68322-84-9

Basic information

• Product Name: 3-Bromo-4-fluorobenzotrifluoride
• Synonyms: 2-FLUORO-5-(TRIFLUOROMETHYL)BROMOBENZENE;2-BROMO-1-FLUORO-4-(TRIFLUOROMETHYL)BENZENE;3-BROMO-4-FLUOROBENZOTRIFLUORIDE;3-BROMO-ALPHA,ALPHA,ALPHA,4-TETRAFLUOROTOLUENE;3-bromo-4-trifluorotoluene;2-Bromo-1-fluoro-4-(trifluoromethyl)benzene~2-Fluoro-5-(trifluoromethyl)bromobenzene;4-fluoro-3-bromobenzoTrifluoride;3-Bromo-4-fluorobenzotrifluori
• CAS NO: 68322-84-9
• Molecular Formula: C₇H₃BrF₄
• Molecular Weight: 243
• Product Categories: Trifluoromethylbenzene serise;Fluorobenzene;Miscellaneous;Benzotrifluoride Series;Aryl;C7;Halogenated Hydrocarbons;Fluorine series;alkyl bromide| alkyl Fluorine
• Mol File: 68322-84-9.mol
• Article Data: 1

Chemical Properties

• Boiling Point: 148-149 °C(lit.)
• Flash Point: 161 °F
• Appearance: clear colorless liquid
• Density: 1.706 g/mL at 25 °C(lit.)
• Vapor Pressure: 4.42mmHg at 25°C
• Refractive Index: n20/D 1.459(lit.)
• Storage Temp.: 0-10°C
• BRN: 2093911
• CAS DataBase Reference: 3-Bromo-4-fluorobenzotrifluoride(CAS DataBase Reference)
• NIST Chemistry Reference: 3-Bromo-4-fluorobenzotrifluoride(68322-84-9)
• EPA Substance Registry System: 3-Bromo-4-fluorobenzotrifluoride(68322-84-9)

Safety Data

• Hazard Codes: C,Xi,Xn
• Statements: 34-36/37/38-20/21/22
• Safety Statements: 45-36/37/39-26-36/37-36-24/25
• RIDADR: UN1760
• WGK Germany: 3
• HazardClass: IRRITANT
• Hazardous Substances Data: 68322-84-9(Hazardous Substances Data)

Usage

Chemical Properties

clear colorless liquid

InChI:InChI=1/C7H3BrF4/c8-5-3-4(7(10,11)12)1-2-6(5)9/h1-3H

Synthetic route

4-Fluorobenzotrifluoride (402-44-8) → 2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9)

Conditions	Yield
With ferric(III) bromide; sulfuric acid; tetrabutylammomium bromide; bromine; lithium bromide at 35 - 45℃; for 6h;	95.94%

2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) + bis(pinacol)diborane (73183-34-3) → 2-[3-bromo-2-fluoro-5-(trifluoromethyl)phenyl]-4,4,5,5-tetramethyl-1,3 ,2-dioxaborolane

Conditions	Yield
With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; cyclopentyl methyl ether; 1,1'-di(pyridin-2-yl)-1,1',3,3'-tetrahydro-2,2'-bibenzo[d][1,3,2]diazaborole at 100℃; for 16h; Schlenk technique; Inert atmosphere;	100%
With bis(1,5-cyclooctadiene)diiridium(I) dichloride; 1-(4,4'-di-tert-butyl-[2,2'-bipyridin]-6-yl)-2-(dimethyl(phenyl)silyl)-2,3-dihydro-1H-benzo[d][1,3,2]diazaborole Inert atmosphere; Schlenk technique; Sealed tube;	98%
With (1,5-cyclooctadiene)(methoxy)iridium(l) dimer; 4,4'-di-tert-butyl-2,2'-bipyridine In tetrahydrofuran at 80℃; for 24h; Inert atmosphere;

2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) + 2,4-dimethylbenzeneboronic acid (55499-44-0) → 2'-fluoro-2,4-dimethyl-5'-(trifluoromethyl)-1,1'-biphenyl

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,2-dimethoxyethane; water at 80℃; for 8h; Suzuki-Miyaura Coupling; Inert atmosphere;	99%

2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) + 4-tert-butylphenylboronic acid (123324-71-0) → 4'-(tert-butyl)-2-fluoro-5-(trifluoromethyl)-1,1'-biphenyl

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,2-dimethoxyethane; water at 80℃; for 12h; Suzuki-Miyaura Coupling; Inert atmosphere;	98%

2-Iodophenol (533-58-4) + 2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) → 2-bromo-1-(2-iodophenoxy)-4-(trifluoromethyl)benzene (1325219-84-8)

Conditions	Yield
With potassium carbonate In dimethyl sulfoxide at 95℃; for 20h; Inert atmosphere;	95%
With potassium carbonate In dimethyl sulfoxide at 95℃; for 48h; Sealed tube;	91%

isovanillin (621-59-0) + 2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) → 3-(2-bromo-4-trifluoromethyl-phenoxy)-4-methoxy-benzaldehyde (1188267-41-5)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 20 - 140℃; for 5.25h; Inert atmosphere;	94%

3-[4-(3-hydroxy-4-methyl-phenoxy)-2-methyl-phenyl]propionic acid ethyl ester (850793-73-6) + 2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) → 3-{4-[3-(2-bromo-4-trifluoromethyl-phenoxy)-4-methyl-phenoxy]-2-methyl-phenyl}propionic acid ethyl ester

Conditions	Yield
With potassium carbonate In dimethyl sulfoxide at 100℃; for 6h; Heating;	88%

2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) + 4-tert-butyl-dimethylsilyloxyphenylboronic acid anhydride (123088-32-4) → 2'-fluoro-5'-trifluoromethyl-biphenyl-4-ol

Conditions	Yield
With sodium carbonate; tetrakis(triphenylphosphine) palladium(0) In 1,2-dimethoxyethane; water at 95℃; Suzuki reaction;	87%

2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) → 2-bromo-4-(trifluoromethyl)phenol (81107-97-3)

Conditions	Yield
With acetylhydroxamic acid; potassium carbonate In dimethyl sulfoxide at 80℃; for 18h; Sealed tube;	86%

3-[4-(5-hydroxy-2-methyl-phenoxy)-2-methyl-phenyl]propionic acid ethyl ester (850793-70-3) + 2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) → 3-{4-[5-(2-bromo-4-trifluoromethyl-phenoxy)-2-methyl-phenoxy]-2-methyl-phenyl}propionic acid ethyl ester

Conditions	Yield
With potassium carbonate In dimethyl sulfoxide at 100℃; for 6h; Heating;	81%

3-[4-(3-hydroxy-phenoxy)-2-methyl-phenyl]propionic acid methyl ester (850793-81-6) + 2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) → 3-{4-[3-(2-bromo-4-trifluoromethyl-phenoxy)phenoxy]-2-methyl-phenyl}propionic acid methyl ester

Conditions	Yield
With potassium carbonate In dimethyl sulfoxide at 100℃; for 6h; Product distribution / selectivity; Heating;	81%

2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) + 3-(benzyloxy)-5-hydroxytoluene (36776-44-0) → C21H16BrF3O2 (850793-46-3)

Conditions	Yield
With potassium carbonate In dimethyl sulfoxide at 100℃; for 8h; Product distribution / selectivity; Heating;	81%

2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) + t-butyl 4-hydroxy piperidine-1-carboxylate (109384-19-2) → tert-butyl 4- [2-bromo-4-(trifluoromethyl)phenoxy]piperidine-1-carboxylate

Conditions	Yield
Stage #1: t-butyl 4-hydroxy piperidine-1-carboxylate With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 1h; Stage #2: 2-bromo-1-fluoro-4-(trifluoromethyl)benzene In tetrahydrofuran; mineral oil at 20℃;	81%

2,4-difluorophenol (367-27-1) + 2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) → 2-bromo-1-(2,4-difluorophenoxy)-4-(trifluoromethyl)benzene (183110-63-6)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 16h;	80%
With potassium carbonate In N,N-dimethyl-formamide at 80℃;	80%

3-[4-(3-fluoro-5-hydroxy-phenoxy)-2-methyl-phenyl]propionic acid ethyl ester (850793-29-2) + 2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) → 3-{4-[3-(2-bromo-4-trifluoromethyl-phenoxy)-5-fluoro-phenoxy]-2-methyl-phenyl}propionic acid ethyl ester

Conditions	Yield
With potassium carbonate In dimethyl sulfoxide at 100℃; for 2.5h; Heating;	78%

orcinol (504-15-4) + 2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) → C14H10O2F3Br

Conditions	Yield
With sodium hydroxide In dimethyl sulfoxide at 80 - 86℃;	72%
With sodium hydroxide In dimethyl sulfoxide at 90℃; for 1.66667h;	67%

3-[4-(3-hydroxy-5-methyl-phenoxy)-2-methyl-phenyl]propionic acid ethyl ester (850793-06-5) + 2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) → 3-{4-[3-(2-bromo-4-trifluoromethyl-phenoxy)-5-methyl-phenoxy]-2-methyl-phenyl}propionic acid ethyl ester (850793-07-6)

Conditions	Yield
With potassium carbonate In dimethyl sulfoxide at 100℃; for 5h; Heating;	71%

4,7,10-trioxa-1,13-diaminotridecane (4246-51-9) + 2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) → N,N'-(((oxybis(ethane-2,1-diyl))bis(oxy))bis(propane-3,1-diyl))bis(5-trifluoromethyl-2-fluoroaniline)

Conditions	Yield
Stage #1: 2-bromo-1-fluoro-4-(trifluoromethyl)benzene With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; bis(dibenzylideneacetone)-palladium(0) In 1,4-dioxane Inert atmosphere; Stage #2: 4,7,10-trioxa-1,13-diaminotridecane With sodium t-butanolate In 1,4-dioxane for 8h; Reflux;	70%

2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) + vanillin (121-33-5) → 4-(2-bromo-4-trifluoromethylphenoxy)-3-methoxybenzaldehyde (1055361-85-7)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 150℃; for 5h;	65%

2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → 3-bromo-2-fluoro-5-(trifluoromethyl)benzaldehyde (1236538-66-1)

Conditions	Yield
Stage #1: 2-bromo-1-fluoro-4-(trifluoromethyl)benzene With lithium diisopropyl amide In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran; hexane at -78℃; for 0.25h;	64.6%
Stage #1: 2-bromo-1-fluoro-4-(trifluoromethyl)benzene With lithium diisopropyl amide In tetrahydrofuran; hexane at -70℃; for 0.5h; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran; hexane for 0.25h; Stage #3: With acetic acid In tetrahydrofuran; hexane

2-(Trimethylsilyl)ethanol (2916-68-9) + 2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) → [2-(2-bromo-4-trifluoromethyl-phenoxy)-ethyl]-trimethyl-silane

Conditions	Yield
With potassium hexamethylsilazane In tetrahydrofuran; toluene at 20℃; for 1h;	59%

2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) + C13H19N7 (1400692-21-8) → N-[2-fluoro-5-(trifluoromethyl)phenyl]-1-methyl-3-[4-(4-pyridinylmethyl)-1-piperazinyl]-1H-1,2,4-triazol-5-amine (1400691-89-5)

Conditions	Yield
With caesium carbonate; XPhos; tris-(dibenzylideneacetone)dipalladium(0) In tert-butyl alcohol at 100℃; for 16h; Inert atmosphere;	53%

2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) + recorcinol (108-46-3) → C13H8BrF3O2 + C20H10Br2F6O2

Conditions	Yield
With sodium hydroxide In dimethyl sulfoxide at 50℃;	A 52.6% B 12%

pyrrolidin-3-ol (40499-83-0) + 2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) → 1-[2-fluoro-5-(trifluoromethyl)phenyl]pyrrolidin-3-ol (1198181-21-3)

Conditions	Yield
With caesium carbonate; palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In toluene at 85℃; for 16h; Inert atmosphere;	49%
With caesium carbonate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; palladium diacetate In toluene at 85℃; for 16h; Inert atmosphere;	49%

(2S)-((2S)-cyanopyrrolidine-1-carbonyl)-5R-hydroxymethyl-pyrrolidine-1-carboxylic acid tert-butyl ester (847943-39-9) + 2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) → C23H27BrF3N3O4 (847943-57-1)

Conditions	Yield
With sodium hydride In DMF (N,N-dimethyl-formamide) at 20℃; for 1h;	40%
With sodium hydride In DMF (N,N-dimethyl-formamide) at 20℃; for 1h;	40%

2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) + N-butylamine (109-73-9) → 2-bromo-N-butyl-4-(trifluoromethyl)benzeneamine (1048344-63-3)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 60℃;	34%

carbon dioxide (124-38-9) + 2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) → 3-bromo-2-fluoro-5-(trifluoromethyl)benzoic acid

Conditions	Yield
Stage #1: 2-bromo-1-fluoro-4-(trifluoromethyl)benzene With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78℃; for 3h; Stage #2: carbon dioxide In tetrahydrofuran; hexane at 20℃;	29%

2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) + C13H19N7O (1400692-13-8) → N-[2-fluoro-5-(trifluoromethyl)phenyl]-1-methyl-3-{4-[(6-methyl-4-pyrimidinyl)oxy]-1-piperidinyl}-1H-1,2,4-triazol-5-amine (1400691-83-9)

Conditions	Yield
With caesium carbonate; XPhos; tris-(dibenzylideneacetone)dipalladium(0) In tert-butyl alcohol at 100℃; for 16h; Inert atmosphere;	28%

2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) + C12H17N7 (1400692-17-2) + C12H17N7 (1400692-18-3) → C19H19F4N7 (1400691-86-2) + N-[2-fluoro-5-(trifluoromethyl)phenyl]-1-methyl-3-[4-(4-pyridinyl)-1-piperazinyl]-1H-1,2,4-triazol-5-amine (1400691-85-1)

Conditions	Yield
With caesium carbonate; XPhos; tris-(dibenzylideneacetone)dipalladium(0) In tert-butyl alcohol at 100℃; for 16h; Inert atmosphere;	A 20% B 28%

2-bromo-1-fluoro-4-(trifluoromethyl)benzene (68322-84-9) + 1,N5,N5-tris-(4-methoxybenzyl)-1H-[1,2,4]triazole-3,5-diamine (1533425-28-3) → N3-(2-fluoro-5-trifluoromethylphenyl)-1,N5,N5-tris(4-methoxybenzyl)-1H-[1,2,4]triazole-3,5-diamine (1533425-38-5)

Conditions	Yield
With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; tert-butyl XPhos In toluene at 110℃; under 760.051 Torr; for 3h; Inert atmosphere;	28%

Upstream product

• 402-44-8 4-Fluorobenzotrifluoride 

Downstream Products

• 850793-46-3 C₂₁H₁₆BrF₃O₂ 
• 847943-57-1 C₂₃H₂₇BrF₃N₃O₄ 
• 1160065-73-5 (3,5-bis-tpfluoromethyl-benzyl)-[(3S,5R)-1-(2-bromo-4-trifluoromethyl-phenyl)-5-ethyl-pyrrolidin-3-yl]-[5-(1-methyl-1H-pyrazol-4-yl)-pypmidin-2-yl]-amine 
• 1188267-41-5 3-(2-bromo-4-trifluoromethyl-phenoxy)-4-methoxy-benzaldehyde 
• 1188446-61-8 ((2-fluoro-5-(trifluoromethyl)phenyl)ethynyl)trimethylsilane 
• 1236538-66-1 3-bromo-2-fluoro-5-(trifluoromethyl)benzaldehyde 
• 1198181-71-3 C₁₃H₁₃F₄NO₃ 
• 1198181-21-3 1-[2-fluoro-5-(trifluoromethyl)phenyl]pyrrolidin-3-ol 
• 1055361-54-0 5-[4-(2-bromo-4-trifluoromethylphenoxy)-3-methoxybenzylidene]thiazolidine-2,4-dione 
• 1055361-85-7 4-(2-bromo-4-trifluoromethylphenoxy)-3-methoxybenzaldehyde 

Relevant articles and documents

A process for preparing 2 - bromo - 5 - fluoro-toluene method

The invention discloses a method for preparing 2-bromine-5-fluorobenzotrifluoride. According to the preparation method, fluorobenzotrifluoride serves as a raw material, under the condition of concentrated sulfuric acid and composite catalysts, bromine is stirred and added dropwise, and 2-bromine-5-fluorobenzotrifluoride is obtained after separation and purification. The yield reaches over 91.1%, the reaction conversion rate is larger than 99%, and selectivity is 92-95%. The raw material applied in the reaction process is convenient to purchase, production cost is low, waste acid obtained in the reaction process can be recycled, post-processing is easy, and the whole technology does not generate a large amount of wastewater containing salt and organic matter. Economic benefits and social benefits are good.