1868-53-7

Basic information

• Product Name: Dibromofluoromethane
• Synonyms: FC-21B2;HALON 1102;DIBROMOFLUOROMETHANE;Dibromofluoromethane (FC-21B2);DIBROMOFLUOROMETHANE, 1X1ML, MEOH, 2000U G/ML;DIBROMOFLUOROMETHANE 1000MG NEAT;dibromofluoromethane solution;Dibromofluoromethane (FC-21B2) 99.9%
• CAS NO: 1868-53-7
• Molecular Formula: CHBr₂F
• Molecular Weight: 191.83
• Product Categories: Alpha Sort;BromoVolatiles/ Semivolatiles;Chemical Class;D;DAlphabetic;DIA - DIC;Halogenated
• Mol File: 1868-53-7.mol
• Article Data: 4

Chemical Properties

• Melting Point: -78°C
• Boiling Point: 65°C
• Flash Point: >212°C
• Appearance: /
• Density: 2,426 g/cm3
• Vapor Pressure: 5.48mmHg at 25°C
• Refractive Index: 1.468
• Storage Temp.: 2-8°C
• CAS DataBase Reference: Dibromofluoromethane(CAS DataBase Reference)
• NIST Chemistry Reference: Dibromofluoromethane(1868-53-7)
• EPA Substance Registry System: Dibromofluoromethane(1868-53-7)

Safety Data

• Hazard Codes: Xi,N,Xn,T,F
• Statements: 23/24/25-59-22-39/23/24/25-11
• Safety Statements: 24/25-41-59-45-36/37-16
• RIDADR: 2810
• WGK Germany: 2
• Hazardous Substances Data: 1868-53-7(Hazardous Substances Data)

Usage

Chemical Properties

Clear Colourless Oil

Uses

Dibromofluoromethane is used in the synthesis of phosphinate haptens which are used to neutralize organophosphorus chemical weapons.

InChI:InChI=1/C7H3F7N2/c8-2-1(7(12,13)14)3(9)5(11)6(16-15)4(2)10/h16H,15H2

Synthetic route

tribromofluoromethane (353-54-8) → dibromofluoromethane (1868-53-7)

Conditions	Yield
Stage #1: tribromofluoromethane With triphenylphosphine In N,N-dimethyl-formamide for 0.5h; Stage #2: With zinc In N,N-dimethyl-formamide at 20℃; for 0.25h;	56%

Bromoform (75-25-2) → dibromofluoromethane (1868-53-7)

Conditions	Yield
With mercury(II) fluoride
With bromine; antimony(III) fluoride
With potassium fluoride; antimony(III) chloride
With calcium fluoride; antimony(III) chloride
With bromine; antimony(III) fluoride at 110 - 120℃;

dibromofluoroacetic acid (353-99-1) → dibromofluoromethane (1868-53-7)

Conditions	Yield
beim Kochen der Loesung;

dibromofluoromethyltriphenylphosphonium bromide (81962-38-1) → dibromofluoromethane (1868-53-7) + tribromofluoromethane (353-54-8) + fluorodibromoiodomethane (1478-04-2) + fluorobromodiiodomethane (753-67-3)

Conditions	Yield
With potassium fluoride; iodine In various solvent(s)	A 10 % Spectr. B 31 % Spectr. C 57 % Spectr. D 15 % Spectr.
With potassium fluoride; iodine In various solvent(s) Title compound not separated from byproducts;	A 10 % Spectr. B 31 % Spectr. C 57 % Spectr. D 15 % Spectr.

dibromofluoromethyltriphenylphosphonium bromide (81962-38-1) → dibromofluoromethane (1868-53-7) + Triphenylphosphine oxide (791-28-6)

Conditions	Yield
With water In chloroform for 1h; Mechanism;

silver-salt of/the/ (+-)-bromo-fluoro-acetic acid → dibromofluoromethane (1868-53-7)

Conditions	Yield
With bromine at 100℃;

Bromoform (75-25-2) + bromine (7726-95-6) + antimony(III) fluoride (7783-56-4) → bromodifluoromethane (1511-62-2) + dibromofluoromethane (1868-53-7)

bromine (7726-95-6) + bromo-fluoro-acetic acid ; silver-salt (359-16-0) → dibromofluoromethane (1868-53-7)

2,3-Dimethyl-2-butene (563-79-1) + diethyl dibromofluoromethylphosphonate (65094-25-9) → dibromofluoromethane (1868-53-7) + diethyl fluorophosphate (358-74-7) + 1-bromo-1-fluoro-2,2,3,3-tetramethylcyclopropane (34636-25-4)

Conditions	Yield
With potassium fluoride In Triethylene glycol dimethyl ether at 20℃;	A 8 %Spectr. B 93 %Spectr. C 45 %Spectr.

diethyl dibromofluoromethylphosphonate (65094-25-9) → dibromofluoromethane (1868-53-7) + diethyl fluorophosphate (358-74-7)

Conditions	Yield
With potassium fluoride; ethanol In Triethylene glycol dimethyl ether at 20℃;	A 67 %Spectr. B 72 %Spectr.

dibromofluoromethane (1868-53-7) + 15,15'-Bis(hexaspiro[2.0.2.0.0.0.2.0.2.0.1.0]pentadecylidene) → 24-Bromo-24-fluorotetradecaspiro[2.0.2.0.0.0.0.0.2.0.2.0.0.0.2.0.2.0.0.1.0.0.2.0.2.0.0.0]untriacontane

Conditions	Yield
With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride at 20℃; for 72h; Addition;	94%

dibromofluoromethane (1868-53-7) + 15,15'-Bis(hexaspiro[2.0.2.0.0.0.2.0.2.0.1.0]pentadecylidene) → 24-Bromo-24-fluorotetradecaspiro[2.0.2.0.0.0.0.0.2.0.2.0.0.0.2.0.2.0.0.1.0.0.2.0.2.0.0.0]untriacontane

Conditions	Yield
With sodium hydroxide; ethanol; N-benzyl-N,N,N-triethylammonium chloride In dichloromethane at 20℃; for 72h;	94%

dibromofluoromethane (1868-53-7) + 2-vinyl-3-(methoxy)isoindol-1-one (704908-60-1) → 2-(2-bromo-2-fluoro-cyclopropyl)-3-methoxy-2,3-dihydro-isoindol-1-one

Conditions	Yield
With potassium hydroxide; Bn(n-Bu)3Cl In dichloromethane	92%

bicyclohexylidene (4233-18-5) + dibromofluoromethane (1868-53-7) → 13-Brom-13-fluordispiro<5.0.5.1>tridecan (78775-49-2)

Conditions	Yield
With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride In dichloromethane for 4h; Ambient temperature;	90%

dibromofluoromethane (1868-53-7) + 3-methoxy-3-(2-methoxy-phenyl)-2-vinyl-2,3-dihydro-isoindol-1-one → 2-(2-bromo-2-fluoro-cyclopropyl)-3-methoxy-3-(2-methoxy-phenyl)-2,3-dihydro-isoindol-1-one

Conditions	Yield
With potassium hydroxide; 18-crown-6 ether In dichloromethane at 0℃;	88%

dibromofluoromethane (1868-53-7) + hex-5-en-1-yl 4-(trifluoromethoxy)benzoate → 7-bromo-7-fluoroheptyl 4-(trifluoromethoxy)benzoate

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate; potassium hydrogencarbonate In tetrahydrofuran at 20℃; for 18h; Inert atmosphere; Irradiation;	87%

dibromofluoromethane (1868-53-7) + 3-isopropyl-3-methoxy-2-vinyl-2,3-dihydro-isoindol-1-one → 2-(2-bromo-2-fluoro-cyclopropyl)-3-isopropyl-3-methoxy-2,3-dihydro-isoindol-1-one

Conditions	Yield
With potassium hydroxide; 18-crown-6 ether In dichloromethane at 20℃;	86%

dibromofluoromethane (1868-53-7) + cyclopropylidenecyclohexane (14114-06-8) → 10-bromo-10-fluorodispiro[2.0.5.1]decane (1175147-15-5)

Conditions	Yield
With ethanol; N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide In dichloromethane; water at 0 - 20℃;	86%

1,1-Diphenylethylene (530-48-3) + dibromofluoromethane (1868-53-7) → (2-bromo-2-fluorocyclopropane-1,1-diyl)dibenzene (64859-37-6)

Conditions	Yield
With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide In dichloromethane at 20℃;	84%
With potassium tert-butylate In hexane

dibromofluoromethane (1868-53-7) + hex-5-en-1-yl 4-iodobenzoate → 7-bromo-7-fluoroheptyl 4-iodobenzoate

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate; potassium hydrogencarbonate In tetrahydrofuran at 20℃; for 18h; Inert atmosphere; Irradiation;	83%

dibromofluoromethane (1868-53-7) + Methyl 10-undecenoate (111-81-9) → methyl-10,12-dibromo-12-fluoro dodecanoate

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate In water; N,N-dimethyl-formamide at 20℃; for 18h; Inert atmosphere; Irradiation;	82%

dibromofluoromethane (1868-53-7) + hex-5-en-1-yl 4-iodobenzoate → 5,7-dibromo-7-fluoroheptyl-4-iodo benzoate

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate In water; N,N-dimethyl-formamide at 20℃; for 18h; Inert atmosphere; Irradiation;	82%

dibromofluoromethane (1868-53-7) + 1-ethylcyclohexene (1453-24-3) → 7-Brom-1-ethyl-7-fluorbicyclo<4.1.0>heptan (78775-52-7)

Conditions	Yield
With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride In dichloromethane for 4h; Ambient temperature; also: 6h, reflux;	80%

dibromofluoromethane (1868-53-7) + hex-5-en-1-yl 4-methylbenzoate → 7-bromo-7-fluoroheptyl 4-methylbenzoate

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate; potassium hydrogencarbonate In tetrahydrofuran at 20℃; for 18h; Inert atmosphere; Irradiation;	80%

dibromofluoromethane (1868-53-7) + hex-5-en-1-yl 4-fluorobenzoate → 5,7-dibromo-7-fluoroheptyl 4-fluorobenzoate

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate In water; N,N-dimethyl-formamide at 20℃; for 18h; Inert atmosphere; Irradiation;	80%

dibromofluoromethane (1868-53-7) + hex-5-en-1-yl 4-bromobenzoate (1352390-87-4) → 7-bromo-7-fluoroheptyl 4-bromobenzoate

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate; potassium hydrogencarbonate In tetrahydrofuran at 20℃; for 18h; Inert atmosphere; Irradiation;	79%

dibromofluoromethane (1868-53-7) + 3-methoxy-3-m-tolyl-2-vinyl-2,3-dihydro-isoindol-1-one → 2-(2-bromo-2-fluoro-cyclopropyl)-3-methoxy-3-m-tolyl-2,3-dihydro-isoindol-1-one

Conditions	Yield
With potassium hydroxide; 18-crown-6 ether In dichloromethane at 20℃;	78%

dibromofluoromethane (1868-53-7) + methylenecyclopentane (1528-30-9) → 1-bromo-1-fluorospiro[2.4]heptane

Conditions	Yield
With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide In dichloromethane; benzene at 20℃;	78%

dibromofluoromethane (1868-53-7) + 2-methylene-1-tosylpyrrolidine → C13H15BrFNO2S

Conditions	Yield
With sodium hydroxide	78%
With benzyltrimethylammonium chloride; sodium hydroxide In dichloromethane at 20℃; for 25.5h;	1.0 g

dibromofluoromethane (1868-53-7) + 1-dodecene (112-41-4) → 1,3-dibromo-1-fluorotridecane

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate In water; N,N-dimethyl-formamide at 20℃; for 18h; Inert atmosphere; Irradiation;	78%

dibromofluoromethane (1868-53-7) + hex-5-en-1-yl 4-bromobenzoate (1352390-87-4) → 5,7-dibromo-7-fluoroheptyl 4-bromobenzoate

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate In water; N,N-dimethyl-formamide at 20℃; for 18h; Inert atmosphere; Irradiation;	78%

dibromofluoromethane (1868-53-7) + benzoic acid hex-5-enyl ester (41795-26-0) → 7-bromo-7-fluoroheptyl benzoate

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate; potassium hydrogencarbonate In tetrahydrofuran at 20℃; for 18h; Inert atmosphere; Irradiation;	77%

dibromofluoromethane (1868-53-7) + hex-5-en-1-yl benzenesulfonate → 5,7-dibromo-7-fluoroheptyl benzenesulfonate

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate In water; N,N-dimethyl-formamide at 20℃; for 18h; Inert atmosphere; Irradiation;	77%

5-Hexen-1-ol (821-41-0) + dibromofluoromethane (1868-53-7) → 5,7-dibromo-7-fluoroheptan-1-ol

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate In water; N,N-dimethyl-formamide at 20℃; for 18h; Inert atmosphere; Irradiation;	77%

dibromofluoromethane (1868-53-7) + Methyl 10-undecenoate (111-81-9) → methyl 12-bromo-12-fluorododecanoate

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate; potassium hydrogencarbonate In tetrahydrofuran at 20℃; for 18h; Inert atmosphere; Irradiation;	76%

dibromofluoromethane (1868-53-7) + hex-5-en-1-yl 4-methoxybenzoate → 5,7-dibromo-7-fluoroheptyl 4-methoxybenzoate

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate In water; N,N-dimethyl-formamide at 20℃; for 18h; Inert atmosphere; Irradiation;	76%

dibromofluoromethane (1868-53-7) + C15H18O4 → 5,7-dibromo-7-fluoroheptyl methyl terephthalate

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate In water; N,N-dimethyl-formamide at 20℃; for 18h; Inert atmosphere; Irradiation;	76%

dibromofluoromethane (1868-53-7) + (hex-5-en-1-yloxy)benzene (74972-56-8) → ((5,7-dibromo-7-fluoroheptyl)oxy)benzene

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate In water; N,N-dimethyl-formamide at 20℃; for 18h; Inert atmosphere; Irradiation;	76%

dibromofluoromethane (1868-53-7) + hex-5-en-1-yl 3,6-dichloro-2-methoxybenzoate → 5,7-dibromo-7-fluoroheptyl 3,6-dichloro-2-methoxybenzoate

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate In water; N,N-dimethyl-formamide at 20℃; for 18h; Inert atmosphere; Irradiation;	76%

2-(pent-4-enyl)-isoindoline-1,3-dione (7736-25-6) + dibromofluoromethane (1868-53-7) → 2-(6-bromo-6-fluorohexyl)isoindoline-1,3-dione (1616366-00-7)

Conditions	Yield
With [4,4’-bis(1,1-dimethylethyl)-2,2’-bipyridine-N1,N1‘]bis [3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-N]phenyl-C]iridium(III) hexafluorophosphate; potassium hydrogencarbonate In tetrahydrofuran at 20℃; for 18h; Inert atmosphere; Irradiation;	75%

Upstream product

• 75-25-2 Bromoform 
• 7726-95-6 bromine 
• 359-16-0 bromo-fluoro-acetic acid ; silver-salt 
• 65094-25-9 diethyl dibromofluoromethylphosphonate 
• 563-79-1 2,3-Dimethyl-2-butene 
• 353-54-8 tribromofluoromethane 
• 7783-56-4 antimony(III) fluoride 
• 81962-38-1 dibromofluoromethyltriphenylphosphonium bromide 
• 353-99-1 dibromofluoroacetic acid 

Downstream Products

• 141-53-7 sodium formate 
• 593-53-3 Methyl fluoride 
• 373-52-4 bromofluoromethane 
• 62359-74-4 1-Brom-1-fluor-2-phenoxy-cyclopropan 
• 1959-48-4 (2-bromo-2-fluoroethene-1,1-diyl)dibenzene 
• 78775-54-9 7-Brom-7-fluor-1-phenylbicyclo<4.1.0>heptan 
• 78775-47-0 1-Cyclohexen-1-fluor-2-methyl-1-propen 
• 78775-48-1 3-Cyclohexyliden-3-fluor-2-methyl-1-propen 
• 78775-50-5 1-Cyclohexenyl(cyclohexyliden)fluormethan 
• 144773-85-3 C₁₆H₁₂BrF 
• 144773-90-0 C₁₆H₁₂BrF 
• 144773-89-7 C₁₆H₁₂BrF 
• 78775-45-8 (E)-3-Fluor-2,4-diphenyl-1,3-pentadien 
• 19466-30-9 (E)-3-fluorostilbene 

Relevant articles and documents

THE HYDROLYSIS OF DIBROMOFLUOROMETHYLTRIPHENYLPHOSPHONIUM BROMIDE

Hydrolysis of Br(1-) afforded a high yield of dibromofluoromethane and triphenylphosphine oxide.Hydrolysis in the presence of a radioactive isotope of bromine gave evidence that the mechanism of this reaction proceeds via the dibromofluoromethide ion and not via a bromofluorocarbene intermediate.

Synthetic and mechanistic aspects of halo-F-methylphosphonates

The synthesis of a variety of new halo-F-methylphosphonates has been achieved by a Michaelis-Arbuzov type reaction between a halo-F-methane and a trialkyl phosphite. This synthesis has proved to be of wide scope and utility for the high yield preparation of a number of heretofore unknown compounds. The 1H, 19F, 13C and 31P NMR spectroscopic properties are reported in detail. The mechanism for the formation of bromodifluoromethylphosphonates has been shown to proceed through the intermediacy of difluorocarbene:CF2. The phosphonate products have been shown to react with a wide variety of reagents. Fluoride and alkoxide ions react by attack at phosphorus with cleavage of the carbon-phosphorus bond and formation of [:CF2] from the bromodifluoromethylphosphonates and the CFBr2- anion from the dibromofluoromethylphosphonates. Iodide ion and tertiary phosphines react by attack at the ester carbon to give stable phosphonate salts. Hydrolysis of the phosphonate esters with 50% aqueous HCl gives the expected phosphonic acids. Trimethylsilyl bromide attacks phosphoryl oxygen to afford the bis(trimethylsilyl) esters.

PREPARATION OF HALO-F-METHANES VIA POTASSIUM FLUORIDE-HALOGEN CLEAVAGE OF HALO-F-METHYLPHOSPHONIUM SALTS

Treatment of halo-F-methylphosphonium salts with potassium fluoride and halogen (I2, Br2, ICl, IBr) gives modest yields of halo-F-methanes.This method of preparation augments the classical Hunsdiecker approach to these materials.