76283-09-5

Basic information

• Product Name: 4-Bromo-2-fluorobenzyl bromide
• Synonyms: 4-BROMO-2-FLUOROBENZYL BROMIDE;4-BROMO-1-(BROMOMETHYL)-2-FLUORO-BENZENE;2-FLUORO-4-BROMOBENZYL BROMIDE;4-Bromo-1-Fluorobenzyl Bromide;4,α-dibromo-2-fluorotoluene;à,4-dibromo-2-fluorotoluene;4-Bromo-2-fluorobenzyl bromide 97%;4-Bromo-2-fluorobenzylbromide97%
• CAS NO: 76283-09-5
• Molecular Formula: C₇H₅Br₂F
• Molecular Weight: 267.92
• EINECS: 278-412-7
• Product Categories: Fluoro-contained benzyl bromide series;Aromatic Halides (substituted);Fluorine series;alkyl bromide| alkyl Fluorine
• Mol File: 76283-09-5.mol
• Article Data: 9

Chemical Properties

• Melting Point: 33-36 °C(lit.)
• Boiling Point: 126 °C (19 mmHg)
• Flash Point: 126°C/9mm
• Appearance: White to off-white/Low Melting Solid
• Density: 1.9094 (rough estimate)
• Vapor Pressure: 0.0281mmHg at 25°C
• Refractive Index: 1.5770 (estimate)
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• Solubility: soluble in Methanol
• Sensitive: Lachrymatory
• BRN: 4307676
• CAS DataBase Reference: 4-Bromo-2-fluorobenzyl bromide(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Bromo-2-fluorobenzyl bromide(76283-09-5)
• EPA Substance Registry System: 4-Bromo-2-fluorobenzyl bromide(76283-09-5)

Safety Data

• Hazard Codes: C
• Statements: 22-34-52/53-20/21/22
• Safety Statements: 26-36/37/39-45-61
• RIDADR: UN 2923 8/PG 3
• WGK Germany: 2
• HazardClass: 8
• PackingGroup: III
• Hazardous Substances Data: 76283-09-5(Hazardous Substances Data)

Usage

Chemical Properties

white to light yellow crystal powder

Uses

4-Bromo-2-fluorobenzyl bromide may be used in the synthesis of 1-(2-fluoro-4-(1-methyl-1H-pyrazol-4-yl)benzyl)indoline-2,3-dione.

General Description

4-Bromo-2-fluorobenzyl bromide is a substituted benzyl bromide. Its density is 1.9094g/ml at 25°C.

InChI:InChI=1/C7H5Br2F/c8-4-5-1-2-6(9)3-7(5)10/h1-3H,4H2

Synthetic route

4-bromo-2-fluorobenzyl alcohol (188582-62-9) → 4-bromo-2-fluorobenzyl bromide (76283-09-5)

Conditions	Yield
With hydrogen bromide at 100℃; for 0.166667h;	91%

2-fluoro-4-bromotoluene (51436-99-8) → 4-bromo-2-fluorobenzyl bromide (76283-09-5)

Conditions	Yield
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane at 100℃; for 13h;	89%
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane at 100℃; for 13h;	89%
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane for 4h; Reflux; Inert atmosphere;	53%

4-bromo-2-fluorobenzaldehyde (57848-46-1) → 4-bromo-2-fluorobenzyl bromide (76283-09-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: sodium tetrahydroborate / methanol / 0.5 h / 20 °C 2: hydrogen bromide / 0.17 h / 100 °C View Scheme

sodium cyanide (773837-37-9) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → (4-bromo-2-fluorophenyl)acetonitrile (114897-91-5)

Conditions	Yield
In ethanol; water at 100℃; for 8.5h;	100%
In DMF (N,N-dimethyl-formamide); water at 70℃; for 1h;	99%
In ethanol at 60℃; for 12h; Solvent; Temperature; Inert atmosphere;	99%

4-bromo-2-fluorobenzyl bromide (76283-09-5) + dimethyl amine (124-40-3) → N,N-dimethyl-4-bromo-2-fluorobenzylamine (1159976-88-1)

Conditions	Yield
With potassium carbonate In water at 0 - 20℃; for 0.166667h;	100%

methyl 3-hydroxybenzoate (19438-10-9) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → 3-(4-bromo-2-fluoro-benzyloxy)-benzoic acid methyl ester

Conditions	Yield
Stage #1: methyl 3-hydroxybenzoate With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: 4-bromo-2-fluorobenzyl bromide In N,N-dimethyl-formamide at 20℃;	99%
Stage #1: methyl 3-hydroxybenzoate With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: 4-bromo-2-fluorobenzyl bromide In N,N-dimethyl-formamide at 80℃;

sodium cyanide (143-33-9) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → (4-bromo-2-fluorophenyl)acetonitrile (114897-91-5)

Conditions	Yield
In water; N,N-dimethyl-formamide at 70℃; for 1h;	99%
In dimethyl sulfoxide at 20℃; for 4h;	96%
In DMF (N,N-dimethyl-formamide); water at 70℃; for 3h;	46%
In water; N,N-dimethyl-formamide at 70℃; for 1h;

2-chloro-1H-benzoimidazole (4857-06-1) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → 1-(4-bromo-2-fluoro-benzyl)-2-chloro-1H-benzoimidazole (388574-68-3)

Conditions	Yield
Stage #1: 2-chloro-1H-benzoimidazole With sodium hydride In N,N-dimethyl-formamide Stage #2: 4-bromo-2-fluorobenzyl bromide In N,N-dimethyl-formamide at 20℃; Further stages.;	97%

ethyl 2-(7-chloro-1,2,3,4-tetrahydro-2,4-dioxoquinazoline-1-yl)acetate (112733-45-6) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → ethyl 2-[3-(4-bromo-2-fluorobenzyl)-7-chloro-1,2,3,4-tetrahydro-2,4-dioxoquinazoline-1-yl)acetate (112733-28-5)

Conditions	Yield
With potassium carbonate; acetic acid In methanol; water; acetone	97%
With potassium carbonate In methanol; acetic acid; acetone	96%
With potassium carbonate In acetone at 20℃; for 5h; Reflux; Large scale;	95.1%
With potassium carbonate; acetic acid In methanol; water; acetone

2-pyrrolidinon (616-45-5) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → 1-[(4-bromo-2-fluorophenyl)methyl]-2-pyrrolidinone (1022931-60-7)

Conditions	Yield
Stage #1: 2-pyrrolidinon With sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.25h; Stage #2: 4-bromo-2-fluorobenzyl bromide In N,N-dimethyl-formamide at 20℃;	97%
Stage #1: 2-pyrrolidinon With sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.25h; Stage #2: 4-bromo-2-fluorobenzyl bromide In N,N-dimethyl-formamide at 20℃;	85%
Stage #1: 2-pyrrolidinon With sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; for 0.25h; Inert atmosphere; Stage #2: 4-bromo-2-fluorobenzyl bromide In N,N-dimethyl-formamide; mineral oil at 20℃; for 5h;	85%
Stage #1: 2-pyrrolidinon With sodium hydride In N,N-dimethyl-formamide; mineral oil for 0.5h; Inert atmosphere; Stage #2: 4-bromo-2-fluorobenzyl bromide In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; Inert atmosphere;	82%

C17H17N3O2 (1415406-28-8) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → 1-(2-(4-bromo-2-fluorobenzyloxy)-2-(4-methoxyphenyl)ethyl)-4-phenyl-1H-1,2,3-triazole (1415406-43-7)

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide for 2h;	97%

4-hydroxy-3-methoxybenzoic acid methyl ester (3943-74-6) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → 4-(4-bromo-2-fluoro-benzyloxy)-3-methoxy-benzoic acid methyl ester

Conditions	Yield
Stage #1: 4-hydroxy-3-methoxybenzoic acid methyl ester With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: 4-bromo-2-fluorobenzyl bromide In N,N-dimethyl-formamide at 20℃;	96%

4-bromo-2-fluorobenzyl bromide (76283-09-5) → (4-bromo-2-fluorophenyl)acetonitrile (114897-91-5)

Conditions	Yield
In dimethyl sulfoxide	96%
With potassium cyanide In ethanol; water; ethyl acetate	84%
With potassium cyanide In ethanol	60%

ethyl 2-(7-chloro-1,2,3,4-tetrahydro-2,4-dioxoquinazoline-1-yl)acetate (112733-45-6) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → zenarestat

Conditions	Yield
With hydrogenchloride; potassium hydroxide; potassium carbonate In water; acetone	96%
Multi-step reaction with 2 steps 1: potassium carbonate / acetone / 5 h / 20 °C / Reflux; Large scale 2: sodium hydroxide / methanol / 45 h / 30 - 40 °C / Reflux; Large scale View Scheme

N-(diphenylmethylene)glycine tert-butyl ester (81477-94-3) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → tert-butyl 3-(4-bromo-2-fluorophenyl)-2-((diphenylmethylene)amino)propanoate (1040528-76-4)

Conditions	Yield
With tetrabutylammomium bromide; potassium hydroxide In toluene at 120℃; for 6h;	96%
Stage #1: N-(diphenylmethylene)glycine tert-butyl ester With lithium diisopropyl amide In tetrahydrofuran at -78℃; for 0.583333h; Stage #2: 4-bromo-2-fluorobenzyl bromide In tetrahydrofuran at -78℃; for 0.583333h;	33%
Stage #1: N-(diphenylmethylene)glycine tert-butyl ester With lithium diisopropyl amide In tetrahydrofuran at -78℃; for 0.416667h; Stage #2: 4-bromo-2-fluorobenzyl bromide In tetrahydrofuran at -78 - 20℃; for 3.58333h; Stage #3: With water; ammonium chloride In tetrahydrofuran

((1R,2R)-2-(1-(5-(methoxymethyl)pyrimidin-2-yl)piperidin-4-yl)cyclopropyl)methanol (1416366-90-9) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → 2-(4-((1R,2R)-2-(((4-bromo-2-fluorobenzyl)oxy)methyl)cyclopropyl)piperidin-1-yl)-5-(methoxymethyl)pyrimidine (1416366-91-0)

Conditions	Yield
Stage #1: ((1R,2R)-2-(1-(5-(methoxymethyl)pyrimidin-2-yl)piperidin-4-yl)cyclopropyl)methanol With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.0833333h; Stage #2: 4-bromo-2-fluorobenzyl bromide In N,N-dimethyl-formamide at 0 - 20℃;	96%
Stage #1: ((1R,2R)-2-(1-(5-(methoxymethyl)pyrimidin-2-yl)piperidin-4-yl)cyclopropyl)methanol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 0.0833333h; Stage #2: 4-bromo-2-fluorobenzyl bromide In N,N-dimethyl-formamide; mineral oil at 0 - 20℃;	96%

saccharin sodium salt (128-44-9) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → 2-<(4-bromo-2-fluorophenyl)methyl>benzoisothiazolin-3-one 1,1-dioxide (127511-40-4)

Conditions	Yield
In N,N-dimethyl-formamide at 100℃; for 1h;	95%

Dimethyl 5-hydroxyisophthalate (13036-02-7) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → 5-(4-bromo-2-fluoro-benzyloxy)-isophthalic acid dimethyl ester

Conditions	Yield
Stage #1: Dimethyl 5-hydroxyisophthalate With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: 4-bromo-2-fluorobenzyl bromide In N,N-dimethyl-formamide at 20℃;	95%

4-bromo-2-fluorobenzyl bromide (76283-09-5) + methyl salicylate (119-36-8) → 2-(4-bromo-2-fluoro-benzyloxy)-benzoic acid methyl ester

Conditions	Yield
Stage #1: methyl salicylate With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: 4-bromo-2-fluorobenzyl bromide In N,N-dimethyl-formamide at 20℃;	95%

potassium cyanide (151-50-8) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → (4-bromo-2-fluorophenyl)acetonitrile (114897-91-5)

Conditions	Yield
In ethanol; water at 60℃; for 2h;	94%
In ethanol; water at 60℃; for 2h;	94%
In ethanol; water at 60℃; for 2h;	93%
In DMF (N,N-dimethyl-formamide); water at 40℃; for 3h;	87%
In ethanol; water at 20℃;

(S)‐2‐nitro‐6,7‐dihydro‐5H‐imidazo[2,1‐b][1,3]oxazin‐6‐ol (187235-08-1) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → (6S)-6-[(4-bromo-2-fluorobenzyl)oxy]-2-nitro-6,7-dihydro-5H-imidazo[2,1-b][1,3]oxazine (1188335-21-8)

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃; Inert atmosphere;	93%
With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 3h; Inert atmosphere;	93%
With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃;	93%
With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃;

C17H16N4O3 + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → 1-(2-(4-bromo-2-fluorobenzyloxy)-2-(3-nitrophenyl)ethyl)-4-phenyl-1H-1,2,3-triazole (1415406-41-5)

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide for 2h;	93%

methanol (67-56-1) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → 4-bromo-2-fluoro-1-(methoxymethyl)benzene (95068-02-3)

Conditions	Yield
With sodium methylate at 20℃; for 4.5h;	93%

morpholine (110-91-8) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → 4-[(4-bromo-2-fluorophenyl)methyl]morpholine (338454-98-1)

Conditions	Yield
Stage #1: morpholine for 0.166667h; Stage #2: 4-bromo-2-fluorobenzyl bromide at 60℃; for 8h;	92.95%
With potassium iodide In N,N-dimethyl-formamide at 60℃; for 13h;	45%
With potassium iodide In N,N-dimethyl-formamide at 60℃; for 13h;	45%
In acetonitrile at 20℃; for 16h;

3-piperidin-3-yl-1H-indole-2-carboxylic acid ethyl ester (1268716-42-2) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → 3-[1-(4-bromo-2-fluoro-benzyl)-piperidin-3-yl]-1H-indole-2-carboxylic acid ethyl ester (1268716-44-4)

Conditions	Yield
With triethylamine In 1,2-dichloro-ethane at 20℃; for 4h;	92.1%
With triethylamine In 1,2-dichloro-ethane at 20℃; for 4h;

2-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2H-indazole (885698-95-3) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → 4-(4-(bromomethyl)-3-fluorophenyl)-2-methyl-2H-indazole

Conditions	Yield
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium carbonate In 1,2-dimethoxyethane at 50℃; for 1h; Microwave irradiation;	92%

4-bromo-2-fluorobenzyl bromide (76283-09-5) + 4-Methoxybenzyl alcohol (105-13-5) → 4-bromo-2-fluoro-1-{[(4-methoxybenzyl)oxy]methyl}benzene (924312-28-7)

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃;	91%

tributyltin chloride (1461-22-9) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → (o-F,p-Br-benzyl)tributylstannane (174473-26-8)

Conditions	Yield
With Zn; NH4Cl In tetrahydrofuran; water air; addn. of organotin (1 equiv.) to suspension of Zn-powder (2 equivs.) in satd. soln. of NH4Cl in H2O:THF, dropwise addn. of benzyl bromide (2 equivs.) with rate maintaining gentle reflux, stirring with cooling toroom temp. for 30 min; sepn. of org. layer, evapn., distillation (vac.); elem. anal.;	91%

tert-butyl (1,3-cis)-N-(3-hydroxycyclobutyl)carbamate (389890-43-1) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → tert-butyl ((1S,3S)-3-((4-bromo-2-fluorobenzyl)oxy)cyclobutyl)carbamate

Conditions	Yield
Stage #1: tert-butyl (1,3-cis)-N-(3-hydroxycyclobutyl)carbamate With sodium hydride In tetrahydrofuran; mineral oil at 0℃; for 1h; Stage #2: 4-bromo-2-fluorobenzyl bromide In tetrahydrofuran; mineral oil at 20℃; for 8h;	91%

4-bromo-2-fluorobenzyl bromide (76283-09-5) + O6-Demethyl-Donepezil (120013-56-1) → 2-[(1-benzylpiperidin-4-yl)methyl]-6-[(4-bromo-2-fluorobenzyl)oxy-5-methoxy-2,3-dihydroinden-1-one]

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 20℃;	91%

pyrrolidine (123-75-1) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → 1-(4-bromo-2-fluorobenzyl)pyrrolidine

Conditions	Yield
Stage #1: pyrrolidine; 4-bromo-2-fluorobenzyl bromide In acetonitrile at 10 - 20℃; for 4h; Stage #2: With sodium carbonate In water; acetonitrile	90%
In acetonitrile at 10 - 20℃; for 4h;	90%
Stage #1: pyrrolidine With potassium carbonate In acetone at 20℃; for 0.25h; Stage #2: 4-bromo-2-fluorobenzyl bromide In acetone at 20℃; for 1.33h;	3.4 g

4-cyclopropyl-1-oxa-4,9-diazaspiro[5.5]undecan-3-one hydrochloride (1375107-47-3) + 4-bromo-2-fluorobenzyl bromide (76283-09-5) → 9-[(4-bromo-2-fluorophenyl)methyl]-4-cyclopropyl-1-oxa-4,9-diazaspiro[5.5]undecan-3-one (1429790-71-5)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In acetonitrile at 125℃; for 0.416667h; Microwave irradiation;	90%
With N-ethyl-N,N-diisopropylamine In acetonitrile at 125℃; for 0.333333h; Microwave irradiation;	6.121 g

Upstream product

• 188582-62-9 4-bromo-2-fluorobenzyl alcohol 
• 57848-46-1 4-bromo-2-fluorobenzaldehyde 
• 51436-99-8 2-fluoro-4-bromotoluene 

Downstream Products

• 159547-10-1 4-(4-bromo-2-fluorobenzyl)-5-n-butyl-2-[2-chloro-5-(methoxycarbonyl)phenyl]-2,4-dihydro-3H-1,2,4-triazol-3-one 
• 114897-91-5 (4-bromo-2-fluorophenyl)acetonitrile 
• 1247406-52-5 4-bromo-1-cyclobutoxymethyl-2-fluoro-benzene 
• 112733-28-5 ethyl 2-[3-(4-bromo-2-fluorobenzyl)-7-chloro-1,2,3,4-tetrahydro-2,4-dioxoquinazoline-1-yl)acetate 
• 112733-06-9 zenarestat 
• 1310251-19-4 4-cyclobutoxymethyl-3-fluoro-benzoic acid 
• 174473-26-8 (o-F,p-Br-benzyl)tributylstannane 
• 1073716-50-3 C₂₇H₂₃BrFN₃O₂ 
• 676445-24-2 N-(4-bromo-2-fluorobenzyl)-4-methyl-3-nitropyridin-2-amine 
• 1188335-21-8 (6S)-6-[(4-bromo-2-fluorobenzyl)oxy]-2-nitro-6,7-dihydro-5H-imidazo[2,1-b][1,3]oxazine 
• 1213565-77-5 3-[(4-bromo-2-fluorophenyl)methyl]-4-methyl-5-(1-methylethyl)-2H-1,3-oxazine-2,6(3H)-dione 
• 875629-56-4 [4-(4-bromo-2-fluoro-benzylamino)-phenyl]-acetic acid 
• 875629-55-3 [3-(4-bromo-2-fluoro-benzylamino)-phenyl]-acetic acid 

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