114772-34-8

Basic information

• Product Name: Methyl 4'-methylbiphenyl-2-carboxylate
• Synonyms: RARECHEM AL BF 1359;METHYL 4'-METHYL[1,1'-BIPHENYL]-2-CARBOXYLATE;METHYL 4'-METHYLBIPHENYL-2-CARBOXYLATE;METHYL 4'-METHYL-2-BIPHENYLCARBOXYLATE;METHYL 2-(4-METHYLPHENYL)BENZOATE;METHYL 2-(P-TOLYL)BENZOATE;AKOS BAR-1135;4'-METHYLBIPHENYL-2-CARBOXYLIC ACID METHYL ESTER
• CAS NO: 114772-34-8
• Molecular Formula: C₁₅H₁₄O₂
• Molecular Weight: 226.27
• Product Categories: Aromatic Esters;INTERMEDIATESOF;Biphenyl & Diphenyl ether;Organic acids
• Mol File: 114772-34-8.mol
• Article Data: 60

Chemical Properties

• Melting Point: 60-61°C
• Boiling Point: 359.4 °C at 760 mmHg
• Flash Point: 164.3 °C
• Appearance: /
• Density: 1.083 g/cm³
• Solubility: soluble in Toluene
• CAS DataBase Reference: Methyl 4'-methylbiphenyl-2-carboxylate(CAS DataBase Reference)
• NIST Chemistry Reference: Methyl 4'-methylbiphenyl-2-carboxylate(114772-34-8)
• EPA Substance Registry System: Methyl 4'-methylbiphenyl-2-carboxylate(114772-34-8)

Safety Data

• Statements: 36/37/38
• Safety Statements: 26-36
• Hazardous Substances Data: 114772-34-8(Hazardous Substances Data)

Usage

Chemical Properties

White or almost white crystalline powder

Uses

Methyl 2-(p-Tolyl)benzoate is an intermediate in the synthesis of Telmisartan (T017000) analogs.

Synthetic route

methanol (67-56-1) + o-tolylbenzoic acid (7148-03-0) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide at 25℃; for 3h; Temperature; Large scale;	98.05%
With sulfuric acid for 5h; Reflux;	94%
With acetyl chloride 1.) 0 deg C, 0.25 h, 2.) reflux, 4 h; Yield given. Multistep reaction;
With sulfuric acid for 5h; Time; Reflux;	13.9 g

2-bromobenzoic acid methyl ester (610-94-6) + 4-methylphenylboronic acid (5720-05-8) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
With tetra-butylammonium acetate; Pd EnCat-30TM In ethanol at 120℃; for 0.166667h; Suzuki cross-coupling; microwave irradiation;	98%
With potassium fluoride; palladium diacetate In toluene at 80℃; for 1h; Suzuki-Miyaura coupling;	93%
With sodium carbonate; [(PPh3)2Pd(N-succ)2] In tetrahydrofuran; water at 60℃; for 10h; Suzuki cross-coupling reaction;	62%

o-tolylbenzoic acid (7148-03-0) + diazomethyl-trimethyl-silane (18107-18-1) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
In methanol for 4h;	97%
In methanol; hexane at 20℃; for 4h;	97%
With methanol In hexane; benzene Methylation;
In methanol; hexane; benzene

o-tolylbenzoic acid (7148-03-0) + methyl iodide (74-88-4) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
Stage #1: o-tolylbenzoic acid With potassium carbonate In acetone for 0.25h; Stage #2: methyl iodide In acetone for 24h; Reflux;	96%

methyl chlorobenzoate (610-96-8) + 5,5-dimethyl-2-(4-methylphenyl)-1,3,2-dioxaborinane (380481-66-3) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
With potassium phosphate tribasic hydrate; NiIICl(1-naphthyl)(tricyclohexylphosphine)2; tricyclohexylphosphine In tetrahydrofuran at 23℃; for 4h; Suzuki-Miyaura Coupling; Inert atmosphere; Glovebox; Sealed tube;	94%

o-iodo-methyl-benzoic acid (610-97-9) + p-tolyltriethoxysilane (18412-57-2) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); tetrabutyl ammonium fluoride In tetrahydrofuran; water at 80℃; for 40h; Hiyama Coupling;	88%

o-iodo-methyl-benzoic acid (610-97-9) + tributyl(p-tolyl)stannane (31614-66-1) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; lithium chloride In N,N-dimethyl-formamide Inert atmosphere;	86%

methyl 2-fluorobenzoate (394-35-4) + p-tolylzinc(II) chloride (90252-89-4) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
Stage #1: methyl 2-fluorobenzoate; p-tolylzinc(II) chloride With bis(tricyclohexylphosphine)nickel(II) dichloride In tetrahydrofuran; 1-methyl-pyrrolidin-2-one at 25 - 100℃; for 10h; Schlenk technique; Inert atmosphere; Stage #2: p-tolylzinc(II) chloride In tetrahydrofuran; 1-methyl-pyrrolidin-2-one at 100℃; for 10h; Inert atmosphere; Schlenk technique;	86%

methyl chlorobenzoate (610-96-8) + 4-methylphenylboronic acid (5720-05-8) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
With potassium fluoride; palladium diacetate In toluene at 80℃; for 2h; Suzuki-Miyaura coupling;	85%
With potassium phosphate; triphenylphosphine; bis(triphenylphosphine)nickel(II) chloride In toluene at 100℃; for 2h; Substitution;	83%

methyl 2-((methylsulfonyl)oxy)benzoate (95667-98-4) + p-tolylzinc bromide (126403-71-2) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
With hydrogenchloride; n-butyllithium; triphenylphosphine; lithium chloride; nickel dichloride In tetrahydrofuran; water	82%
With hydrogenchloride; n-butyllithium; triphenylphosphine; lithium chloride; nickel dichloride In tetrahydrofuran; water	82%

o-tolylbenzoic acid (7148-03-0) + carbonic acid dimethyl ester (616-38-6) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
With sulfuric acid; acetic acid for 10h; Neat (no solvent); Reflux;	75.23%

methyl 2-((N,N-dimethylsulfamoyl)oxy)benzoate + p-tolylzinc(II) chloride (90252-89-4) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
With 1-Methylpyrrolidine; C20H20ClN3Ni In tetrahydrofuran at 50℃; for 12h; Schlenk technique; Inert atmosphere;	62%

o-iodo-methyl-benzoic acid (610-97-9) + 4-methylphenylboronic acid (5720-05-8) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
With tris(dibenzylideneacetone)dipalladium(0) chloroform complex; potassium carbonate; N-benzyl-N-(1-octynyl)-p-toluenesulfonamide In water; acetonitrile at 0 - 70℃; under 760.051 Torr; for 18h; Suzuki-Miyaura Coupling; Inert atmosphere;	27%
palladium
With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In tetrahydrofuran; water at 20 - 80℃; Suzuki Coupling; Schlenk technique; Inert atmosphere;

4-tolyl iodide (624-31-7) + o-iodo-methyl-benzoic acid (610-97-9) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
With copper at 210℃; for 1h;	11%
With bis-triphenylphosphine-palladium(II) chloride; tributyltin chloride; iodine; magnesium; lithium chloride 1.) THF, reflux, 30 min; THF, reflux, 20 h, 2.) DMF, 98 deg C, 24 h; Yield given. Multistep reaction;

sodium methylate (124-41-4) + 2,6-di-tert-butyl-4-methylphenyl 4'-methylbiphenyl-2-carboxylate (146017-83-6) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
In toluene for 2.5h; Heating;

para-bromotoluene (106-38-7) + o-iodo-methyl-benzoic acid (610-97-9) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
With bis(triphenylphosphine)nickel(II) chloride; n-butyllithium; methylmagnesium bromide; zinc(II) chloride Yield given. Multistep reaction;

4-methylphenylboronic acid (5720-05-8) + methyl 2-((methylsulfonyl)oxy)benzoate (95667-98-4) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
With 1,1'-bis-(diphenylphosphino)ferrocene; potassium phosphate; n-butyllithium; [1,1'-bis(diphenylphosphino)ferrocene]nickel(II) chloride; potassium iodide 1.) toluene, room temperature, 30 min, 2.) toluene, 80 deg C, 16 h; Yield given. Multistep reaction;

MeO-PEG5000-[2-(4-methylphenyl)benzoate] → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
With potassium cyanide In methanol at 20℃;

methanol (67-56-1) + ethyl 4′-methyl-[1,1′-biphenyl]-2-carboxylate (143573-45-9) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
With boron trifluoride diethyl etherate Heating;

ethyl 2-chlorobenzoate (7335-25-3) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: K3PO4; 2-(dicyclohexylphosphino)biphenyl based D-gluconamide / Pd(OAc)2 / H2O / 16 h / 80 °C 2: BF3*OEt2 / Heating View Scheme

4-methylphenylboronic acid (5720-05-8) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: K3PO4; 2-(dicyclohexylphosphino)biphenyl based D-gluconamide / Pd(OAc)2 / H2O / 16 h / 80 °C 2: BF3*OEt2 / Heating View Scheme
Multi-step reaction with 2 steps 1: PdCl2; aq. NaOH 2: benzene; methanol; hexane View Scheme
Multi-step reaction with 2 steps 1: PdCl2; aq. NaOH 2: MeOH / hexane; benzene View Scheme
Multi-step reaction with 2 steps 1: palladium diacetate; triphenylphosphine / acetonitrile 2: water / Acidic conditions View Scheme
Multi-step reaction with 2 steps 1.1: palladium diacetate / water / 0.08 h / 20 °C / Inert atmosphere 1.2: 5 h / Inert atmosphere; Reflux 2.1: sulfuric acid / 5 h / Reflux View Scheme

2-bromobenzoic-acid (88-65-3) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: PdCl2; aq. NaOH 2: benzene; methanol; hexane View Scheme
Multi-step reaction with 2 steps 1: PdCl2; aq. NaOH 2: MeOH / hexane; benzene View Scheme
Multi-step reaction with 2 steps 1: sulfuric acid / 5 h / Reflux 2: palladium diacetate; sodium carbonate; dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane / acetonitrile; water / Reflux View Scheme
Multi-step reaction with 2 steps 1.1: palladium diacetate / water / 0.08 h / 20 °C / Inert atmosphere 1.2: 5 h / Inert atmosphere; Reflux 2.1: sulfuric acid / 5 h / Reflux View Scheme

2,6-di-tert-butyl-4-methylphenyl 2-methoxybenzoate (137600-70-5) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 91 percent / diethyl ether; various solvent(s) / room temp., 17 h; reflux, 1 h 2: toluene; various solvent(s) / 2.5 h / Heating View Scheme

2-Methoxybenzoic acid (579-75-9) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: 92 percent / trifluoroacetic anhydride / benzene / 23 h / Ambient temperature 2: 91 percent / diethyl ether; various solvent(s) / room temp., 17 h; reflux, 1 h 3: toluene; various solvent(s) / 2.5 h / Heating View Scheme
Multi-step reaction with 6 steps 1: 95 percent / thionyl chloride / 18 h / 20 °C 2: CH2Cl2 / 2 h / 20 °C 3: thionyl chloride / 1 h / 25 °C 4: tetrahydrofuran / 2 h / 20 °C 5: 88 percent / 4.5 N aq. HCl / 12 h / Heating 6: 1.) acetyl chloride / 1.) 0 deg C, 0.25 h, 2.) reflux, 4 h View Scheme

2-(2-methoxyphenyl)-4,4-dimethyl-2-oxazoline (57598-33-1) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: tetrahydrofuran / 2 h / 20 °C 2: 88 percent / 4.5 N aq. HCl / 12 h / Heating 3: 1.) acetyl chloride / 1.) 0 deg C, 0.25 h, 2.) reflux, 4 h View Scheme
Multi-step reaction with 3 steps 1: magnesium / tetrahydrofuran 2: hydrogenchloride 3: methanol View Scheme

N-(2-hydroxy-1,1-dimethyl)-2-methoxybenzamide (74201-13-1) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
Multi-step reaction with 4 steps 1: thionyl chloride / 1 h / 25 °C 2: tetrahydrofuran / 2 h / 20 °C 3: 88 percent / 4.5 N aq. HCl / 12 h / Heating 4: 1.) acetyl chloride / 1.) 0 deg C, 0.25 h, 2.) reflux, 4 h View Scheme

4,4-dimethyl-2-(4'-methyl-biphenyl-2-yl)-4,5-dihydrooxazole (84392-32-5) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 88 percent / 4.5 N aq. HCl / 12 h / Heating 2: 1.) acetyl chloride / 1.) 0 deg C, 0.25 h, 2.) reflux, 4 h View Scheme
Multi-step reaction with 2 steps 1: hydrogenchloride 2: methanol View Scheme

2-Methoxybenzoyl chloride (21615-34-9) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
Multi-step reaction with 5 steps 1: CH2Cl2 / 2 h / 20 °C 2: thionyl chloride / 1 h / 25 °C 3: tetrahydrofuran / 2 h / 20 °C 4: 88 percent / 4.5 N aq. HCl / 12 h / Heating 5: 1.) acetyl chloride / 1.) 0 deg C, 0.25 h, 2.) reflux, 4 h View Scheme

ethylene diaminetetracetic acid + para-bromotoluene (106-38-7) + o-iodo-methyl-benzoic acid (610-97-9) → methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8)

Conditions	Yield
With n-butyllithium; Zinc chloride; tetrakis(triphenylphosphine)palladium (0) In tetrahydrofuran; hexane; chloroform; water
With n-butyllithium; Zinc chloride; tetrakis(triphenylphosphine)palladium (0) In tetrahydrofuran; hexane; chloroform; water

methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8) → o-tolylbenzoic acid (7148-03-0)

Conditions	Yield
With sodium hydroxide In methanol; water Heating;	99%
With sodium hydroxide In ethanol for 18h; Ambient temperature;	47%
With sodium hydroxide In ethanol for 5h; Reflux;	43%

methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8) → C15H12Br2O2 + Methyl 4'-(bromomethyl)biphenyl-2-carboxylate (114772-38-2)

Conditions	Yield
With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione; 2,2'-azobis(isobutyronitrile) In chloroform at 60 - 65℃;	A n/a B 92.6%

methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8) → Methyl 4'-(bromomethyl)biphenyl-2-carboxylate (114772-38-2)

Conditions	Yield
With N-Bromosuccinimide In dichloromethane at 25℃; for 5h; Temperature; Irradiation; Large scale;	90%
With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane Reflux;	88%
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane	85%

methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8) → methyl 4-(bromomethyl)-[1,1’-biphenyl]-2-carboxylate (152620-34-3)

Conditions	Yield
With sulfuric acid; sodium bromide In dichloromethane; water at 25℃;	80.5%

(S,Z)-1-(2-bromophenyl)-3-iodo-3-(trimethylsilyl)prop-2-en-1-ol + methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8) → (Ra)-(1-(4'-methyl-[1,1'-biphenyl]-2-yl)naphthalen-2-yl)trimethylsilane

Conditions

Yield

Stage #1: (S,Z)-1-(2-bromophenyl)-3-iodo-3-(trimethylsilyl)prop-2-en-1-ol With isopropylmagnesium chloride; magnesium; lithium chloride In diethyl ether at 40℃; for 0.75h; Inert atmosphere; Stage #2: methyl 4'-methylbiphenyl-2-carboxylate In diethyl ether at 20℃; for 1h; Inert atmosphere; Stage #3: With titanium tetra-n-propoxide In tetrahydrofuran; diethyl ether at 20℃; for 3h; Inert atmosphere; stereoselective reaction;

65%

phthalic anhydride (85-44-9) + methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8) → 1-(2-carboxybenzoyl)-2-methylfluorenone + 3'-(2-Carboxy-benzoyl)-4'-methyl-biphenyl-2-carboxylic acid methyl ester

Conditions	Yield
With aluminium trichloride; N,N-dimethyl-formamide at 70℃; for 1h;	A 7% B 60%
With aluminium trichloride; N,N-dimethyl-formamide at 70℃; for 1h;	A 5% B 60%

methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8) → methyl 4'-cyano-[1,1'-biphenyl]-2-carboxylate

Conditions	Yield
With hydroxylamine hydrochloride; 2,4,6-triphenylpyrylium tetrafluoroborate; oxygen; ammonium bromide In acetonitrile at 40℃; under 750.075 Torr; for 24h; Molecular sieve; Irradiation;	60%

azobisisobutyronitrile (34241-39-9) + methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8) → Methyl 4'-(bromomethyl)biphenyl-2-carboxylate (114772-38-2)

Conditions	Yield
With N-Bromosuccinimide In tetrachloromethane	59%
With N-Bromosuccinimide In tetrachloromethane

methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8) → (4′-methyl-[1,1′-biphenyl]-2-yl)methanol (114772-78-0)

Conditions	Yield
With diisobutylaluminium hydride In toluene at -78 - -70℃; for 0.25h;	42.55 g

methyl 4'-methylbiphenyl-2-carboxylate (114772-34-8) → C14H12(2)H2O

Conditions	Yield
With lithium aluminium deuteride

Upstream product

• 137600-70-5 2,6-di-tert-butyl-4-methylphenyl 2-methoxybenzoate 
• 106-38-7 para-bromotoluene 
• 610-97-9 o-iodo-methyl-benzoic acid 
• 88-67-5 2-Iodobenzoic acid 
• 624-31-7 4-tolyl iodide 
• 67-56-1 methanol 
• 7148-03-0 o-tolylbenzoic acid 
• 5720-05-8 4-methylphenylboronic acid 
• 849020-92-4 methyl 2-(aminomethyl)benzoate hydrochloride salt 
• 93-58-3 benzoic acid methyl ester 
• 106-49-0 p-toluidine 
• 610-96-8 methyl chlorobenzoate 
• 380481-66-3 5,5-dimethyl-2-(4-methylphenyl)-1,3,2-dioxaborinane 
• 2042-37-7 o-cyanobromobenzene 

Downstream Products

• 897446-35-4 4'-methylbiphenyl-2-carboxylic acid (2-aminophenyl)amide 
• 16191-28-9 2-(4-methylphenyl)benzaldehyde 
• 133910-06-2 2-<2-fluoro-2-(benzenesulfonyl)ethen-1-yl>-4'-methylbiphenyl 
• 124750-63-6 2-(4'-methylbiphenyl-2-yl)-1-(benzenesulfonyl)acrylonitrile 
• 133910-05-1 2-<2-fluoro-1-hydroxy-2-(benzenesulfonyl)ethyl>-4'-methylbiphenyl 
• 114799-00-7 2-butyl-1-<(2'-carboxybiphenyl-4-yl)methyl>-5-(hydroxymethyl)imidazole 
• 114798-32-2 2-(1E-Butenyl)-4-chloro-1-[(2'-carboxybiphenyl-4-yl)methyl]-5-(hydroxymethyl)imidazole 
• 114772-45-1 2-butyl-1-<(2'-carbomethoxybiphenyl-4-yl)methyl>-5-(hydroxymethyl)imidazole 
• 114772-68-8 2-(1-trans-butenyl)-1-<(2'-carbomethoxybiphenyl-4-yl)methyl>-4-chloroimidazole-5-carboxaldehyde 
• 114772-75-7 2-butyl-4-chloro-1-<<2'-(hydroxymethyl)biphenyl-4-yl>methyl>-5-(methoxymethyl)imidazole 
• 114798-30-0 2-Butyl-4-chloro-1-[(2'-carboxybiphenyl-4-yl)-methyl]imidazole-5-carboxaldehyde 
• 114799-97-2 5-(aminomethyl)-2-butyl-1-<(2'-carboxybiphenyl-4-yl)methyl>-4-chloroimidazole 
• 114772-76-8 2-butyl-4-chloro-1-<<2'-(cyanomethyl)biphenyl-4-yl>methyl>-5-(methoxymethyl)imidazole 
• 114772-69-9 1-[(2'-Carbomethoxybiphenyl-4-yl)methyl]-2-(1-trans-butenyl)-4-chloro-5-hydroxymethylimidazole 

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