610-94-6

Basic information

• Product Name: Methyl 2-bromobenzoate
• Synonyms: RARECHEM AL BF 0014;2-BROMOBENZOIC ACID METHYL ESTER;METHYL 2-BROMOBENZOATE;METHYL O-BROMOBENZOATE;2-bromo-benzoicacimethylester;Benzoicacid,2-bromo-,methylester;O-bromobenzoic acid, methyl ester;Methyl2-bromobenzoate,99%
• CAS NO: 610-94-6
• Molecular Formula: C₈H₇BrO₂
• Molecular Weight: 215.04
• EINECS: 210-241-5
• Product Categories: Aromatic Esters;Acids & Esters;Bromine Compounds;C8 to C9;Carbonyl Compounds;Esters
• Mol File: 610-94-6.mol
• Article Data: 72

Chemical Properties

• Melting Point: 252°C
• Boiling Point: 252 °C(lit.)
• Flash Point: >230 °F
• Appearance: Clear light yellow/Liquid
• Density: 1.532 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.0368mmHg at 25°C
• Refractive Index: n20/D 1.559(lit.)
• Storage Temp.: Sealed in dry,Room Temperature
• Water Solubility: insoluble
• BRN: 1862501
• CAS DataBase Reference: Methyl 2-bromobenzoate(CAS DataBase Reference)
• NIST Chemistry Reference: Methyl 2-bromobenzoate(610-94-6)
• EPA Substance Registry System: Methyl 2-bromobenzoate(610-94-6)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 24/25
• WGK Germany: 3
• TSCA: Yes
• Hazardous Substances Data: 610-94-6(Hazardous Substances Data)

Usage

Chemical Properties

CLEAR LIGHT YELLOW LIQUID

Uses

Methyl 2-bromobenzoate under Heck reaction with acrylonitrile results in lactonization to give the benzofuran-2-one 3-(cyanomethyl)-2-coumaranone. It is an important raw material and intermediate used in Organic Synthesis, Pharmaceuticals, Agrochemicals

Purification Methods

A solution of the ester in ether is washed with 10% aqueous Na 2CO3, water, then dried and distilled. [Beilstein 9

Synthetic route

methanol (67-56-1) + 2-bromobenzoic-acid (88-65-3) → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
With sulfuric acid Reflux; Inert atmosphere;	99%
With sulfuric acid Reflux;	99%
With sulfuric acid at 0℃; for 20.25h; Fischer-Speier Esterification; Reflux;	96%

methanol (67-56-1) + ortho-bromobenzaldehyde (6630-33-7) → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
With perchloric acid; sodium percarbonate; vanadia for 1.3h; Cooling;	96%
With tert.-butylhydroperoxide; potassium carbonate In water at 60℃; for 6h;	87%
With magnesium hydroxide; oxygen at 90℃; under 2250.23 Torr; for 8h;

2-bromophenyl methyl ketone (2142-69-0) → 2-bromobenzoic acid methyl ester (610-94-6) + o-bromophenyl acetate (1829-37-4)

Conditions	Yield
With hydrogenchloride In chloroform at 20℃; for 12h; Baeyer-Villiger oxidation;	A 7% B 91%

2-bromobenzoic-acid (88-65-3) + methyl salicylate (119-36-8) → 2-bromobenzoic acid methyl ester (610-94-6) + salicylic acid (69-72-7)

Conditions	Yield
Stage #1: 2-bromobenzoic-acid With potassium carbonate In N,N-dimethyl acetamide at 110℃; for 0.5h; Stage #2: methyl salicylate at 110℃; for 24h;	A 91% B n/a

methanol (67-56-1) + o-bromobenzyl alcohol (18982-54-2) → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
With oxygen; potassium carbonate at 60℃; under 750.075 Torr; for 20h;	86%
With potassium chloride; dihydrogen peroxide; C5H12CrMo6O25(3-)*3C16H36N(1+) In water at 65℃; for 36h; Schlenk technique;	80%
With sodium hypochlorite; tetrabutylammomium bromide In ethyl acetate at 20℃; for 3.51667h;	17%
With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione at 25℃; for 12h; Temperature; chemoselective reaction;	24 %Chromat.

methanol (67-56-1) + carbon monoxide (201230-82-2) + 1,2-dibromobenzene (583-53-9) → 2-bromobenzoic acid methyl ester (610-94-6) + phthalic acid dimethyl ester (131-11-3) + benzene-1,2-dicarboxylic acid (88-99-3)

Conditions	Yield
With tert-Amyl alcohol; sodium hydride; cobalt(II) acetate In tetrahydrofuran at 40℃; under 760 Torr; for 18h; Irradiation;	A 4% B 85% C 3%

carbon monoxide (201230-82-2) + 1,2-dibromobenzene (583-53-9) → 2-bromobenzoic acid methyl ester (610-94-6) + phthalic acid dimethyl ester (131-11-3) + benzene-1,2-dicarboxylic acid (88-99-3)

Conditions	Yield
With methanol; tert-Amyl alcohol; sodium hydride; cobalt(II) acetate In tetrahydrofuran at 40℃; under 760 Torr; for 18h; Irradiation;	A 4% B 85% C 3%

4-Bromobenzoic acid (586-76-5) + 1,2-dichloro-ethane (107-06-2) → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
With sulfuric acid In methanol	84%

tert.-butylhydroperoxide (75-91-2) + 2-methylphenyl bromide (95-46-5) → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
Stage #1: tert.-butylhydroperoxide; 2-methylphenyl bromide In water; dimethyl sulfoxide Stage #2: In water; dimethyl sulfoxide at 100℃; for 20h; Sealed tube;	84%
With copper (II)-fluoride In water; dimethyl sulfoxide at 120℃; for 12h; Schlenk technique; Inert atmosphere; Green chemistry;	25%
With ultrafine CuO particles dispersed on nitrogen-doped hollow carbon nanospheres In water; dimethyl sulfoxide at 100℃; for 20h; Sealed tube;	86 %Chromat.

1-bromo-2-(methoxymethyl)benzene (52711-30-5) → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
With oxygen In water at 25℃; for 12h; Irradiation; Green chemistry;	80%
With copper(II) choride dihydrate; oxygen; hydroquinone at 30℃; for 16h; Sealed tube; Irradiation; Green chemistry;	41%

benzoic acid methyl ester (93-58-3) → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
With N-Bromosuccinimide; silver hexafluoroantimonate; trifluorormethanesulfonic acid; nickel diacetate In 1,2-dichloro-ethane at 80℃; for 12h; regioselective reaction;	76%
Stage #1: benzoic acid methyl ester With acetic acid Stage #2: With bromine; acetic acid at 0 - 25℃; for 12h;	66.9%
With N-Bromosuccinimide; dibenzoyl peroxide

tert.-butylhydroperoxide (75-91-2) + o-bromobenzyl alcohol (18982-54-2) → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
With copper (II)-fluoride In water; dimethyl sulfoxide at 120℃; for 12h; Schlenk technique; Inert atmosphere; Green chemistry;	72%
With tetraethylammonium bromide; oxygen; potassium carbonate In water; dimethyl sulfoxide at 100℃; under 735.576 Torr; for 16h; Catalytic behavior; Mechanism;	71%

methanol (67-56-1) + 1-Bromo-2-iodobenzene (583-55-1) + carbon monoxide (201230-82-2) → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
With palladium diacetate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene In 1,4-dioxane at 100℃; under 11251.1 Torr; continuous flow reactor;	69%
With palladium diacetate; triethylamine; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; hydrazine In tetrahydrofuran; 1,4-dioxane at 100℃; under 11251.1 Torr; Flow reactor;	69%

tert.-butylhydroperoxide (75-91-2) + ortho-bromobenzaldehyde (6630-33-7) → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
With copper (II)-fluoride In water; dimethyl sulfoxide at 120℃; for 12h; Schlenk technique; Inert atmosphere; Green chemistry;	65%

Monomethyl phthalate (4376-18-5) → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
With [bis(acetoxy)iodo]benzene; bromine In various solvent(s) for 22h; bromodecarboxylation; Heating; irradiation;	57%

1-thiopropane (107-03-9) + methyl 2-bromo-3-aminobenzoate (106896-48-4) → 2-bromobenzoic acid methyl ester (610-94-6) + methyl 2-bromo-3-propylthiobenzoate

Conditions	Yield
Stage #1: methyl 2-bromo-3-aminobenzoate With tert.-butylnitrite; boron trifluoride diethyl etherate In diethyl ether; dichloromethane at -15 - 5℃; Diazotization; Stage #2: 1-thiopropane With triethylamine In acetonitrile at 80℃; for 18h; Alkylation; substitution; decomposition; deamination;	A n/a B 38%

methanol (67-56-1) + ortho-bromobenzaldehyde (6630-33-7) → 2-bromobenzoic acid methyl ester (610-94-6) + 2-bromobenzoic-acid (88-65-3)

Conditions	Yield
With 3,3'-dimethyl-1,1'-(hexane-1,6-diyl)diimidazolium glutarate; 1,8-diazabicyclo[5.4.0]undec-7-ene; 1-(n-butyl)-3-methylimidazolium triflate In tetrahydrofuran at 55℃; for 16h; Molecular sieve;	A 8% B 37%
With C12H22N6(2+)*2C2F6NO4S2(1-); 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran at 55℃; for 16h; Reagent/catalyst; Molecular sieve;	A 25% B 17%
With C14H22N2S2(2+)*2F6P(1-); 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran at 55℃; for 16h; Reagent/catalyst; Molecular sieve;	A 8% B 21%

methanol (67-56-1) + 2-methylphenyl bromide (95-46-5) → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
With carbon tetrabromide; oxygen for 24h; Irradiation;	34%

methanol (67-56-1) + 2-bromobenzoic acid chloride (7154-66-7) → 2-bromobenzoic acid methyl ester (610-94-6)

bromobenzene (108-86-1) + Methyl-tert.-butylperoxyoxalat (57031-51-3) → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
In benzene Heating;

diazomethane (186581-53-3, 908094-01-9) + sodium acetoacetonate (15435-71-9) + copper(I) 2-bromobenzoate (121619-96-3) → benzoic acid methyl ester (93-58-3) + 2-bromobenzoic acid methyl ester (610-94-6) + diphenic acid dimethyl ester (5807-64-7) + 3-(o-methoxycarbonylphenyl)pentane-2,4-dione (56741-51-6)

Conditions	Yield
1.) toluene, 1 h, 80 deg C; 2.) diethyl ether; Yield given. Multistep reaction. Yields of byproduct given;
Mechanism; Product distribution;

mesitylcopper(I) (75732-01-3) + copper(I) 2-bromobenzoate (121619-96-3) → 2-bromobenzoic acid methyl ester (610-94-6) + Mesityl 2-bromobenzoate (128499-36-5) + Mesityl 2-mesitylbenzoate (128499-34-3) + Mesityl methyl biphenyl-2,2'-dicarboxylate (128499-37-6)

Conditions	Yield
With oxygen 1.) toluene, 30 min, roomtemp.; 2.) 2 h, 80 deg C; Yield given. Multistep reaction. Further byproducts given. Yields of byproduct given;

sodium methylate (124-41-4) + 1-(2-bromobenzoyl)-3-(4-chlorophenyl)urea (107485-55-2) → 2-bromobenzoic acid methyl ester (610-94-6) + N-(4-chlorophenyl)urea (140-38-5)

Conditions	Yield
In methanol at 25℃; Kinetics; Mechanism; Rate constant;

1-thiopropane (107-03-9) + C8H6BrN2O2(1+)*BF4(1-) → 2-bromobenzoic acid methyl ester (610-94-6) + methyl 2-bromo-3-propylthiobenzoate

Conditions	Yield
With triethylamine In acetonitrile at 80℃; for 18h; Alkylation; substitution; decomposition;	A n/a B 1.10 g

methyl iodide (74-88-4) + 2-bromo-benzoate silver → 2-bromobenzoic acid methyl ester (610-94-6)

2-bromo-3-nitro-benzoic acid (573-54-6) → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: PCl5 / 0.08 h / 150 °C 1.2: 94 percent / 1 h / Heating 2.1: 87 percent / glacial acetic acid; iron / 2 h / 120 °C 3.1: 91 percent / BF3*Et2O; t-butyl nitrite / CH2Cl2; diethyl ether / -15 - 5 °C 4.1: triethylamine / acetonitrile / 18 h / 80 °C View Scheme
Multi-step reaction with 3 steps 1.1: PCl5 / 0.08 h / 150 °C 1.2: 94 percent / 1 h / Heating 2.1: 87 percent / glacial acetic acid; iron / 2 h / 120 °C 3.1: BF3*Et2O; t-butyl nitrite / CH2Cl2; diethyl ether / -15 - 5 °C 3.2: triethylamine / acetonitrile / 18 h / 80 °C View Scheme

2-bromo-3-nitro-benzoic acid methyl ester (5337-09-7) → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
Multi-step reaction with 3 steps 1: 87 percent / glacial acetic acid; iron / 2 h / 120 °C 2: 91 percent / BF3*Et2O; t-butyl nitrite / CH2Cl2; diethyl ether / -15 - 5 °C 3: triethylamine / acetonitrile / 18 h / 80 °C View Scheme
Multi-step reaction with 2 steps 1.1: 87 percent / glacial acetic acid; iron / 2 h / 120 °C 2.1: BF3*Et2O; t-butyl nitrite / CH2Cl2; diethyl ether / -15 - 5 °C 2.2: triethylamine / acetonitrile / 18 h / 80 °C View Scheme

methyl 2-bromo-3-aminobenzoate (106896-48-4) → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: 91 percent / BF3*Et2O; t-butyl nitrite / CH2Cl2; diethyl ether / -15 - 5 °C 2: triethylamine / acetonitrile / 18 h / 80 °C View Scheme

anhydro-2-hydroxymercuri-3-nitrobenzoic acid → 2-bromobenzoic acid methyl ester (610-94-6)

Conditions	Yield
Multi-step reaction with 5 steps 1.1: bromine; base 2.1: PCl5 / 0.08 h / 150 °C 2.2: 94 percent / 1 h / Heating 3.1: 87 percent / glacial acetic acid; iron / 2 h / 120 °C 4.1: 91 percent / BF3*Et2O; t-butyl nitrite / CH2Cl2; diethyl ether / -15 - 5 °C 5.1: triethylamine / acetonitrile / 18 h / 80 °C View Scheme
Multi-step reaction with 4 steps 1.1: bromine; base 2.1: PCl5 / 0.08 h / 150 °C 2.2: 94 percent / 1 h / Heating 3.1: 87 percent / glacial acetic acid; iron / 2 h / 120 °C 4.1: BF3*Et2O; t-butyl nitrite / CH2Cl2; diethyl ether / -15 - 5 °C 4.2: triethylamine / acetonitrile / 18 h / 80 °C View Scheme

2-bromobenzoic acid methyl ester (610-94-6) + 2-methoxynaphthylamine (2246-42-6) → methyl 2-[(2-methoxy-1-naphthyl)amino]benzoate

Conditions	Yield
With caesium carbonate; palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In toluene at 20 - 80℃; for 15.525h;	100%
With palladium diacetate; caesium carbonate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In toluene at 20 - 80℃; for 15.5h; Inert atmosphere;	100%

2-bromobenzoic acid methyl ester (610-94-6) + methylmagnesium chloride (676-58-4) → 2-(2-bromophenyl)propanol (7073-69-0)

Conditions	Yield
Stage #1: 2-bromobenzoic acid methyl ester; methylmagnesium chloride In tetrahydrofuran; 2-methyltetrahydrofuran at 20℃; Cooling with ice; Stage #2: With hydrogenchloride In tetrahydrofuran; 2-methyltetrahydrofuran; water at 0℃; pH=6; Product distribution / selectivity;	100%
In tetrahydrofuran at 0℃; Inert atmosphere;	82%
In tetrahydrofuran at 5 - 20℃; Inert atmosphere;

2-bromobenzoic acid methyl ester (610-94-6) → 2-bromobenzoic-acid (88-65-3)

Conditions	Yield
With water; sodium hydroxide In ethanol at 10 - 20℃; for 1.08333h;	100%
With iodine; aluminium In acetonitrile at 80℃; for 18h;	99%

2-bromobenzoic acid methyl ester (610-94-6) → benzoic acid methyl ester (93-58-3)

Conditions	Yield
With 2-H-1,3-di-tert-butyl-1,3,2-diazaphosphorinane; 2,2'-azobis(isobutyronitrile) In toluene at 90℃; for 5h;	99%
Stage #1: 2-bromobenzoic acid methyl ester With sec.-butyllithium In tetrahydrofuran; hexane; cyclohexane at -48℃; for 7.77778E-06h; Stage #2: With methanol In tetrahydrofuran; hexane; cyclohexane at -48℃; for 0.000638889h;	74%
With copper(I) chloride; methanol; sodium tetrahydroborate at 0℃;	93 % Chromat.

2-bromobenzoic acid methyl ester (610-94-6) + m-nitrobenzene boronic acid (13331-27-6) → methyl 3’-nitro-[1,1’-biphenyl]-2-carboxylate (83527-96-2)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,4-dioxane at 85℃; Suzuki cross-coupling;	99%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In water; toluene at 20 - 80℃; for 6h; Inert atmosphere;	17%
With tetra-butylammonium acetate; Pd EnCat-30TM In ethanol Suzuki cross-coupling; microwave irradiation;

2-bromobenzoic acid methyl ester (610-94-6) + 2-Methoxyphenylboronic acid (5720-06-9) → 2'-methoxy-biphenyl-2-carboxylic acid methyl ester (63506-58-1)

Conditions	Yield
With palladium diacetate; sodium carbonate; triphenylphosphine; [BMIM][Cl] In water; toluene for 3.5h; Suzuki coupling reaction; Heating;	99%
With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; potassium carbonate In ethanol; water; toluene at 78 - 80℃; for 8h; Inert atmosphere;	92%
With dichloro[1,1'-bis(di-t-butylphosphino)ferrocene]palladium(II); potassium carbonate In water; acetonitrile at 60℃; Suzuki-Miyaura reaction; Inert atmosphere; Sealed vessel;
With 1,1'-bis-(diphenylphosphino)ferrocene; potassium phosphate; palladium diacetate In 1,2-dimethoxyethane at 80℃; for 12h; Suzuki-Miyaura Coupling; Inert atmosphere; Schlenk technique;

2-bromobenzoic acid methyl ester (610-94-6) + N-Methylurea (598-50-5) → 3-methyl-2,4(1H,3H)-quinazolinedione (607-19-2)

Conditions	Yield
With tris(dibenzylideneacetone)dipalladium (0); caesium carbonate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene In 1,4-dioxane at 100℃; for 48h;	99%
With tris-(dibenzylideneacetone)dipalladium(0); caesium carbonate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene In 1,4-dioxane at 100℃; for 24h;	61%

2-bromobenzoic acid methyl ester (610-94-6) + 3,4,5-trimethoxyphenylboronic Acid (182163-96-8) → 3',4',5'-trimethoxybiphenyl-2-carboxylic acid methyl ester (928847-09-0)

Conditions	Yield
With sodium carbonate; tetrakis(triphenylphosphine) palladium(0) In water; toluene at 100℃;	99%
With sodium carbonate; tetrakis(triphenylphosphine) palladium(0) In toluene at 100℃; Suzuki reaction;	45%

Octanethiol (111-88-6) + 2-bromobenzoic acid methyl ester (610-94-6) → methyl 2-octylthiobenzenecarboxylate (211228-57-8)

Conditions	Yield
With 1,1'-bis-(diphenylphosphino)ferrocene; tris-(dibenzylideneacetone)dipalladium(0); N-ethyl-N,N-diisopropylamine In toluene for 3h; Inert atmosphere; Reflux;	99%

2-bromobenzoic acid methyl ester (610-94-6) + tri-n-butyl(thien-3-yl)tin (119405-65-1) → methyl 2-(thiophen-3-yl)benzoate

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0) In toluene for 24h; Stille Cross Coupling; Reflux; Inert atmosphere;	99%

Thien-3-ylboronic acid (6165-69-1) + 2-bromobenzoic acid methyl ester (610-94-6) → methyl 2-(thiophen-3-yl)benzoate

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In tetrahydrofuran; water at 70℃; for 16h; Inert atmosphere; Schlenk technique;	99%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In tetrahydrofuran; water at 70℃; for 16h; Suzuki Coupling; Inert atmosphere;	98%
With trans-bis(triphenylphosphine)palladium dichloride; sodium carbonate In tetrahydrofuran; water at 70℃; Suzuki-Miyaura Coupling; Inert atmosphere;	92%
With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In tetrahydrofuran; water at 70℃; for 36h; Inert atmosphere; Schlenk technique;	89%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate

2-bromobenzoic acid methyl ester (610-94-6) + 2,4-dichlorophenylboronic acid (68716-47-2) → 2',4'-Dichloro-biphenyl-2-carboxylic acid methyl ester

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 120℃; for 3h;	99%

2-bromobenzoic acid methyl ester (610-94-6) + 4-(pentafluorosulfanyl)aniline (2993-24-0) → N-(4-(pentafluorosulfanyl)phenyl)anthranilic acid methyl ester

Conditions	Yield
With palladium diacetate; caesium carbonate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In toluene at 110℃; for 18h; Buchwald-Hartwig Coupling; Inert atmosphere; Schlenk technique;	99%

2-bromobenzoic acid methyl ester (610-94-6) + (E)-3-methoxy-1-propenylboronic acid pinacol ester (165059-42-7) → methyl (E)-2-(3-methoxyprop-1-en-1-yl)benzoate (1255651-89-8)

Conditions	Yield
With potassium phosphate; chloro(2-dicyclohexylphosphino-2’,4’,6’-triisopropyl-1,1‘-biphenyl)[2-(2’-amino-1,1‘-biphenyl’)]palladium(II) In tetrahydrofuran; water at 45℃; for 23h; Inert atmosphere; Sealed tube;	99%

2-bromobenzoic acid methyl ester (610-94-6) + potassium vinyltrifluoroborate → methyl o-vinylbenzoate (27326-44-9)

Conditions	Yield
With caesium carbonate; triphenylphosphine; palladium dichloride In tetrahydrofuran; water at 85℃; for 12h; Suzuki Coupling; Inert atmosphere;	99%

2-bromobenzoic acid methyl ester (610-94-6) + methylmagnesium bromide (75-16-1) → 2-(2-bromophenyl)propanol (7073-69-0)

Conditions	Yield
Stage #1: 2-bromobenzoic acid methyl ester; methylmagnesium bromide In tetrahydrofuran at 20℃; Cooling with ice; Stage #2: With hydrogenchloride In water pH=5 - 6;	98.2%
Stage #1: 2-bromobenzoic acid methyl ester; methylmagnesium bromide In tetrahydrofuran; diethyl ether at 2 - 15℃; for 19.5h; Stage #2: With hydrogenchloride In tetrahydrofuran; diethyl ether; water at 0 - 15℃; for 2h; Product distribution / selectivity;	97.48%
In tetrahydrofuran at 0 - 15℃; Inert atmosphere;	97.5%

2-bromobenzoic acid methyl ester (610-94-6) + 1-amino-3-methylbenzene (108-44-1) → N-(3-methylphenyl)anthranilic acid methyl ester (23868-14-6)

Conditions	Yield
With potassium phosphate; johnphos; tris(dibenzylideneacetone)dipalladium (0) In 1,2-dimethoxyethane at 100℃; for 24h; Arylation;	98%

2-bromobenzoic acid methyl ester (610-94-6) + tributyl(3-methoxyphenyl)stannane (122439-11-6) → methyl 3'-methoxy-[1,1'-biphenyl]-2-carboxylate

Conditions	Yield
With lithium chloride; dichlorobis(tris[4-(heptadecafluorooctyl)phenyl]phosphine-kP)palladium In N,N-dimethyl-formamide at 80℃; for 3h; Stille cross-coupling reaction;	98%
With carbon dioxide; tetrabutyl-ammonium chloride; [(m-C8H17-C6H4)3P]2*PdCl2 at 90℃; for 24h; Stille coupling;	61 % Spectr.

2-bromobenzoic acid methyl ester (610-94-6) + phenylacetylene (536-74-3) → methyl 2-(phenylethynyl)benzoate (33578-05-1)

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 20℃; Sonogashira coupling; Inert atmosphere;	98%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 80℃; Cooling with liquid nitrogen; Sealed tube;	97%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃; for 18h; Sonogashira coupling;	96%

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%

2-bromobenzoic acid methyl ester (610-94-6) + tert-Butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,6-dihydro-1(2H)-pyridinecarboxylate (375853-82-0, 286961-14-6) → tert-butyl 4-(2-(methoxycarbonyl)phenyl)-5,6-dihydropyridine-1(2H)-carboxylate

Conditions	Yield
With sodium hydrogencarbonate; tetrakis(triphenylphosphine) palladium(0) In 1,4-dioxane; water at 140℃; for 0.0833333h; Microwave irradiation;	98%
With potassium carbonate; PdCl2*1,1'-bis(diphenylphosphine)ferrocene In N,N-dimethyl-formamide at 90℃; for 5h;

2-bromobenzoic acid methyl ester (610-94-6) + tributyl(thien-2-yl)stannane (54663-78-4) → o-(2-thienyl)benzoic acid methyl ester (17595-84-5)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0) In toluene for 17h; Stille coupling; Inert atmosphere; Reflux;	98%

3‐methyl‐1‐(2‐methylphenyl)‐1H‐pyrazol‐5‐amine (91331-68-9) + 2-bromobenzoic acid methyl ester (610-94-6) → methyl 2-((3-methyl-1-(2-methylphenyl)-1H-pyrazol-5-yl)amino)benzenecarboxylate (1209485-73-3)

Conditions	Yield
Stage #1: 3‐methyl‐1‐(2‐methylphenyl)‐1H‐pyrazol‐5‐amine; palladium diacetate; bis[2-(diphenylphosphino)phenyl] ether In toluene at 20℃; for 0.0833333h; Inert atmosphere; Stage #2: 2-bromobenzoic acid methyl ester With caesium carbonate In toluene at 95℃; Inert atmosphere;	98%
With tris-(dibenzylideneacetone)dipalladium(0); caesium carbonate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In toluene for 16h; Buchwald-Hartwig type cross-coupling; Reflux;

2-bromobenzoic acid methyl ester (610-94-6) + acetone (67-64-1) → 1-(2-bromophenyl)-butane-1,3-dione (57279-20-6)

Conditions	Yield
With sodium hydride In tetrahydrofuran at 100℃; for 18.5h;	98%
With sodium hydride In tetrahydrofuran at 20℃; for 18h; Reflux;

tert-butylisonitrile (119072-55-8, 7188-38-7) + 2-bromobenzoic acid methyl ester (610-94-6) → 4-(tert-butylamino)phthalazin-1(2H)-one (1346229-07-9)

Conditions	Yield
With palladium diacetate; hydrazine hydrate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene In dimethyl sulfoxide at 150℃; for 0.0833333h; Microwave irradiation; Inert atmosphere; regioselective reaction;	98%

tert-butylisonitrile (119072-55-8, 7188-38-7) + 2-bromobenzoic acid methyl ester (610-94-6) + hydrazine (302-01-2) → 4-(tert-butylamino)phthalazin-1(2H)-one (1346229-07-9)

Conditions	Yield
With palladium diacetate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene In dimethyl sulfoxide at 150℃; for 0.0833333h; Inert atmosphere; Microwave irradiation; Sealed tube;	98%

2-bromobenzoic acid methyl ester (610-94-6) + 3-pentafluorosulfuraniline (2993-22-8) → N-(3-(pentafluorosulfanyl)phenyl)anthranilic acid methyl ester

Conditions	Yield
With palladium diacetate; caesium carbonate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In toluene at 110℃; for 18h; Buchwald-Hartwig Coupling; Inert atmosphere; Schlenk technique;	98%

2-bromobenzoic acid methyl ester (610-94-6) + (E)-4,4,5,5-tetramethyl-2-(3-phenylprop-1-en-1-yl)-1,3,2-dioxaborolane (177573-86-3) → methyl (E)-2-(3-phenylprop-1-en-1-yl)benzoate (1027255-60-2)

Conditions	Yield
With potassium phosphate; chloro(2-dicyclohexylphosphino-2’,4’,6’-triisopropyl-1,1‘-biphenyl)[2-(2’-amino-1,1‘-biphenyl’)]palladium(II) In tetrahydrofuran; water at 45℃; for 17h; Inert atmosphere; Sealed tube;	98%

Upstream product

• 67-56-1 methanol 
• 88-65-3 2-bromobenzoic-acid 
• 107-03-9 1-thiopropane 
• 106896-48-4 methyl 2-bromo-3-aminobenzoate 
• 6630-33-7 ortho-bromobenzaldehyde 
• 108-86-1 bromobenzene 
• 57031-51-3 Methyl-tert.-butylperoxyoxalat 
• 7154-66-7 2-bromobenzoic acid chloride 
• 18107-18-1 diazomethyl-trimethyl-silane 
• 583-55-1 1-Bromo-2-iodobenzene 
• 186581-53-3 diazomethane 
• 75-91-2 tert.-butylhydroperoxide 
• 95-46-5 2-methylphenyl bromide 
• 18982-54-2 o-bromobenzyl alcohol 

Downstream Products

• 166956-53-2 Methyl 2-<5-(2-methyl-1,3-dioxolan-2-yl)-1-butynyl>benzoate 
• 27326-44-9 methyl o-vinylbenzoate 
• 1077-79-8 methyl 2-acetylbenzoate 
• 107793-07-7 methyl 2-(2-trimethylsilyl-1-ethynyl)benzoate 
• 970-93-4 dimethyl 2,2'-(ethyne-1,2-diyl)dibenzoate 
• 101169-58-8 methyl 2-(3,4-dimethoxyphenoxy)benzoate 
• 93-58-3 benzoic acid methyl ester 
• 4877-93-4 2,2'-Dimethoxybiphenyl 
• 792-74-5 4,4'-biphenyldicarboxylic acid dimethyl ester 
• 63506-58-1 2'-methoxy-biphenyl-2-carboxylic acid methyl ester 
• 47230-38-6 diethyl biphenyl-4,4'-dicarboxylate 
• 462637-40-7 2-(1-hexynyl)benzoic acid methyl ester 
• 152771-69-2 methyl (+/-)-2-(3-hydroxybut-1-yn-1-yl)benzoate 

Relevant articles and documents

POLYCYCLIC AMIDES AS UBE2K MODULATORS FOR TREATING CANCER

Provided are compounds of Formula (I) and pharmaceutically acceptable salts and compositions thereof, which are useful for treating conditions associated with modulation of UBE2K.

Development of phenyltriazole thiol-based derivatives as highly potent inhibitors of DCN1-UBC12 interaction

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Oxidative esterification of alcohols by a single-side organically decorated Anderson-type chrome-based catalyst

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