606-28-0

Basic information

• Product Name: Methyl 2-benzoylbenzoate
• Synonyms: O-BENZOYLBENZOIC ACID METHYL ESTER;O-BENZOYL BENZOMETHOXYCARBONYL;OBM;BENZOPHENONE-2-CARBOXYLIC ACID METHYL ESTER;METHYL 2-BENZOYLBENZOATE;METHYL BENZOPHENONE-2-CARBOXYLATE;METHYL O-BENZOYLBENZOATE;METHYL O-BENZOYLE BENZOATE
• CAS NO: 606-28-0
• Molecular Formula: C₁₅H₁₂O₃
• Molecular Weight: 240.25
• EINECS: 210-112-3
• Product Categories: Industrial/Fine Chemicals;FINE Chemical & INTERMEDIATES;Aromatic Esters;API intermediates;Functional Materials;Photopolymerization Initiators;C12 to C63;Carbonyl Compounds;Esters;Building Blocks;C12 to C63;Carbonyl Compounds;Chemical Synthesis;Organic Building Blocks
• Mol File: 606-28-0.mol
• Article Data: 22

Chemical Properties

• Melting Point: 48-53 °C(lit.)
• Boiling Point: 352 °C
• Flash Point: >230 °F
• Appearance: /
• Density: 1,69 g/cm3
• Vapor Pressure: 0Pa at 20℃
• Refractive Index: 1.5740 (estimate)
• Storage Temp.: Sealed in dry,Room Temperature
• Solubility: Insoluble in water
• Water Solubility: 117.7mg/L at 20℃
• CAS DataBase Reference: Methyl 2-benzoylbenzoate(CAS DataBase Reference)
• NIST Chemistry Reference: Methyl 2-benzoylbenzoate(606-28-0)
• EPA Substance Registry System: Methyl 2-benzoylbenzoate(606-28-0)

Safety Data

• Hazard Codes: N
• Statements: 50/53
• Safety Statements: 60-61
• RIDADR: UN 3077 9/PG 3
• WGK Germany: 3
• Hazardous Substances Data: 606-28-0(Hazardous Substances Data)

Usage

Chemical Properties

White or yellowish granule crystals, soluble in alcohol and alkali solution, almost insoluble in water when precipitated in acid.

Uses

Methyl 2-benzoylbenzoate is used as an anti-ultraviolet absorber and a preservative for food and beverages.

Preparation

Methyl-2-benzoylbenzoate can be synthesized from the reaction between corresponding 2-substituted benzoic acid and thionyl chloride in methanol.

General Description

Methyl-2-benzoylbenzoate is a 2-acylarylcarboxylate. It can undergo asymmetric transfer hydrogenation reaction in propanol in the presence of a Ruthenium catalyst. Methyl-2-benzoylbenzoate is formed as one of the reaction products during the reaction between methyl benzoate and lithium 2,2,6,6-tetramethylpiperidide (LiTMP) at -117°C.

Flammability and Explosibility

Nonflammable

InChI:InChI=1/C15H12O3/c1-18-15(17)13-10-6-5-9-12(13)14(16)11-7-3-2-4-8-11/h2-10H,1H3

Synthetic route

3-methoxy-3-phenyl-phthalide (7335-63-9) → methyl o-benzoylbenzoate (606-28-0)

Conditions	Yield
With methanesulfonic acid In toluene for 6h; Reflux;	99.2%

tert.-butylhydroperoxide (75-91-2) + 2-Benzoylbenzoic acid (85-52-9) → methyl o-benzoylbenzoate (606-28-0)

Conditions	Yield
With copper quinolate In water; dimethyl sulfoxide at 120℃; for 24h;	98%

carbon monoxide (201230-82-2) + o-iodo-methyl-benzoic acid (610-97-9) + triphenylbismuthane (603-33-8) → methyl o-benzoylbenzoate (606-28-0)

Conditions	Yield
With potassium carbonate In water; N,N-dimethyl-formamide at 80℃; under 760.051 Torr; for 5h; Green chemistry;	87%

trimethoxonium tetrafluoroborate (420-37-1) + N,N-bis(methylethyl)[2-(phenylcarbonyl)phenyl]carboxamide → methyl o-benzoylbenzoate (606-28-0)

Conditions	Yield
Stage #1: trimethoxonium tetrafluoroborate; N,N-bis(methylethyl)[2-(phenylcarbonyl)phenyl]carboxamide With disodium hydrogenphosphate In acetonitrile at 20℃; Methylation; Stage #2: With sodium hydrogencarbonate for 18h; Hydrolysis;	84%

2-(hydroxy-phenyl-methyl)-benzoic acid methyl ester → methyl o-benzoylbenzoate (606-28-0)

Conditions	Yield
With sodium methylate; potassium iodide In methanol at 20℃; Electrochemical reaction;	82%

2-Benzoylbenzoic acid (85-52-9) + methyl iodide (74-88-4) → methyl o-benzoylbenzoate (606-28-0)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 0.166667h; Inert atmosphere; Schlenk technique;	75%
With sodium hydrogencarbonate In N,N-dimethyl-formamide Ambient temperature;	6.2 g

o-iodo-methyl-benzoic acid (610-97-9) + benzaldehyde (100-52-7) → methyl o-benzoylbenzoate (606-28-0)

Conditions	Yield
With tert.-butylhydroperoxide; palladium diacetate; silver(l) oxide In water at 120℃; for 12h; Catalytic behavior; Reagent/catalyst; Solvent; Temperature; Inert atmosphere; Schlenk technique;	74%
With tert.-butylhydroperoxide; palladium diacetate; silver(l) oxide In water at 120℃; for 14h; Inert atmosphere;

o-iodo-methyl-benzoic acid (610-97-9) + molybdenum hexacarbonyl (13939-06-5, 199620-15-0) + phenylboronic acid (98-80-6) → methyl o-benzoylbenzoate (606-28-0)

Conditions	Yield
With C35H20F34NO3(1-)*Pd(2+)*Cl(1-); N-ethyl-N,N-diisopropylamine In water at 140℃; for 0.2h; Catalytic behavior; Reagent/catalyst; Concentration; Temperature; Microwave irradiation;	73%
With palladium diacetate; potassium carbonate In methoxybenzene at 140℃; for 12h; Suzuki coupling;	60%

3-methoxy-3-phenyl-phthalide (7335-63-9) → methyl o-benzoylbenzoate (606-28-0) + 9,10-phenanthrenequinone (84-65-1)

Conditions	Yield
With aluminium trichloride In nitromethane at 80℃; for 5h;	A 8% B 65%

o-iodo-methyl-benzoic acid (610-97-9) + benzyl alcohol (100-51-6) → methyl o-benzoylbenzoate (606-28-0)

Conditions	Yield
With tert.-butylhydroperoxide; palladium diacetate; silver(l) oxide In water at 120℃; Reagent/catalyst; Schlenk technique; Inert atmosphere;	64%

2-bromobenzoic acid methyl ester (610-94-6) + Benzoylformic acid (611-73-4) → methyl o-benzoylbenzoate (606-28-0)

Conditions	Yield
With (1,2-dimethoxyethane)dichloronickel(II); 2-Chlorothioxanthone; lithium carbonate; 4,4'-di-tert-butyl-2,2'-bipyridine In water; N,N-dimethyl-formamide for 24h; Inert atmosphere; Irradiation; Green chemistry;	49%

N,N-phenyl-p-toluenesulfonylbenzamide (74542-54-4) + 2-methoxycarbonylphenylboronic acid (374538-03-1) → methyl o-benzoylbenzoate (606-28-0)

Conditions	Yield
With (bis(tricyclohexyl)phosphine)palladium(II) dichloride; potassium carbonate; tricyclohexylphosphine In 1,4-dioxane at 110℃; for 12h; Suzuki Coupling; Inert atmosphere; Schlenk technique;	37%

diazomethane (186581-53-3, 908094-01-9) + 2-Benzoylbenzoic acid (85-52-9) → methyl o-benzoylbenzoate (606-28-0)

Conditions	Yield
With ethanol
With diethyl ether

methanol (67-56-1) + 2-Benzoylbenzoic acid (85-52-9) → methyl o-benzoylbenzoate (606-28-0)

Conditions	Yield
With sulfuric acid
With hydrogenchloride
With hydrogen cation
With sulfuric acid for 3h; Heating;

methanol (67-56-1) + 2-Benzoylbenzoic acid (85-52-9) → methyl o-benzoylbenzoate (606-28-0) + 3-methoxy-3-phenyl-phthalide (7335-63-9)

methanol (67-56-1) + 2-benzoylbenzoyl chloride (22103-85-1) → methyl o-benzoylbenzoate (606-28-0)

phthalic acid dimethyl ester (131-11-3) + phenylmagnesium bromide → methyl o-benzoylbenzoate (606-28-0)

phthalic acid dimethyl ester (131-11-3) + phenylmagnesium bromide → methyl o-benzoylbenzoate (606-28-0) + o-dibenzoylbenzene (1159-86-0)

Conditions	Yield
je nach Bedingungen;

methanol (67-56-1) + 3-methoxy-3-phenyl-phthalide (7335-63-9) + sodium methylate (124-41-4) → methyl o-benzoylbenzoate (606-28-0)

phthalic monoacid monomethyl ester chloride (4397-55-1) + benzene (71-43-2) → methyl o-benzoylbenzoate (606-28-0)

Conditions	Yield
With aluminium trichloride at 10℃; anschl. Erhitzen auf 80grad;

piperidine (110-89-4) + methanol (67-56-1) + 3-p-menthan-3-yloxy-3-phenyl-phthalide (7499-46-9, 21090-19-7) → methyl o-benzoylbenzoate (606-28-0) + (-)-menthol (2216-51-5)

Conditions	Yield
at 25 - 35℃; Rate constant; (-)(Ξ)-3-<(1R)-menthyloxy>-3-phenyl-phthalide;

methanol (67-56-1) + sodium methylate (124-41-4) + 3-p-menthan-3-yloxy-3-phenyl-phthalide (7499-46-9, 21090-19-7) → methyl o-benzoylbenzoate (606-28-0) + (-)-menthol (2216-51-5)

Conditions	Yield
at 15 - 35℃; Rate constant; (-)(Ξ)-3-<(1R)-menthyloxy>-3-phenyl-phthalide;

methanol (67-56-1) + N-butylamine (109-73-9) + 3-p-menthan-3-yloxy-3-phenyl-phthalide (7499-46-9, 21090-19-7) → methyl o-benzoylbenzoate (606-28-0) + (-)-menthol (2216-51-5)

Conditions	Yield
at 35℃; Rate constant; (-)(Ξ)-3-<(1R)-menthyloxy>-3-phenyl-phthalide;

methanol (67-56-1) + triethylamine (121-44-8) + 3-p-menthan-3-yloxy-3-phenyl-phthalide (7499-46-9, 21090-19-7) → methyl o-benzoylbenzoate (606-28-0) + (-)-menthol (2216-51-5)

Conditions	Yield
at 35℃; Rate constant; (-)(Ξ)-3-<(1R)-menthyloxy>-3-phenyl-phthalide;

methanol (67-56-1) + benzophenone (119-61-9) + carbon monoxide (201230-82-2) → methyl o-benzoylbenzoate (606-28-0)

Conditions	Yield
With trifluoroacetic acid; lithium chloride; palladium dichloride; thallium(III) trifluoroacetate 1.) 25 deg C, 4 days, 2.) room temperature, overnight; Yield given. Multistep reaction;

sodium methylate (124-41-4) + anhydride of/the/ 2-benzoyl-benzoic acid → methyl o-benzoylbenzoate (606-28-0)

pseudomethyl ester of/the/ 2-benzoyl-benzoic acid → methyl o-benzoylbenzoate (606-28-0)

Conditions	Yield
With methanol; thionyl chloride
With methanol; sulfuric acid

methyl iodide (74-88-4) + silver salt of/the/ 2-benzoyl-benzoic acid → methyl o-benzoylbenzoate (606-28-0)

dimethyl sulfate (77-78-1) + sodium salt of/the/ 2-benzoyl-benzoic acid → methyl o-benzoylbenzoate (606-28-0)

propylamine (107-10-8) + methyl o-benzoylbenzoate (606-28-0) → 3-hydroxy-3-phenyl-2-propyl-2,3-dihydroisoindol-1-one (27687-35-0)

Conditions	Yield
In toluene for 15h; Heating;	100%

methyl o-benzoylbenzoate (606-28-0) + tert-Butyl acrylate (1663-39-4) → tert-butyl 3-(3-oxo-1-phenyl-1,3-dihydroisobenzofuran-1-yl) propanoate

Conditions	Yield
With zinc/copper couple; ammonia; water In N,N-dimethyl-formamide at 20℃; under 760.051 Torr; for 20h; chemoselective reaction;	99%

methyl o-benzoylbenzoate (606-28-0) + acrylonitrile (107-13-1) → 3-(3-oxo-1-phenyl-1,3-dihydroisobenzofuran-1-yl)propanenitrile (101600-69-5)

Conditions	Yield
With ammonia; water; zinc In acetonitrile at 20℃; under 760.051 Torr; Reagent/catalyst; Solvent; Temperature; chemoselective reaction;	99%

methyl o-benzoylbenzoate (606-28-0) + trimethylsilyl cyanide (7677-24-9) → 3-cyano-3-phenylisobenzofuran-1(3H)-one

Conditions	Yield
Stage #1: trimethylsilyl cyanide With diethylaluminium chloride In hexane at 20℃; for 0.5h; Stage #2: methyl o-benzoylbenzoate In hexane; dichloromethane at 0℃; for 1h;	97%

methyl o-benzoylbenzoate (606-28-0) → (S)-3-phenyl-1,3-dihydro-2-benzofuran-1-one (5398-11-8, 78772-69-7, 87481-14-9, 87481-13-8)

Conditions	Yield
With [RuCl(benzene){(2,2,2',2'-tetramethyl[4,4'-bibenzo[d][1,3]dioxole]-5,5'-diyl)bis(diphenylphosphine)}]Cl; hydrogen In methanol at 50℃; under 30402 Torr; for 15h; Autoclave; enantioselective reaction;	95%
With C27H30Cl2CoN4; sodium triethylborohydride; 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane In tetrahydrofuran at 20℃; for 18h; Schlenk technique; Inert atmosphere; enantioselective reaction;	66%

methyl o-benzoylbenzoate (606-28-0) + ethyl acrylate (140-88-5) → ethyl 3-(3-oxo-1-phenyl-1,3-dihydroisobenzofuran-1-yl)propanoate

Conditions	Yield
With ammonia; water; zinc In acetonitrile at 20℃; under 760.051 Torr; for 20h; chemoselective reaction;	93%

methyl o-benzoylbenzoate (606-28-0) → (2-hydroxymethylphenyl)phenylmethanol (1586-01-2)

Conditions	Yield
With lithium aluminium tetrahydride	88%
With lithium aluminium tetrahydride In diethyl ether

methyl o-benzoylbenzoate (606-28-0) + urea (57-13-6) → 3-phenyl-2,3-dihydro-isoindol-1-one (835-18-7)

Conditions	Yield
In formic acid at 180 - 190℃; for 20h;	88%

methyl o-benzoylbenzoate (606-28-0) + acrylic acid methyl ester (292638-85-8) → methyl 3-(3-oxo-1-phenyl-1,3-dihydroisobenzofuran-1-yl)propanoate

Conditions	Yield
With ammonia; water; zinc In acetonitrile at 20℃; under 760.051 Torr; for 30h; chemoselective reaction;	88%

methyl o-benzoylbenzoate (606-28-0) + phenethylamine (64-04-0) → 2-(2-phenylethyl)-3-hydroxy-3-phenyl-2,3-dihydroisoindol-1-one (17416-55-6)

Conditions	Yield
In toluene for 15h; Heating;	79%

methyl o-benzoylbenzoate (606-28-0) + propynoic acid methyl ester (922-67-8) → methyl 3-(3-oxo-1-phenyl-1,3-dihydroisobenzofuran-1-yl)propanoate

Conditions	Yield
With ammonia; water; zinc In acetonitrile at 20℃; under 760.051 Torr; for 20h; chemoselective reaction;	76%

methyl o-benzoylbenzoate (606-28-0) + N,N'-Dimethylurea (96-31-1) → 2-methyl-3-phenyl-2,3-dihydro-1H-isoindol-1-one (15836-66-5)

Conditions	Yield
In formic acid at 180 - 190℃; for 27h;	70%

methyl o-benzoylbenzoate (606-28-0) + (2-nitrophenyl)hydrazine (3034-19-3) → 2-methoxycarbonylbenzophenone 2'-nitrophenylhydrazone (297132-08-2)

Conditions	Yield
With hydrogenchloride In methanol for 22h; Condensation; Heating;	63%

methyl o-benzoylbenzoate (606-28-0) + 2-propenamide (79-06-1) → 3-phenylphthalide (5398-11-8) + 3-(3-oxo-1-phenyl-1,3-dihydroisobenzofuran-1-yl)propanamide

Conditions	Yield
With zinc/copper couple; ammonia; water In N,N-dimethyl-formamide at 20℃; under 760.051 Torr; for 20h; Solvent; Reagent/catalyst; chemoselective reaction;	A 30% B 62%

methyl o-benzoylbenzoate (606-28-0) + methyl crotonate (623-43-8, 4358-59-2, 18707-60-3, 130981-57-6) → methyl 3-(3-oxo-1-phenyl-1,3-dihydroisobenzofuran-1-yl)butanoate

Conditions	Yield
With zinc/copper couple; ammonia; water In N,N-dimethyl-formamide at 20℃; under 760.051 Torr; for 20h; chemoselective reaction;	56%

α-methylene-γ-butyrolactone (547-65-9) + methyl o-benzoylbenzoate (606-28-0) → 3-((2-oxotetrahydrofuran-3-yl)methyl)-3-phenylisobenzofuran-1(3H)-one

Conditions	Yield
With zinc/copper couple; ammonia; water In N,N-dimethyl-formamide at 20℃; under 760.051 Torr; for 20h; chemoselective reaction;	56%

methyl o-benzoylbenzoate (606-28-0) + Phenyl vinyl sulfoxide (20451-53-0) → 3-phenyl-3-(2-(phenylsulfinyl)ethyl)isobenzofuran-1(3H)-one

Conditions	Yield
With zinc/copper couple; ammonia; water In N,N-dimethyl-formamide at 20℃; under 760.051 Torr; for 20h; chemospecific reaction;	54%

methyl o-benzoylbenzoate (606-28-0) + dimethylsulfoxonium methylide (70775-39-2, 5367-24-8) → 4-phenyl-1H-2-benzopyran-1-one (92439-00-4)

Conditions	Yield
In N,N-dimethyl-formamide at 50℃; for 1.5h;	52%

methyl o-benzoylbenzoate (606-28-0) → 3-phenyl-3H-benzofuran-2-one (3117-37-1)

Conditions	Yield
With chromium(III) chloride In N,N-dimethyl-formamide electrolysis;	51%

methyl o-benzoylbenzoate (606-28-0) + N-methylacrylamide (1187-59-3) → N-methyl-3-(3-oxo-1-phenyl-1,3-dihydroisobenzofuran-1-yl)propanamide

Conditions	Yield
With zinc/copper couple; ammonia; water In N,N-dimethyl-formamide at 20℃; under 760.051 Torr; for 20h; chemoselective reaction;	49%

Upstream product

• 186581-53-3 diazomethane 
• 85-52-9 2-Benzoylbenzoic acid 
• 67-56-1 methanol 
• 119-61-9 benzophenone 
• 201230-82-2 carbon monoxide 
• 7335-63-9 3-methoxy-3-phenyl-phthalide 
• 610-97-9 o-iodo-methyl-benzoic acid 
• 13939-06-5 molybdenum hexacarbonyl 
• 98-80-6 phenylboronic acid 
• 131-11-3 phthalic acid dimethyl ester 
• 100-59-4 phenylmagnesium chloride 
• 100-58-3 phenylmagnesium bromide 
• 22103-85-1 2-benzoylbenzoyl chloride 
• 28144-70-9 anthranilic acid amide 

Downstream Products

• 27687-35-0 3-hydroxy-3-phenyl-2-propyl-2,3-dihydroisoindol-1-one 
• 5398-11-8 3‐phenylisobenzofuran‐1(3H)‐one 
• 5398-11-8 (S)-3-phenyl-1,3-dihydro-2-benzofuran-1-one 
• 60456-75-9 1,1'-diphenyl-1H,1'H-[1,1']biisobenzofuranyl-3,3'-dione 
• 835-18-7 3-phenyl-2,3-dihydro-isoindol-1-one 
• 157017-51-1 4-hydroxy-4-phenyl-1,2,3,4-tetrahydroisoquinoline 
• 21147-22-8 2-carbomethoxy-2‘-hydroxybenzophenone 
• 101600-69-5 3-(3-oxo-1-phenyl-1,3-dihydroisobenzofuran-1-yl)propanenitrile 

Relevant articles and documents

Aromatization as an Impetus to Harness Ketones for Metallaphotoredox-Catalyzed Benzoylation/Benzylation of (Hetero)arenes

Herein we report ketones as feedstock materials in radical cross-coupling reactions under Ni/photoredox dual catalysis. In this approach, simple condensation first converts ketones into prearomatic intermediates that then act as activated radical sources for cross-coupling with aryl halides. Our strategy enables the direct benzylation/benzoylation of (hetero)arenes under mild reaction conditions with high functional group tolerance.

Metal-Free Arylation-Lactonization Sequence of γ-Alkenoic Acids Using Anilines as Aryl Radical Precursors

The presence of salicylic acid (10 mol-%) and H2O (10 equiv.) significantly improves the arylation-lactonization sequence of γ-alkenoic acids with in situ formed diazonium salts (from bench stable anilines). The reaction is finished in less than 5 h without thermal or photochemical activation, giving access to a variety of γ,γ-disubstituted butyrolactones. The protocol is user-friendly and can be used at gram-scale or adapted to transform alkenols into phthalanes. Control experiments revealed that aryl radicals participate in the reaction and a plausible mechanism is proposed to include this and other mechanistic investigations, for the catalyzed and the background reaction.