872-31-1

Basic information

• Product Name: 3-Bromothiophene
• Synonyms: 3-bromo-thiophen;beta-Bromothiophene;thiophene,3-bromo-;β-bromothiophene;TIMTEC-BB SBB003930;TIMTEC-BB SBB003931;ALPHA-THIENYL BROMIDE;3-THIENYL BROMIDE
• CAS NO: 872-31-1
• Molecular Formula: C₄H₃BrS
• Molecular Weight: 163.04
• EINECS: 213-699-4
• Product Categories: Thiophenes;Heterocycles;Halides;Thiophenes & Benzothiophenes;Thiophene&Benzothiophene;Miscellaneous;Thiophene Derivatives (for Conduting Polymer Research);Functional Materials;Reagents for Conducting Polymer Research;Thiophen;Thiophenes & Benzothiophenes;Heterocycle-oher series;alkyl bromide
• Mol File: 872-31-1.mol
• Article Data: 30

Chemical Properties

• Melting Point: <-10°C
• Boiling Point: 158 °C
• Flash Point: 140 °F
• Appearance: Clear colorless to slightly yellow/Liquid
• Density: 1.74 g/mL at 25 °C(lit.)
• Vapor Pressure: 3.41mmHg at 25°C
• Refractive Index: n20/D 1.591(lit.)
• Storage Temp.: 0-6°C
• Solubility: Chloroform (Slightly), Methanol (Slightly)
• Water Solubility: IMMISCIBLE
• Sensitive: Light Sensitive/Stench
• BRN: 105338
• CAS DataBase Reference: 3-Bromothiophene(CAS DataBase Reference)
• NIST Chemistry Reference: 3-Bromothiophene(872-31-1)
• EPA Substance Registry System: 3-Bromothiophene(872-31-1)

Safety Data

• Hazard Codes: T,Xi,N,Xn
• Statements: 10-25-41-51/53-36/37/38-23/24/25-20/21/22-43-36/37
• Safety Statements: 26-36/37/39-45-61-38-28A-16-24/25-23-36-36/37-24/35
• RIDADR: UN 2929 6.1/PG 2
• WGK Germany: 3
• F: 8
• TSCA: T
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 872-31-1(Hazardous Substances Data)

Usage

Chemical Properties

clear colourless to slightly yellow liquid

Uses

Different sources of media describe the Uses of 872-31-1 differently. You can refer to the following data:
1. 3-Bromothiophene is used in the preparation of derivatives such as thienylenic alpha, μ-diformyl-alpha-oligothiophenes and 3-lithiothiophene. It is also used in the synthesis of 3-lithiothiophene by reacting with n-butyllithium.
2. 3-Bromothiophene can be used as a reactant to synthesize:3,3-Bithiophene via borylation followed by Suzuki coupling.3-Alkylthiophenes by NiDPPP++ catalyzed cross-coupling with Grignard reagents.3-Lithiothiophene by treating with n-butyllithium in hexane.Derivatives of thienylenic α, ω?diformyl?α?oligothiophenes.N-(2-(3-bromothiophen-2-yl)phenyl)methanesulfonamides by coupling at the 2-position with N-arylmethanesulfonamides, mediated by iodobenzene diacetate (178721).

Preparation

Preparation of 3-bromothiophene using 2,5-dibromothiophene2,5-Dibromothiophene (121g, 0.5 moles), tris (3,6-dioxaheptyl) amine (1.0g, 0.003 mole), thiophene (500 cm3) and sodium amide (58.5g, 1.5 mole) were successively charged to a flask which had previously been purged with nitrogen. The reaction mixture was stirred and heated under nitrogen at 50-60°C for 6 hours. The product, after work up as described in Example 3, was found to contain 138.5g 3-bromothiophene and 2.6g 2-bromothiophene. The yield of 3-bromothiophene was 85% and the monobromothiophenes were in the ratio of 2 parts 2-bromothiophene to 98 parts 3-bromothiophene.

Synthesis Reference(s)

Journal of the American Chemical Society, 74, p. 2965, 1952 DOI: 10.1021/ja01132a004Synthetic Communications, 11, p. 25, 1981 DOI: 10.1080/00397918108064278

InChI:InChI=1/C4H3BrS/c5-4-1-2-6-3-4/h1-3H

Synthetic route

2,3-dibromothiophen (3140-93-0) → 3-Bromothiophene (872-31-1)

Conditions	Yield
With dibutylbis(cyclopentadienyl)zirconium at 0℃; for 3h;	98%
With ethyl bromide; diethyl ether; magnesium erhitzen des Reaktionsprodukts mit Wasser;

2,3,5-tribromothiophene (3141-24-0) → 3-Bromothiophene (872-31-1)

Conditions	Yield
With acetic acid; zinc In water for 3h; Reflux;	90%
With acetic acid; zinc In water at 0℃; for 5h; Reflux;	70%
	64%

Tetrabromothiophene (3958-03-0) → 3-Bromothiophene (872-31-1)

Conditions	Yield
With hydrogen bromide; lead acetate In methanol electrolysis;	82%
In methanol at 35℃; for 5h; Product distribution; electrolysis in presence of Pb(OAc)2*2H2O, MeN+(C8H17)3Cl-, and HBr at 50 mA/cm2, anolyt : 10percent NH3 in MeOH; other conditions and other bromothiophenes investigated;	82%
In N,N-dimethyl-formamide divided cell electrolysis at constant potential (-1.70 V); 0.1 M tetraethylammonium bromide, mercury electrode;	38%
With quinoline; copper

thiophene (188290-36-0) → 3-Bromothiophene (872-31-1)

Conditions	Yield
Stage #1: thiophene With bromine In chloroform at 0℃; Reflux; Stage #2: With sodium hydroxide In chloroform Stage #3: With acetic acid; zinc In water for 8h; Reflux;	80.8%
Stage #1: thiophene With hydrogen bromide; bromine In diethyl ether; water at 22℃; for 22.5h; Inert atmosphere; Stage #2: With acetic acid; zinc In water for 7h; Reflux; Inert atmosphere;	48%
With bromine; sodium acetate; zinc 1) water, reflux, 8 h; 2) reflux, 3 h, water; Yield given. Multistep reaction;

2,3,4-tribromothiophene (3141-25-1) → 3-Bromothiophene (872-31-1) + 3,4-dibromothiophene (3141-26-2)

Conditions	Yield
In N,N-dimethyl-formamide divided cell electrolysis at constant potential (-1.70 V); 0.1 M tetraethylammonium bromide, mercury electrode;	A 74% B 3%

2-bromothiophene (1003-09-4) → 3-Bromothiophene (872-31-1) + 3,4-dibromothiophene (3141-26-2)

Conditions	Yield
With sodium amide; ferric nitrate In ammonia	A 72% B n/a

3,4-dibromothiophene (3141-26-2) → 3-Bromothiophene (872-31-1)

Conditions	Yield
In N,N-dimethyl-formamide divided cell electrolysis at constant potential (-1.70 V); 0.1 M tetraethylammonium bromide, mercury electrode;	60%

thiophene (188290-36-0) → 3-Bromothiophene (872-31-1) + 3,4-dibromothiophene (3141-26-2)

Conditions	Yield
Stage #1: thiophene With bromine In chloroform for 4h; Heating; Stage #2: With acetic acid; zinc In water Heating;	A 23% B 51%

3-Bromo-2-iodothiophene (60404-24-2) + sodium methylate (124-41-4) → 3-Bromothiophene (872-31-1) + 4-bromo-2-methoxythiophene (73882-42-5)

Conditions	Yield
With copper(II) oxide In methanol for 30h; Heating;	A n/a B 25%

sodium methylate (124-41-4) + 3-bromo-4-iodothiophene (73882-41-4) → 3-Bromothiophene (872-31-1) + 4-bromo-2-methoxythiophene (73882-42-5)

Conditions	Yield
With copper(II) oxide In methanol for 72h; Heating;	A n/a B 15%

2,3,5-tribromothiophene (3141-24-0) + n-butyllithium (109-72-8, 29786-93-4) + diethyl ether (60-29-7) → 3-Bromothiophene (872-31-1)

Conditions	Yield
anschliessend mit Wasser behandeln;

4-bromo-thiophene-2-carboxylic acid (16694-18-1) → 3-Bromothiophene (872-31-1)

Conditions	Yield
With quinoline; copper at 220℃;

4,5-Dibromo-thiophene-2-carboxylic acid (6324-10-3) → 3-Bromothiophene (872-31-1)

Conditions	Yield
With quinoline; copper

2-bromothiophene (1003-09-4) → thiophene (188290-36-0) + 3-Bromothiophene (872-31-1)

Conditions	Yield
zeolithe at 100℃;

3-Bromo-2-iodothiophene (60404-24-2) + sodium methylate (124-41-4) → 3-Bromothiophene (872-31-1) + bromotriiodothiophene

Conditions	Yield
With copper(II) oxide In methanol for 30h; Product distribution; Heating;	A n/a B 25 % Chromat.

3-Bromo-2-iodothiophene (60404-24-2) → 3-Bromothiophene (872-31-1) + bromotriiodothiophene + 3-bromo-4-iodothiophene (73882-41-4) + 4-bromo-2-iodothiophene (73882-40-3)

Conditions	Yield
With sodium methylate In methanol for 72h; Product distribution; Heating; another solvents;	A 32 % Chromat. B 4 % Chromat. C 32 % Chromat. D 5 % Chromat.

sodium methylate (124-41-4) + 3-bromo-4-iodothiophene (73882-41-4) → 3-Bromothiophene (872-31-1) + bromotriiodothiophene

Conditions	Yield
With copper(II) oxide In methanol for 72h; Product distribution; Heating;	A n/a B 15 % Chromat.

sodium methylate (124-41-4) + 4-bromo-2-iodothiophene (73882-40-3) → 3-Bromothiophene (872-31-1) + bromotriiodothiophene

Conditions	Yield
With copper(II) oxide In methanol Product distribution; Heating; different reaction times;

2-(trimethylsilyl)-3-bromothiophene (77998-62-0) → 3-Bromothiophene (872-31-1)

Conditions	Yield
In methanol; perchloric acid at 50℃;
In methanol; perchloric acid at 50℃; Rate constant; 1.) other solvents, 2.) k (excit.);
With sodium methylate In methanol at 50℃; Rate constant; deuterium isotope effect;

3-bromo-4-iodothiophene (73882-41-4) → 3-Bromothiophene (872-31-1) + bromotriiodothiophene + 3-Bromo-2-iodothiophene (60404-24-2) + 4-bromo-2-iodothiophene (73882-40-3)

Conditions	Yield
With sodium methylate In pyridine at 60℃; for 72h; Product distribution;	A 32 % Chromat. B 4 % Chromat. C 8 % Chromat. D 5 % Chromat.

4-bromo-2-iodothiophene (73882-40-3) → 3-Bromothiophene (872-31-1) + bromotriiodothiophene + 3-Bromo-2-iodothiophene (60404-24-2) + 3-bromo-4-iodothiophene (73882-41-4)

Conditions	Yield
With sodium methylate In pyridine for 72h; Product distribution; Ambient temperature; different reaction times;	A 32 % Chromat. B 4 % Chromat. C 8 % Chromat. D 32 % Chromat.

(4-bromo-thiophen-2-yl)trimethylsilane (77998-61-9) → 3-Bromothiophene (872-31-1)

Conditions	Yield
In sulfuric acid; acetic acid at 50℃;
In methanol; perchloric acid at 50℃; Rate constant; 1.) other solvents, 2.) k (excit.);
With sodium methylate In methanol at 50℃; Rate constant; deuterium isotope effect;

2,5-dibromothiophen (3141-27-3) → thiophene (188290-36-0) + 2-bromothiophene (1003-09-4) + 3-Bromothiophene (872-31-1) + 3,4-dibromothiophene (3141-26-2)

Conditions	Yield
With tetramethylammonium perchlorate In N,N-dimethyl-formamide Product distribution; Mechanism; controlled-potential electrolysis at reticulated vitreous carbon; further reagents;

2,3,5-tribromothiophene (3141-24-0) → 3-Bromothiophene (872-31-1) + 2,3-dibromothiophen (3140-93-0) + 2,4-dibromothiophene (3140-92-9)

Conditions	Yield
With sodium tetrahydroborate In dimethyl sulfoxide at 26℃; for 4h; Product distribution; Mechanism; other catalysts, var. solvent;
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium tetrahydroborate; N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran for 6h; Reagent/catalyst; Time; Reflux; Inert atmosphere; regioselective reaction;

thiophene (188290-36-0) + bromine (7726-95-6) → 3-Bromothiophene (872-31-1)

Conditions	Yield
at 700 - 750℃;

quinoline (91-22-5) + 4,5-Dibromo-thiophene-2-carboxylic acid (6324-10-3) + copper-powder → 3-Bromothiophene (872-31-1)

quinoline (91-22-5) + Tetrabromothiophene (3958-03-0) + copper → 3-Bromothiophene (872-31-1)

2,3,5-tribromothiophene (3141-24-0) + acetic acid (64-19-7) + zinc → 3-Bromothiophene (872-31-1)

Tetrabromothiophene (3958-03-0) + acetic acid (64-19-7) + zinc → 3-Bromothiophene (872-31-1) + 3,4-dibromothiophene (3141-26-2)

3-Bromothiophene (872-31-1) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → 3-bromo-2-thiophenecarboxaldehyde (930-96-1)

Conditions	Yield
Stage #1: 3-Bromothiophene With lithium diisopropyl amide In tetrahydrofuran at 0 - 5℃; for 0.5h; Inert atmosphere; Large scale; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran at 0 - 5℃; for 3h; Inert atmosphere; Large scale;	100%
Stage #1: 3-Bromothiophene With lithium diisopropyl amide In tetrahydrofuran at 0℃; for 0.5h; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran at 0℃; for 3h;	100%
Stage #1: 3-Bromothiophene With lithium diisopropyl amide In tetrahydrofuran at 0℃; for 1h; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran at 0 - 20℃; for 4h;	94%

3-Bromothiophene (872-31-1) + phenylacetylene (536-74-3) → 1-phenyl-2-(3-thienyl)ethyne (131423-29-5)

Conditions	Yield
With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine In acetonitrile at 60℃; for 16h; Sonogashira coupling;	100%
With 1,4-diaza-bicyclo[2.2.2]octane; bis(η3-allyl-μ-chloropalladium(II)); tri-tert-butyl phosphine In hexane; acetonitrile at 20℃; for 16h; Sonogashira coupling;	96%
With pyrrolidine; bis(η3-allyl-μ-chloropalladium(II)); triphenylphosphine; 1-butyl-3-methylimidazolium Tetrafluoroborate at 100℃; for 4h; Heck alkynylation; Inert atmosphere;	95%

3-Bromothiophene (872-31-1) + 1-t-Butoxycarbonylpiperazine (57260-71-6) → tert-butyl 4-(3-thienyl)piperazine-1-carboxylate

Conditions	Yield
Stage #1: 3-Bromothiophene; 1-t-Butoxycarbonylpiperazine With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In xylene at 50℃; Stage #2: With macroporous polymer-supported isocyanate In xylene at 50℃; for 24h;	100%

3-Bromothiophene (872-31-1) + styrene (292638-84-7) → 3-styryl-thiophene (35022-11-8)

Conditions	Yield
With C50H64Cl2N12Pd2(6+)*6F6P(1-); sodium acetate In N,N-dimethyl-formamide at 140℃; for 4h; Reagent/catalyst; Heck Reaction;	100%
With sodium acetate In water at 20℃; for 0.5h; Heck Reaction; Green chemistry;	95%
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 5h; Catalytic behavior;	88%

3-Bromothiophene (872-31-1) + o-fluorophenylboronic acid (1993-03-9) → 3-(2-fluorophenyl)thiophene (193958-89-3)

Conditions	Yield
With potassium fluoride; palladium diacetate In tetrahydrofuran at 20℃; for 1h; Schlenk technique; Inert atmosphere;	100%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 85℃; for 4h; Inert atmosphere;	99%

3-Bromothiophene (872-31-1) + potassium phosphate + bis(di-tert-butyl(3,5-di-(tert-butyl)phenyl)phosphine)dichloropalladium + 3-pyridylboronic acid (1692-25-7) + butan-1-ol (71-36-3) → 3-(thiophen-3-yl)pyridine (21308-81-6)

Conditions	Yield
In water	100%

3-Bromothiophene (872-31-1) + di-n-heptadecyl ketone (504-53-0) → C39H74OS

Conditions	Yield
Stage #1: 3-Bromothiophene With n-butyllithium In diethyl ether; hexane at -68℃; for 2.5h; Inert atmosphere; Stage #2: di-n-heptadecyl ketone In diethyl ether; hexane at -78 - 25℃; for 5.16667h;	100%
Stage #1: 3-Bromothiophene With n-butyllithium In diethyl ether; hexane at -68℃; for 2.5h; Inert atmosphere; Stage #2: di-n-heptadecyl ketone In diethyl ether; hexane at -78 - 20℃; for 15h; Inert atmosphere;	100%

3-Bromothiophene (872-31-1) + diethylaluminium chloride (96-10-6) → 3-thienyl(diethyl)aluminum

Conditions	Yield
With n-butyllithium In diethyl ether; hexane at -40℃; for 3h; Inert atmosphere;	100%

3-Bromothiophene (872-31-1) → 2,3-dibromothiophen (3140-93-0)

Conditions	Yield
With N-Bromosuccinimide; perchloric acid In tetrachloromethane for 24h; Ambient temperature;	99%
With bromine In acetic acid	89%
Stage #1: 3-Bromothiophene With N-Bromosuccinimide; perchloric acid In hexane; water at 20℃; for 24h; Stage #2: With potassium carbonate In hexane; water	89%

3-Bromothiophene (872-31-1) + dimethylenecyclourethane (497-25-6) → 3-thiophen-3-yl-oxazolidin-2-one

Conditions	Yield
With potassium phosphate; copper(l) iodide; N,N`-dimethylethylenediamine at 110℃;	99%
With copper(l) iodide; potassium carbonate; N,N`-dimethylethylenediamine In 1,4-dioxane at 110℃; for 24h;	99%

morpholine (110-91-8) + 3-Bromothiophene (872-31-1) → 4-(thiophen-3-yl)-morpholine (1006-76-4)

Conditions	Yield
With (1,3-bis(2,6-diisopropylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene)Pd(cinnamyl, 3-phenylallyl)Cl; sodium t-butanolate In neat (no solvent) at 110℃; for 12h; Buchwald-Hartwig Coupling; Inert atmosphere; Green chemistry;	99%
With [Pd(N,N'-bis(2,6-bis(di-p-tolylmethyl)-4-methylphenyl)-imidazol-2-ylidene)(acetylacetonate)Cl]; lithium hexamethyldisilazane In 1,4-dioxane at 110℃; for 3h; Buchwald-Hartwig Coupling; Inert atmosphere; Sealed tube;	89%
With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In xylene at 120℃; for 24h;	80%

3-Bromothiophene (872-31-1) + N-methylaniline (100-61-8) → 3-(N-methyl-N-phenylamino)thiophene

Conditions	Yield
With palladium diacetate; sodium t-butanolate; ruphos In neat (no solvent) at 110℃; for 12h; Buchwald-Hartwig Coupling; Green chemistry;	99%
With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In toluene at 20℃; for 16h;	93%
With Pd(π-crotyl)(QPhos)Cl; sodium t-butanolate In toluene at 100℃; for 3h; Buchwald-Hartwig coupling reaction; Inert atmosphere;	90%
With [(1,3-(2,6-diisopropylphenyl)imidazol-2-ylidene)(3-chloropyridyl)palladium(II) dichloride]; potassium tert-butylate In toluene at 100℃; Buchwald-Hartwig amination; Inert atmosphere;	73%

3-Bromothiophene (872-31-1) + (4aR)-1-(4-fluorophenyl)-4a-methyl-4,4a,5,6,7,8-hyxahydro-1H-benzo[f]indazole-5-carbaldehyde → (R)-(3-thienyl)[(4aR,5S)-1-(4-fluorophenyl)-4a-methyl-4,4a,5,6,7,8-hexahydro-1H-benzo[f]indazol-5-yl]methanol (614761-27-2)

Conditions	Yield
With tert.-butyl lithium In diethyl ether at -78℃;	99%

1H-imidazole (288-32-4) + 3-Bromothiophene (872-31-1) → 1-(thiophen-3'-yl)-1H-imidazole

Conditions	Yield
With copper(l) iodide; N-((4-nitro-1-oxy-pyridin-2-yl)methyl)oxalamic acid; tetrabutylammomium bromide; potassium hydroxide In water at 100℃; for 48h; Schlenk technique; Inert atmosphere; Sealed tube;	99%
With copper(l) iodide; potassium carbonate; heptakis(6-amino-6-deoxy)-β-cyclodextrin In dimethyl sulfoxide at 110℃; for 24h; Sealed tube;	97%
With [bmim]BF4; potassium carbonate; L-proline; copper(l) iodide at 110℃; for 36h;	72%

3-Bromothiophene (872-31-1) + ammonium chloride + 1-(2-diethylaminoethyl)-4-bromoisatin (259667-46-4) → 1-(2-Diethylaminoethyl)-3-hydroxy-3-(3-thienyl)-4-bromooxindole (259667-00-0)

Conditions	Yield
With tert.-butyl lithium In tetrahydrofuran; methanol; chloroform; pentane	99%

3-Bromothiophene (872-31-1) + 2-phenylpyridine (1008-89-5) → 2-di[2-(3-thiophenyl)]phenylpyridine (1042718-94-4)

Conditions	Yield
With potassium carbonate; triphenylphosphine; RuCl2(η6-C6H6) In 1-methyl-pyrrolidin-2-one at 120℃; for 20h;	99%

3-Bromothiophene (872-31-1) + (3-(morpholinosulfonyl)phenyl)boronic acid (871329-60-1) → 4-(3-thiophen-3-yl-benzenesulfonyl)-morpholine (1142947-25-8)

Conditions	Yield
With sodium carbonate; tetrakis(triphenylphosphine) palladium(0) In N,N-dimethyl-formamide at 180℃; for 0.333333h; Microwave irradiation;	99%

3-Bromothiophene (872-31-1) + 5-methoxy-7-methylbicyclo[4.2.0]octa-1,3,5-trien-7-ol (681478-55-7) → 1-[3-methoxy-2-(thiophen-3-yl)phenyl]propan-2-one (1338700-28-9)

Conditions	Yield
Stage #1: 5-methoxy-7-methylbicyclo[4.2.0]octa-1,3,5-trien-7-ol With tris-(dibenzylideneacetone)dipalladium(0); silver carbonate; DavePhos In toluene for 0.0833333h; Inert atmosphere; Stage #2: 3-Bromothiophene In toluene at 65℃; Inert atmosphere;	99%

3-Bromothiophene (872-31-1) + (1,5-anhydro-2-deoxy-4,6-O-bis(tert-butylsilylidene)-3-O-triisopropylsilyl-D-arabino-hex-1-enitol)boronic acid pinacol ester (842132-50-7) → 3-(1,5-anhydro-2-deoxy-4,6-O-di(tert-butyl)silanediyl-3-O-triisopropylsilyl-D-arabino-hex-1-enitolyl)thiophene (1384173-55-0)

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In 1,2-dimethoxyethane; water for 4h; Reflux;	99%

3-Bromothiophene (872-31-1) + 4-methylphenylboronic acid (5720-05-8) → 3-(4-tolyl)thiophene (16939-05-2)

Conditions	Yield
With (1,3-bis(2,6-diisopropylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene)Pd(cinnamyl, 3-phenylallyl)Cl; tetrabutylammomium bromide; sodium hydrogencarbonate In water for 1h; Catalytic behavior; Suzuki-Miyaura Coupling; Reflux;	99%

3-Bromothiophene (872-31-1) + 2-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxoborole (24388-23-6) → 3-phenylthiophene (2404-87-7)

Conditions	Yield
With potassium carbonate In water at 20℃; for 6h; Suzuki-Miyaura Coupling;	99%

3-Bromothiophene (872-31-1) + 1-methyl-4-((phenylethynyl)sulfonyl)benzene (28995-88-2) → 1-phenyl-2-(3-thienyl)ethyne (131423-29-5)

Conditions	Yield
Stage #1: 3-Bromothiophene With n-butyllithium In tetrahydrofuran; hexane at -78℃; Stage #2: 1-methyl-4-((phenylethynyl)sulfonyl)benzene In tetrahydrofuran for 0.25h; Reagent/catalyst; Inert atmosphere;	99%

3-Bromothiophene (872-31-1) + 4-methoxyphenylboronic acid (5720-07-0) → 3-phenylthiophene (2404-87-7)

Conditions	Yield
With [(di-tert-butylneopentylphosphine)PdCl2]2; sodium carbonate In water; acetonitrile at 23℃; for 18h; Reagent/catalyst; Suzuki-Miyaura Coupling; Sealed tube; Inert atmosphere;	99%

3-Bromothiophene (872-31-1) + decylthiol (143-10-2) → 3-decylsulfanylthiophene (92372-03-7)

Conditions	Yield
With C30H32Cl3N4Ni2(1+)*Cl(1-); potassium hydroxide In 1,4-dioxane at 40℃; for 6h; Reagent/catalyst;	99%

3-Bromothiophene (872-31-1) + 2-(aminomethyl)-benzoic acid (25672-97-3) → 1,3-di(thiophen-3-yl)isoquinoline

Conditions	Yield
With bismuth(lll) trifluoromethanesulfonate; triethylamine; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 2-methyltetrahydrofuran; water at 20 - 110℃; for 13h; Reagent/catalyst; Temperature; Solvent;	98.6%

3-Bromothiophene (872-31-1) + octylmagnesium bromide (17049-49-9) → 3-octylthiophene (65016-62-8)

Conditions	Yield
With 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) In diethyl ether at 0 - 5℃; for 0.25h; Kumada Cross-Coupling; Inert atmosphere;	98.2%
With 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) In tetrahydrofuran for 15h; Kumada Cross-Coupling; Reflux;	86%
With 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) In tetrahydrofuran at 20℃; for 12h;	78%

3-Bromothiophene (872-31-1) + acetyl chloride (75-36-5) → 1-(3-bromothiophen-2-yl)ethanone (42877-08-7)

Conditions	Yield
Stage #1: acetyl chloride With aluminium trichloride In dichloromethane cooling; Stage #2: 3-Bromothiophene In dichloromethane at 0 - 20℃; for 1.66667h; Friedel-Crafts acylation;	98%
Stage #1: acetyl chloride With aluminum (III) chloride In dichloromethane at 0℃; for 0.666667h; Inert atmosphere; Stage #2: 3-Bromothiophene In dichloromethane at 0 - 20℃; for 1.5h; Inert atmosphere;	98%
With tin(IV) chloride	90%

3-Bromothiophene (872-31-1) + phenylboronic acid (98-80-6) → 3-phenylthiophene (2404-87-7)

Conditions	Yield
With [(t-Bu)3PH]BF4; palladium diacetate; sodium hydroxide In water; butan-1-ol at 20℃; for 0.0833333h; Suzuki Coupling; Inert atmosphere; Glovebox;	98%
With potassium carbonate In water; N,N-dimethyl-formamide at 85℃; for 0.05h; Suzuki Coupling; Microwave irradiation;	97%
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); tri-tert-butyl phosphine In 1,1,1,2,3,3,3-Heptafluoropropane; ethanol; 1,1,1,3,3-pentafluorobutane at 20℃; for 24h; Suzuki-Miyaura cross-coupling reaction; Inert atmosphere;	96%

3-Bromothiophene (872-31-1) + trimethylsilylacetylene (1066-54-2) → 3-(trimethylsilylethynyl)thiophene (130995-13-0)

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine at 80℃;	98%
Stage #1: 3-Bromothiophene In diisopropylamine for 0.5h; Sonogashira coupling; Inert atmosphere; Stage #2: trimethylsilylacetylene With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide In diisopropylamine at 60℃; for 8h; Sonogashira coupling; Inert atmosphere;	81%
Stage #1: 3-Bromothiophene With copper(l) iodide; triethylamine In N,N-dimethyl-formamide for 0.05h; Stage #2: trimethylsilylacetylene; bis-triphenylphosphine-palladium(II) chloride In N,N-dimethyl-formamide at 140℃; for 0.25h; Microwave irradiation;	66%

Upstream product

• 3140-93-0 2,3-dibromothiophen 
• 3141-24-0 2,3,5-tribromothiophene 
• 109-72-8 n-butyllithium 
• 60-29-7 diethyl ether 
• 6324-10-3 4,5-Dibromo-thiophene-2-carboxylic acid 
• 188290-36-0 thiophene 
• 1003-09-4 2-bromothiophene 
• 3141-26-2 3,4-dibromothiophene 
• 60404-24-2 3-Bromo-2-iodothiophene 
• 124-41-4 sodium methylate 
• 7664-41-7 ammonia 
• 3141-27-3 2,5-dibromothiophen 
• 70384-51-9 Tris(3,6-dioxaheptyl)amine 
• 19090-02-9 thiophen-3(2H)-one 

Downstream Products

• 114628-60-3 4-<3-(1-hydroxy-1-phenylmethyl)-2-thienyl>-1-methyl-piperidine-4-ol 
• 114628-55-6 4-<2-(1-hydroxy-1-phenylmethyl)-3-thienyl>-1-methyl-piperidin-4-ol 
• 17964-88-4 3-Bromo-α-(3-thienyl)-2-thiophenemethanol 
• 22913-26-4 methyl thiophene-3-carboxylate 
• 88-13-1 3-Thiophene carboxylic acid 
• 34722-01-5 3-butylthiophene 
• 3140-93-0 2,3-dibromothiophen 
• 94547-24-7 2-(3-Thienoyl)benzoic acid 
• 104861-88-3 1,2-Di(3-thienoyl)benzene 
• 88-99-3 benzene-1,2-dicarboxylic acid 
• 1795-01-3 3-ethylthiophene 
• 79428-77-6 3-cyclopentylthiophene 
• 188290-36-0 thiophene 
• 2404-87-7 3-phenylthiophene 

Relevant articles and documents

Orthogonal Stability and Reactivity of Aryl Germanes Enables Rapid and Selective (Multi)Halogenations

While halogenation is of key importance in synthesis and radioimaging, the currently available repertoire is largely designed to introduce a single halogen per molecule. This report makes the selective introduction of several different halogens accessible. Showcased here is the privileged stability of nontoxic aryl germanes under harsh fluorination conditions (that allow selective fluorination in their presence), while displaying superior reactivity and functional-group tolerance in electrophilic iodinations and brominations, outcompeting silanes or boronic esters under rapid and additive-free conditions. Mechanistic experiments and computational studies suggest a concerted electrophilic aromatic substitution as the underlying mechanism.

Sterics vs electronics: Revisiting the catalytic regioselective hydrodebromination of 2,3,5-tribromothiophene

The application of sterically hindered palladium catalysts to the regioselective hydrodebromination of 2,3,5-tribromothiophene has been studied in detail, including the effects of catalyst choice, solvent, reaction time, and temperature, as well as the method of NaBH4 addition and the role of chelating additives to effect NaBH4 solubility. Ultimately it was determined that the background reaction between NaBH4 and bromothiophenes is too facile to allow both total conversion and high selectivity. Optimized conditions finally allowed a selectivity of ca. 16:1 with overall conversion of 100%. However, complications of overdebromination under these conditions still limit the yield of the desired 2,3-dibromothiophene to 65%.

Enatioselective Chalcogeno-Baylis-Hillman reaction of arylaldehydes with MVK and acrylates catalyzed by chiral thiepin-TiCl4 complex

In a rational chiral molecular design of chalcogenides, optically active thiepin with C2-symmetric chirality was synthesized from commercially available thiophene. Then enatioselective Chalcogeno-Baylis-Hillman reactions of arylaldehydes with methyl vinyl ketone (MVK) and acrylates were investigated in the presence of thiepin-Lewis acid complex. Finally, up to 64% ee was achieved in the presence of 0.2 equiv. of (S)-thiepin at 20°C. Enatioselective Chalcogeno-Baylis-Hillman reactions between benzaldehydes and acrylates were investigated in the presence of chiral thiepin-Lewis acid complex. Finally, up to 64% ee was achieved in the presence of 0.2 equiv. of (S)-thiepin at 20°C. Copyright