl sulfoxide In methanol

metsulfovax (21452-18-6) → 1-chloro-3-methoxy-2-methylbenzene (3260-88-6)

1,3-dimethyl-2-imidazolidinone (80-73-9) + 2,6-dichlorotoluene (118-69-4) → 1-chloro-3-methoxy-2-methylbenzene (3260-88-6) + 3-chloro-o-cresol (3260-87-5)

Conditions	Yield
With sodium methylate In methanol

2,6-dichlorotoluene (118-69-4) → 1-chloro-3-methoxy-2-methylbenzene (3260-88-6) + 3-chloro-o-cresol (3260-87-5)

Conditions	Yield
With sodium methylate; dimethyl sulfoxide In methanol

2,6-dichlorotoluene (118-69-4) + sodium methylate (124-41-4) → 1-chloro-3-methoxy-2-methylbenzene (3260-88-6)

Conditions	Yield
With copper(l) cyanide In N,N-dimethyl-formamide at 110℃; Large scale;
With copper(l) cyanide In N,N-dimethyl-formamide at 110℃; Reagent/catalyst; Temperature;
Stage #1: 2,6-dichlorotoluene; sodium methylate In dimethyl sulfoxide at 180℃; for 2h; Stage #2: With dimethyl sulfate at 80℃; for 1.5h; Temperature;	906.1 g

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) → 1-(2-chloro-4-methoxy-3-methyl-phenyl)ethanone

Conditions	Yield
aluminium chloride In dichloromethane	97.7%

tetrafluoroboric acid + [(OC)4Mn(Cl)2Mn(CO)4] + 1-chloro-3-methoxy-2-methylbenzene (3260-88-6) → Mn(CO)3(C6H3Cl(CH3)(OCH3))(1+)*BF4(1-) = {Mn(CO)3(C6H3Cl(CH3)(OCH3))}BF4 (126055-60-5)

Conditions	Yield
In water; trifluoroacetic acid inert atmosphere; addn. of aq. soln. of HBF4 to cooled suspn. of Mn-compd. and org. compd. in CF3CO2H (ice-bath), refluxing (3 h); concn. (vac.), dissoln. (acetone), addn. (Et2O), filtration, washing (Et2O); elem. anal.;	94%

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) + acetyl chloride (75-36-5) → 1-(2-chloro-4-methoxy-3-methyl-phenyl)ethanone

Conditions	Yield
With aluminum (III) chloride In dichloromethane at 10 - 20℃; for 1.61667h;	94%

metallic magnesium powder + 1-chloro-3-methoxy-2-methylbenzene (3260-88-6) + isopropyl bromide (75-26-3) → 3-methoxy-2-methylbenzoic acid (55289-06-0)

Conditions	Yield
With hydrogenchloride; sodium hydroxide In tetrahydrofuran; water; toluene	93%

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) → 2-(2-chloro-6-methoxyphenyl)acetonitrile (83781-95-7)

Conditions	Yield
With N-Bromosuccinimide; Perbenzoic acid In tetrachloromethane for 12h; Heating;	80%
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane at 100℃; for 3h; Inert atmosphere;	66%
With N-Bromosuccinimide; azobisisobutyronitrile In tetrachloromethane

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) → C8H8BrClO (1155264-58-6)

Conditions	Yield
With bromine In acetic acid at 18 - 25℃; for 2h;	79%

potassium cyanide + 1-chloro-3-methoxy-2-methylbenzene (3260-88-6) → 3-methoxy-2-methylbenzonitrile (77533-17-6)

Conditions	Yield
Stage #1: 1-chloro-3-methoxy-2-methylbenzene With triphenylphosphine; nickel dibromide; zinc In tetrahydrofuran at 60℃; for 0.5h; Inert atmosphere; Stage #2: potassium cyanide In tetrahydrofuran at 50 - 60℃; Inert atmosphere;	68%

ethyl bromide (74-96-4) + metallic magnesium powder + 1-chloro-3-methoxy-2-methylbenzene (3260-88-6) → 3-methoxy-2-methylbenzoic acid (55289-06-0)

Conditions	Yield
With hydrogenchloride; sodium hydroxide; sulfuric acid In tetrahydrofuran; 5,5-dimethyl-1,3-cyclohexadiene; water	57%

phthalic anhydride (85-44-9) + 1-chloro-3-methoxy-2-methylbenzene (3260-88-6) → 2-(2-chloro-4-methoxy-3-methyl-benzoyl)-benzoic acid

Conditions	Yield
With carbon disulfide; aluminium trichloride

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) → 2-chloro-6-methoxybenzoic acid (3260-89-7)

Conditions	Yield
With potassium permanganate
With potassium permanganate
With sodium hydroxide; potassium permanganate

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) → (2-chloro-4-methoxy-3-methyl-phenylsulfanyl)-acetic acid

Conditions	Yield
ueber 2-Chlor-4-methoxy-3-methyl-benzol-sulfonsaeure-(1)-chlorid und 2-Chlor-4-methoxy-3-methyl-thiophenol;

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) + copper(I) cyanide (544-92-3) → 3-methoxy-2-methylbenzonitrile (77533-17-6)

Conditions	Yield
With pyridine

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) + 2-cyclopentyl-2-methylmalonyl chloride (57296-38-5) → 4-Chloro-2-cyclopentyl-6-methoxy-2,5-dimethyl-indan-1,3-dione (57296-39-6)

Conditions	Yield
With aluminium trichloride In hexane for 2h; Heating;

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) + cyclopentane-1,1-dicarbonyl dichloride (53179-95-6) → 4'-chloro-5'-methyl-6'-methoxyspiro(cyclopentane-1,2'-indan)-1',3'-dione (57296-52-3)

Conditions	Yield
With aluminium trichloride In hexane for 2h; Heating;

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) + (2R)-2,5-dihydro-2-isopropyl-3,6-dimethoxypyrazine (109838-85-9) + (R)-N-tert-butoxycarbonyl-3-hydroxyphenylglycine methyl ester (130633-31-7) → (R)-tert-Butoxycarbonylamino-{3-[5-((2S,5R)-5-isopropyl-3,6-dimethoxy-2,5-dihydro-pyrazin-2-yl)-3-methoxy-2-methyl-phenoxy]-phenyl}-acetic acid methyl ester (130633-33-9) + (R)-tert-Butoxycarbonylamino-{3-[5-((2R,5R)-5-isopropyl-3,6-dimethoxy-2,5-dihydro-pyrazin-2-yl)-3-methoxy-2-methyl-phenoxy]-phenyl}-acetic acid methyl ester (130697-97-1)

Conditions	Yield
Yield given. Multistep reaction. Yields of byproduct given;

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) + (2R)-2,5-dihydro-2-isopropyl-3,6-dimethoxypyrazine (109838-85-9) + methyl (2R)-<<(1,1-dimethylethoxy)carbonyl>amino>-2-(3-hydroxy-4-methoxyphenyl)acetate (144864-73-3) → (S)-tert-Butoxycarbonylamino-[4-methoxy-3-(3-methoxy-2-methyl-phenoxy)-phenyl]-acetic acid methyl ester (144864-81-3) + 3-(2-methyl-3-methoxyphenyloxy) methyl ester (144864-81-3) + 3-<2-methyl-3-methoxy-5-<(4R)-isopropyl-3,6-dimethoxypyrazinyl>phenyloxy> (144864-82-4) + (R)-tert-Butoxycarbonylamino-{3-[5-((2R,5R)-5-isopropyl-3,6-dimethoxy-2,5-dihydro-pyrazin-2-yl)-3-methoxy-2-methyl-phenoxy]-4-methoxy-phenyl}-acetic acid methyl ester (144864-82-4)

Conditions	Yield
Yield given. Multistep reaction. Yields of byproduct given;

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) + (R)-N-tert-butoxycarbonyl-3-hydroxyphenylglycine methyl ester (130633-31-7) → methyl phenylglycinate (130633-32-8)

Conditions	Yield
Yield given. Multistep reaction;

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) + methyl (2R)-<<(1,1-dimethylethoxy)carbonyl>amino>-2-(3-hydroxy-4-methoxyphenyl)acetate (144864-73-3) → (S)-tert-Butoxycarbonylamino-[4-methoxy-3-(3-methoxy-2-methyl-phenoxy)-phenyl]-acetic acid methyl ester (144864-81-3) + 3-(2-methyl-3-methoxyphenyloxy) methyl ester (144864-81-3)

Conditions	Yield
Yield given. Multistep reaction;

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) + carbon dioxide (124-38-9) → 3-methoxy-2-methylbenzoic acid (55289-06-0)

Conditions	Yield
With iodine; magnesium
Stage #1: 1-chloro-3-methoxy-2-methylbenzene With magnesium In ethyl bromide; dibutyl ether at 40 - 45℃; for 3.16667h; Stage #2: carbon dioxide In ethyl bromide; dibutyl ether at -10 - 10℃; for 3h; Temperature;
Stage #1: 1-chloro-3-methoxy-2-methylbenzene With iodine; magnesium In tetrahydrofuran; 1,2-dimethoxyethane; toluene at 35 - 60℃; for 3.5h; Stage #2: carbon dioxide In tetrahydrofuran; 1,2-dimethoxyethane; toluene at 0 - 10℃; under 0 - 375.038 Torr; for 6h; Reagent/catalyst; Temperature; Solvent; Autoclave;	264.5 g

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) → 2-chloro-6-methoxybenzaldehyde (29866-54-4)

Conditions	Yield
(i) Br2, (irradiation), (ii) (hydrolysis); Multistep reaction;

carbon disulfide (75-15-0) + phthalic anhydride (85-44-9) + aluminium trichloride (7446-70-0) + 1-chloro-3-methoxy-2-methylbenzene (3260-88-6) → 2'-chloro-4'-methoxy-3'-methyl-benzophenone-carboxylic acid-(2)

Conditions	Yield
Dampfbad;

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) + CuCN → 3-methoxy-2-methylbenzonitrile (77533-17-6)

Conditions	Yield
With pyridine

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) → 2-cyclopentyl-2,5-dimethyl-4-chloro-6-hydroxy-indan-1,3-dione (57296-40-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: AlCl3 / hexane / 2 h / Heating 2: pyridine hydrochloride / 6 h / 180 °C View Scheme

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) → methyl 5-methoxy-1,2,3,4-tetrahydronaphthalene-2-carboxylate (83781-71-9)

Conditions	Yield
Multi-step reaction with 5 steps 1: 80 percent / N-nromosuccinimide, benzoyl peroxide / CCl4 / 12 h / Heating 2: 85 percent / ethanol; H2O / 0.25 h / Ambient temperature 3: 80 percent / benzene; diethyl ether / 36 h / Ambient temperature 4: 97 percent 5: CsF / acetonitrile / 1 h / Ambient temperature View Scheme

1-chloro-3-methoxy-2-methylbenzene (3260-88-6) → (2-chloro-6-methoxybenzyl)dimethylamine (83781-50-4)

Conditions	Yield
Multi-step reaction with 2 steps 1: 80 percent / N-nromosuccinimide, benzoyl peroxide / CCl4 / 12 h / Heating 2: 85 percent / ethanol; H2O / 0.25 h / Ambient temperature View Scheme

Upstream product

• 21452-18-6 metsulfovax 
• 118-69-4 2,6-dichlorotoluene 
• 124-41-4 sodium methylate 
• 77-78-1 dimethyl sulfate 
• 67-56-1 methanol 
• 80-73-9 1,3-dimethyl-2-imidazolidinone 
• 83-42-1 6-chloro-2-nitrotoluene 
• 87-60-5 3-chloro-2-methylbenzenamine 
• 3260-87-5 3-chloro-o-cresol 

Downstream Products

• 55289-06-0 3-methoxy-2-methylbenzoic acid 
• 29866-54-4 2-chloro-6-methoxybenzaldehyde 
• 161050-58-4 methoxyfenoside 
• 55289-25-3 2-chloro-4-methoxy-3-methyl-benzaldehyde 
• 1588424-12-7 C₁₆H₁₂Cl₂N₂O₂ 
• 1588424-11-6 C₁₇H₁₄Cl₂N₂O₂ 
• 1588424-10-5 C₁₇H₁₅Cl₂N₃O 
• 170737-91-4 2-(2-chloro-6-methoxyphenyl)acetonitrile 
• 1588422-93-8 3-(2-chloro-6-hydroxyphenyl)-7-((5-(2-(diethylamino)ethoxy)pyridin-2-yl)amino)-1-ethyl-1,6-naphthyridin-2(1H)-one 
• 1588422-92-7 3-(2-chloro-6-methoxyphenyl)-7-((5-(2-(diethylamino)ethoxy)pyridin-2-yl)amino)-1-ethyl-1,6-naphthyridin-2(1H)-one 
• 77533-17-6 3-methoxy-2-methylbenzonitrile 
• 1155264-58-6 C₈H₈BrClO 
• 3260-87-5 3-chloro-o-cresol 
• 29866-52-2 3-bromo-2-chloro-6-methoxybenzaldehyde 

Relevant articles and documents

Preparation method of 6-chloro-2-methoxytoluene and synthesis process of methoxyfenozide

The invention relates to the field of insecticides, in particular to a preparation method of 6-chloro-2-methoxytoluene and a synthesis process of methoxyfenozide. The preparation method of the 6-chloro-2-methoxytoluene comprises the following steps: in a solvent, mixing 2, 6-dichlorotoluene with sodium methoxide, and carrying out a substitution reaction to prepare a first reaction solution containing 3-chloro-2-sodium methylphenolate and the 6-chloro-2-methoxytoluene; and dropwise adding dimethyl sulfate into the first reaction solution, carrying out etherification reaction, removing 3-chloro-2-sodium methylphenolate to obtain a second reaction solution, and carrying out post-treatment to obtain the 6-chloro-2-methoxytoluene. The synthesis process of the methoxyfenozide comprises the following steps: preparing 3-methoxy-2-methyl benzoic acid by taking 6-chloro-2-methoxytoluene as an intermediate; using 3-methoxy-2-methyl benzoic acid and 3, 5-dimethyl benzoic acid as intermediates, and preparing to obtain the methoxyfenozide. According to the synthesis process disclosed by the invention, the yield and the purity of methoxyfenozide can be remarkably improved.

Preparation method of 2-methyl-3-methoxybenzoic acid

The invention relates to a preparation method of 2-methyl-3-methoxybenzoic acid. The preparation method comprises the following specific steps: A, adding a proper amount of a sodium methoxide solution, 2,6-dichlorotoluene, dimethylformamide and cuprous salt into a reaction kettle; stirring and raising the temperature; controlling the temperature to 80 DEG C to 150 DEG C and reacting to obtain 2-methyl-3-chloroanisole; B, adding a proper amount of tetrahydrofuran and magnesium into the other reaction kettle; controlling the temperature to be 30 DEG C to 60 DEG C; adding a mixed solution of bromoethane and the 2-methyl-3-chloroanisole; after reacting for 20min to 40min, controlling the temperature to be 40 DEG C to 60 DEG C and dropwise adding the 2-methyl-3-chloroanisole; after dropwise adding, keeping heat and reacting for 1.5h to 2.5h; then cooling to -15 DEG C to -5 DEG C; adding dry ice by batches; controlling the temperature to be 0 DEG C to 20 DEG C, keeping the heat and reactingfor 2h to 4h; then recycling the tetrahydrofuran; adjusting the pH (Potential of Hydrogen) value to separate out white powder, namely the 2-methyl-3-methoxybenzoic acid. The preparation method of the2-methyl-3-methoxybenzoic acid, provided by the invention, is simple in route and high in yield.

Method for synthesizing 6-chloro-2-methoxytoluene

The invention discloses a method for synthesizing 6-chloro-2-methoxytoluene. The method comprises the following steps: dissolving 2,6-dichlorotoluene in an aprotic polar solvent, dripping sodium methylate for reacting, maintaining the temperature to be 40-170 DEG C after dripping completion, and performing a reaction for 2-20 hours; reducing the temperature to be 20-120 DEG C after temperature maintaining is completed; adding a phase transfer catalyst into the reaction solution, introducing a chloromethane gas for reacting until the mass fraction of 6-chloro-2-hydroxy methylbenzene in the reaction solution is less than 1%, and maintaining the temperature and performing a reaction for 0.1-2 hours; performing cooling to room temperature after the reaction; and recovering the aprotic polar solvent under negative pressure, performing after-treatment, thereby obtaining the 6-chloro-2-methoxytoluene. According to the method, the 6-chloro-2-methoxytoluene is synthesized by chloromethane, the reaction speed of the chloromethane is improved by using a small amount of catalysts in the method, and the chloromethane can serve as a methylation reagent under normal pressure; and moreover, the yield of the 6-chloro-2-methoxytoluene is greater than 93%, and the method disclosed by the invention is easy to operate, low in cost and slight in environmental hazards.