95-65-8

Basic information

• Product Name: 3,4-Dimethylphenol
• Synonyms: 1,2-Dimethyl-4-hydroxybenzene;1,3,4-Xylenol;3,4-dimethyl-pheno;4,5-Dimethylphenol;4-Hydroxy-1,2-dimethylbenzene;ai3-01552;as-o-xylenol;o-4-Xylenol
• CAS NO: 95-65-8
• Molecular Formula: C₈H₁₀O
• Molecular Weight: 122.16
• EINECS: 202-439-5
• Product Categories: Industrial/Fine Chemicals;Aromatic Phenols;Aromatics
• Mol File: 95-65-8.mol
• Article Data: 78

Chemical Properties

• Melting Point: 65-68 °C
• Boiling Point: 227 °C(lit.)
• Flash Point: 61 °C
• Appearance: Off-white to pale cream/Crystalline Powder
• Density: 1,138 g/cm3
• Vapor Pressure: 0.053mmHg at 25°C
• Refractive Index: 1.5442
• Storage Temp.: 2-8°C
• Solubility: Chloroform (Slightly), Ethyl Acetate (Slightly), Methanol (Slightly)
• PKA: pK1:10.32 (25°C)
• Explosive Limit: 1.4%(V)
• Water Solubility: SLIGHTLY SOLUBLE
• Merck: 14,10082
• BRN: 1099267
• CAS DataBase Reference: 3,4-Dimethylphenol(CAS DataBase Reference)
• NIST Chemistry Reference: 3,4-Dimethylphenol(95-65-8)
• EPA Substance Registry System: 3,4-Dimethylphenol(95-65-8)

Safety Data

• Hazard Codes: T,N
• Statements: 24/25-34-51/53
• Safety Statements: 26-36/37/39-45-61
• RIDADR: UN 2261 6.1/PG 2
• WGK Germany: 3
• RTECS: ZE6300000
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 95-65-8(Hazardous Substances Data)

Usage

Description

3,4-methylphenol (also 3,4-xylenol) has a flat, dry odor. It can be used as a flavoring agent without safety concern at current levels of intake. 3,4-dimethylphenol is used as an agent in the spectrophotometric method to determine nitrate in plants, soils, and water. It is also used to produce adhesive/sealant and resins as negative photoresist for electroplating.

References

[1] R. R. Elton-Bott, A modified spectrophotometric method for nitrate in plants, soils and water by nitration of 3,4-dimethylphenol, Analytica Chimica Acta, 1977, vol. 90, 215-221 [2] George A. Burdock, Fenaroli’s Handbook of Flavor Ingredients, Sixth Edition, 2010 [3] Chia L. Wang, John Davis, Bryan Lienke, Polyurethane systems having non-sag paintability and primerless adhesion on concrete, Patent, 2012 [4] Yasuo Masuda, Yasushi Washio, Koji Saito, Method of forming plated product using negative photoresist composition and photosensitive composition used therein, Patent, 2012

Chemical Properties

YELLOW TO BROWNISH CRYSTALLINE MASS

Occurrence

Reported found in coffee, tomato, parmesan and romano cheese, smoked fatty fish, white wine, katsuobushi (dried bonito) and wood vinegar.

Uses

Applications of 3,4-dimethylphenol:It can react with ethyl cinnamates in trifluoroacetic acid to form the corresponding dihydrocoumarin derivatives.Bromination of 3,4-dimethylphenol using bromine can lead to 6-bromo-3,4-dimethylphenol.It can react with 1-fluoro-4-chloromethyl-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoro-borate) (Selectfluor? F-TEDA-BF4) to form 4-fluoro-3,4-dimethylcyclohexa-2,5-dienone.

Aroma threshold values

Detection: 1.2 ppm

General Description

Colorless to light tan crystalline powder or solid. Odor threshold 1.2 mg/L. Taste threshold 0.05 mg/L.

Reactivity Profile

3,4-Dimethylphenol is incompatible with bases, acid chlorides, acid anhydrides, and oxidizing agents. 3,4-Dimethylphenol corrodes steel, brass, copper, and copper alloys.

Fire Hazard

Flash point data for 3,4-Dimethylphenol are not available. 3,4-Dimethylphenol is probably combustible.

Purification Methods

Heat 3,4-xylenol with an equal weight of conc H2SO4 at 103-105o for 2-3hours, then dilute it with four volumes of water, reflux it for 1hour, and either steam distil or extract it repeatedly with diethyl ether after cooling to room temperature. The steam distillate is also extracted and evaporated to dryness. (The purification process depends on the much slower sulfonation of 3,4-dimethylphenol than most of its likely contaminants.). It can also be crystallised from water, hexane or pet ether, and sublimed in a vacuum. [Kester Ind Eng Chem (Anal Ed) 24 770 1932, Bernasconi & Paschalis J Am Chem Soc 108 29691986, Beilstein 6 IV 3099.]

Synthetic route

3,4-dimethyliodobenzene (31599-61-8) → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
Stage #1: 3,4-dimethyliodobenzene With copper(l) iodide; tetra(n-butyl)ammonium hydroxide In water at 60℃; for 24h; Inert atmosphere; Sealed tube; Stage #2: With hydrogenchloride In water; ethyl acetate at 20℃; for 2h; Inert atmosphere; chemoselective reaction;	97%
Stage #1: 3,4-dimethyliodobenzene With copper(l) iodide; 2-methyl-8-quinolinol; tetra(n-butyl)ammonium hydroxide In water; dimethyl sulfoxide at 100℃; for 10h; Stage #2: With hydrogenchloride In water; N,N-dimethyl-formamide at 20℃;	96%
With lithium salt of proline; tetrabutylammomium bromide; potassium hydroxide; copper dichloride In water at 120℃; for 0.666667h; Microwave irradiation; Green chemistry;	79%

1,2-dimethyl-4-trimethylsilyloxybenzene (17994-04-6) → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
With methanol; 1,3-disulfonic acid imidazolium hydrogen sulfate at 20℃; for 0.0833333h; Green chemistry;	97%

2-<3,4-Dimethyl-phenoxy>-tetrahydro-pyran (17355-90-7) → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
With boron trifluoride diethyl etherate; sodium cyanoborohydride In tetrahydrofuran for 8h; Ambient temperature;	95%

3,4-dimethylphenyl acetate (22618-23-1) → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
With aluminium trichloride; potassium iodide In water; acetonitrile at 80℃; for 5h;	95%

4-amino-o-xylene (95-64-7) → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
With sulfuric acid; sodium nitrite at 0 - 85℃; for 0.5h; Solvent;	94.5%
Diazotization.Zersetzung der Diazoniumsulfatloesung mit Dampf;

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%

4,4-dimethylcyclohexa-2,5-dienone (1073-14-9) + recorcinol (108-46-3) → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
With hydrogenchloride In diethyl ether; dichloromethane for 24h; Heating;	92%

3,4-dimethyl phenylboronic acid (55499-43-9) → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
With tert.-butylhydroperoxide; potassium hydroxide In water at 20℃; for 0.166667h;	91%
With water; triethylamine In acetonitrile at 20℃; for 36h; Irradiation;	73%

3,4-dimethylphenyl tosylate (94002-18-3) → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
With potassium fluoride on basic alumina for 0.05h; Substitution; microwave irradiation;	90%

N-[(2-acetoxy-5,6-dimethyl)benzoyl]-S-methyl-S-phenylsulfoximine (1377585-21-1) → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
With hydrogenchloride In water at 80℃; for 48h;	89%

3,4-dimethylcyclohexanol (5715-23-1) → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
With 7.2mol% Au9-Pd alloy nanoparticles supported on Mg-Al-layered double hydroxide (LDH); air In N,N-dimethyl acetamide at 130℃; under 760.051 Torr; for 3h;	74%
With Pd(OH)x/Ni1Mg2Al1-layered triple hydroxide In N,N-dimethyl acetamide at 150℃; under 760.051 Torr; for 8h; Schlenk technique; Inert atmosphere;	97 %Chromat.

methanol (67-56-1) + p-cresol (106-44-5) → 3,4-Dimethylphenol (95-65-8) + 4-Methylanisole (104-93-8) + Mesitol (527-60-6) + 3-methyl-phenol (108-39-4) + 2,4-Xylenol (105-67-9)

Conditions	Yield
With hydrogen; nickel at 380℃; Product distribution; var. temp.;	A 8.3% B 2.4% C 9.6% D 1.5% E 72.1%

o-xylene (95-47-6) → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
With dihydrogen peroxide; bis(triphenyl)oxodiphosphonium trifluoromethanesulfonate salt In ethanol; water at 20℃; for 0.666667h;	70%
With sulfuric acid at 90℃; bei der elektrolytischen Oxydation;
With dihydrogen peroxide In water at 40℃; under 1500.15 Torr; for 1h; Inert atmosphere; regioselective reaction;
Multi-step reaction with 2 steps 1: Al View Scheme
Multi-step reaction with 2 steps 1: Al View Scheme

4-(4-Methoxy-benzyloxy)-1,2-dimethyl-benzene → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
With boron trifluoride diethyl etherate; sodium cyanoborohydride In tetrahydrofuran for 6h; Heating;	65%

o-xylene (95-47-6) → 3,4-Dimethylphenol (95-65-8) + 2.6-dimethylphenol (576-26-1) + 2,3-Dimethylphenol (526-75-0) + ortho-cresol (95-48-7)

Conditions	Yield
With O(3P) Product distribution; Mechanism; Mechanism of O(3P) oxidation via triplet diradical intermediates.;	A 13% B 2% C 23% D 62%
With 3-methylpyridazine-2-oxide at -25℃; for 0.1h; Product distribution; Mechanism; Irradiation;	A 48 % Chromat. B 8 % Chromat. C 40 % Chromat. D 4 % Chromat.
With 3-methylpyridazine-2-oxide In dichloromethane at -25℃; for 0.1h; Product distribution; Mechanism; Irradiation;	A 49 % Chromat. B 9 % Chromat. C 39 % Chromat. D 3 % Chromat.
With 3-methylpyridazine-2-oxide In methanol at -25℃; for 0.1h; Product distribution; Mechanism; Irradiation;	A 44 % Chromat. B 16 % Chromat. C 39 % Chromat. D 2 % Chromat.
With tert.-butylhydroperoxide; aluminium trichloride Product distribution; var. of reagents;	A 60 % Chromat. B 5 % Chromat. C 26 % Chromat. D 9 % Chromat.

1,2-Dimethyl-7-oxa-bicyclo[4.1.0]hepta-2,4-diene (38440-90-3) → 3,4-Dimethylphenol (95-65-8) + 2.6-dimethylphenol (576-26-1) + 2,3-Dimethylphenol (526-75-0)

Conditions	Yield
Product distribution; Mechanism; Decomposition by an ionic mechanism via a dipolar transient.;	A 14% B 53% C 33%

isobutene (115-11-7) + phenol (108-95-2) → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
Stage #1: isobutene; phenol; sulfuric acid at 65℃; under 1520.1 Torr; Stage #2: With potassium chromate In acetic acid	50%

1,2-dimethyl-4-(1-phenylethyl)benzene (6196-95-8) → 3,4-Dimethylphenol (95-65-8) + acetophenone (98-86-2) + 3,4-dimethylacetophenone (3637-01-2) + phenol (108-95-2)

Conditions	Yield
Stage #1: 1,2-dimethyl-4-(1-phenylethyl)benzene With oxygen; N-hydroxyphthalimide; 2,2'-azobis(isobutyronitrile) In acetonitrile at 75℃; under 760.051 Torr; for 6h; Stage #2: With sulfuric acid In water; acetonitrile at 0℃; for 0.5h;	A 46% B 50% C 2.7% D n/a
Stage #1: 1,2-dimethyl-4-(1-phenylethyl)benzene With oxygen; N-hydroxyphthalimide; 2,2'-azobis(isobutyronitrile) In acetonitrile at 75℃; under 760.051 Torr; for 6h; Stage #2: In acetonitrile at 0℃; for 1h; Product distribution / selectivity;	A 50% B 50% C 1% D n/a

3,4-dimethylbenzoic acid (619-04-5) → 3,4-Dimethylphenol (95-65-8) + 4-amino-o-xylene (95-64-7) + 2,3-Dimethylaniline (87-59-2)

Conditions	Yield
With ammonia; water; copper(II) oxide at 220℃; for 0.5h;	A 3.5% B 43.1% C 0.9%

o-xylene (95-47-6) → 3,4-Dimethylphenol (95-65-8) + 2,3-Dimethylphenol (526-75-0)

Conditions	Yield
Stage #1: o-xylene With spiro[bicyclo[2.2.1]heptane-2,4′-[1,2]dioxolane]-3′,5′-dione at 40℃; for 96h; Sealed tube; Stage #2: With methylamine In ethanol	A 41% B 24%
With dihydrogen peroxide In water at 50℃; under 1500.15 Torr; for 1h; Inert atmosphere; chemoselective reaction;
With hydroxyammonium sulfate; sulfuric acid; acetic acid In water at 80℃; for 4h;

o-xylene (95-47-6) → 3,4-Dimethylphenol (95-65-8) + 2-Ethyltoluene (611-14-3) + 1,2,4-Trimethylbenzene (95-63-6) + 2,3-Dimethylphenol (526-75-0) + 2-methyl-benzyl alcohol (89-95-2) + 1,2-bis(2-methylphenyl)ethane (952-80-7)

Conditions	Yield
With peracetic acid at 20 - 22℃; Product distribution; Irradiation; λ=2537 Angstroem;	A n/a B 24.3% C n/a D n/a E 15.1% F n/a

o-xylene (95-47-6) → 3,4-Dimethylphenol (95-65-8) + 2.6-dimethylphenol (576-26-1) + 2,3-Dimethylphenol (526-75-0) + 3,3,10,10-Tetramethyl-tricyclo[6.2.2.02,7]dodeca-5,11-diene-4,9-dione (69886-23-3, 95190-98-0)

Conditions	Yield
With bis-trimethylsilanyl peroxide; trifluorormethanesulfonic acid at -50℃; for 0.5h; Yields of byproduct given;	A n/a B n/a C n/a D 21%

4-Methylanisole (104-93-8) → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
With aluminium trichloride at 100℃;

3,4-dimethylanisole (4685-47-6) + pyridine hydrochloride (628-13-7) → 3,4-Dimethylphenol (95-65-8)

2-hydroxy-4,5-dimethyl-isophthalic acid → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
With quinoline

methoxybenzene (100-66-3) → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
With aluminium trichloride at 100℃;

1-methoxy-3-methyl-benzene (100-84-5) → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
With aluminium trichloride at 100℃;

4,4-dimethylcyclohexa-2,5-dienone (1073-14-9) → 3,4-Dimethylphenol (95-65-8)

Conditions	Yield
With trifluoroacetic acid In water at 38.5℃; Rate constant;

3,4-Dimethylphenol (95-65-8) → 2-bromo-4,5-dimethylphenol (22802-39-7)

Conditions	Yield
With bromine In dichloromethane at -78℃; for 1h;	100%
With tetra-N-butylammonium tribromide In methanol; dichloromethane at 20℃; for 1h;	97%
With tetra-N-butylammonium tribromide In methanol; dichloromethane for 0.5h; Ambient temperature; reagent 1.0 equivalent;	93%

3,4-Dimethylphenol (95-65-8) + isobutene (115-11-7) → 2-(1,1-dimethylethyl)-4,5-dimethylphenol (1445-23-4)

Conditions	Yield
With sulfuric acid at 65℃; under 1034.3 Torr; for 3h;	100%
With sulfuric acid at 70℃;
sulfuric acid at 65℃; under 1520.1 Torr;
With sulfuric acid at 65 - 70℃; for 2h;	114.1 g

3,4-Dimethylphenol (95-65-8) + bromoacetic acid methyl ester (96-32-2) → (3,4-dimethyl-phenoxy)-acetic acid methyl ester (95450-81-0)

Conditions	Yield
With potassium carbonate In butanone for 5.5h; Heating;	100%
With potassium carbonate In butanone for 4h; Heating / reflux;	93%

3,4-Dimethylphenol (95-65-8) + ethyl (E)-3,4-dimethoxycinnamate (20583-78-2, 24393-65-5) → 4-(3,4-dimethoxyphenyl)-6,7-dimethyl-3,4-dihydrocoumarin

Conditions	Yield
With trifluoroacetic acid at 20℃; for 24h;	100%

3,4-Dimethylphenol (95-65-8) + (E)-3-(4-methoxyphenyl)acrylic acid (943-89-5) → 6,7-dimethyl-4-(4'-methoxyphenyl)-3,4-dihydrocoumarin (85903-43-1)

Conditions	Yield
With trifluoroacetic acid In dichloromethane at 20℃; for 24h;	100%

3,4-Dimethylphenol (95-65-8) + ethyl (E)-3-(4-methoxyphenyl)prop-2-enoate (24393-56-4) → 6,7-dimethyl-4-(4'-methoxyphenyl)-3,4-dihydrocoumarin (85903-43-1)

Conditions	Yield
With trifluoroacetic acid at 20℃; for 24h;	100%

3,4-Dimethylphenol (95-65-8) + ethyl 4-hydroxy-3-methoxycinnamate (4046-02-0) → 4-(4-hydroxy-3-methoxyphenyl)-6,7-dimethyl-3,4-dihydrocoumarin

Conditions	Yield
With trifluoroacetic acid at 20℃; for 24h;	100%

3,4-Dimethylphenol (95-65-8) + tantalum pentachloride (7721-01-9) → (3,4-dimethylphenoxo)TaCl4 (130136-96-8)

Conditions	Yield
In dichloromethane to a suspension of TaCl5 in CH2Cl2 was added 3,4-dimethylphenole; was stirred by refluxing for 4 h; stoichiometric ratio of TaCl5:3,4-dimethylphenole=1:1; excess of the solvent was removed under reduced pressure; elem. anal.;	100%

3,4-Dimethylphenol (95-65-8) → C8H8(2)H2O

Conditions	Yield
With perchloric acid; d(4)-methanol at 75℃; for 144h; Inert atmosphere;	100%

3,4-Dimethylphenol (95-65-8) + 2,2'-bipyridinedichlorocopper(II) (220632-01-9, 22393-36-8) → Cu(3,4-dimethylphenoxo)2(2,2'-bipyridine) (138827-21-1)

Conditions	Yield
With Na In tetrahydrofuran byproducts: NaCl; refluxing 3,4-dimethylphenol and Na (16 h), addn. to CuCl2 suspn., stirring (room temp., 18 h); filtration off of NaCl, evapn. (0.3 torr), crystn. (THF); elem. anal.;	99%

3,4-Dimethylphenol (95-65-8) + chlorobenzene (108-90-7) → 3,4-dimethylphenyl phenyl ether (52509-74-7)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 12h;	99%
With sodium dodecyl-sulfate; potassium carbonate In water at 80℃; under 760.051 Torr; for 9h; Ullmann Condensation; Green chemistry; chemoselective reaction;	79%

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) + trifluoromethylsulfonic anhydride (358-23-6) → 3,4-dimethylphenyl trifluoromethanesulfonate (255837-23-1)

Conditions	Yield
With pyridine In dichloromethane at 0 - 20℃; for 16h; Inert atmosphere;	99%
With triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere; Schlenk technique;

3,4-Dimethylphenol (95-65-8) + Diphenylphosphine oxide (4559-70-0) → (3,4-dimethylphenoxy)diphenylphosphinoxide (1329040-45-0)

Conditions	Yield
With chloroform; 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 25℃; for 3h; Atherton-Todd Synthesis;	99%
With 1,4-diaza-bicyclo[2.2.2]octane; potassium iodide In acetonitrile at 20℃; for 3h; Electrolysis;	41%

3,4-Dimethylphenol (95-65-8) + (E)-2-(azetidin-1-yl)ethene-1-sulfonyl fluoride → 3,4-dimethylphenyl (E)-2-(pyrrolidin-1-yl)ethene-1-sulfonate

Conditions	Yield
With potassium hydroxide In acetonitrile at 50℃; stereoselective reaction;	99%

3,4-Dimethylphenol (95-65-8) + tantalum pentachloride (7721-01-9) → (3,4-dimethylphenoxo)2TaCl3 (130136-97-9)

Conditions	Yield
In benzene byproducts: HCl; to a suspension of TaCl5 in C6H6 was added 3,4-dimethylphenole; was refluxed for 18 h; stoichiometric ratio of the TaCl5:3,4-dimethylphenole=1:2; excess of the solvent was removed under reduced pressure; elem. anal.;	98.8%

3,4-Dimethylphenol (95-65-8) + 1-(phenylsulfonyl)-1H-benzo[d][1,2,3]triazole (4106-18-7) → 3,4-dimethylphenyl benzenesulfonate (107775-23-5)

Conditions	Yield
With sodium hydride In tetrahydrofuran for 20h; Ambient temperature;	98%

3,4-Dimethylphenol (95-65-8) + acetyl chloride (75-36-5) → 2-acetyl-4,5-dimethylphenol (36436-65-4)

Conditions	Yield
With aluminium trichloride at 180℃; for 0.5h;	98%
With aluminum (III) chloride In 1,2-dichloro-ethane at 100℃; for 5h; Inert atmosphere;	85%

3,4-Dimethylphenol (95-65-8) + triethylamine (121-44-8) → C16H19O2PS2*C6H15N

Conditions	Yield
Stage #1: 3,4-Dimethylphenol With tetraphosphorus decasulfide In toluene at 40℃; Schlenk technique; Stage #2: triethylamine In toluene Schlenk technique;	98%

3,4-Dimethylphenol (95-65-8) + 1-(4-(tert-butyl)phenyl)pyrrolidine → C22H29NO

Conditions	Yield
With Difluoroacetic acid; 5% palladium on Al2O3; oxygen at 20℃; for 70h;	98%

3,4-Dimethylphenol (95-65-8) + thianthrene cation radical perchlorate (35787-71-4) → 5-(2-Hydroxy-4,5-dimethyl-phenyl)-thianthren-5-ium; perchlorate

Conditions	Yield
In acetonitrile for 0.5h;	97%

3,4-Dimethylphenol (95-65-8) + iodobenzene (591-50-4) → 3,4-dimethylphenyl phenyl ether (52509-74-7)

Conditions	Yield
With copper(II) glycinate monohydrate; potassium hydroxide In dimethyl sulfoxide at 80℃; for 8h; Ullmann reaction;	97%
With 2,2,6,6-tetramethylheptane-3,5-dione; iron(III) chloride; caesium carbonate In N,N-dimethyl-formamide at 135℃; for 20h;	92%
With potassium carbonate In N,N-dimethyl-formamide at 110℃;	85%

3,4-Dimethylphenol (95-65-8) + 3,5-dimethylphenyl 16-chloro-16-oxohexadecanoate → C32H46O4

Conditions	Yield
With triethylamine In dichloromethane at 35℃; for 12h;	97%

3,4-Dimethylphenol (95-65-8) → 2,6-dibromo-3,4-dimethylphenol (22802-40-0)

Conditions	Yield
With benzyltrimethylammonium tribromide In methanol; dichloromethane	96%
With benzyltrimethylazanium tribroman-2-uide In methanol; dichloromethane for 0.5h; Ambient temperature; reagent 2.1 equivalent;	93%
With bromine; sodium acetate In acetic acid at 20℃; for 25h; Inert atmosphere;	69%
With bromine; acetic acid

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℃;

3,4-Dimethylphenol (95-65-8) + 1,1,1,3,3,3-hexamethyl-disilazane (999-97-3) → 1,2-dimethyl-4-trimethylsilyloxybenzene (17994-04-6)

Conditions	Yield
With 1,3-disulfonic acid imidazolium hydrogen sulfate In neat (no solvent) at 20℃; for 0.0333333h; Green chemistry;	96%
With 3-methyl-1-sulfonic acid imidazolium hydrogen sulfate at 20℃; for 0.0333333h; Neat (no solvent);	95%
at 125℃; for 0.166667h; Microwave irradiation;

3,4-Dimethylphenol (95-65-8) + formaldehyd (50-00-0) + dibenzylamine (103-49-1) → 2-((dibenzylamino)methyl)-4,5-dimethylphenol

Conditions	Yield
for 0.583333h; Microwave irradiation;	96%

3,4-Dimethylphenol (95-65-8) + formaldehyd (50-00-0) → 4,5-dimethyl-2-hydroxybenzyl alcohol (10496-92-1)

Conditions	Yield
With sodium metaborate tetrahydrate In water at 40℃; for 10h; Green chemistry; regioselective reaction;	95%
With sodium hydroxide In water for 1.5h; Ambient temperature;	51%
With sodium hydroxide

Upstream product

• 100-66-3 methoxybenzene 
• 95-64-7 4-amino-o-xylene 
• 67-56-1 methanol 
• 7499-12-9 3,4-dimethyl-4-trichloromethyl-2,5-cyclohexadien-1-one 
• 95-47-6 o-xylene 
• 4685-47-6 3,4-dimethylanisole 
• 69083-80-3 4-bromo-5,5-dimethyl-2-cyclohexen-1-one 
• 38440-90-3 1,2-Dimethyl-7-oxa-bicyclo[4.1.0]hepta-2,4-diene 
• 90963-41-0 1-(3,4-dimethylphenoxy)silatrane 
• 619-04-5 3,4-dimethylbenzoic acid 
• 23586-56-3 C₁₂H₉F₆O₄Tl 
• 17355-90-7 2-<3,4-Dimethyl-phenoxy>-tetrahydro-pyran 
• 22289-05-0 3-methyleneheptane-2,6-dione 
• 1073-14-9 4,4-dimethylcyclohexa-2,5-dienone 

Downstream Products

• 34221-43-7 2-(3,4-dimethyl-phenoxy)-ethanol 
• 100617-78-5 4,5-Dimethyl-2-pyrrolidinomethyl-phenol 
• 58704-23-7 4,5-Dimethyl-2-piperidinomethyl-phenol 
• 60372-42-1 4,5-dimethyl-2-(morpholinomethyl)phenol 
• 132675-12-8 2-[[4-(hydroxymethyl)piperidin-1-yl]methyl]-4,5-dimethylphenol 
• 132912-47-1 4,5-Dimethyl-2-(4-methyl-piperidinomethyl)-phenol 
• 132647-30-4 2-hexahydroazepin-1-ylmethyl-4,5-dimethyl-phenol 
• 108980-46-7 2-(4-ethyl-piperidinomethyl)-4,5-dimethyl-phenol 
• 7499-12-9 3,4-dimethyl-4-trichloromethyl-2,5-cyclohexadien-1-one 
• 35124-61-9 4,5-Dimethyl-2-(1,1,3,3-tetramethyl-butyl)-phenol 
• 10496-92-1 4,5-dimethyl-2-hydroxybenzyl alcohol 
• 67730-48-7 2-Hydroxy-4.5-dimethyl-1.3-bis-hydroxymethyl-benzol 
• 16885-89-5 4,5-dimethyl-2-(1-methyl-1-phenyl-ethyl)-phenol 
• 52509-74-7 3,4-dimethylphenyl phenyl ether 

Relevant articles and documents

A Hydroperoxide Method for 3,4-Xylenol Synthesis

The aerobic oxidation reaction of 1,2-dimethyl-4-isopropylbenzene to a hydroperoxide in the presence of N-hydroxyphthalimide and its derivatives has been studied. It has been found that up to a hydrocarbon (HC) conversion of 25–30%, the selectivity for the tertiary hydroperoxide of 1,2-dimethyl-4-isopropylbenzene is over 90–95%. A method for assessing the catalytic activity of phthalimide compounds in liquid-phase oxidation reactions of 1,2-dimethyl-4-isopropylbenzene with the use of quantum-chemically calculated values for the energies of singly occupied molecular orbitals (ΔЕSOMO) has been proposed.

REARRANGEMENT OF DIMETHYLPHENYLACYLATES USING ZEOLITES

The present invention relates to a Fries rearrangement of specific dimethylphenylacylates to form the desired respective hydroxyaryl ketones having two methyl groups bound to the aromatic ring. It has been found that the process is surprisingly very specific in view of the number and position of the methyl group(s) bound to the aromatic ring.

Method for synthesizing phenol or derivative thereof in aqueous phase by photocatalytic one-pot method

The invention discloses a method for synthesizing phenol or a derivative thereof in an aqueous phase by a photocatalytic one-pot method. The method comprises the following steps: by taking a compoundaryl halide shown in formula (I) as a raw material and water as a solvent, adding a catalyst and an auxiliary agent, and carrying out reacting under the conditions of alkali and visible light to obtain the phenol or the derivative (II) thereof. Compared with the prior art, the method is applicable to a large number of functional groups, high in yield, few in byproducts, simple and safe to operate,low in cost and environmentally friendly, wherein R is selected from substituted or non-substituted phenyl, pyridyl, quinolyl or pyrimidinyl; X is selected from halogen; the substituted phenyl is substituted by C1-C4 alkyl, C1-C4 alkoxy, hydroxyl, halogen, cyano, aldehyde group, nitro, amino, acetyl or carboxyl; and the substituted pyridyl, quinolyl or pyrimidinyl is pyridyl, quinolyl or pyrimidinyl substituted by C1-C4 alkyl.