126213-50-1

Basic information

• Product Name: 3,4-Ethylenedioxythiophene
• Synonyms: EDOT;EDT;3,4-ETHYLENEDIOXOTHIOPHENE;3,4-ETHYLENEDIOXYTHIOPHENE;AKOS BBS-00006360;2,3-DIHYDROTHIENO[3,4-B]-1,4-DIOXIN;2,3-DIHYDROTHIENO[3,4-B][1,4]DIOXINE;3,4-ETHYLENEDIOXO THIOPHENE 98+% GC
• CAS NO: 126213-50-1
• Molecular Formula: C₆H₆O₂S
• Molecular Weight: 142.18
• EINECS: 1806241-263-5
• Product Categories: Thiophenes;Sulphur Derivatives;Thiophens;Thiophen;fine chemicals, specialty chemicals, intermediates, electronic chemical, organic synthesis, thiophen;fine chemicals, specialty chemicals, intermediates, electronic chemical, organic synthesis, functional materials;EDOT;OLED materials,pharm chemical,electronic;Pharmaceutical intermediates
• Mol File: 126213-50-1.mol
• Article Data: 25

Chemical Properties

• Melting Point: 10 °C
• Boiling Point: 193 °C(lit.)
• Flash Point: 230 °F
• Appearance: /
• Density: 1.331 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.278mmHg at 25°C
• Refractive Index: n20/D 1.5765(lit.)
• Storage Temp.: 2-8°C
• Water Solubility: Immsicible with water. Miscible with alcohol and ether.
• CAS DataBase Reference: 3,4-Ethylenedioxythiophene(CAS DataBase Reference)
• NIST Chemistry Reference: 3,4-Ethylenedioxythiophene(126213-50-1)
• EPA Substance Registry System: 3,4-Ethylenedioxythiophene(126213-50-1)

Safety Data

• Hazard Codes: Xn,Xi
• Statements: 21/22-36
• Safety Statements: 26-36
• RIDADR: UN 2810 6.1/PG 3
• WGK Germany: 2
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: III
• Hazardous Substances Data: 126213-50-1(Hazardous Substances Data)

Usage

Chemical Properties

Light yellow liquid

Uses

3,4-Ethylenedioxythiophene is used as a monomer to synthesize the conductive polymers and used as a reductant in the one-pot synthesis of gold nanoparticles from chloroauric acid, as starting material used in palladium-catalyzed mono and bis-arylation reactions and in the synthesis of conjugated polymers and copolymers, with potential optical applications. It is also used in redox activity, electroactivity and conductivity.

General Description

3,4-Ethylenedioxythiophene (EDOT) is an electro-active conductive monomer with a thiol group that combines an electron donor and electron acceptor in a donor-acceptor-donor arrangement.

InChI:InChI=1/C6H6O2S/c1-2-8-6-4-9-3-5(6)7-1/h3-4H,1-2H2

Synthetic route

3,4-ethylenedioxythiophene-2,5-dicarboxyllic acid (18361-03-0) → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
copper In ethylene glycol at 20 - 140℃; for 8.5h;	98%
copper (II) carbonate hydroxide In polyethylene glycol 300 for 20h; Heating / reflux;	96%
copper (II) carbonate hydroxide In sulfolane at 140℃; for 8h;	95%

2,3-dihydro-thieno[3,4-b][1,4]dioxine-5,7-dicarboxylic acid diethyl ester (154934-13-1) → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
With copper(II) oxide; zinc(II) oxide In water; N,N-dimethyl-formamide at 115℃; for 3h; Catalytic behavior; Temperature;	97.9%
With sodium chloride In dimethyl sulfoxide at 120℃; for 6h; Time;	84%
Multi-step reaction with 2 steps 1: 95 percent / KOH / ethanol / 3 h / Heating 2: 68 percent / CuO; quinoline / 5 h / 200 °C View Scheme
Multi-step reaction with 2 steps 1: 100 percent / potassium hydroxide / ethanol / 3 h / Heating 2: 54 percent / copper bronze, quinoline / 4 h / 180 - 200 °C View Scheme
Multi-step reaction with 2 steps 1.1: sodium hydroxide; water / 0.08 h / 100 °C / Microwave irradiation 1.2: 20 °C / pH 2.0 2.1: copper chromite / N,N-dimethyl-formamide / 0.33 h / 153 °C / Microwave irradiation View Scheme

2,3-dimethoxythiophene (51792-34-8) + ethylene glycol (107-21-1) → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
With toluene-4-sulfonic acid In toluene at 95℃; for 96h; Inert atmosphere;	84%
With toluene-4-sulfonic acid In toluene Heating;	65%
With toluene-4-sulfonic acid In methanol; toluene at 100℃; for 3h; Reagent/catalyst; Inert atmosphere;	46.7%

ethylene glycol (107-21-1) + 3,4-diethoxythiophene (122721-91-9) → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
With toluene-4-sulfonic acid; hydroquinone In o-xylene at 137 - 142℃; for 4h; Reagent/catalyst; Inert atmosphere;	84%

3,4-ethylenedioxythiophene; 3,4-dimethoxythiophene → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
Purification / work up;	76%

2,5-bis(trimethylsilyl)-3,4-ethylenedioxythiophene (195602-16-5) → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
With tetrabutyl ammonium fluoride	70%

diethinyl glycol (101537-27-3) → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile); tiolacetic acid In toluene at 80℃; for 5h; Inert atmosphere; Schlenk technique; Green chemistry;	48%

3,4-dibromothiophene (3141-26-2) + ethylene glycol (107-21-1) → 3-bromo-4-(1-hydroxyethyl)oxythiophene + 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
With potassium phosphate; copper(l) iodide; 8-quinolinol In N,N-dimethyl-formamide at 120℃; for 24h; Reagent/catalyst; Solvent;	A 43% B 15%

2,3-dimethoxy-2,3-dimethyl-1,4-dioxane → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
With sulfur; copper(l) iodide In toluene at 180℃; for 6h; Reagent/catalyst; Temperature; Microwave irradiation; Sealed tube;	37%

(3S*,4R*)-tetrahydro-3,4-ethylenedioxythiophene (1271145-38-0) → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In chlorobenzene for 9h; Inert atmosphere; Reflux;	23%

(3S*,4S*)-tetrahydro-3,4-ethylenedioxythiophene → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In chlorobenzene at 80℃; for 6h; Inert atmosphere;	21%

(2R*,3R*)-2,3-bis(methanesulfonyloxymethyl)-1,4-dioxane → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: sodiumsulfide nonahydrate / N,N-dimethyl-formamide / 17 h / 50 °C / Inert atmosphere 2: 2,3-dicyano-5,6-dichloro-p-benzoquinone / chlorobenzene / 6 h / 80 °C / Inert atmosphere View Scheme

(2R*,3S*)-3-(2-bromoethoxy)-1,4-bis(benzyloxy)butan-2-ol → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions

Yield

Multi-step reaction with 5 steps 1: potassium hydroxide / ethanol / 12 h / Inert atmosphere; Reflux 2: hydrogenchloride; palladium 10% on activated carbon; water; hydrogen / methanol / 24 h / 20 °C / 760.05 Torr 3: triethylamine / dichloromethane / 0 - 20 °C / Inert atmosphere 4: sodiumsulfide nonahydrate / ethanol / 12 h / Inert atmosphere; Reflux 5: 2,3-dicyano-5,6-dichloro-p-benzoquinone / chlorobenzene / 9 h / Inert atmosphere; Reflux View Scheme

(2R*,3S*)-2,3-bis(benzyloxymethyl)-1,4-dioxane (1271145-22-2) → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
Multi-step reaction with 4 steps 1: hydrogenchloride; palladium 10% on activated carbon; water; hydrogen / methanol / 24 h / 20 °C / 760.05 Torr 2: triethylamine / dichloromethane / 0 - 20 °C / Inert atmosphere 3: sodiumsulfide nonahydrate / ethanol / 12 h / Inert atmosphere; Reflux 4: 2,3-dicyano-5,6-dichloro-p-benzoquinone / chlorobenzene / 9 h / Inert atmosphere; Reflux View Scheme

(2R*,3S*)-2,3-bis(hydroxymethyl)-1,4-dioxane (876607-67-9) → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
Multi-step reaction with 3 steps 1: triethylamine / dichloromethane / 0 - 20 °C / Inert atmosphere 2: sodiumsulfide nonahydrate / ethanol / 12 h / Inert atmosphere; Reflux 3: 2,3-dicyano-5,6-dichloro-p-benzoquinone / chlorobenzene / 9 h / Inert atmosphere; Reflux View Scheme

(2R*,3S*)-2,3-bis(methanesulfonyloxymethyl)-1,4-dioxane (1271330-69-8) → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: sodiumsulfide nonahydrate / ethanol / 12 h / Inert atmosphere; Reflux 2: 2,3-dicyano-5,6-dichloro-p-benzoquinone / chlorobenzene / 9 h / Inert atmosphere; Reflux View Scheme

(2R*,3R*)-3-(2-bromoethoxy)-1,4-bis(benzyloxy)butan-2-ol → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions

Yield

Multi-step reaction with 5 steps 1: potassium hydroxide / ethanol / 6 h / Inert atmosphere; Reflux 2: hydrogenchloride; palladium 10% on activated carbon; water; hydrogen / methanol / 4 h / 20 °C / 760.05 Torr 3: triethylamine / dichloromethane / 5.5 h / 0 °C / Inert atmosphere 4: sodiumsulfide nonahydrate / N,N-dimethyl-formamide / 17 h / 50 °C / Inert atmosphere 5: 2,3-dicyano-5,6-dichloro-p-benzoquinone / chlorobenzene / 6 h / 80 °C / Inert atmosphere View Scheme

(2R*,3R*)-2,3-bis(benzyloxymethyl)-1,4-dioxane → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions

Yield

Multi-step reaction with 4 steps 1: hydrogenchloride; palladium 10% on activated carbon; water; hydrogen / methanol / 4 h / 20 °C / 760.05 Torr 2: triethylamine / dichloromethane / 5.5 h / 0 °C / Inert atmosphere 3: sodiumsulfide nonahydrate / N,N-dimethyl-formamide / 17 h / 50 °C / Inert atmosphere 4: 2,3-dicyano-5,6-dichloro-p-benzoquinone / chlorobenzene / 6 h / 80 °C / Inert atmosphere View Scheme

(2R*,3R*)-2,3-bis(hydroxymethyl)-1,4-dioxane → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
Multi-step reaction with 3 steps 1: triethylamine / dichloromethane / 5.5 h / 0 °C / Inert atmosphere 2: sodiumsulfide nonahydrate / N,N-dimethyl-formamide / 17 h / 50 °C / Inert atmosphere 3: 2,3-dicyano-5,6-dichloro-p-benzoquinone / chlorobenzene / 6 h / 80 °C / Inert atmosphere View Scheme

2,3-dimethoxythiophene (51792-34-8) + ethylene glycol (107-21-1) → C7H10O3S + C8H12O4S + 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
With [(1S)-7,7-dimethyl-2-oxobicyclo[2.2.1]hept-1-yl]methanesulfonic acid In methanol; toluene at 100℃; for 1h; Reagent/catalyst; Inert atmosphere;	A 19.3 %Chromat. B 12.84 %Chromat. C 56.29 %Chromat.
With 2-aminonaphthalenesulfonic acid In methanol; toluene at 100℃; for 3h; Reagent/catalyst; Inert atmosphere;	A 7.3 %Chromat. B 11.78 %Chromat. C 70.74 %Chromat.

2,3-dimethoxythiophene (51792-34-8) + ethylene glycol (107-21-1) → C7H10O3S + 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
With para-dodecylbenzenesulfonic acid In methanol; toluene at 100℃; for 1h; Reagent/catalyst; Inert atmosphere;	A 13.67 %Chromat. B 79.08 %Chromat.

2,3-dimethoxythiophene (51792-34-8) + ethylene glycol (107-21-1) → C8H12O4S + 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
With naphthalene-2-sulfonate In methanol; toluene at 100℃; for 3h; Inert atmosphere;	A 14.42 %Chromat. B 78.58 %Chromat.

thieno[3,4-b]-1,4-dioxine-5,7-dicarboxylic acid → 3,4-(ethylenedioxy)thiophene (126213-50-1)

Conditions	Yield
With copper oxide nanoparticles coated on Ni-Cr alloy In N,N-dimethyl-formamide at 110℃; for 2.25h; Temperature;

N,N-dimethyl-formamide (68-12-2, 33513-42-7) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → 3,4-ethylenedioxythiophene-2-carboxaldehyde (204905-77-1)

Conditions	Yield
With trichlorophosphate at -10 - 20℃; for 1.25h;	100%
With n-butyllithium In tetrahydrofuran at -78 - 20℃; Formylation;	95%
With trichlorophosphate at 20℃; Vilsmeier-Haack Formylation; Cooling with ice;	95%

3,4-(ethylenedioxy)thiophene (126213-50-1) → 5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxine (174508-31-7)

Conditions	Yield
With N-Bromosuccinimide; acetic acid In tetrahydrofuran at 20℃; for 2h;	100%
With N-Bromosuccinimide In N,N-dimethyl-formamide at 0 - 20℃; for 2h;	95%
With N-Bromosuccinimide In N,N-dimethyl-formamide at -15℃; for 1h;	91%

3,4-(ethylenedioxy)thiophene (126213-50-1) → 3,4-ethylenedioxythiophene-2-carboxaldehyde (204905-77-1)

Conditions	Yield
With N,N-dimethyl-formamide; trichlorophosphate at -10 - 20℃; Vilsmeier formylation;	100%

3,4-(ethylenedioxy)thiophene (126213-50-1) → 2,2'-bis(3,4-ethylenedioxythiophene) (195602-17-6)

Conditions	Yield
Stage #1: 3,4-(ethylenedioxy)thiophene With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran at -10℃; for 0.5h; Metallation; Stage #2: With iron(III)-acetylacetonate In tetrahydrofuran for 6h; Oxidation; Heating;	99%
With n-butyllithium; copper dichloride In tetrahydrofuran; hexane at -78 - 0℃; for 12h; Dimerization;	84%
With n-butyllithium; copper dichloride In tetrahydrofuran at -80 - -40℃;	76%

3,4-(ethylenedioxy)thiophene (126213-50-1) + methyl iodide (74-88-4) → 5-methyl-2,3-dihydrothieno[3,4-b][1,4]dioxine

Conditions	Yield
Stage #1: 3,4-(ethylenedioxy)thiophene In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: methyl iodide In tetrahydrofuran; hexane at -78 - 20℃;	99%
Stage #1: 3,4-(ethylenedioxy)thiophene With 2,2,6,6-tetramethyl-piperidine; tert.-butyl lithium In tetrahydrofuran; pentane for 1.5h; Sealed tube; Inert atmosphere; Cooling with acetone-dry ice; Stage #2: methyl iodide In tetrahydrofuran; pentane	97%

triethylsilane (617-86-7) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → 2,5-bis(triethylsilyl)-3,4-ethylenedioxythiophene

Conditions	Yield
With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; 3,4,7,8-Tetramethyl-o-phenanthrolin; norbornene In di-isopropyl ether at 80℃; for 22h; Inert atmosphere;	99%

n-butyllithium (109-72-8, 29786-93-4) + tributyltin chloride (1461-22-9) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → tributyl(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-stannane (175922-79-9)

Conditions	Yield
In tetrahydrofuran; hexane	98%

bromobenzene (108-86-1) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → 5,7-diphenyl-2,3-dihydrothieno[3,4-b][1,4]-dioxine

Conditions	Yield
With palladium diacetate; caesium carbonate; tri(m-tolyl)phosphine In toluene at 110℃; for 24h; Inert atmosphere;	98%
With palladium diacetate; caesium carbonate; triphenylphosphine In toluene at 110℃; for 24h; Inert atmosphere;	75%

dimethyl(2-(((tetrahydro-2H-pyran-2-yl)oxy)methyl)phenyl)silane (853955-58-5) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → 2,5-bis[2-{(2-tetrahydropyranyloxy)methyl}phenyldimethylsilyl]-3,4-ethylenedioxythiophene

Conditions	Yield
With norborn-2-ene; (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; 3,4,7,8-Tetramethyl-o-phenanthrolin In di-isopropyl ether at 80℃; for 5h; Inert atmosphere; Sealed tube;	98%

3-Bromopyridine (626-55-1) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → 5,7-di(pyridin-3-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxine

Conditions	Yield
With {N,N-(1,2-diphenylethane-1,2-diylidene)bis(2-benzhydryl-4,6-dimthylaniline)}dichloropalladium; potassium carbonate; Trimethylacetic acid In N,N-dimethyl acetamide at 130℃; for 12h; Catalytic behavior;	98%

4-bromoisoquinoline (1532-97-4) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → 5,7-di(isoquinolin-4-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxine

Conditions	Yield
With {N,N-(1,2-diphenylethane-1,2-diylidene)bis(2-benzhydryl-4,6-dimthylaniline)}dichloropalladium; potassium carbonate; Trimethylacetic acid In N,N-dimethyl acetamide at 130℃; for 12h; Catalytic behavior;	97%

3,4-(ethylenedioxy)thiophene (126213-50-1) → C6H4(2)H2O2S

Conditions	Yield
With potassium carbonate; silver carbonate; johnphos In dimethyl sulfoxide at 25℃; for 12h;	97%
With deuteromethanol; silver carbonate; johnphos at 50 - 80℃;	91%

3,4-(ethylenedioxy)thiophene (126213-50-1) + 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane (25015-63-8) → 2-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-4,4,5,5-tetramethyl-2-thiophen-2-yl-1,3,2-dioxaborolane (250726-93-3)

Conditions	Yield
With 1-(difluoromethoxyborato)-2-TMP-benzene In chloroform at 80℃; for 16h; Inert atmosphere;	96%
With 1-(2-borylphenyl)-2,2,6,6-tetramethylpiperidine dimer In chloroform at 80℃; for 16h;	87%
With 1-(trifluoroborato)-2-TMP-benzene In neat (no solvent) at 80℃; for 6h; Reagent/catalyst; Inert atmosphere;	85%
With 1-(trifluoroborato)-2-TMP-benzene In neat (no solvent) at 80℃; for 6h; Inert atmosphere; regioselective reaction;	85%
With poly((2-(piperidin-1-ium-1-yl)-5-vinylphenyl)trifluoroborate) In neat (no solvent) at 90℃; for 16h; Reagent/catalyst; Inert atmosphere; Glovebox; Sealed tube;

2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (61676-62-8) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → 2-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-4,4,5,5-tetramethyl-2-thiophen-2-yl-1,3,2-dioxaborolane (250726-93-3)

Conditions	Yield
Stage #1: 3,4-(ethylenedioxy)thiophene With n-butyllithium Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane	95%
Stage #1: 3,4-(ethylenedioxy)thiophene With n-butyllithium In tetrahydrofuran at -78 - 0℃; for 0.333333h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at -78 - 20℃; for 17h; Irradiation;	78%
With n-butyllithium In tetrahydrofuran at -78 - 20℃; for 6h; Substitution;	71%

mercury(II) diacetate (1600-27-7) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → 2,5-diacetoxymercuro-3,4-ethylenedioxythiophene (640737-73-1)

Conditions	Yield
In acetic acid to soln. 3,4-ethylenedioxythiophene in acetic acid soln. Hg(OAc)2 in acetic acid was added dropwise and stirred overnight; ppt. was filtered, washed with MeOH and et2O and dried in vacuo; elem. anal.;	95%

[hydroxy(tosyloxy)iodo]benzene (27126-76-7) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → (2,3-dihydro-thieno[3,4-b][1,4]dioxin-5-yl)(phenyl)iodonium tosylate (1222887-22-0)

Conditions	Yield
In 2,2,2-trifluoroethanol at 20℃; for 3h;	94%

C10H18BrClSi + 3,4-(ethylenedioxy)thiophene (126213-50-1) → C16H23ClO2SSi

Conditions	Yield
Stage #1: 3,4-(ethylenedioxy)thiophene With n-butyllithium In 1,2-dimethoxyethane Stage #2: With copper(l) cyanide Stage #3: C10H18BrClSi at -78 - -30℃;	94%

3,4-(ethylenedioxy)thiophene (126213-50-1) → 5,7-diiodo-2,3-dihydrothieno[3,4-b][1,4]dioxine (640737-72-0)

Conditions	Yield
With iodine monochloride-pyridine In dichloromethane at 20℃; for 1h;	93%
With N-iodo-succinimide; acetic acid In tetrahydrofuran at 20℃;	88%
With N-iodo-succinimide; toluene-4-sulfonic acid In ethanol at 25℃; for 0.166667h; Green chemistry; regioselective reaction;	87%

para-bromotoluene (106-38-7) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → 5-(p-tolyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine (925674-57-3) + 2,3-dihydro-5,7-bis(4-methylphenyl)thieno[3,4-b][1,4]dioxine (1579939-66-4)

Conditions	Yield
With C40H36N2O2Pd(2+)*2C2H4O2; potassium carbonate; Trimethylacetic acid In N,N-dimethyl acetamide at 100℃; for 24h; Inert atmosphere; Schlenk technique; regioselective reaction;	A 7% B 93%

3,4-(ethylenedioxy)thiophene (126213-50-1) → 5-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxine

Conditions	Yield
With N-Bromosuccinimide; acetic acid In tetrahydrofuran at 0 - 20℃; for 2h; Schlenk technique;	92%
With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; for 1h; Inert atmosphere; Darkness;	52%
With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; for 1h; Bromination;

Ethyl 4-bromobenzoate (5798-75-4) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → 2,5-di(4-ethoxycarbonylphenyl)-3,4-ethylenedioxythiophene

Conditions	Yield
With potassium acetate; tetra(n-tert-butyl)ammonium bromide; palladium diacetate In N,N-dimethyl-formamide at 80℃; for 1h;	92%

3,4-(ethylenedioxy)thiophene (126213-50-1) → 5,7-ditributyltin-2,3-dihydrothieno[3,4-b][1,4]dioxin

Conditions	Yield
With lithium diisopropyl amide In tetrahydrofuran at 0 - 20℃;	92%

3,4-(ethylenedioxy)thiophene (126213-50-1) + 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane (25015-63-8) → 2,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4-ethylenedioxythiophene

Conditions	Yield
With 1-(2-borylphenyl)-2,2,6,6-tetramethylpiperidine dimer In chloroform at 80℃; for 16h;	92%
With 1-(2-borylphenyl)-2,2,6,6-tetramethylpiperidine dimer In chloroform at 80℃; for 16h; Sealed tube; Microwave irradiation; Glovebox; Inert atmosphere;	92%
With 1-(trifluoroborato)-2-TMP-benzene In neat (no solvent) at 80℃; for 24h; Inert atmosphere; regioselective reaction;	91%

Di-t-butyl ketone (815-24-7) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → 3,4-ethylenedioxy-2-[3-(2,2,4,4-tetramethylpentan-3-ol)]thiophene

Conditions	Yield
Stage #1: 3,4-(ethylenedioxy)thiophene With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In diethyl ether; hexane at 20℃; for 0.5h; Stage #2: Di-t-butyl ketone In diethyl ether at 20℃; for 0.5h; Further stages.;	91%

morpholine (110-91-8) + formaldehyd (50-00-0) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → 2,5-bis(morpholin-4-ylmethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin

Conditions	Yield
With acetic acid In water at 100℃; for 4h; Mannich reaction;	91%

3,4-(ethylenedioxy)thiophene (126213-50-1) + [(difluoroiodomethyl)sulfonyl]benzene (802919-90-0) → C13H10F2O4S2 (1609470-37-2)

Conditions	Yield
With dipotassium hydrogenphosphate; tris(bipyridine)ruthenium(II) dichloride hexahydrate In dichloromethane at 40℃; for 48h; Sealed tube; Inert atmosphere; Irradiation;	91%

3,4-(ethylenedioxy)thiophene (126213-50-1) → 5-iodo-2,3-dihydrothieno[3,4-b][1,4]dioxine (219621-78-0)

Conditions	Yield
Stage #1: 3,4-(ethylenedioxy)thiophene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: With iodine In tetrahydrofuran; hexane at 20℃; for 1h; Further stages.;	90%
With potassium dichloroiodate monohydrate In water at 25℃; for 1h;	63%
With n-butyllithium; iodine In tetrahydrofuran

Upstream product

• 107-21-1 ethylene glycol 
• 122721-91-9 3,4-diethoxythiophene 
• 101537-27-3 diethinyl glycol 
• 51792-34-8 2,3-dimethoxythiophene 
• 3141-26-2 3,4-dibromothiophene 
• 1271145-38-0 (3S*,4R*)-tetrahydro-3,4-ethylenedioxythiophene 
• 1271330-69-8 (2R*,3S*)-2,3-bis(methanesulfonyloxymethyl)-1,4-dioxane 
• 876607-67-9 (2R*,3S*)-2,3-bis(hydroxymethyl)-1,4-dioxane 
• 1271145-22-2 (2R*,3S*)-2,3-bis(benzyloxymethyl)-1,4-dioxane 
• 195602-16-5 2,5-bis(trimethylsilyl)-3,4-ethylenedioxythiophene 
• 154934-13-1 2,3-dihydro-thieno[3,4-b][1,4]dioxine-5,7-dicarboxylic acid diethyl ester 
• 18361-03-0 3,4-ethylenedioxythiophene-2,5-dicarboxyllic acid 

Downstream Products

• 459409-72-4 2-phenyl-3,4-ethylenedioxythiophene 
• 175922-79-9 tributyl(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-stannane 
• 640737-72-0 2,5-diiodo-3,4-ethylenedioxythiophene 
• 225518-49-0 2,5-dichloro-3,4-ethylenedioxythiophene 
• 174508-31-7 5,7-dibromo-2,3-dihydrothieno[3,4-b][1,4]dioxine 
• 302554-82-1 5-bromo-2,3-dihydrothieno[3,4-b][1,4]dioxine 
• 250726-93-3 2-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-4,4,5,5-tetramethyl-2-thiophen-2-yl-1,3,2-dioxaborolane 
• 211235-87-9 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde 
• 204905-77-1 3,4-ethylenedioxythiophene-2-carboxaldehyde 
• 195602-17-6 2,2'-bis(3,4-ethylenedioxythiophene) 
• 300806-18-2 5?(4?nitrophenyl)?2,3?dihydrothieno[3,4?b][1,4]dioxine 
• 925674-61-9 2-(2-pyridyl)-3,4-ethylenedioxythiophene 
• 853797-51-0 bis(3,4-ethylenedioxy-2-thienyl)phenylphosphine 
• 569665-30-1 2-n-hexyl-3,4-ethylenedioxythiophene 

Relevant articles and documents

Simple one-step synthesis of 3,4-dimethoxythiophene and its conversion into 3,4-ethylenedioxythiophene (EDOT)

3,4-Dimethoxythiophene (2) was synthesized in one-step from readily available bulk chemicals via a ring closure reaction, and was then trans-etherified with ethylene glycol to give 3,4-ethylenedioxythiophene (3) (EDOT).

The first direct experimental comparison between the hugely contrasting properties of PEDOT and the all-sulfur analogue PEDTT by analogy with well-defined EDTT-EDOT copolymers

The structures of poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-ethylenedithiathiophene) (PEDTT) vary only in the substituent chalcogen atoms, yet the electronic properties of the materials are surprisingly dissimilar. The difference in electronic band gaps is approximately 0.8 eV and the polymers behave very differently upon p-doping. Two new terthiophenes have been synthesised using Negishi coupling methods. The X-ray crystal structures of EDOT-EDTT-EDOT (OSO) and EDTT-EDOT-EDTT (SOS) show strong intramolecular chalcogen-chalcogen contacts which are responsible for persistent conformers in solution and solid state, although significant interchain interactions should also influence the properties of the materials. SOS and OSO can be polymerised by electrochemical oxidation to give the corresponding, well-defined poly(terthiophenes) PSOS and POSO. Spectroelectrochemical studies on all four polymers reveal strong similarities between PEDTT and PSOS, and between PEDOT and POSO. Together with independent electrochemical and absorption studies, the results indicate that the unique properties of PEDOT are influenced more by conformational effects (intrachain S...O contacts) than substituent effects. The Royal Society of Chemistry 2005.

3,4-ethylenedioxythiophene and 3,4-ethylenedioxyselenophene: Synthesis and reactivity of Cα-Si bond

(Figure Presented) A synthetic approach to synthesize EDOT and EDOS from a common precursor 5 is reported. The method involves zirconocene dichloride mediated reaction of a common diyne 5 followed by treatment with disulfur dichloride (S2Cl2) and in situ prepared selenium dichloride (SeCl2). The higher lability of α-trimethylsilyl group in EDOS compared to EDOT is explained using DFT calculations.

Synthesis process of 3, 4-ethylenedioxythiophene

The invention discloses a synthesis process of 3, 4-ethylene dioxythiophene, which comprises the following steps: by using diethyl 2, 5-dicarboxylate-3, 4-ethylene dioxythiophene as a raw material anda dimethylformamide water solution as a solvent, heating to 110-120 DEG C in the presence of a catalyst, reacting for 2-4 hours, filtering, and carrying out vacuum distillation to obtain 3, 4-ethylene dioxythiophene, wherein the catalyst is a mixture of copper oxide and zinc oxide. Copper oxide and zinc oxide are used as catalysts, one-step degreasing is achieved, the steps are simple, the synergistic effect of copper oxide and zinc oxide can be fully achieved, the reaction temperature is reduced, the reaction time is shortened, the reaction selectivity is improved, by-products are reduced, and the yield and purity of a target product are improved.

Polymer material monomer 3, 4 - ethylene dioxy thiophene preparation method

The invention relates to a method for preparing polymer monomer 3,4-ethylenedioxythiophene. The method includes firstly dissolving ethyl chloroacetate and sodium sulphide in acetone to react to obtain diethyl thioglycolate; secondly, dissolving the diethyl thioglycolate to ethanol, adding sodium ethoxide and diethyl oxalate into the ethanol, heating and reflowing to obtain ethanol solution of 2,5-dioctyl phthalate ethyl ester-3,4-thiophene glycol sodium; thirdly, adding dichloroethane and tetrabutylammonium bromide into the ethanol solution of the 2,5-dioctyl phthalate ethyl ester-3,4-thiophene glycol sodium, heating and reflowing to obtain 3,4-ethylenedioxy-2,5-dioctyl phthalate ethyl ester thiophene; fourthly, dissolving the 3,4-ethylenedioxy-2,5-dioctyl phthalate ethyl ester thiophene in mixed solvent, adding sodium chloride, heating and reacting, and finally reducing pressure and rectifying. The method for preparing polymer monomer 3,4-ethylenedioxythiophene is few in procedures, low in cost, safe and reliable in technique, simple and fast in post-treatment method, and products are high in yield and purity.