4685-47-6

Basic information

• Product Name: 3,4-DIMETHYLANISOLE
• Synonyms: 3,4-DIMETHYLANISOLE;1,2-DIMETHYL-4-METHOXYBENZENE;4-METHOXY-O-XYLENE;4-Methoxy-1,2-dimethylbenzene;Benzene, 4-methoxy-1,2-dimethyl-;3,4-Dimethylphenyl methyl ether;3,4-Dimethylanisole,99%;3,4-DiMethylanisole, 99% 50GR
• CAS NO: 4685-47-6
• Molecular Formula: C₉H₁₂O
• Molecular Weight: 136.19
• EINECS: 225-142-2
• Product Categories: Aromatic Ethers;Anisoles, Alkyloxy Compounds & Phenylacetates;Ethers;Organic Building Blocks;Oxygen Compounds;Building Blocks;C9;Chemical Synthesis;Organic Building Blocks;Oxygen Compounds
• Mol File: 4685-47-6.mol
• Article Data: 8

Chemical Properties

• Boiling Point: 200-201 °C(lit.)
• Flash Point: 168 °F
• Appearance: clear colourless liquid
• Density: 0.974 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.402mmHg at 25°C
• Refractive Index: n20/D 1.517(lit.)
• Storage Temp.: Store below +30°C.
• BRN: 2040907
• CAS DataBase Reference: 3,4-DIMETHYLANISOLE(CAS DataBase Reference)
• NIST Chemistry Reference: 3,4-DIMETHYLANISOLE(4685-47-6)
• EPA Substance Registry System: 3,4-DIMETHYLANISOLE(4685-47-6)

Safety Data

• Hazard Codes: Xi,Xn
• Statements: 36/37/38-41-37/38-22
• Safety Statements: 24/25-39-26
• RIDADR: 1993
• WGK Germany: 3
• Hazardous Substances Data: 4685-47-6(Hazardous Substances Data)

Usage

Chemical Properties

CLEAR COLOURLESS LIQUID

Uses

3,4-Dimethylanisole was used as starting reagent in the synthesis of 3- and 4-methoxy-N-hydroxyphthalimide.

InChI:InChI=1/C9H12O/c1-7-4-5-9(10-3)6-8(7)2/h4-6H,1-3H3

Synthetic route

3,4-Dimethylphenol (95-65-8) + carbonic acid dimethyl ester (616-38-6) → 3,4-dimethylanisole (4685-47-6)

Conditions	Yield
With dimanganese decacarbonyl at 180℃; for 1h; Reagent/catalyst;	99%

3,4-Dimethylphenol (95-65-8) + dimethyl sulfate (77-78-1) → 3,4-dimethylanisole (4685-47-6)

Conditions	Yield
With sodium hydroxide at 0 - 50℃; for 2h;	96%
With aluminum oxide; potassium hydroxide for 10h; microwave irradiation;	75%
With sodium hydroxide at 90℃;

4-bromo-o-xylene (583-71-1) + sodium methylate (124-41-4) → 3,4-dimethylanisole (4685-47-6)

Conditions	Yield
With copper(I) bromide In methanol at 125 - 130℃; for 4h; Autoclave;	96%

3,4-Dimethylphenol (95-65-8) + methyl iodide (74-88-4) → 3,4-dimethylanisole (4685-47-6)

Conditions	Yield
With potassium hydroxide In methanol; water	81%

3,4-Dimethylphenol (95-65-8) + potassium methyl sulfate (562-54-9) → 3,4-dimethylanisole (4685-47-6)

Conditions	Yield
With sodium hydroxide

4-methoxysalicylaldehyde (52289-54-0) → 3,4-dimethylanisole (4685-47-6)

Conditions	Yield
With potassium hydroxide; hydrazine hydrate; diethylene glycol

2-methyl-4-methoxybenzyl chloride (84658-09-3) → 3,4-dimethylanisole (4685-47-6)

Conditions	Yield
palladium on activated charcoal

4-chloro-1,2-dimethylbenzene (615-60-1) + potassium methanolate (865-33-8) → 3,4-dimethylanisole (4685-47-6)

Conditions	Yield
With 18-crown-6 ether; iodine; chromium(0) hexacarbonyl 1.) diglyme, cyclohexane, reflux, 75 h, 2.) benzene, 60 deg C, 2.0 h, 3.) THF, R.T., 30 min; Yield given. Multistep reaction;

1-methoxy-3-methyl-benzene (100-84-5) → 3,4-dimethylanisole (4685-47-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: POCl3 2: N2H4+H2O; KOH; diethylene glycol View Scheme
Multi-step reaction with 2 steps 1: (chloromethylation) 2: Pd-C View Scheme

3,4-dimethylanisole (4685-47-6) → 4-methoxysalicylaldehyde (52289-54-0)

Conditions	Yield
With dipotassium peroxodisulfate; copper(ll) sulfate pentahydrate In water; acetonitrile at 90℃; for 0.5h;	100%
With dipotassium peroxodisulfate; copper(II) sulfate In water; acetonitrile for 0.5h; Heating;	92%
With ammonium cerium(IV) nitrate In methanol at 27 - 28℃; for 0.0833333h;	86%

3,4-dimethylanisole (4685-47-6) → 3-methyl-4-anisaldehyde (32723-67-4)

Conditions	Yield
With dipotassium peroxodisulfate; copper(II) sulfate In water; acetonitrile for 0.5h; Heating / reflux;	100%

3,4-dimethylanisole (4685-47-6) → 4-methoxy-2-methylbenzonitrile (21883-13-6)

Conditions	Yield
With tert.-butylnitrite; N-hydroxyphthalimide; palladium diacetate In acetonitrile at 80℃; for 24h; Concentration; Inert atmosphere; Sealed tube;	99%
With sodium azide; copper(ll) sulfate pentahydrate; [bis(acetoxy)iodo]benzene In acetonitrile at -40 - 25℃; Inert atmosphere;	76%

3,4-dimethylanisole (4685-47-6) → 2,6-Dibromo-1-methoxy-3,4-dimethylbenzene (129633-42-7)

Conditions	Yield
With benzyltrimethylazanium tribroman-2-uide; zinc(II) chloride In acetic acid for 1h; Ambient temperature;	95%

3,4-dimethylanisole (4685-47-6) → 3,4-Dimethylphenol (95-65-8) + 3,4-dimethyl-cyclohex-2-enone (10463-42-0)

Conditions	Yield
With N,N,N,N,N,N-hexamethylphosphoric triamide; lithium In tetrahydrofuran; ethanol at -30℃; for 2h;	A 3% B 94%

3,4-dimethylanisole (4685-47-6) → 1,2-bis(bromomethyl)-4-methoxybenzene (36132-96-4)

Conditions	Yield
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane for 4h; Heating;	94%
With N-Bromosuccinimide; dibenzoyl peroxide In dimethyl sulfoxide	68%
With N-Bromosuccinimide; Perbenzoic acid In tetrachloromethane for 15h; Heating;	65%

3,4-dimethylanisole (4685-47-6) + benzoyl chloride (98-88-4) → (4,5-dimethyl-2-methoxyphenyl)(phenyl)methanone (4072-15-5)

Conditions	Yield
With lithium perchlorate; scandium tris(trifluoromethanesulfonate) In nitromethane at 20℃; for 72h;	93%

3,4-dimethylanisole (4685-47-6) → 2-iodo-4,5-dimethyl-anisole (50772-82-2)

Conditions	Yield
With N,N,N-trimethylbenzenemethanaminium dichloroiodate; zinc(II) chloride In acetic acid for 0.5h; Ambient temperature;	92%
Multi-step reaction with 3 steps 1: acetic acid; concentrated aqueous HNO3 2: Raney nickel; ethanol 3: aqueous H2SO4; NaNO2 / Diazotization.Erwaermen der erhaltenen Diazoniumsalz-Loesung mit KI auf dem Dampfbad View Scheme
With iron(III) chloride; N-iodo-succinimide; 1-butyl-3-methylimidazolium trifluoromethanesulfonimide In toluene at 70℃; for 5h; Inert atmosphere; regioselective reaction;

3,4-dimethylanisole (4685-47-6) → 1-bromo-2-methoxy-4,5-dimethylbenzene (33500-88-8)

Conditions	Yield
With bromine In dichloromethane at -70℃; Inert atmosphere;	91%
With bromine In dichloromethane at -70℃; for 1h;	91%
With tetra-N-butylammonium tribromide In methanol; dichloromethane at 20℃;	75%
With N-Bromosuccinimide In acetonitrile at 35℃; for 20h; Inert atmosphere;	45%
With carbon disulfide; bromine

3,4-dimethylanisole (4685-47-6) → 3,4-dimethyl-2,6-dinitroanisole (160754-06-3)

Conditions	Yield
Stage #1: 3,4-dimethylanisole With nitric acid In 1,2-dichloro-ethane at 20 - 25℃; for 5h; Stage #2: With sulfuric acid; nitric acid at 55 - 60℃; for 5h;	90%

3,4-dimethylanisole (4685-47-6) + chromium(0) hexacarbonyl (199620-14-9, 13007-92-6) → (η6-3,4-dimethylanisole)tricarbonyl chromium (77490-94-9)

Conditions	Yield
With THF (catalyst) In tetrahydrofuran; dibutyl ether under N2, educts heated under reflux in n-Bu2O-THF for 21 h in the dark; cooled soln. filtered through Kieselguhr, evapd. in vac., solid dissolved in acetone, filtered, pptd. by addn. of light petroleum, recrystd. from acetone/light petroleum; elem. anal.;	87%
In tetrahydrofuran at 150℃; for 48h; Inert atmosphere;	87%

3,4-dimethylanisole (4685-47-6) → 1-methoxy-4,5-dimethylcyclohexa-1,4-diene (43087-42-9)

Conditions	Yield
With ethanol; ammonia; sodium In tetrahydrofuran for 3h;	84%
Birch reduction;	67%
With methanol; ammonia; sodium
(i) Li, liq. NH3, Et2O, (ii) EtOH; Multistep reaction;

3,4-dimethylanisole (4685-47-6) + C12H20F2 → C21H29FO

Conditions	Yield
With 1-oxothiolane; dimethyldiacetoxysilane; cesium adamantane-1-carboxylate; C44H34Cl4F12Ir2; oxygen; copper diacetate In para-xylene at 85℃; Sealed tube; diastereoselective reaction;	80%

1-[(4-methoxyphenyl)sulfanyl]pyrrolidine-2,5-dione (80172-73-2) + 3,4-dimethylanisole (4685-47-6) → (2-methoxy-4,5-dimethylphenyl)(4′-methoxyphenyl)sulfane

Conditions	Yield
With iron(III) chloride; 1-butyl-3-methylimidazolium trifluoromethanesulfonimide In chloroform at 40℃; for 5h; regioselective reaction;	76%

3,4-dimethylanisole (4685-47-6) + triethyloxonium fluoroborate (368-39-8) + chromium(0) hexacarbonyl (199620-14-9, 13007-92-6) → (CO)5CrC(OC2H5)C6H2(CH3)2OCH3

Conditions	Yield
With n-butyl lithium In diethyl ether aryllithium (10-20°C, n-BuLi, (C2H5)2O, 20 h at room temp.) was treated with Cr(CO)6 in (C2H5)2O, the temp. was raised to 20-25°C for 30 min, evapd., dissolved in min cold H2O, a soln. of (C2H5)3OBF4 inCH2Cl2 was added (Ar); extd. with petroleum ether, filtered through silica;	69%

2-Methoxy-4-methylphenol (93-51-6) + 3,4-dimethylanisole (4685-47-6) → 2',3-dimethoxy-2-hydroxy-4',5,5'-trimethylbiphenyl

Conditions	Yield
With 1,1,1,3',3',3'-hexafluoro-propanol at 50℃; Electrolysis;	63%

cyclohexene-1-carboxylic acid (636-82-8) + 3,4-dimethylanisole (4685-47-6) → (4aR,9aS)-8-Methoxy-5,6-dimethyl-1,2,3,4,4a,9a-hexahydro-fluoren-9-one (118104-49-7)

Conditions	Yield
With PPA; Polyphosphoric acid (PPA) at 100℃; for 3h;	60%

1,3-dimethoxy-2-hydroxy-benzene (91-10-1) + 3,4-dimethylanisole (4685-47-6) → 2',3,5-trimethoxy-4',5'-dimethyl-[1,1'-biphenyl]-4-ol

Conditions	Yield
With dipotassium peroxodisulfate; tetra(n-butyl)ammonium hydrogensulfate; trifluoroacetic acid at 20℃; for 2h; Schlenk technique; regioselective reaction;	60%

1,2,4,5-Tetrafluorobenzene (327-54-8) + 3,4-dimethylanisole (4685-47-6) → 2,3,5,6-tetrafluoro-2'-methoxy-4',5'-dimethyl-1,1'-biphenyl

Conditions	Yield
With (triphenylphosphine)gold(I) chloride; 1-pivaloyloxy-1,2-benziodoxol-3(1H)-one; silver pivalate; dimethyl sulfoxide In 1,4-dioxane at 120℃; for 16h; Inert atmosphere; regioselective reaction;	59%

carbon dioxide (124-38-9) + 3,4-dimethylanisole (4685-47-6) → 4-methoxy-2-methylphenylacetic acid (942-97-2)

Conditions	Yield
With bis(2-pyridyl)methane; xanth-9-one; nickel(II) chloride hexahydrate; potassium tert-butylate In benzene at 20℃; under 760.051 Torr; for 4h; Irradiation; Schlenk technique;	58%

3,4-dimethylanisole (4685-47-6) → 4,5-dimethyl-2-nitro-anisole (18087-11-1)

Conditions	Yield
With trifluoroacetic acid; sodium nitrite In water	55%
With nitric acid; acetic acid
With nitric acid; acetic anhydride

methanol (67-56-1) + 3,4-dimethylanisole (4685-47-6) → methyl 4-methoxy-2-methylbenzoate (35598-05-1)

Conditions	Yield
With tetradecyl(tributyl)phosphonium methanesulfonate at 20℃; for 18h; Inert atmosphere; Electrolysis; Sealed tube; Green chemistry;	53%

cyclopent-1-enecarboxylic acid (1560-11-8) + 3,4-dimethylanisole (4685-47-6) → (3aR,8aS)-7-Methoxy-4,5-dimethyl-2,3,3a,8a-tetrahydro-1H-cyclopenta[a]inden-8-one (124703-10-2)

Conditions	Yield
With PPA; Polyphosphoric acid (PPA) at 100℃; for 3h;	50%

Upstream product

• 95-65-8 3,4-Dimethylphenol 
• 562-54-9 potassium methyl sulfate 
• 77-78-1 dimethyl sulfate 
• 615-60-1 4-chloro-1,2-dimethylbenzene 
• 865-33-8 potassium methanolate 
• 100-84-5 1-methoxy-3-methyl-benzene 
• 74-88-4 methyl iodide 
• 616-38-6 carbonic acid dimethyl ester 
• 583-71-1 4-bromo-o-xylene 
• 124-41-4 sodium methylate 
• 84658-09-3 4-methoxy-2-methylbenzyl chloride 
• 52289-54-0 4-methoxysalicylaldehyde 

Downstream Products

• 856809-80-8 4-(2-methoxy-4,5-dimethyl-phenyl)-4-oxo-butyric acid 
• 65081-27-8 2'-methoxy-4',5'-dimethyl-trans-chalcone 
• 91969-74-3 2'-methoxy-4',5'-dimethylacetophenone 
• 86582-31-2 2-methoxy-4,5-dimethylbenzaldehyde 
• 874487-55-5 4-(2-methoxy-4,5-dimethyl-phenyl)-2-methyl-4-oxo-butyric acid 
• 95-65-8 3,4-Dimethylphenol 
• 10463-42-0 3,4-dimethyl-cyclohex-2-enone 
• 52289-54-0 4-methoxysalicylaldehyde 
• 6245-57-4 4-methoxy-2-methylbenzoic acid 
• 50772-82-2 2-iodo-4,5-dimethyl-anisole 
• 129633-42-7 2,6-Dibromo-1-methoxy-3,4-dimethylbenzene 
• 52289-56-2 1-(bromomethyl)-4-methoxy-2-methylbenzene 
• 75854-83-0 dimethyl-3,4 phenyl-4 cyclohexene-2 one-1 
• 6500-51-2 4-methoxybenzene-1,2-dicarbaldehyde 

Relevant articles and documents

A 4-methoxy-2-methyl-benzyl cyanide synthesis method

The invention relates to a synthesis method for 4-methoxy-2-methyl benzyl cyanide. The synthesis method takes 3, 4-dimethylphenol which is cheap and simple and easy to purchase as the raw material, and comprises six steps: methylation, oxidation, Witting reaction, alkene ether hydrolysis, oximation and dehydration. The synthesis method uses the simple and cheap raw material, is simple to operate, is easy for industrial production, has short production cycle, only needs purification in the last step of the six so as to obtain high-quality 4-methoxy-2-methyl benzyl cyanide, and avoids using extremely toxic substances like NaCN and KCN, thus filling the blank home and abroad.

Synthesis and blocking activities of isoindolinone- and isobenzofuranone-containing phenoxylalkylamines as potent α1- adrenoceptor antagonists

This paper describes the synthesis and blocking activities of twelve new isoindolinone- and isobenzofura-none-containing phenoxylalkylamines as potent α1-Adrenoceptor antagonists. These compounds were synthesized in moderate to good yields starting from 3,4-dimethylphenol, and characterized with 1H-NMR, MS, IR and elemental analysis. Their blocking activities toward α1-Adrenoceptors were evaluated on isolated rat anococcygeus muscles. The results indicated that these compounds were very strong in blocking α1-Adrenoceptors, and most of them exhibited activities that were comparable to that of known potent α1- Adrenoceptor antagonist 1-(2,6-dimethylphenoxy)-2-(3,4- dimethoxyphenylethylamino)propane hydrochloride (DDPH).

Solid state S-methylation of thiols and O-methylation of phenols and naphthols with dimethyl sulfate under microwave irradiation

Mild and efficient S-methylation of thiols and o-methylation of phenols and naphthals occurs with dimethyl sulfate (DMS) supported on basic alumina under microwave irradiation in solventless system. Copyright Taylor & Francis Inc.