77771-02-9

Basic information

• Product Name: 3-Bromo-4-fluorobenzaldehyde
• Synonyms: 3-BROMO-4-FLUOROBENZALDEHYDE;LABOTEST-BB LT01143325;3-Bromo-4-fluorobenzaldehyde 98%;3-Bromo-4-fluorobenzaldehyde98%;Benzaldehyde, 3-bromo-4-fluoro-;3-Bromo-4-fluorobenzaldehyde,99%;3-Bromo-4-fluorobenz;3 - broMine - 4 - fluoro benzaldehyde
• CAS NO: 77771-02-9
• Molecular Formula: C₇H₄BrFO
• Molecular Weight: 203.01
• EINECS: 278-764-1
• Product Categories: Fluorin-contained benzaldehyde series;Fluorobenzene;Aromatic Aldehydes & Derivatives (substituted);Benzaldehyde;Miscellaneous;Adehydes, Acetals & Ketones;Bromine Compounds;Fluorine Compounds;Aldehydes;C7;Carbonyl Compounds;Benzaldehyde series;Halogenated Heterocycles ,Pyrans
• Mol File: 77771-02-9.mol
• Article Data: 15

Chemical Properties

• Melting Point: 31-33 °C(lit.)
• Boiling Point: 138-139 °C2.5 mm Hg(lit.)
• Flash Point: >230 °F
• Appearance: White to light yellow/Low Melting Solid
• Density: 1.6698 (rough estimate)
• Vapor Pressure: 0.004mmHg at 25°C
• Refractive Index: 1.574
• Storage Temp.: Keep in dark place,Sealed in dry,Room Temperature
• Water Solubility: INSOLUBLE
• Sensitive: Air Sensitive
• BRN: 5806226
• CAS DataBase Reference: 3-Bromo-4-fluorobenzaldehyde(CAS DataBase Reference)
• NIST Chemistry Reference: 3-Bromo-4-fluorobenzaldehyde(77771-02-9)
• EPA Substance Registry System: 3-Bromo-4-fluorobenzaldehyde(77771-02-9)

Safety Data

• Hazard Codes: Xn,Xi
• Statements: 22-36/37/38
• Safety Statements: 26-36-37/39
• WGK Germany: 2
• TSCA: Yes
• HazardClass: IRRITANT
• Hazardous Substances Data: 77771-02-9(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 77771-02-9 differently. You can refer to the following data:
1. 3-Bromo-4-fluorobenzaldehyde can be used for pest control.
2. 3-Bromo-4-fluorobenzaldehyde was used in the synthesis of 4-fluoro-3-phenoxybenzoic acid-glycine. It was also used in the synthesis of Schiff bases of 4-nitroaniline/ 2,4-dinitroaniline/3,4-dichloroaniline/4-methoxy-3-nitro aniline via ultrasound irradiation method.

InChI:InChI=1/C7H4BrClO/c8-6-3-5(4-10)1-2-7(6)9/h1-4H

Synthetic route

4-fluorobenzaldehyde (459-57-4) → 3-bromo-4-fluorobenzaldehyde (77771-02-9)

Conditions	Yield
With sulfuric acid; sulfur trioxide; bromine; iodine; zinc dibromide at 30 - 40℃; for 5.91667h; Product distribution / selectivity; Inert atmosphere;	97%
With hydrogenchloride; sodium hypochlorite solution; sodium bromide In dichloromethane; water at 20 - 25℃; for 1.5h; Irradiation;	91.9%
With bromine; aluminium trichloride In dichloromethane

3-bromo-4-fluoro-benzyl alcohol (77771-03-0) → 3-bromo-4-fluorobenzaldehyde (77771-02-9)

Conditions	Yield
With dipotassium peroxodisulfate at 55℃; for 0.25h; Ionic liquid;	87%
With pyridine; hydrogenchloride In dichloromethane
With potassium dichromate; sulfuric acid In dichloromethane; water
With sodium hydroxide; nitric acid In water; toluene

3-bromo-4-hydroxybenzylaldehyde (2973-78-6) → 3-bromo-4-fluorobenzaldehyde (77771-02-9)

Conditions	Yield
With Cl(1-)*C27H36ClN2(1+)*Cs(1+)*F(1-) In toluene at 23 - 110℃; for 24h; Inert atmosphere;	61%

2-bromo-1-fluoro-4-vinyl-benzene (701914-09-2) → 2-azido-1-(3-bromo-4-fluorophenyl)ethanone + 3-bromo-4-fluorobenzaldehyde (77771-02-9)

Conditions	Yield
With trimethylsilylazide; oxygen; copper(II) bis(trifluoromethanesulfonate) at 20℃; for 18h; Overall yield = 75 %Spectr.;	A 54% B n/a

4-fluorobenzaldehyde (459-57-4) + 1,2-dichloro-ethane (107-06-2) → 3-bromo-4-fluorobenzaldehyde (77771-02-9)

Conditions	Yield
With bromine; aluminium trichloride

3-bromo-4-fluorobenzaldehyde (77771-02-9) → 3-bromo-4-fluorobenzoic acid (1007-16-5)

Conditions	Yield
With sodium chlorite; sodium dihydrogenphosphate; 2-methyl-but-2-ene In tetrahydrofuran; water; tert-butyl alcohol at 20℃; for 3h;	100%
With oxygen; Langlois reagent In acetonitrile at 25℃; under 760.051 Torr; for 12h; Irradiation; Green chemistry;	96%
With sodium chlorite In tetrahydrofuran; water at 50℃; for 5h;	91%

copper(l) cyanide + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → 2-fluoro-5-formylbenzonitrile (218301-22-5)

Conditions	Yield
Stage #1: copper(l) cyanide; 3-bromo-4-fluorobenzaldehyde In 1-methyl-pyrrolidin-2-one at 170℃; for 24h; Stage #2: With celite In 1-methyl-pyrrolidin-2-one at 80℃; for 1h;	100%
In 1-methyl-pyrrolidin-2-one at 170℃; for 24h;	100%
In 1-methyl-pyrrolidin-2-one at 170℃;	65.4%
In 1-methyl-pyrrolidin-2-one at 170℃; for 24h;	52%
In 1-methyl-pyrrolidin-2-one at 25 - 170℃;

3-bromo-4-fluorobenzaldehyde (77771-02-9) + 2,2-dimethoxyethylamine (22483-09-6) → N-[(3-bromo-4-fluoro-phenyl)methyl]-2,2-dimethoxy-ethanamine (1036712-61-4)

Conditions	Yield
Stage #1: 3-bromo-4-fluorobenzaldehyde; 2,2-dimethoxyethylamine In toluene at 20℃; Inert atmosphere; Stage #2: With sodium tetrahydroborate In methanol at 20℃; for 2h; Inert atmosphere;	100%

acetoacetamido (5977-14-0) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → 6-(3-bromo-4-fluorophenyl)-5-cyano-3,6-dihydro-4-methyl-2-oxo-(2H)-pyrimidine (464192-73-2)

Conditions	Yield
With urea	99%

3-fluorobenzene-1,2-diamine (18645-88-0) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → C14H9BrF2N2

Conditions	Yield
With C23H3BF16N2O In toluene at 25℃; for 3h; Green chemistry;	99%

4-Chloro-1,2-phenylenediamine (95-83-0) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → C14H9BrClFN2

Conditions	Yield
With C23H3BF16N2O In toluene at 25℃; for 3h; Green chemistry;	99%

3-bromo-4-fluorobenzaldehyde (77771-02-9) + 5-(aminomethyl)-2-chloropyridine (97004-04-1) → C13H11BrClFN2

Conditions	Yield
Stage #1: 3-bromo-4-fluorobenzaldehyde; 5-(aminomethyl)-2-chloropyridine In methanol at 20℃; Stage #2: With sodium tetrahydroborate In methanol at 20℃; for 0.333333h;	98.1%

di-tert-butyl dicarbonate (24424-99-5) + 2-(tributylstannyl)furan (118486-94-5) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → 4-fluoro-3-(furan-2-yl)-benzaldehyde (359867-36-0)

Conditions	Yield
tetrakis(triphenylphosphine)palladium (0) In diethyl ether; N,N-dimethyl-formamide	98%
tetrakis(triphenylphosphine)palladium (0) In diethyl ether; N,N-dimethyl-formamide	98%

1.3-propanedithiol (109-80-8) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → 2-(3-bromo-4-fluorophenyl)-1,3-dithiane (1035267-53-8)

Conditions	Yield
With boron trifluoride diethyl etherate In dichloromethane at 0℃; for 1.5h;	98%

3-bromo-4-fluorobenzaldehyde (77771-02-9) + phosphonic acid diethyl ester (762-04-9) + 4-amino-4'-chlorodiphenyl ether (101-79-1) → C23H23BrClFNO4P

Conditions	Yield
With ZnBr2/SiO2 In neat (no solvent) for 0.0833333h; Kabachnik-Fields Reaction; Microwave irradiation; Green chemistry; chemoselective reaction;	98%

3-bromo-4-fluorobenzaldehyde (77771-02-9) → 3-bromo-4-fluorobenzonitrile (79630-23-2)

Conditions	Yield
With ammonium hydroxide; iodine In tetrahydrofuran at 5 - 20℃; Solvent; Reagent/catalyst;	97.5%

ethane-1,2-dithiol (540-63-6) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → 2-(3-bromo-4-fluorophenyl)-1,3-dithiolane (1262048-10-1)

Conditions	Yield
With iodine In dichloromethane at 20℃; for 1h;	97%

dimethyl (3-oxo-1,3-dihydroisobenzofuran-1-yl)phosphonate (61260-15-9) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → 2-fluoro-5-(3-oxo-3H-isobenzofuran-1-ylmethylene)-1-bromobenzene (63964-50-1)

Conditions	Yield
With triethylamine In tetrahydrofuran at 30℃; for 6h; Solvent;	97%
With triethylamine In dichloromethane at 6 - 20℃; for 4h;	95%
With triethylamine In tetrahydrofuran at 0 - 20℃;	78.5%

2-(2,5-dimethylthiazol-4-yl)acetohydrazide + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → (E)-N'-(3-bromo-4-fluorobenzylidene)-2-(2,5-dimethyl-1,3-thiazol-4-yl)acetohydrazide

Conditions	Yield
With acetic acid In ethanol	97%

S-tert-butylsulfinimide (146374-27-8) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → (E)-N-tert-butanesulfinyl 3-bromo-4-fluorophenyl-aldimine

Conditions	Yield
With titanium(IV) tetraethanolate In tetrahydrofuran at 65℃; for 12h;	96%
With titanium(IV) tetraethanolate In tetrahydrofuran at 65℃; for 12h;	96%

4,4-ethylenedioxy-piperidine (177-11-7) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → 3-bromo-4-(1,4-dioxa-8-aza-spiro[4.5]dec-8-yl)-benzaldehyde

Conditions	Yield
With potassium carbonate In 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; acetonitrile	96%

3-bromo-4-fluorobenzaldehyde (77771-02-9) + phosphonic acid diethyl ester (762-04-9) + malononitrile (109-77-3) → [1-(3-bromo-4-fluorophenyl)-2,2-dicyanoethyl]phosphonic acid diethyl ester (1537917-45-5)

Conditions	Yield
With 1,4-diazabicyclo[2.2.2]octane hydroacetate In neat (no solvent) at 25℃; for 0.416667h; Green chemistry;	96%

N-methoxylamine hydrochloride (593-56-6) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → 3-bromo-4-fluorobenzaldehyde O-methyloxime (646051-34-5)

Conditions	Yield
	95%

sodium chlorite (7758-19-2) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → 3-bromo-4-fluoroaniline (656-64-4)

Conditions	Yield
With hydrogenchloride; sodium hydroxide; sulfuric acid In tetrahydrofuran; chloroform; water; ethyl acetate	95%

4-hydroxy-1-methyl-2(1H)-quinolone (1677-46-9) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) + malononitrile (109-77-3) → 2-amino-4-(3-bromo-4-fluorophenyl)-6-methyl-5-oxo-5,6-dihydro-4H-pyrano[3,2-c]quinoline-3-carbonitrile (1019060-10-6)

Conditions	Yield
With triethylamine In ethanol for 0.833333h; Heating;	95%

2,4-difluorophenol (367-27-1) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → 3-bromo-4-(2,4-difluorophenoxy)benzaldehyde

Conditions	Yield
With caesium carbonate In dimethyl sulfoxide at 100℃; for 1h; Temperature;	95%
With caesium carbonate In dimethyl sulfoxide at 100℃; for 1h;	95%
With caesium carbonate In dimethyl sulfoxide at 100℃; for 1h; Inert atmosphere;	95%

2.6-dimethylphenol (576-26-1) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → 3-bromo-4-(2,6-dimethylphenoxy)benzaldehyde

Conditions	Yield
With caesium carbonate In dimethyl sulfoxide at 20℃;	95%
With caesium carbonate In dimethyl sulfoxide at 90℃; Inert atmosphere;	7 g

(E)-3,3-diisopropyl-1-(phenylethynyl)triaz-1-ene + 4-methoxy-aniline (104-94-9) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) + benzoic acid (65-85-0) → (E)-N-(1-(3-bromo-4-fluorophenyl)-3-(3,3-diisopropyltriaz-1-en-1-yl)-3-oxo-2-phenylpropyl)-N-(4-methoxyphenyl)benzamide

Conditions	Yield
With scandium tris(trifluoromethanesulfonate) In 1,2-dichloro-ethane at 80℃; Molecular sieve; Schlenk technique; diastereoselective reaction;	95%

3-o-chlorobenzyl-4-amino-4,5-dihydro-1H-1,2,4-triazole-5-one (877315-80-5) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → 5-(o-chlorobenzyl)-4-m-bromo-4-fluorobenzyliden amino-2,4-dihydro-2H-1,2,4-triazol-3-one (1470364-72-7)

Conditions	Yield
With acetic acid at 115℃; for 0.0666667h; Time; Microwave irradiation;	94%

3-bromo-4-fluorobenzaldehyde (77771-02-9) + malononitrile (109-77-3) + triethyl phosphite (122-52-1) → [1-(3-bromo-4-fluorophenyl)-2,2-dicyanoethyl]phosphonic acid diethyl ester (1537917-45-5)

Conditions	Yield
With HCNC-4 In neat (no solvent) at 20℃; for 0.416667h; UV-irradiation; Green chemistry;	94%

4-chloro-2-iodo phenol (71643-66-8) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → 3-bromo-4-(4-chloro-2-iodophenoxy)benzaldehyde

Conditions	Yield
With caesium carbonate In dimethyl sulfoxide at 90℃;	94%
With caesium carbonate In dimethyl sulfoxide at 90℃; for 18h; Inert atmosphere;	94%

2-benzofuran-1(3H)-one (87-41-2) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) → 2-fluoro-5-(3-oxo-3H-isobenzofuran-1-ylmethylene)-1-bromobenzene (63964-50-1)

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 20℃; for 2.5h; Inert atmosphere;	94%
With sodium hydride In tetrahydrofuran at 20℃; for 2.5h; Solvent; Inert atmosphere;	92%

1,3-cylohexanedione (504-02-9) + 3-bromo-4-fluorobenzaldehyde (77771-02-9) + 3-aminohex-2-enoic acid methyl ester → 4-(3-bromo-4-fluoro-phenyl)-5-oxo-2-propyl-1,4,5,6,7,8-hexahydro-quinoline-3-carboxylic acid methyl ester (927669-87-2)

Conditions	Yield
In ethanol at 80℃; for 16h;	93%

3-bromo-4-fluorobenzaldehyde (77771-02-9) → 3-bromo-4-fluoro-benzyl alcohol (77771-03-0)

Conditions	Yield
With methanol; sodium tetrahydroborate at 20℃;	93%
With sodium tetrahydroborate In ethanol for 2h;
With sodium tetrahydroborate In ethanol for 2h;

Upstream product

• 459-57-4 4-fluorobenzaldehyde 
• 107-06-2 1,2-dichloro-ethane 
• 77771-03-0 3-bromo-4-fluoro-benzyl alcohol 
• 2973-78-6 3-bromo-4-hydroxybenzylaldehyde 
• 701914-09-2 2-bromo-1-fluoro-4-vinyl-benzene 

Downstream Products

• 145438-90-0 1-(3-Bromo-4-fluoro-phenyl)-propan-1-ol 
• 145438-90-0 1-(3-Bromo-4-fluoro-phenyl)-propan-1-ol 
• 77771-04-1 2-(3-Bromo-4-fluorophenyl)-1,3-dioxolane 
• 218301-22-5 2-fluoro-5-formylbenzonitrile 
• 265321-19-5 8-benzyl-5-(3-bromo-4-fluorophenyl)-5,8,9,10-tetrahydro-1H-pyrano[3,4-b][1,7]naphthyridine-4,6(3H,7H)-dione 

Relevant articles and documents

A 3 - bromo -4 - fluoro benzaldehyde synthetic method

The present invention relates to the technical field of agricultural chemicals or pharmaceutical intermediate synthesis, in particular to a 3 - bromo - 4 - fluoro benzaldehyde synthetic method, comprises the following steps: (1) the 4 - fluorophenyl formaldehyde dissolved in methylene chloride, to obtain solution A; (2) the sodium bromide is dissolved in pure water, stirring while adding 35% hydrochloric acid, to obtain solution B; (3) the solution and the solution after mixing A B, opening ultrasonic, dropping sodium hypochlorite aqueous solution; (4) [...], ultrasonic, thermal insulation under stirring, then standing; (5) split-phase, dichloromethane phase washed to neutral, drying desolvation; (6) it is crude, 31 °C body melt crystallization, to get the pure product. The synthetic method does not require the use of a catalyst, in the process does not involve the precursor chemicals or toxic chlorine bromine; raw materials are easy, low-risk; high yield; process green, easy operation, and environmental protection.

PhenoFluorMix: Practical chemoselective deoxyfluorination of phenols

A practical deoxyfluorination with novel deoxyfluorinating reagent PhenoFluorMix, a mixture of N,N'-1,3-bis(2,6-diisopropylphenyl)chloroimidazolium chloride and CsF, is presented. PhenoFluorMix overcomes the challenges associated with hydrolysis of PhenoFluor. PhenoFluorMix does not hydrolyze, is readily available on decagram scale, and is storable in air. In this paper, we demonstrate the practicality of the reagent and exhibit the deoxyfluorination of a variety of phenols and heterocycles.

Solvent-free oxidation of alcohols with potassium persulphate in the presence of bronsted acidic ionic liquids

An efficient conversion of alcohols to aldehydes was achieved using potassium persulphate and 3-methylimidazolinium methane sulfonate. Copyright Taylor & Francis Group, LLC.