344-04-7

Basic information

• Product Name: Bromopentafluorobenzene
• Synonyms: BroMopentafluorobenzene, 98%+;Pentafluorophenyl bromide;pentafluorophenylbromide;Brimopentafluorobenzene;Bromopentefluorobenzene;Bromopentafluorobenzene,99%;pentafluroaniline;C6F5Br,Bromopentafluorobenzene
• CAS NO: 344-04-7
• Molecular Formula: C₆BrF₅
• Molecular Weight: 246.96
• EINECS: 206-449-0
• Product Categories: Pharmaceutical Intermediates;Fluoro-Aromatics;Aryl;C6;Halogenated Hydrocarbons;organofluorine compounds;Aryl Fluorinated Building Blocks;Building Blocks;Chemical Synthesis;Fluorinated Building Blocks;Halogenated Hydrocarbons;Organic Building Blocks;Organic Fluorinated Building Blocks;Other Fluorinated Organic Building Blocks;alkyl bromide | alkyl Fluorine
• Mol File: 344-04-7.mol
• Article Data: 29

Chemical Properties

• Melting Point: −31 °C(lit.)
• Boiling Point: 137 °C(lit.)
• Flash Point: 190 °F
• Appearance: Clear colorless to very faintly colored/Liquid
• Density: 1.981 g/mL at 25 °C(lit.)
• Vapor Pressure: 9.17mmHg at 25°C
• Refractive Index: n20/D 1.449(lit.)
• Storage Temp.: Room temperature.
• Solubility: Chloroform (Sparingly), Methanol (Slightly)
• Water Solubility: Insoluble in water.
• BRN: 1819390
• CAS DataBase Reference: Bromopentafluorobenzene(CAS DataBase Reference)
• NIST Chemistry Reference: Bromopentafluorobenzene(344-04-7)
• EPA Substance Registry System: Bromopentafluorobenzene(344-04-7)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36-37/39
• WGK Germany: 3
• RTECS: CY9040552
• TSCA: T
• HazardClass: IRRITANT
• Hazardous Substances Data: 344-04-7(Hazardous Substances Data)

Usage

Chemical Properties

Clear colorless to very faintly colored liquid

Uses

Different sources of media describe the Uses of 344-04-7 differently. You can refer to the following data:
1. It is used as pharmaceutical intermediate. It is a Grignard reagent (with CuBr in dioxane) can introduce pentafluorophenyl groups.
2. Bromopentafluorobenzene is a polyfluorinated chemical that is widely distributed in the environment and released because of its use in different household and industrial products. Bromopentafluorobenzene is also used in the synthesis of phenylproparginols which have herbicidal activity.

InChI:InChI=1/C6BrF5/c7-1-2(8)4(10)6(12)5(11)3(1)9

Synthetic route

C6F9Si(1-)*C4H12N(1+) → bromopentafluorobenzene (344-04-7)

Conditions	Yield
With bromine In diethylene glycol dimethyl ether at 10℃; for 0.0833333h;	100%

Pentafluorobenzene (363-72-4) → bromopentafluorobenzene (344-04-7)

Conditions	Yield
With N-Bromosuccinimide; boron trifluoride at 20℃; for 1h;	96%
With tris(pentafluorophenyl)borate; bromine; chlorine In chloroform at 30 - 35℃; for 2h; Reagent/catalyst; Solvent; Temperature; Large scale;	93%
With aluminum (III) chloride; bromine at 45℃; for 18h;	90.5%

trimethyl(pentafluorophenyl)silane (1206-46-8) → bromopentafluorobenzene (344-04-7)

Conditions	Yield
With bromine; cesium fluoride In acetonitrile at 20℃; for 3h;	93%

2,3,5,6-tetrafluorothiophenol (769-40-4) → 1-bromo-2,3,5,6-tetrafluorobenzene (1559-88-2) + bromopentafluorobenzene (344-04-7)

Conditions	Yield
With bromine at 500 - 510℃;	A 87% B n/a

Hexafluorobenzene (392-56-3) → bromopentafluorobenzene (344-04-7)

Conditions	Yield
Stage #1: Hexafluorobenzene With iron(III)-acetylacetonate; ethylmagnesium bromide In tetrahydrofuran at -30℃; for 1.5h; Stage #2: With bromine In tetrahydrofuran at -30 - 20℃;	83%

bromine (7726-95-6) + pentafluorophenylmagnesium chloride (879-06-1) → bromopentafluorobenzene (344-04-7)

Conditions	Yield
In diethyl ether reaction at 20°C, 1 hour;;	69%
In diethyl ether reaction at 20°C, 1 hour;;	69%

bis(pentafluorophenyl) disulfide (1494-06-0) → bromopentafluorobenzene (344-04-7)

Conditions	Yield
With bromine at 500℃;	68%

C6F5NN(1+)*F(1-)=C6F5NNF + copper(I) bromide (7787-70-4) → bromopentafluorobenzene (344-04-7)

Conditions	Yield
at 100°C in HBr;	63%
at 100°C in HBr;	63%

Pentafluorobenzene (363-72-4) → bromopentafluorobenzene (344-04-7) + 3-H-pentafluoro-2,5-cyclohexadien-1-one (60890-52-0) + 1,2,3,3,4,6,6-heptafluorocyclohexa-1,4-diene (773-53-5)

Conditions	Yield
With bromine trifluoride; antimony pentafluoride In fluorosulfonylchloride at -90 - -80℃; for 0.5h;	A 57% B 13% C 9%

Pentafluorobenzene (363-72-4) → bromopentafluorobenzene (344-04-7) + 1-H-heptafluoro-1,4-cyclohexadiene + 1-bromoheptafluoro-1,4-cyclohexadiene (70557-89-0)

Conditions	Yield
With bromine trifluoride; boron trifluoride In fluorosulfonylchloride at -90 - -80℃; for 0.333333h; Title compound not separated from byproducts;	A 47% B 10 % Chromat. C 10 % Chromat.
With bromine trifluoride; boron trifluoride In fluorosulfonylchloride at -90 - -80℃; for 0.333333h;	A 47 % Chromat. B 10% C 10 % Chromat.

Pentafluorobenzene (363-72-4) → bromopentafluorobenzene (344-04-7) + 3-H-pentafluoro-2,5-cyclohexadien-1-one (60890-52-0) + 2,3,3,4,5,6,6-heptafluoro-1-bromo-cyclohexa-1,4-diene (57113-81-2)

Conditions	Yield
With bromine trifluoride; boron trifluoride In fluorosulfonylchloride at -90 - -80℃; for 0.333333h;	A 46% B 26% C 10%

potassium perfluorophenyltrifluoroborate → bromopentafluorobenzene (344-04-7) + 2,3,3,4,5,6,6-heptafluoro-1-bromo-cyclohexa-1,4-diene (57113-81-2) + 1-bromo nonafluoro cyclohexene (4933-59-9) + bis(pentafluorophenyl)bromonium tetrafluoroborate

Conditions	Yield
With bromine trifluoride; hydrogen fluoride at -40 - -30℃; Inert atmosphere;	A 0.1 mmol B 0.16 mmol C 0.06 mmol D 45%

perfluoropropylene (116-15-4) + pentafluorophenyl lithium (1076-44-4) → bromopentafluorobenzene (344-04-7) + cis-1-perfluoro(phenylpropylene) (37600-06-9) + trans-1-perfluoro(phenylpropylene) (37600-07-0)

Conditions	Yield
In diethyl ether byproducts: trans-perfluoro(α-(4-biphenyl)propylene); stream of dry argon between -80 and 50°C, keeping the mixt. at -70°Cfor 3 h, then acidifying with 10 % HCl at 10°C;	A 5% B 8% C 40%
In diethyl ether

Pentafluorobenzene (363-72-4) → bromopentafluorobenzene (344-04-7) + 3-H-pentafluoro-2,5-cyclohexadien-1-one (60890-52-0) + 1,2,3,3,4,6,6-heptafluorocyclohexa-1,4-diene (773-53-5) + 2,3,3,4,5,6,6-heptafluoro-1-bromo-cyclohexa-1,4-diene (57113-81-2)

Conditions	Yield
With bromine trifluoride; antimony pentafluoride In fluorosulfonylchloride at -90 - -80℃; for 0.5h;	A 35% B 1% C 26% D 17%

pentafluorophenyl hydrazine (828-73-9) → 2,3,4,5,6-pentafluoroaniline (771-60-8) + bromopentafluorobenzene (344-04-7)

Conditions	Yield
With bromine In ethanol with ethanolic Br2 soln. at -60°C (2 h);	A 5% B 24%
With Br2 In ethanol with ethanolic Br2 soln. at -60°C (2 h);	A 5% B 24%

tribromofluoromethane (353-54-8) → Hexafluorobenzene (392-56-3) + 1,2-difluorotetrabromoethane (594-79-6) + bromopentafluorobenzene (344-04-7)

Conditions	Yield
at 630 - 640℃;

chloro-trimethyl-silane (75-77-4) + pentafluorphenylbrom(V)tetrafluorid (75822-05-8) → trimethylsilyl fluoride (420-56-4) + bromopentafluorobenzene (344-04-7)

Conditions	Yield
In acetonitrile

2,3,4,5,6-pentafluoroaniline (771-60-8) → bromopentafluorobenzene (344-04-7) + Pentafluorobenzene (363-72-4)

Conditions	Yield
With copper(I) bromide; sulfuric acid; copper(II) sulfate; potassium bromide; sodium nitrite; tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anion 1) 0 deg C, dichloromethane, water 2) dichloromethane, water, 100 min, rt.; Yield given. Multistep reaction. Yields of byproduct given;
With copper(I) bromide; sulfuric acid; copper(II) sulfate; potassium bromide; sodium nitrite; tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anion 1) 0 deg C, dichloromethane, water, 2) dichloromethane, water, 100 min, rt.; Yield given. Multistep reaction. Yields of byproduct given;

trimethyl(pentafluorophenyl)silane (1206-46-8) → bromopentafluorobenzene (344-04-7) + Pentafluorobenzene (363-72-4) + decafluorobiphenyl (434-90-2)

Conditions	Yield
With xenon difluoride; Bromoform; cesium fluoride In acetonitrile at 20 - 25℃; for 0.5h;	A 25 % Chromat. B 14 % Chromat. C 1 % Chromat.
With xenon difluoride; Bromoform; cesium fluoride prototype reaction (oth. aryltrimethylsilanes);

pentafluorphenylbrom(V)tetrafluorid (75822-05-8) + triphenylphosphine (603-35-0) → bromopentafluorobenzene (344-04-7) + triphenyldifluorophosphorane (845-64-7)

Conditions	Yield
In acetonitrile at 0℃;

pentafluorphenylbrom(V)tetrafluorid (75822-05-8) + tris(pentafluorophenyl)phosphine (1259-35-4) → bromopentafluorobenzene (344-04-7) + difluorotris(pentafluorphenyl)phosphorane (22474-72-2, 54082-67-6)

Conditions	Yield
In acetonitrile at 0℃;

1-chloro-2,3,4,5,6-pentafluorobenzene (344-07-0) → bromopentafluorobenzene (344-04-7)

Conditions	Yield
With bromine In gaseous matrix at 40℃; Thermodynamic data; collision energy E(c);

trifluoro(pentafluorophenyl)silane (5272-26-4) → bromopentafluorobenzene (344-04-7)

Conditions	Yield
With aluminum tri-bromide; bromine at -20℃; for 76h;
Multi-step reaction with 2 steps 1: 76 percent / acetonitrile / 0.25 h / Ambient temperature 2: 100 percent / Br2 / bis-(2-methoxy-ethyl) ether / 0.08 h / 10 °C View Scheme

trifluoro(pentafluorophenyl)silane (5272-26-4) → bromopentafluorobenzene (344-04-7) + Bromo-difluoro-pentafluorophenyl-silane

Conditions	Yield
With bromine for 240h; Product distribution; Ambient temperature;

1-bromo-2,3,4,5-tetrafluorobenzene (1074-91-5) → bromopentafluorobenzene (344-04-7) + 1-Bromo-2H-hexafluoro-1,4-cyclohexadiene + 1-Bromo-2H-octafluorocyclohexene

Conditions	Yield
With xenon difluoride; hydrogen fluoride for 0.416667h; Ambient temperature; Title compound not separated from byproducts;	A 2 % Spectr. B 29 % Spectr. C 11 % Spectr.

iodotrifluoromethane (2314-97-8) + 1-Bromo-2,3,4,5,6-pentafluoro-benzene → trifluoromethyl radical (2264-21-3) + bromopentafluorobenzene (344-04-7) + trifluoro-iodo-methane radical anion (2314-97-8)

Conditions	Yield
In gas at 36.9℃; Rate constant;

trimethyl(pentafluorophenyl)silane (1206-46-8) → trimethylsilyl bromide (2857-97-8) + bromopentafluorobenzene (344-04-7)

Conditions	Yield
With aluminum tri-bromide; bromine -20 deg C -> rt., 15 min; Yield given;

di-(pentafluoro phenyl) dimethyl silane (10536-62-6) → dimethyldibromosilane (4095-10-7) + bromopentafluorobenzene (344-04-7)

Conditions	Yield
With aluminum tri-bromide; bromine Ambient temperature; -20 deg C -> r.t., 15 min; Yield given;

di-(pentafluoro phenyl) dimethyl silane (10536-62-6) → bromopentafluorobenzene (344-04-7) + Pentafluorobenzene (363-72-4) + Brom-dimethyl-pentafluorphenyl-silan (23761-73-1)

Conditions	Yield
With aluminum tri-bromide In various solvent(s) for 0.5h; Ambient temperature; Yield given. Yields of byproduct given;

pyridine (110-86-1) + dichloro(ethylenediamine)platinum(II) (14096-51-6) + bromopentafluorobenzene (344-04-7) → [N,N'-bis(4-bromo-2,3,5,6-tetrafluorophenyl)ethane-1,2-diaminato]dipyridineplatinum(II) (108089-51-6) + carbon dioxide (124-38-9)

Conditions	Yield
With Tl2CO3 In pyridine N2-atmosphere; stirring (115°C, 1 h); evapn. (vac.), light petroleum addn., stirring (1 h), decanting, extg. (Me2CO), filtering, concg., light petroleum addn., crystn. on concg., re crystn. (Me2CO / light petroleum);	A 60% B 100%
With K2CO3 In pyridine N2-atmosphere; stirring (115°C, 1 h); evapn. (vac.), light petroleum addn., stirring (1 h), decanting, extg. (Me2CO), filtering, concg., light petroleum addn., crystn. on concg., re crystn. (Me2CO / light petroleum);	A 26% B 30%

bromopentafluorobenzene (344-04-7) → lithium tetrakis(pentafluorophenyl)borate (2797-28-6)

Conditions	Yield
With n-butyllithium; carbon dioxide; boron trichloride In hexane; water; pentane	99%

bromopentafluorobenzene (344-04-7) + diethylmagnesium (557-18-6) → bis-(pentafluoro phenyl) magnesium (17436-90-7)

Conditions	Yield
In tetrahydrofuran reaction at 0°C;;	99%

tetrahydrofuran (109-99-9) + indium (7440-74-6) + bromopentafluorobenzene (344-04-7) + bromine (7726-95-6) → bis(tetrahydrofuran)(pentafluorophenyl)indium dibromide (399511-25-2)

Conditions	Yield
In tetrahydrofuran	99%

pyridine (110-86-1) + indium (7440-74-6) + bromopentafluorobenzene (344-04-7) + bromine (7726-95-6) → bis(pyridine)(pentafluorophenyl)indium dibromide

Conditions	Yield
In dichloromethane	99%

pyridine (110-86-1) + indium(I) bromide + bromopentafluorobenzene (344-04-7) → bis(pyridine)(pentafluorophenyl)indium dibromide

Conditions	Yield
In dichloromethane elem. anal.;	99%

bromopentafluorobenzene (344-04-7) + 1-cyclobutyl-1-phenyl-methanone (5407-98-7) → C17H11F5O (1361052-41-6)

Conditions	Yield
Stage #1: 1-cyclobutyl-1-phenyl-methanone With sodium hexamethyldisilazane In tetrahydrofuran; 1,4-dioxane for 0.0833333h; Inert atmosphere; Stage #2: bromopentafluorobenzene In tetrahydrofuran; 1,4-dioxane for 0.25h; Inert atmosphere;	99%

tetrakis(trimethylphosphine)iron(0) (63835-22-3) + bromopentafluorobenzene (344-04-7) → C18H41BrFeP4

Conditions	Yield
In diethyl ether at 20℃; for 3h; Inert atmosphere;	99%

bromopentafluorobenzene (344-04-7) + tert-butyl (1R,5R)-8-oxo-10-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,5,6,8-tetrahydro-2H-1,5-methanopyrido[1,2-a][1,5]diazocine-3(4H)-carboxylate → N-Boc 10-(perfluorophenyl)cytisine

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; caesium carbonate In tetrahydrofuran for 18h; Inert atmosphere; Reflux;	99%
With bis-triphenylphosphine-palladium(II) chloride; caesium carbonate In tetrahydrofuran at 80℃; for 18h;

styrene (292638-84-7) + bromopentafluorobenzene (344-04-7) → (E)-1,2,3,4,5-pentafluoro-6-styrylbenzene (80365-31-7, 19292-25-2)

Conditions	Yield
With (NBu4)2[Pd2(μ-Br)2(C6F5)2Br2]; calcium carbonate In 1-methyl-pyrrolidin-2-one; water at 130℃; for 24h; Heck reaction;	98%
With 1,3-bis(2-(diphenylphosphinomethyl)-phenyl)benzene*PdCl2; potassium carbonate In N,N-dimethyl-formamide at 120℃; for 25h; Heck coupling;	67 % Chromat.

bromopentafluorobenzene (344-04-7) + ethylmagnesium bromide (925-90-6) → 2,3,4,5,6-pentafluorophenylmagnesium bromide (879-05-0)

Conditions	Yield
In tetrahydrofuran reaction at 0°C;;	98%
In diethyl ether
In di-isopropyl ether

bromopentafluorobenzene (344-04-7) + tin(IV) chloride (7646-78-8) + tetraallyltin (1522-03-8, 1871-05-2, 68628-90-0, 68628-91-1, 68628-92-2, 77626-11-0) → (C6F5)2Sn(CH2CHCH2)2

Conditions	Yield
With magnesium In diethyl ether Ar-atmosphere; addn. of 1 equiv. of SnCl4 to tetraallyltin at -50°C, warming to 0°C, dropwise addn. of excess of Grignard reagent (prepd. from Mg and C6F5Br), stirring (room temp., 38-75 h); filtration (celite), chromy. (SiO2, hexane), evapn., chromy. (SiO2, hexane); elem. anal.;	98%

tetrahydrofuran (109-99-9) + indium(I) bromide + bromopentafluorobenzene (344-04-7) → bis(tetrahydrofuran)(pentafluorophenyl)indium dibromide (399511-25-2)

Conditions	Yield
In tetrahydrofuran InBr suspended in THF, C6F5Br added, stirred for 16 h at ambient temp.; volatile distilled off in vac. at ambient temp.; elem. anal.;	98%

bromopentafluorobenzene (344-04-7) + 1,1,3,3-tetramethylbutane isonitrile (14542-93-9) + 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (88284-48-4) → N-[(2-bromophenyl)(pentafluorophenyl)methylene]-tert-octylamine (1352657-86-3)

Conditions	Yield
With potassium fluoride; 18-crown-6 ether In 1,2-dimethoxyethane at 0℃; for 14h; Inert atmosphere; regioselective reaction;	98%

potassium cyclopentadienyldicarbonyliron(0) + bromopentafluorobenzene (344-04-7) → cyclopentadienyl iron(II) dicarbonyl dimer (38117-54-3) + p-HC6F4Fe(CO)2Cp (12110-35-9)

Conditions	Yield
With (C6H5)(C2H5)CHCN In tetrahydrofuran byproducts: C6F5H; at room temp. using Ph(Et)CHCN as radical trap; not isolated, detected by NMR;	A 97% B 3%

pyridine (110-86-1) + cis-(N,N-dimethyl-ethylenediamine)diiodoplatinum(II) (104034-36-8) + thallous 2,3,5,6-tetrafluorobenzoate (75669-81-7) + bromopentafluorobenzene (344-04-7) → c(N),d(N')-{N,N-dimethyl-N'-(4-bromo-2,3,5,6-tetrafluorophenyl)ethane-1,2-diaminato(1-)}-b-iodo-a-pyridineplatinum(II) (117533-85-4) + carbon dioxide (124-38-9)

Conditions	Yield
In pyridine Heating under stirring (105-110°C, N2, 25 min).; Cooling, evapn. to dryness (vacuum), washed (light petroleum), dried, extn. with Me2CO, filtn. of TlI, evapn. to dryness, washed (cold EtOH), recrystn. (pyridine/H2O and ether/light petroleum), elem. anal.;	A 27% B 97%

bromopentafluorobenzene (344-04-7) + tribenzyltin(IV) chloride (3151-41-5) → (C6F5)Sn(CH2C6H5)3 (221363-75-3)

Conditions	Yield
With magnesium In tetrahydrofuran; diethyl ether Ar-atmosphere; mixing equimolar amts. of Mg and PhBr (in ether, 0°C), stirring for 2 h, dropwise addn. of Sn-compd. (in THF) to slight excess of Grignard reagent at 0°C, stirring (room temp., 63 h); filtration (celite), chromy. (SiO2, hexane), evapn., chromy. (SiO2, hexane); elem. anal.;	97%

bromopentafluorobenzene (344-04-7) + trimethylsilylacetylene (1066-54-2) → ((trimethylsilyl)ethynyl)pentafluorobenzene (52168-00-0)

Conditions	Yield
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); diisopropylamine In toluene at 80℃; for 19h; Inert atmosphere;	96%
With bis(benzonitrile)palladium(II) dichloride; copper diacetate; diisopropylamine; triphenylphosphine 1.) RT, 1 h, 2.) reflux, 1 h;	20%
With copper(l) iodide; diisopropylamine; triphenylphosphine; bis-triphenylphosphine-palladium(II) chloride
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; N-ethyl-N,N-diisopropylamine at 72℃; for 24h; Sonogashira Cross-Coupling; Inert atmosphere;

bromopentafluorobenzene (344-04-7) + 4-Vinylphenylboronic acid (2156-04-9) → 2,3,4,5,6-pentafluoro-4’-vinylbiphenyl

Conditions	Yield
With [Pd(η2-dibenzylideneacetone)(tris(o-tolyl)phosphine)2]; potassium carbonate In ethanol; water; toluene at 85℃; Suzuki-Miyaura Coupling; Inert atmosphere;	96%
With bis(trisphenylphosphine)(dibenzylideneacetone)palladium(0); sodium carbonate In ethanol; toluene at 60 - 90℃; for 2 - 20h; Reagent/catalyst; Temperature; Time; Suzuki-Miyaura Coupling;	92%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; toluene Heating;

Trimethyl borate (121-43-7) + bromopentafluorobenzene (344-04-7) → pentafluorophenylboronic acid (1582-24-7)

Conditions	Yield
With n-butyllithium In tetrahydrofuran; hexane at -30℃; Temperature; Flow reactor;	95.2%
Stage #1: bromopentafluorobenzene With ethylmagnesium bromide In octamethylcyclotetrasiloxane at 20℃; for 0.00972222h; Inert atmosphere; Stage #2: Trimethyl borate In octamethylcyclotetrasiloxane at 10℃; for 0.0138889h; Solvent; Temperature; Reagent/catalyst; Inert atmosphere;	94.5%
With magnesium In diethyl ether Grignard-comp. prepd. from Br-compd. and Mg in ether was cooled with ice-water bath and added dropwise to 1.5 equiv. of pre-cooled (ice-water bath) soln. of B(OMe)3 in ether, stirring at 0-4 °C for 1 h; pouring into 5 % HCl, org. layer was sepd., aq. layer was extd. with ether, extracts were combined, dried with MgSO4, evapd. under vac., solid was recrystd. from hot toluene, elem. anal.;	90%
Stage #1: bromopentafluorobenzene With magnesium In tetrahydrofuran at 40 - 45℃; for 5h; Inert atmosphere; Large scale; Stage #2: Trimethyl borate In tetrahydrofuran at -5℃; for 2h; Inert atmosphere; Large scale; Stage #3: With hydrogenchloride In tetrahydrofuran; water for 0.5h; Reagent/catalyst; Temperature; Solvent; Inert atmosphere; Large scale;	90.33%

bromopentafluorobenzene (344-04-7) + antimony(III) chloride (10025-91-9) → tris(pentafluorophenyl)antimony (3910-39-2)

Conditions	Yield
Stage #1: bromopentafluorobenzene With n-butyllithium at -78℃; for 0.25h; Stage #2: antimony(III) chloride at -78 - 20℃; for 2h;	95%
With magnesium In diethyl ether at -10 - 20℃; for 2h; Heating / reflux;	65%

bromopentafluorobenzene (344-04-7) + dimethyltin dichloride (753-73-1) → dimethylbis(pentafluorophenyl)tin (801-79-6)

Conditions	Yield
With BuLi; H2O In diethyl ether; hexane Ar-atmosphere; stirring (-78°C, 45 min), Sn-compd. addn., stirring (-78°C, 15 min, room temp., 12 h), wet hexanes addn.; evapn. (reduced pressure), extg. (hexanes), evapn., distg. (reduced pressure);	95%
Stage #1: bromopentafluorobenzene With iodine; magnesium In diethyl ether for 4h; Heating / reflux; Stage #2: dimethyltin dichloride In diethyl ether at 0 - 20℃;	90%

bromopentafluorobenzene (344-04-7) + boron trifluoride diethyl etherate (109-63-7) → tris(pentafluorophenyl)borate (1109-15-5)

Conditions	Yield
Stage #1: bromopentafluorobenzene With magnesium In diethyl ether at 20℃; Stage #2: boron trifluoride diethyl etherate In toluene at 0℃; for 1h; Schlenk technique; Inert atmosphere; Stage #3: In diethyl ether; toluene at 100℃; for 1h; Schlenk technique; Inert atmosphere;	95%
Stage #1: bromopentafluorobenzene With magnesium In diethyl ether for 1h; Reflux; Stage #2: boron trifluoride diethyl etherate In toluene at 100℃; for 1h;	88%
Stage #1: bromopentafluorobenzene With magnesium In diethyl ether at 20℃; for 1h; Inert atmosphere; Stage #2: boron trifluoride diethyl etherate In toluene at 100℃; for 1h; Inert atmosphere;	88%

bromopentafluorobenzene (344-04-7) + 1-(4-vinylbenzyl)-1H-imidazole (78430-91-8) → 1-(4-ethenylbenzyl)-3-(pentafluorobenzyl)-1H-imidazol-3-ium bromide

Conditions	Yield
In acetonitrile at 60℃; for 2h; Inert atmosphere;	95%

bromopentafluorobenzene (344-04-7) + naphthalene-2-boronic acid (32316-92-0) → 2-(2,3,4,5,6-pentafluorophenyl)naphthalene (52331-48-3)

Conditions	Yield
With potassium phosphate tribasic trihydrate; palladium diacetate; tricyclohexylphosphine In water; toluene for 12h; Inert atmosphere; Reflux;	95%

bromopentafluorobenzene (344-04-7) → pentafluorophenyl lithium (1076-44-4)

Conditions	Yield
With n-butyllithium In diethyl ether; hexane at -78 - 20℃; for 2h; Inert atmosphere;	94.3%
With n-butyllithium In hexane; Petroleum ether at -78℃; for 1h;
With p-tolyllithium In tetrahydrofuran at -70 - -55℃; for 1h;

bromopentafluorobenzene (344-04-7) + 4,4'-Difluorobenzophenone (345-92-6) → 2,3,4,4',4'',5,6-heptafluoro-triphenylmethanol (241823-93-8)

Conditions	Yield
Stage #1: bromopentafluorobenzene With magnesium In diethyl ether Metallation; Stage #2: 4,4'-Difluorobenzophenone In diethyl ether for 3h; Grignard reaction; Heating;	94%

bromopentafluorobenzene (344-04-7) + N-(2,4,6-tri-tert-butylphenyl)-N-trimethylsilylamino(dichloro)phosphane → 1,1-bis(pentafluorophenyl)-2,4-bis(2,4,6-tri-tert-butylphenyl)-1,3-diphospha-2,4-diazene (1309766-99-1)

Conditions	Yield
Stage #1: bromopentafluorobenzene With n-butyllithium In diethyl ether at -80℃; for 0.25h; Stage #2: N-(2,4,6-tri-tert-butylphenyl)-N-trimethylsilylamino(dichloro)phosphane In diethyl ether at -80℃;	93.4%

Upstream product

• 353-54-8 tribromofluoromethane 
• 5272-26-4 trifluoro(pentafluorophenyl)silane 
• 2314-97-8 iodotrifluoromethane 
• 1206-46-8 trimethyl(pentafluorophenyl)silane 
• 10536-62-6 di-(pentafluoro phenyl) dimethyl silane 
• 771-62-0 pentafluorophenylthiol 
• 769-40-4 2,3,5,6-tetrafluorothiophenol 
• 1494-06-0 bis(pentafluorophenyl) disulfide 
• 116-15-4 perfluoropropylene 
• 1076-44-4 pentafluorophenyl lithium 
• 828-73-9 pentafluorophenyl hydrazine 
• 7726-95-6 bromine 
• 879-06-1 pentafluorophenylmagnesium chloride 
• 30123-12-7 silver(I)pentafluorobenzene 

Downstream Products

• 22096-10-2 1,2,3,4-Tetrafluor-9-phenaethyl-9,10-dihydro-phenanthren 
• 13014-50-1 1,3-di-(pentafluoro phenyl) hexamethyl trisilane 
• 25959-54-0 Trifluormethyl-bis-(pentafluor-phenyl)-carbinol 
• 35369-96-1 bis-(pentafluoro phenyl) bromo ethoxy silane 
• 33558-55-3 (pentafluoro phenyl) pentamethyl disilane 
• 53104-17-9 N-tert-Butyl-N-pentafluorophenyl-hydroxylamine 
• 652-23-3 perfluorostyrene 
• 10536-62-6 di-(pentafluoro phenyl) dimethyl silane 
• 55810-44-1 4-Brom-tetrafluorphenylmalonester 
• 1736-60-3 1-allyl-2,3,4,5,6-pentafluorobenzene 
• 15368-91-9 4-bromo-2,3,5,6-tetrafluoro-1-piperidinobenzene 
• 137812-27-2 1-bromo-4-propoxytetrafluorobenzene 
• 653-34-9 2,3,4,5,6-pentafluorostyrene 
• 101565-24-6 perfluoro-2-methyl-3-phenyl-2-pentene 

Relevant articles and documents

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One-pot route to X-perfluoroarenes (X = Br, I) based on FeIII-assisted C-F functionalization and utilization of these arenes as building blocks for crystal engineering involving halogen bonding

Perfluorinated arenes (benzeneF derivatives, diphenylF, naphthaleneF) were converted into X-perfluoroarenes (X = Br, I) via the developed one-pot protocol based on [Fe(acetylacetonate)3]-assisted C-F functionalization. The syntheses proceed under mild conditions and employ readily available perfluorinated arenes, which are treated with EtMgBr followed by addition of X2/[Fe(acetylacetonate)3] (0.8 mol %); yields range from good to moderate. The σ-hole donor properties of the obtained mono- and di-X-perfluoroarenes and the significance of these species for halogen-bonding-based crystal engineering was illustrated in a series of postsynthetic experiments, all supported by density functional theory (DFT) energy calculations, molecular electrostatic potential (MEP) surface analysis, and the quantum theory of atoms in molecules (QTAIM). These include (i) a solid-state X-ray diffraction study of X-perfluoroarene self-association (dimerization) via iodine σ-hole - electron belt interactions (three X-ray structures) and (ii) verification of X-perfluoroarene σ-hole donor abilities by their interactions with iodides acting as external σ-hole acceptors (five X-ray structures); a Hirshfeld surface analysis was performed for all eight structures.

Unexpected reactivity of cyclic perfluorinated iodanes with electrophiles

We have found that cyclic perfluorinated iodanes react with electrophiles (E+ = Br, Cl, F, I) to afford perfluorinated E-RF compounds. This reactivity is unexpected since cyclic perfluorinated iodanes are considered as electrophilic reagents that normally react with nucleophiles (e.g. Nu- = SR, OR) to afford Nu-RF products. The utility of this new transformation is demonstrated for a [18F]CF3CF2-containing compound which was prepared from [18F]XeF2 obtained from cyclotron produced [18F]fluoride.

Unexpected distinction in reactivity of pentafluorobenzenesulfonyl halides toward organolithiums and organomagnesium halides

C6F5SO2Cl reacts with organolithiums and organomagnesium halides RM (R = Me, Bu, Ph; M = Li, MgX) to give mainly C6F5H and C6F5Cl. C6F5SO2Br and