106-39-8

Basic information

• Product Name: 4-Bromochlorobenzene
• Synonyms: 1-Bomo-4-chlorobenzene;1-Chloro-4-bromobenzene;4-Chlorophenyl bromide;4-Chloro-1-bromobenzene;4-Chlorobromobenzene;Benzene, 1-bromo-4-chloro-;p-Bromophenyl chloride;p-Chlorophenyl bromide;p-Bromochlorobenzene;p-Chlorobromobenzene;para-Bromo Chlorobenzene;p-Chlorobromobenzen;4-Bromo Chlorobenzene
• CAS NO: 106-39-8
• Molecular Formula: C₆H₄BrCl
• Molecular Weight: 191.453
• EINECS: 203-392-3
• Product Categories: alkyl bromide| alkyl chloride;Building Blocks;Chemical Synthesis;Halogenated Hydrocarbons;Organic Building Blocks;C6;Halogenated Hydrocarbons;BENZENE BASED BROMO;A-BAlphabetic;Alpha Sort;B;BI - BZChemical Class;BromoChemical Class;Chloro;Halogenated;Volatiles/ Semivolatiles;Aryl
• Mol File: 106-39-8.mol
• Article Data: 72

Chemical Properties

• Melting Point: 64-67℃
• Boiling Point: 192.651 °C at 760 mmHg
• Flash Point: 78.434 °C
• Appearance: white to almost white crystalline powder
• Density: 1.628 g/cm³
• Vapor Pressure: 0.674mmHg at 25°C
• Refractive Index: 1.574
• Storage Temp.: 2-8°C
• Solubility: 0.045g/l
• Water Solubility: insoluble
• BRN: 1099014
• CAS DataBase Reference: 4-Bromochlorobenzene(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Bromochlorobenzene(106-39-8)
• EPA Substance Registry System: 4-Bromochlorobenzene(106-39-8)

Safety Data

• Hazard Codes: Xn:Harmful
• Statements: R20/22:; R36/37/38:
• Safety Statements: S26:; S37/39:
• RIDADR: UN 1230 3/PG 2
• WGK Germany: 3
• RTECS: CY9006000
• TSCA: Yes
• HazardClass: 6.1
• Hazardous Substances Data: 106-39-8(Hazardous Substances Data)

Usage

Chemical Properties

white to almost white crystalline powder

Uses

1-Bromo-4-chlorobenzene is used as a pharmaceutical intermediate.

Synthesis Reference(s)

Journal of the American Chemical Society, 86, p. 964, 1964 DOI: 10.1021/ja01059a073The Journal of Organic Chemistry, 55, p. 3415, 1990 DOI: 10.1021/jo00297a087

InChI:InChI=1/C6H4BrCl/c7-5-1-3-6(8)4-2-5/h1-4H

Synthetic route

p-chlorobenzenediazonium tetrafluoroborate (673-41-6) → bromochlorobenzene (106-39-8)

Conditions	Yield
With dibenzo-18-crown-6; potassium bromide; copper(ll) bromide; 1,10-Phenanthroline; copper(I) bromide In acetonitrile at 20℃; for 0.333333h; Sandmeyer bromination;	99%
With N-Bromosuccinimide; tetrabutylammonium perchlorate In methanol; N,N-dimethyl-formamide at 20℃; for 3h; Sandmeyer Reaction; Electrochemical reaction;	52%

chlorobenzene (108-90-7) → bromochlorobenzene (106-39-8)

Conditions	Yield
With sulfuric acid; tetramethylammonium bromide at 120℃; for 3h; Product distribution; Further Variations:; Reagents;	98%
With sulfuric acid; potassium bromide at 60℃; for 2h;	95%
With Oxone; sodium bromide In water at 20℃; for 3h; regioselective reaction;	90%

p-Toluolsulfonylnitrit (66021-66-7) → bromochlorobenzene (106-39-8) + N,N'-bis(p-toluenesulfonyl)hydroxylamine (56410-24-3)

Conditions	Yield
With 4-bromo-aniline; copper dichloride In acetonitrile at 25℃; for 1h;	A 93% B 83%

4-bromo-aniline (106-40-1) → bromochlorobenzene (106-39-8) + N,N'-bis(p-toluenesulfonyl)hydroxylamine (56410-24-3)

Conditions	Yield
With p-toluenesulfonyl nitrite; copper dichloride In acetonitrile for 0.75h;	A 93% B n/a

4-Chlorophenylboronic acid (1679-18-1) → bromochlorobenzene (106-39-8)

Conditions	Yield
With sodium nitrite In acetonitrile at 80℃; for 1h; Sealed tube;	93%
With N-Bromosuccinimide In acetonitrile at 81℃; for 8h;	65%

4-bromo-benzenediazonium; tetrachloro cuprate(II) → bromochlorobenzene (106-39-8)

Conditions	Yield
In dimethyl sulfoxide Ambient temperature;	92%

4-bromo-2,4,6-trimethyldiphenyliodonium trifluoromethanesulfonate (1203709-75-4) → bromochlorobenzene (106-39-8)

Conditions	Yield
With copper(l) chloride In acetonitrile at 80℃; for 2h;	89%

(4-chlorophenyl)(mesityl)iodonium trifluoromethanesulfonate (1204518-00-2) → bromochlorobenzene (106-39-8)

Conditions	Yield
With copper(I) bromide In acetonitrile at 80℃; for 2h;	85%

4-bromo-aniline (106-40-1) → bromochlorobenzene (106-39-8)

Conditions	Yield
With N-chloro-succinimide; sodium nitrite In N,N-dimethyl-formamide at 20℃; for 6h;	83%
With tert.-butylnitrite; N-benzyl-N,N,N-triethylammonium chloride; copper dichloride; 10-camphorsulfonic acid In acetonitrile at 20℃; for 24h; Time; Solvent;	43%

1-(p-chlorophenyl)-3,3-dimethyl-1-triazene (7203-90-9) → bromochlorobenzene (106-39-8)

Conditions	Yield
With methanesulfonic acid; tetrabutyl-ammonium chloride; copper In acetonitrile at 40℃; for 0.25h;	82%

potassium 4-bromophenyltrifluoroborate (374564-35-9) → bromochlorobenzene (106-39-8)

Conditions	Yield
With trichloroisocyanuric acid In water; ethyl acetate at 20℃; for 1h; Open flask;	81%

4-chloro-aniline (106-47-8) → bromochlorobenzene (106-39-8) + N,N'-bis(p-toluenesulfonyl)hydroxylamine (56410-24-3)

Conditions	Yield
With p-toluenesulfonyl nitrite; copper(ll) bromide In acetonitrile at 25℃; for 0.0166667h;	A 79% B n/a

4-bromo-phenol (106-41-2) → bromochlorobenzene (106-39-8)

Conditions	Yield
With phenylphosphorus tetrachloride at 160℃;	78%

4-(chloro)benzenediazonium benzo[d][1,3,2]dithiazol-2-ide-1,1,3,3-tetraoxide → bromochlorobenzene (106-39-8)

Conditions	Yield
With tetrabutylammomium bromide; copper In acetonitrile at 20℃; for 0.75h; Substitution;	75%
With tetrabutylammomium bromide In acetonitrile at 60℃; for 0.75h; Substitution;	73%
Multi-step reaction with 2 steps 1: 90 percent / aq. NaOH / 0.5 h / 0 - 5 °C 2: 82 percent / Bu4N(+)Cl(-); MeSO3H; Cu / acetonitrile / 0.25 h / 40 °C View Scheme

4-Bromobenzenediazonium o-benzenedisulfonimide → bromochlorobenzene (106-39-8)

Conditions	Yield
With N-benzyl-N,N,N-triethylammonium chloride; copper In acetonitrile at 20℃; Substitution;	74%

4-chlorophenylhydrazine hydrochloride (1073-70-7) → bromochlorobenzene (106-39-8)

Conditions	Yield
With boron tribromide; dimethyl sulfoxide at 80℃; for 1h;	72%

4-chlorophenyldiazonium salt (17333-85-6) → bromochlorobenzene (106-39-8)

Conditions	Yield
With tin(II); chloride; copper(II) nitrate In water for 0.5h; Ambient temperature;	70%
With copper(I) bromide

4-chloro-aniline (106-47-8) → bromochlorobenzene (106-39-8)

Conditions	Yield
With N-Bromosuccinimide; sodium nitrite In N,N-dimethyl-formamide at 20℃; for 6h;	68%
With tert.-butylnitrite; tetrabutylammomium bromide; copper(I) bromide; 10-camphorsulfonic acid In acetonitrile at 20℃; for 24h; Reagent/catalyst; Time; Solvent;	61%
With tert.-butylnitrite; tetrabutylammomium bromide; toluene-4-sulfonic acid; copper(ll) bromide In acetonitrile at 20℃; for 23h;	58%

2-methylenesuccinic acid (97-65-4) + (4-bromophenyl)diazonium chloride (2028-85-5) → bromochlorobenzene (106-39-8) + C11H10BrClO4 (1427331-03-0)

Conditions	Yield
With copper(II) choride dihydrate In [(2)H6]acetone; water at 25℃; for 2.5h; Meerwein Arylation;	A n/a B 62%

chlorobenzene (108-90-7) → bromochlorobenzene (106-39-8) + 2-bromo-1-chlorobenzene (694-80-4)

Conditions	Yield
With N-Bromosuccinimide; iron(III) chloride In acetonitrile for 2h;	A 57% B 38%
With potassium bromate In sulfuric acid; acetic acid for 1h; Heating; Yields of byproduct given;	A 52% B n/a
With potassium bromate In sulfuric acid; acetic acid for 1h; Heating; Yield given;	A 52% B n/a

bromobenzene (108-86-1) → bromochlorobenzene (106-39-8)

Conditions	Yield
With lead(IV) acetate; tin(IV) chloride In dichloromethane for 20h;	56%
With thallium chloride at 100℃; durch Chlorierung;
With iron(III) chloride

1-(4-chlorophenyl)silatrane (29025-67-0) → bromochlorobenzene (106-39-8)

Conditions	Yield
With N-Bromosuccinimide In dichloromethane for 8h; Ambient temperature;	52%

Trichloroethylene (79-01-6) + (4-bromophenyl)diazonium chloride (2028-85-5) → bromochlorobenzene (106-39-8) + 1-Brom-4-<1,2,2,2-tetrachlor-ethyl>-benzol (4714-31-2)

Conditions	Yield
With potassium chloride; copper dichloride In water; acetone	A n/a B 52%

(4-bromophenyl)diazonium chloride (2028-85-5) → bromochlorobenzene (106-39-8) + 1-Brom-4-<1,2,2,2-tetrachlor-ethyl>-benzol (4714-31-2)

Conditions	Yield
With Trichloroethylene; potassium chloride; copper dichloride In water; acetone	A n/a B 52%

C7H6ClN7 (93680-29-6) → bromochlorobenzene (106-39-8)

Conditions	Yield
With tetrabutylammomium bromide; trifluoroacetic acid In acetonitrile at 70 - 80℃;	40%

p-chlorobenzenediazonium tetrafluoroborate (673-41-6) → bromochlorobenzene (106-39-8) + 1-Chloro-4-fluorobenzene (352-33-0) + chlorobenzene (108-90-7)

Conditions	Yield
With trimethylsilyl bromide; 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate; copper(I) bromide at 70℃; Schiemann reaction;	A 4% B 61 % Chromat. C 35%

2-nitro-aniline (88-74-4) → bromochlorobenzene (106-39-8)

Conditions	Yield
With tert-Butyl thionitrate; Bromoform for 0.5h; Heating;	25%

chlorobenzene (108-90-7) → bromochlorobenzene (106-39-8) + 1-bromo-3-chlorobenzene (108-37-2)

Conditions	Yield
With bromine trifluoride; bromine at 0 - 10℃;	A 25% B 5%

para-chlorobenzoic acid (74-11-3) → bromochlorobenzene (106-39-8)

Conditions	Yield
With bromine; mercury(II) oxide In nitrobenzene at 180 - 185℃; for 2h;	22%

bromochlorobenzene (106-39-8) → 4,4'-dichlorobiphenyl (2050-68-2)

Conditions	Yield
With [Pd{C6H4(CH2N(CH2Ph)2)}(μ-Br)]2; potassium carbonate In 1-methyl-pyrrolidin-2-one at 130℃; for 3h; Microwave irradiation; chemoselective reaction;	100%
Stage #1: bromochlorobenzene With tert.-butyl lithium In diethyl ether at -78℃; Stage #2: In diethyl ether Stage #3: With Duroquinone In diethyl ether	96%
With potassium carbonate In N,N-dimethyl-formamide for 0.666667h;	96%

bromochlorobenzene (106-39-8) → benzene (71-43-2)

Conditions	Yield
With potassium hydroxide; hydrogen; palladium on activated charcoal; Aliquat 336 In water at 50℃; for 0.833333h;	100%
With di-tert-butyl peroxide; caesium carbonate; isopropyl alcohol at 120℃; for 3h; Inert atmosphere;	93 %Chromat.
With ammonium formate In methanol at 20℃; for 16h;

bromochlorobenzene (106-39-8) + phenylboronic acid (98-80-6) → 4'-biphenyl chloride (2051-62-9)

Conditions	Yield
With potassium carbonate In ethanol at 80℃; for 36h; Suzuki-Miyaura Coupling; Inert atmosphere;	100%
With C28H38Cl2N2O6PdS2(2-)*2Na(1+); tetrabutylammomium bromide; potassium carbonate In water at 75℃; Suzuki coupling; Inert atmosphere;	99%
With Br(1-)*C28H29BrN5O2Pd(1+); potassium carbonate In methanol; water at 100℃; for 3h; Suzuki-Miyaura coupling;	99%

bromochlorobenzene (106-39-8) + diphenylamine (122-39-4) → (p-chlorophenyl)diphenylamine (4316-56-7)

Conditions	Yield
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; palladium 10% on activated carbon; sodium t-butanolate In 1,3,5-trimethyl-benzene for 24h; Inert atmosphere; Reflux;	100%
With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene at 80℃;	90.7%
With tris-(dibenzylideneacetone)dipalladium(0); johnphos; sodium t-butanolate In toluene at 100℃; for 24h; Buchwald-Hartwig Coupling; Sealed tube; Inert atmosphere;	79%

bromochlorobenzene (106-39-8) + tert-butyl 1,4-diazepine-1-carboxylate (112275-50-0) → tert-butyl 4-(4-chlorophenyl)-1,4-diazepane-1-carboxylate (868063-67-6)

Conditions	Yield
With sodium t-butanolate; tris-(dibenzylideneacetone)dipalladium(0); 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In toluene for 23h; Heating / reflux;	100%
With sodium t-butanolate; tris-(dibenzylideneacetone)dipalladium(0); 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In toluene for 23h; Heating / reflux;	100%

bromochlorobenzene (106-39-8) + potassium 3-aminothiophene-2-carboxylate (1210469-45-6) → 3-amino-2-(4-chlorophenyl)thiophene (183676-87-1)

Conditions	Yield
With 1,1'-bis-(diphenylphosphino)ferrocene; tetrabutylammomium bromide; palladium dichloride In 1-methyl-pyrrolidin-2-one at 100℃; Inert atmosphere;	100%
With 1,1'-bis-(diphenylphosphino)ferrocene; tetrabutylammomium bromide; palladium dichloride In 1-methyl-pyrrolidin-2-one; N,N-dimethyl-formamide at 80℃; for 16h; Inert atmosphere;	77%

4-tributylstannanyl-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester (208465-07-0) + bromochlorobenzene (106-39-8) → 4-(4-Chloro-phenyl)-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester (138647-50-4)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0) In toluene at 120℃; for 17h;	100%

bromochlorobenzene (106-39-8) + tert-butyl (3aR,6aS)-5-methylene-1,3,3a,4,6,6a-hexahydrocyclopenta[c]pyrrole-2-carboxylate (139228-12-9) → (3aR,6aS)-tert-butyl 5-(4-chlorobenzyl)hexahydrocyclopenta[c]pyrrole-2(1H)-carboxylate

Conditions	Yield
Stage #1: tert-butyl (3aR,6aS)-5-methylene-1,3,3a,4,6,6a-hexahydrocyclopenta[c]pyrrole-2-carboxylate With 9-bora-bicyclo[3.3.1]nonane In tetrahydrofuran at 65℃; for 1h; Stage #2: bromochlorobenzene With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium carbonate In tetrahydrofuran; 1,4-dioxane; water at 65℃; for 48h;	100%

bromochlorobenzene (106-39-8) → 4,4'-dichlorobiphenyl (2050-68-2) + chlorobenzene (108-90-7)

Conditions	Yield
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; cesium fluoride In 2-pentanol at 100℃; for 57h; Inert atmosphere;	A 0.8% B 99.2%
In 1,2-dimethoxyethane at 85℃; Product distribution; var. solvents; var. times; Ni from NiI2 or NiBr2;
With nickel In 1,2-dimethoxyethane at 85℃; for 20h;	A 61 % Chromat. B 32 % Chromat.

bromochlorobenzene (106-39-8) + allyl bromide (106-95-6) → 1-allyl-4-chlorobenzene (1745-18-2)

Conditions	Yield
Stage #1: bromochlorobenzene With iodine; magnesium In diethyl ether Inert atmosphere; Reflux; Stage #2: allyl bromide In diethyl ether at 0 - 20℃; for 2.08333h; Inert atmosphere;	99%
(i) Mg, Et2O, (ii) /BRN= 605308/; Multistep reaction;
Stage #1: bromochlorobenzene With iodine; magnesium In diethyl ether for 2h; Reflux; Inert atmosphere; Stage #2: allyl bromide In diethyl ether at 20℃; Cooling with ice; Inert atmosphere;

bromochlorobenzene (106-39-8) + triethyl phosphite (122-52-1) → diethyl (4-chlorophenyl)phosphonate (2373-43-5)

Conditions	Yield
With tri-n-propylamine; tetrabutylammomium bromide; palladium dichloride In water at 100℃; for 4h; Green chemistry; chemoselective reaction;	99%
With triethylamine In water at 100℃; for 5h; Green chemistry;	92%
With triethylamine In water at 100℃; for 5h; Arbuzov Reaction; Green chemistry;	91%

bromochlorobenzene (106-39-8) + acrylic acid n-butyl ester (141-32-2) → butyl p-chlorocinnamate (123248-22-6, 42175-12-2)

Conditions	Yield
With [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(ll) dichloride; tetrabutylammomium bromide; triethylamine In N,N-dimethyl-formamide at 140℃; for 20h; Reagent/catalyst; Heck Reaction; Sealed tube; Inert atmosphere; Schlenk technique;	99%
With potassium carbonate at 120℃; for 2.25h; Catalytic behavior; Heck Reaction;	98%
With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 3h; Catalytic behavior; Heck Reaction;	97%

bromochlorobenzene (106-39-8) + 2-(6-bromo-pyridin-2-yl)-4-methylpyrimidine (122918-19-8) → 2-[6-(4-chloro-phenyl)-pyridin-2-yl]-4-methyl-pyrimidine

Conditions	Yield
Stage #1: bromochlorobenzene With n-butyllithium In tetrahydrofuran Dehalogenation; Stage #2: With zinc(II) chloride In diethyl ether at 20℃; Metallation; Stage #3: 2-(6-bromo-pyridin-2-yl)-4-methylpyrimidine; tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran; diethyl ether for 2h; Substitution; Heating;	99%

styrene (292638-84-7) + bromochlorobenzene (106-39-8) → (E)-1-(4-chlorophenyl)-2-phenylethene (1657-50-7) + 1-(4-chlorophenyl)-1-phenylethene (18218-20-7)

Conditions	Yield
With sodium carbonate; Pd-montmorillonite In 1-methyl-pyrrolidin-2-one at 150℃; for 2h; Heck reaction;	A 99% B n/a
With 1-methyl-pyrrolidin-2-one; sodium acetate; palladium diacetate at 135℃; for 15h; Heck reaction;
With sodium acetate; PdCl2[2-[(1-MeS-S)-3-[(Ph2P-P)oxy]propyl]-N,N-Me2-aniline] In N,N-dimethyl-formamide at 130℃; for 24h; Heck reaction; Title compound not separated from byproducts;
With tetrabutyl-ammonium chloride; sodium carbonate; Pd-MCM-41 In 1-methyl-pyrrolidin-2-one at 150℃; for 6h; Heck coupling; Title compound not separated from byproducts;

bromochlorobenzene (106-39-8) + sodium tetraphenyl borate (143-66-8) → 4'-biphenyl chloride (2051-62-9)

Conditions	Yield
With potassium carbonate In water at 50℃; for 0.333333h; Suzuki Coupling;	99%
With sodium carbonate at 80℃; for 0.333333h; Green chemistry;	98%
With potassium carbonate at 100℃; for 1h; Catalytic behavior;	97%

1H-imidazole (288-32-4) + bromochlorobenzene (106-39-8) → 1-(4-chlorophenyl)imidazole (51581-54-5)

Conditions	Yield
With copper(l) iodide; potassium carbonate; heptakis(6-amino-6-deoxy)-β-cyclodextrin In dimethyl sulfoxide at 110℃; for 24h; Sealed tube;	99%
With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 8h; chemoselective reaction;	98%
With copper(I) oxide; potassium phosphate; N1,N2-bis(furan-2-ylmethyl)oxalamide In dimethyl sulfoxide at 120℃; for 24h;	97%

bromochlorobenzene (106-39-8) + ortho-nitrobenzoic acid (552-16-9) → 4'-chloro-2-nitrobiphenyl (6271-80-3)

Conditions	Yield
Stage #1: ortho-nitrobenzoic acid With potassium carbonate In various solvent(s) at 120℃; for 0.5h; Stage #2: bromochlorobenzene With 1,10-Phenanthroline; copper(l) iodide In various solvent(s) at 160℃; for 24h; Further stages.;	99%
With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; N,N-dimethyl-aniline; silver carbonate; palladium dichloride at 150℃; for 2h;	35%
Stage #1: ortho-nitrobenzoic acid; copper(II) carbonate In 1-methyl-pyrrolidin-2-one Stage #2: bromochlorobenzene; bis(acetylacetonato)palladium(II); triphenylphosphine In 1-methyl-pyrrolidin-2-one at 120℃; for 24h; Product distribution / selectivity;	9 %Chromat.

bromochlorobenzene (106-39-8) + 4-methylphenylboronic acid (5720-05-8) → 4-chloro-4'-methylbiphenyl (19482-11-2)

Conditions	Yield
With 2C60H80NaO12*Cl6Pd2; potassium carbonate In methanol; water at 20℃; for 0.166667h; Suzuki coupling;	99%
With sodium hydroxide In ethanol; water at 25℃; for 4.5h; Suzuki Coupling;	98%
With sodium carbonate In 1-methyl-pyrrolidin-2-one at 100℃; for 10h; Suzuki-Miyaura Coupling; Inert atmosphere;	98%

bromochlorobenzene (106-39-8) + acrylic acid methyl ester (292638-85-8) → methyl 3-(4-chlorophenyl)propenoate (20754-21-6) + methyl 2-(4-chlorophenyl)acrylate (50415-59-3)

Conditions	Yield
With sodium carbonate; Pd-montmorillonite In 1-methyl-pyrrolidin-2-one at 150℃; for 2h; Heck reaction;	A 99% B n/a

bromochlorobenzene (106-39-8) + potassium 4-tolyltriolborate → 4-chloro-4'-methylbiphenyl (19482-11-2)

Conditions	Yield
palladium diacetate In water; N,N-dimethyl-formamide at 20℃; for 5h;	99%
With C24H25Cl3FeN3PPd*C3H6O In ethanol; water at 80℃; for 3h; Suzuki-Miyaura Coupling; Schlenk technique; Inert atmosphere; Sealed tube;	89%

bromochlorobenzene (106-39-8) + phenol (108-95-2) → 4-chlorodiphenyl ether (7005-72-3)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 12h;	99%
With potassium carbonate In N,N-dimethyl-formamide at 110℃;	97%
With copper(l) iodide; iron(III)-acetylacetonate; potassium carbonate In N,N-dimethyl-formamide at 135℃; for 12h; Inert atmosphere;	93%

bromochlorobenzene (106-39-8) + C17H20N2O4S (1207202-14-9) → 1-[1-(4-chlorophenyl)-2-methoxyvinyl]-4-methoxybenzene (1207201-99-7)

Conditions	Yield
Stage #1: C17H20N2O4S With tris(dibenzylideneacetone)dipalladium (0); lithium tert-butoxide; XPhos In 1,4-dioxane for 0.0166667h; Inert atmosphere; Stage #2: bromochlorobenzene In 1,4-dioxane at 90℃; for 14h; Inert atmosphere;	99%

bromochlorobenzene (106-39-8) + thiophenol (108-98-5) → 1,4-bis(phenylthio)benzene (3459-94-7)

Conditions	Yield
With 1,2,3,4-tetrahydroquinolin-8-ol; caesium carbonate; copper(I) bromide In N,N-dimethyl-formamide at 130℃; for 48h; Inert atmosphere; chemoselective reaction;	99%

bromochlorobenzene (106-39-8) + benzaldehyde (100-52-7) → (S)-4-chlorobenzhydrol (101402-04-4)

Conditions	Yield
With triisopropoxytitanium(IV) chloride; phenyllithium In diethyl ether; cyclohexane at -78 - 20℃; for 0.25h; Inert atmosphere; enantioselective reaction;	99%
Stage #1: bromochlorobenzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: With titanium(IV) isopropylate; magnesium bromide In tetrahydrofuran; diethyl ether; hexane for 0.5h; Inert atmosphere; Stage #3: benzaldehyde With titanium(IV) isopropylate; (R)-3-(3,5-diphenylphenyl)-2,2'-dihydroxy-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl In diethyl ether; dichloromethane at 0℃; for 3h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	80%
Multi-step reaction with 2 steps 1.1: C36H31F2N2(1+)*BF4(1-); copper(l) chloride; sodium trimethylsilanolate / toluene / 0.42 h / 25 °C / Inert atmosphere; Sealed tube 1.2: 3 h / 60 °C / Inert atmosphere; Sealed tube 2.1: tetrabutyl ammonium fluoride / Inert atmosphere View Scheme

benzoxazole (273-53-0) + bromochlorobenzene (106-39-8) → 2-(4-chlorophenyl)benzoxazole (1141-35-1)

Conditions	Yield
With palladium diacetate; sodium t-butanolate; nixantphos In N,N-dimethyl-formamide at 24℃; for 12h; Heck Reaction; Inert atmosphere;	99%
With [(N,N'-bis-(2,6-di(isopropyl)phenyl)imidazolidin-2-ylidene)Pd(allyl)]2(μ2-trans-4,4'-bipyridylethylene)(BF4)2; lithium tert-butoxide In 1,2-dimethoxyethane at 10℃; for 12h; Catalytic behavior; Reagent/catalyst; Sealed tube;	94%
With palladium diacetate; copper(II) acetate monohydrate; potassium carbonate; triphenylphosphine In toluene for 3h; Reflux; under air;	87%
With n-butyllithium; palladium diacetate; C45H35P2(1+)*CF3O3S(1-); caesium carbonate In dimethyl sulfoxide at 50℃; for 14h; Inert atmosphere;	85%

bromochlorobenzene (106-39-8) + ethanolamine (141-43-5) → 2-(4-chlorophenylamino)ethanol (2933-81-5)

Conditions	Yield
With copper(l) chloride; potassium hydroxide at 90℃; for 8h; Neat (no solvent);	99%

bromochlorobenzene (106-39-8) + benzaldehyde (100-52-7) → 4-chlorobenzophenone (134-85-0)

Conditions	Yield
With palladium diacetate; N-picolinoylcyclohexylamine; potassium hydrogencarbonate In tert-Amyl alcohol at 150℃; for 24h;	99%

bromochlorobenzene (106-39-8) + 3-(methylsulphinyl)thiophene (133361-97-4) → 2,5-bis(4-chlorophenyl)-3-(methylsulfinyl)thiophene

Conditions	Yield
With di(1-adamantyl)-n-butylphosphine; cesium acetate; bis(dibenzylideneacetone)-palladium(0) at 100℃; for 12h; Inert atmosphere; regioselective reaction;	99%

bromochlorobenzene (106-39-8) + 4,5-dimethyl-9-phenyl-9H-fluoren-9-ol → C27H21ClO

Conditions	Yield
With chloro(2’-amino-1,1’-biphenyl-2-yl)palladium(II) dimer; C60H54NO5P; sodium hydride In toluene at 80℃; for 12h; Inert atmosphere; enantioselective reaction;	99%

Upstream product

• 17333-85-6 4-chlorophenyldiazonium salt 
• 17333-82-3 4-bromo-benzenediazonium ion 
• 108-86-1 bromobenzene 
• 2396-00-1 4-chlorophenyl radical 
• 108-90-7 chlorobenzene 
• 79-01-6 Trichloroethylene 
• 2028-85-5 (4-bromophenyl)diazonium chloride 
• 7726-95-6 bromine 
• 7446-70-0 aluminium trichloride 
• 56-23-5 tetrachloromethane 
• 75-15-0 carbon disulfide 
• 7727-15-3 aluminium bromide 
• 563-70-2 bromonitromethane 
• 7782-50-5 chlorine 

Downstream Products

• 34328-31-9 (4-chloro-phenyl)-(4-trifluoromethyl-phenyl)-methanone 
• 5120-72-9 p-chlorophenyl ethyl sulfide 
• 29480-19-1 adamant-2-yl(4-chlorophenyl)methanol 
• 93310-14-6 1-p-Chlorphenylcyclooctanol 
• 825-93-4 4-chlorophenyl-methyl-dichlorosilane 
• 29480-09-9 1-(4-chlorophenyl)cyclobutan-1-ol 
• 18985-56-3 1,4-Bis--benzol 
• 90350-28-0 4-bromo-1-chloro-2-isopropylbenzene 
• 17881-26-4 Dimethoxy-methyl-<4-chlor-phenyl>-silan 
• 35107-80-3 1-(4-Chloro-phenyl)-1,1,2,2-tetramethyl-disilane 
• 18759-07-4 Hexadecyl-tri--silan 
• 18817-86-2 Octadecyl-tri--silan 
• 29304-86-7 7-(4-chlorophenyl)-cyclohepta-1,3,5-triene 
• 36229-23-9 2,4-Di-p-chlorphenyl-2,4-pentandiol 

Relevant articles and documents

-

-

Eco-compatible zeolite-catalysed continuous halogenation of aromatics

A completely eco-compatible halogenation reaction of arenes has been developed allowing high conversions (>95%) of iodobenzene with nearly 100 kg iodobenzene converted per kgcat in one day. Several solid acids, zeolites being the most promising, have been successfully tested in the chlorination reaction of iodobenzene by using trichloroisocyanuric acid (TCCA), a green chlorination agent. H-?BEA zeolites were found to be the most active catalysts for this model halogenation reaction. A strong structure-activity relationship could be established by thorough characterisation (SEM, BET, XRD, FTIR) of various synthetic zeolites. Indeed, nano-sized ?BEA zeolites and more specifically nanosponge-like ?BEA crystals exhibited the highest catalytic performance with a conversion up to 100% and a selectivity toward monochlorinated products up to 98%. Finally, the gained knowledge was applied to set-up an eco-compatible continuous flow halogenation process of different aromatics catalysed by H-?BEA zeolites.

Highly para-Selective Mono-Chlorination of Aromatic Compounds Under Mild Conditions by t-Butyl Hypochlorite in the Presence of Zeolites

t-Butyl hypochlorite supported on H(1+), Na(1+) faujasite X (zeolite X) produces para-selective monochlorination of alkyl-, phenyl-, and halobenzenes under mild conditions; for example, chlorobenzene in acetonitrile (at 40 deg C) is chlorinated in high yield of isolated product (92percent) to give dichlorobenzene with an isomer ratio 97percent para/3percent ortho.

-

-

Decarboxylative Ipso Halogenation of Mercury(II) Pyridinecarboxylates. Facile Formation of 3-Iodo- and 3-Bromopyridines

Treatment of mercury(II) nicotinate with iodine and bromine in nitrobenzene at 180-185 deg C for 2 h afforded 3-iodo- and 3-bromopyridines in 44percent and 27percent yields, respectively, without any regioisomers and dihalopyridines.From mercury(II) picolinate only 2-3percent of 2-bromopyridine was obtained under similar reaction conditions, while the reaction using mercury(II) isonicotinate did not give any products.When a mixture of nicotinic acid and HgO was used in place of mercury(II) nicotinate, the halodecarboxylation occurred with similar ease.An ionic pathway involving the initial attack of electrophilic Hg(II) species on the ring-C bearing carboxyl group to afford a 3-pyridylmercury(II) compound and the subsequent replacement of the Hg(II) moiety by electrophilic iodine and bromine was proposed for this reaction.

Poly-N-bromosulfonamide-melamine as a novel brominating reagent for regioselective ipso-bromination of arylboronic acids

A practical synthetic method for the synthesis of aryl bromide was developed through regioselective bromination of boronic acid in the presence of poly-N-bromosulfonamide-melamine (PBBSM). In this regard, a novel heterogeneous support, cross-linked poly sulfonamide-melamine, has been successfully synthesized to stabilize bromine with high surface functional group density (6.6?mmol Br+/g). The prepared reagent is a novel brominating reagent that combines the effective functions of N-bromosulfonamide, N-bromosulfonamide-melamine, and melamine groups. The structure of PBBSM was characterized using XRD, FT–IR, 1H NMR, TGA, FE-SEM, EDX, and TGA analysis. Graphic abstract: [Figure not available: see fulltext.]

Metal- and base-free synthesis of aryl bromides from arylhydrazines

An efficient method was developed to synthesize brominated aromatic compounds from arylhydrazine hydrochlorides by using BBr3 in DMSO/CPME (cyclopentyl methyl ether) under air at 80 °C for 1 h without the use of bases or metal catalysts. In particular, this method could be carried out satisfactorily using electron-withdrawing groups to afford aryl bromides in a moderate to excellent yields.