99-75-2

Basic information

• Product Name: Methyl 4-methylbenzoate
• Synonyms: P-TOLUIC ACID METHYL ESTER;P-TOLULYL ACID METHYL ESTER;RARECHEM AL BF 0113;4-METHYL METHYLBENZOATE;4-METHYLBENZOIC ACID METHYL ESTER;METHYL 4-TOLUATE;METHYL 4-METHYLBENZOATE;METHYL P-TOLUATE
• CAS NO: 99-75-2
• Molecular Formula: C9H10O2
• Molecular Weight: 150.17
• EINECS: 202-784-1
• Product Categories: CARBOXYLICESTER;Aromatic Esters;Organics;Acids & Esters;C8 to C9;Carbonyl Compounds;Esters
• Mol File: 99-75-2.mol
• Article Data: 424

Chemical Properties

• Melting Point: 32-35 °C(lit.)
• Boiling Point: 103-104 °C15 mm Hg(lit.)
• Flash Point: 90 °C
• Appearance: crystals, melting is a colorless liquid
• Density: 1.06
• Vapor Density: 4.7 (vs air)
• Vapor Pressure: 1 mm Hg ( 39 °C)
• Refractive Index: 1.5002 (estimate)
• Storage Temp.: Store below +30°C.
• Solubility: Chloroform (Slightly), DMSO (Slightly), Ethyl Acetate (Slightly)
• Explosive Limit: 1-9.5%(V)
• Water Solubility: <0.1 g/100 mL at 22℃
• Stability: Unstable in Solution
• BRN: 1100609
• CAS DataBase Reference: Methyl 4-methylbenzoate(CAS DataBase Reference)
• NIST Chemistry Reference: Methyl 4-methylbenzoate(99-75-2)
• EPA Substance Registry System: Methyl 4-methylbenzoate(99-75-2)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 37/39-26-36
• WGK Germany: 2
• RTECS: XU2150000
• TSCA: Yes
• Hazardous Substances Data: 99-75-2(Hazardous Substances Data)

Usage

Chemical Properties

white low melting crystalline solid and/or

Uses

Methyl p-toluate has been employesd as catalyst to investigate the effect of internal/external donor pair in high-yield catalysts for propylene polymerization.

Synthesis Reference(s)

The Journal of Organic Chemistry, 54, p. 1144, 1989 DOI: 10.1021/jo00266a028Synthetic Communications, 20, p. 3273, 1990

General Description

Opaque colorless to white shiny crystalline solid. Intense unpleasant odor.

Air & Water Reactions

Insoluble in water.

Reactivity Profile

Methyl 4-methylbenzoate is an ester. Esters react with acids to liberate heat along with alcohols and acids. Strong oxidizing acids may cause a vigorous reaction that is sufficiently exothermic to ignite the reaction products. Heat is also generated by the interaction of esters with caustic solutions. Flammable hydrogen is generated by mixing esters with alkali metals and hydrides.

Fire Hazard

Methyl 4-methylbenzoate is combustible.

InChI:InChI=1/C9H10O2/c1-7-3-5-8(6-4-7)9(10)11-2/h3-6H,1-2H3

Synthetic route

methanol (67-56-1) + p-Toluic acid (99-94-5) → 4-methyl-benzoic acid methyl ester (99-75-2)

Conditions	Yield
With boron trifluoride at 65℃; for 0.333333h;	100%
With sulfuric acid for 4h; Reflux;	100%
With sulfuric acid Fischer-Speier esterification method; Reflux;	100%

p-Toluic acid (99-94-5) + methyl iodide (74-88-4) → 4-methyl-benzoic acid methyl ester (99-75-2)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 20℃; Inert atmosphere;	100%
With potassium carbonate In N,N-dimethyl-formamide at 50℃; for 5h;
With N'',N'''''-1,8-naphthalenediyl bis[N,N,N',N'-tetramethyl]guanidine In N,N-dimethyl-formamide at 20℃; Kinetics;
With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 10h; Inert atmosphere; Sealed tube;

methanol (67-56-1) + carbon monoxide (201230-82-2) + 4-tolyl iodide (624-31-7) → 4-methyl-benzoic acid methyl ester (99-75-2)

Conditions	Yield
With triethylamine at 100℃; under 3750.38 Torr; for 1.5h; Inert atmosphere;	99%
With triethylamine at 100℃; under 3750.38 Torr; for 1h; Autoclave;	98%
With palladium diacetate; caesium carbonate; 1,3,5,7-tetramethyl-8-phenyl-2,4,6-trioxa-8-phosphatricyclo[3.3.1.13,7]decane In N,N-dimethyl-formamide at 80℃; under 2327.23 Torr;	97%

methanol (67-56-1) + 4-Methylbenzyl alcohol (589-18-4) → 4-methyl-benzoic acid methyl ester (99-75-2)

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; benzyl chloride In tetrahydrofuran at 65 - 70℃; for 20h; Concentration; Inert atmosphere; Schlenk technique;	99%
With potassium carbonate at 60℃; under 750.075 Torr; for 2h; Temperature; Pressure;	98.8%
With palladium 10% on activated carbon; oxygen; sodium carbonate at 120℃; under 15001.5 Torr; for 1.5h; Microwave irradiation; Green chemistry;	97%

methanol (67-56-1) + para-methylbenzamide (619-55-6) → 4-methyl-benzoic acid methyl ester (99-75-2)

Conditions	Yield
With thionyl chloride at 0 - 55℃; for 6h;	99%
With potassium hydrogensulfate at 65℃; for 48h;	91%

p-Toluic acid (99-94-5) + carbonic acid dimethyl ester (616-38-6) → 4-methyl-benzoic acid methyl ester (99-75-2)

Conditions	Yield
With diiron nonacarbonyl at 180℃; for 1h; Sealed tube;	99%
With sulfuric acid at 80 - 85℃; for 10h; Neat (no solvent);	95.7%

methanol (67-56-1) + 4-methyl-benzaldehyde (104-87-0) → 4-methyl-benzoic acid methyl ester (99-75-2)

Conditions	Yield
With perchloric acid; sodium percarbonate; vanadia for 0.75h; Cooling;	98%
With palladium 10% on activated carbon; oxygen; sodium carbonate at 100℃; under 15001.5 Torr; for 1h; Microwave irradiation; Green chemistry;	98%
With oxygen; potassium carbonate at 60℃; for 2h; Autoclave;	97%

1-methoxy-2,2,6,6-tetramethylpiperidine (34672-84-9) + p-Toluic acid (99-94-5) → 4-methyl-benzoic acid methyl ester (99-75-2)

Conditions	Yield
With 2,6-di-tert-butyl-pyridine In acetonitrile at 21 - 25℃; for 18h; Electrochemical reaction;	97%

methanol (67-56-1) + (1H-pyrrol-1-yl)(p-tolyl)methanone (70971-70-9) → 4-methyl-benzoic acid methyl ester (99-75-2)

Conditions	Yield
With [2,2]bipyridinyl; bis(1,5-cyclooctadiene)nickel (0) In toluene at 20℃; for 1h; Sealed tube; chemoselective reaction;	97%

para-methylacetophenone (122-00-9) → 4-methyl-benzoic acid methyl ester (99-75-2)

Conditions	Yield
With Co4HP2Mo15V3O62; N-(4-sulfonic acid)butyl triethylammonium tetrafluoroborate; dihydrogen peroxide at 50℃; for 4h; Green chemistry;	96%
With oxygen; 1-(n-butyl)-3-methylimidazolium triflate at 20℃; for 0.333333h; Baeyer-Villiger Ketone Oxidation; Electrochemical reaction; Green chemistry;	95%

4-methylbenzaldehyde dimethylacetal (3395-83-3) → 4-methyl-benzoic acid methyl ester (99-75-2)

Conditions	Yield
With 3,3-dimethyldioxirane In acetone at 25℃; Kinetics;	95%
With 3,3-dimethyldioxirane In acetone at 25℃;	95%
With boron trifluoride diethyl etherate; 1,8-diazabicyclo[5.4.0]undec-7-ene; 3-chloro-benzenecarboperoxoic acid In chloroform for 1h; Ambient temperature; Yield given;

4-methyl-1-[dimethoxy(methylthio)methyl]benzene → 4-methyl-benzoic acid methyl ester (99-75-2) + 1-(methanesulfinyl-dimethoxy-methyl)-4-methyl-benzene

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; for 3h;	A 95% B 5%
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at -78℃; for 1h;	A 49% B 9%

4-methyl-benzaldehyde (104-87-0) → 4-methyl-benzoic acid methyl ester (99-75-2)

Conditions	Yield
With maghemite-supported nanogold; oxygen; potassium carbonate In methanol at 80℃; for 7h; Green chemistry;	95%
Multi-step reaction with 2 steps 1: 55 - 60 °C 2: dihydrogen peroxide / 8 h / 55 - 60 °C View Scheme
Multi-step reaction with 2 steps 1: dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; 2,2':6,2''-terpyridine; sodium hydrogencarbonate / 6 h / 90 °C / Sealed tube; Green chemistry 2: trichloro(2,2':6',2''-terpyridine)rhodium(III); sodium hydrogencarbonate / 12 h / 90 °C / Green chemistry View Scheme
Multi-step reaction with 2 steps 1: dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; 2,2':6,2''-terpyridine; sodium hydroxide; methanol / 6 h / 90 °C / Sealed tube; Green chemistry 2: trichloro(2,2':6',2''-terpyridine)rhodium(III); sodium hydrogencarbonate / 12 h / 90 °C / Green chemistry View Scheme
Multi-step reaction with 2 steps 1: recombinant aldehyde dehydrogenase from bovine lens; 1,4-dithio-D,L-threitol; water‐forming NADH oxidase from Streptococcus mutans; NAD / aq. phosphate buffer / 4 h / 40 °C / pH 8.5 / Green chemistry; Enzymatic reaction 2: methanol; ethyl acetate / 1 h / 30 °C View Scheme

methyl 4-formylbenzoate (1571-08-0) → 4-methyl-benzoic acid methyl ester (99-75-2)

Conditions	Yield
With hydrogen In ethanol at 80℃; under 2250.23 Torr; for 2h; Inert atmosphere;	95%

Upstream product

• 67-56-1 methanol 
• 106-43-4 para-chlorotoluene 
• 107-31-3 Methyl formate 
• 94224-92-7 methyl 4-(iodomethyl)benzoate 
• 874-60-2 4-methyl-benzoyl chloride 
• 104-85-8 para-methylbenzonitrile 
• 99-94-5 p-Toluic acid 
• 186581-53-3 diazomethane 
• 93-58-3 benzoic acid methyl ester 
• 127841-18-3 N-(4-Methoxy-2-trimethylsilanylmethyl-phenyl)-4-methyl-benzamide 
• 874-58-8 4-methylbenzoyl bromide 
• 22693-32-9 4-methylbenzoyl azide 
• 14271-73-9 4-methylbenzoyl cyanide 
• 36930-95-7 2,2,2-trichloro-1-(4-methylphenyl)ethanone 

Downstream Products

• 72076-59-6 1-(4-methylphenyl)-2-(2-pyridinyl)-ethanone 
• 5440-76-6 (4-methylphenyl)diphenylmethanol 
• 589-18-4 4-Methylbenzyl alcohol 
• 2318-82-3 N-hydroxy-4-methylbenzamide 
• 1679-64-7 Monomethyl terephthalate 
• 34040-64-7 p-methyloxycarbonylbenzyl chloride 
• 797-21-7 1,2-bis(4-methoxycarbonylphenyl)ethane 
• 7356-11-8 4-methyl-3-nitro-benzoic acid methyl ester 
• 619-55-6 para-methylbenzamide 
• 61054-27-1 5-(4-tolyl)tetrahydrobenzo[c]isoxazole 
• 62834-90-6 2,4-dimethyl-1-p-tolyl-pent-4-en-1-one 
• 109866-22-0 p-Toluylsaeure-(4-diethylamino-but-2-inylester) 
• 20973-75-5 ω-Dimethylamino-4-methoxycarbonyl-styrol 
• 7714-85-4 N-Phenyl-N-benzhydryl-p-toluamid 

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