211235-87-9

Basic information

• Product Name: 2,3-DIHYDROTHIENO[3,4-B][1,4]DIOXINE-5,7-DICARBALDEHYDE
• Synonyms: 2,3-DIHYDROTHIENO[3,4-B][1,4]DIOXINE-5,7-DICARBALDEHYDE
• CAS NO: 211235-87-9
• Molecular Formula: C₈H₆O₄S
• Molecular Weight: 198.2
• Mol File: 211235-87-9.mol
• Article Data: 10

Chemical Properties

• Melting Point: 155 °C
• Boiling Point: 403.4 °C at 760 mmHg
• Flash Point: 197.8 °C
• Appearance: /
• Density: 1.511 g/cm³
• Vapor Pressure: 1.02E-06mmHg at 25°C
• Refractive Index: 1.668
• Storage Temp.: under inert gas (nitrogen or Argon) at 2–8 °C
• CAS DataBase Reference: 2,3-DIHYDROTHIENO[3,4-B][1,4]DIOXINE-5,7-DICARBALDEHYDE(CAS DataBase Reference)
• NIST Chemistry Reference: 2,3-DIHYDROTHIENO[3,4-B][1,4]DIOXINE-5,7-DICARBALDEHYDE(211235-87-9)
• EPA Substance Registry System: 2,3-DIHYDROTHIENO[3,4-B][1,4]DIOXINE-5,7-DICARBALDEHYDE(211235-87-9)

Safety Data

• Hazardous Substances Data: 211235-87-9(Hazardous Substances Data)

Usage

General Description

2,3-Dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarbaldehyde is a chemical compound with the molecular formula C8H6O4S. It is a heterocyclic compound that contains both oxygen and sulfur in its structure. 2,3-Dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarbaldehyde has a unique cyclic structure and is often used in organic synthesis and medicinal chemistry as a building block or intermediate for the synthesis of various pharmaceuticals and organic compounds. Its aldehyde functional groups make it a versatile reagent for the formation of carbon-carbon and carbon-heteroatom bonds in organic reactions. It is also known for its potential pharmacological properties and has been studied for its potential applications in drug discovery and development.

InChI:InChI=1/C8H6O4S/c9-3-5-7-8(6(4-10)13-5)12-2-1-11-7/h3-4H,1-2H2

Synthetic route

3,4-ethylenedioxythiophene-2,5-dicarbonitrile (1269767-35-2) → 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9)

Conditions	Yield
With diisobutylaluminium hydride In toluene at 0℃;	80%

N,N-dimethyl-formamide (68-12-2, 33513-42-7) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9)

Conditions	Yield
Stage #1: 3,4-(ethylenedioxy)thiophene With n-butyllithium In tetrahydrofuran at -78 - 0℃; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran at -78 - 20℃; for 2h; Inert atmosphere;	75%
With n-butyllithium In tetrahydrofuran at -78 - 20℃; Formylation;	72%
With n-butyllithium In tetrahydrofuran at -78 - 20℃;	62%
With n-butyllithium
Stage #1: 3,4-(ethylenedioxy)thiophene With n-butyllithium In tetrahydrofuran at -78 - 0℃; for 0.333333h; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran at -78 - 0℃; for 2h; Inert atmosphere;

2,5-di(hydroxymethyl)-3,4-ethylenedioxythiophene (350474-52-1) → 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9)

Conditions	Yield
With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In dimethyl sulfoxide at 20℃; for 96h;	66%

bromodichloromethane (75-27-4) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) + 3,4-ethylenedioxythiophene-2-carboxaldehyde (204905-77-1)

Conditions	Yield
Stage #1: bromodichloromethane; 3,4-(ethylenedioxy)thiophene With 1,1'-bis-(diphenylphosphino)ferrocene; potassium phosphate; palladium diacetate; acetic anhydride; silver carbonate In acetonitrile at 60℃; for 48h; Schlenk technique; Inert atmosphere; Stage #2: With hydrogenchloride In dichloromethane at 30℃; Overall yield = 66 %;	A 43% B 22%

N,N-dimethyl-formamide (68-12-2, 33513-42-7) + 3,4-ethylenedioxythiophene-2-carboxaldehyde (204905-77-1) → 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9)

Conditions	Yield
Stage #1: N,N-dimethyl-formamide; 3,4-ethylenedioxythiophene-2-carboxaldehyde With trichlorophosphate In 1,2-dichloro-ethane at 20℃; for 0.5h; Vilsmeier-Haack Formylation; Stage #2: In 1,2-dichloro-ethane at 80℃; for 5h; Vilsmeier-Haack Formylation; Stage #3: With hydrogenchloride In water at 20℃; Vilsmeier-Haack Formylation;	21%

N,N-dimethyl-formamide (68-12-2, 33513-42-7) + 3,4-(ethylenedioxy)thiophene (126213-50-1) → 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) + 3,4-ethylenedioxythiophene-2-carboxaldehyde (204905-77-1)

Conditions	Yield
With n-butyllithium; potassium tert-butylate; lithium bromide 1.) THF, hexane, -90 deg C, 30 min, 2.) -90 deg c to room temperature; Yield given; Multistep reaction. Yields of byproduct given;

potassium 2,5-dicyanothiophene-3,4-bis(olate) → 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: potassium carbonate; tetrabutylammomium bromide / N,N-dimethyl-formamide / 135 °C / Inert atmosphere 2: diisobutylaluminium hydride / toluene / 0 °C View Scheme

3,4-(ethylenedioxy)thiophene (126213-50-1) → 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: trichlorophosphate / 1,2-dichloro-ethane / 5 h / 80 °C 2.1: trichlorophosphate / 1,2-dichloro-ethane / 0.5 h / 20 °C 2.2: 5 h / 80 °C 2.3: 20 °C View Scheme

1-Methyl-1-phenylhydrazine (618-40-6) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → 3,4-ethylenedioxythiophene-2,5-dicarbaldehyde di(N-methyl-N-phenylhydrazone) (1141893-87-9)

Conditions	Yield
In ethanol Reflux;	85%

N,N-diphenylhydrazine hydrochloride (530-47-2) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → 3,4-ethylenedioxythiophene-2,5-dicarbaldehyde di(N,N-diphenylhydrazone) (1141893-88-0)

Conditions	Yield
In ethanol Reflux;	79%

5,10,15-trihexyl-10,15-dihydro-5H-diindolo[3,2-a:3’,2’-c]carbazole-2-amine + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → C92H106N8O2S

Conditions	Yield
With toluene-4-sulfonic acid In chloroform; isopropyl alcohol for 24h; Inert atmosphere; Reflux;	77%

4,4’-dimethoxy-4’’-aminotriphenylamine + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → C48H42N4O6S

Conditions	Yield
With toluene-4-sulfonic acid In chloroform for 72h; Reflux; Inert atmosphere;	75%

2-thienylmethyltriphenylphosphonium bromide (23259-98-5) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → 2,2'-dithienyl-ω,ω'-2,5-(2,4-ethylenedioxy)divinyl thiophene

Conditions	Yield
With sodium hydride In tetrahydrofuran at 20℃; for 10h; Condensation; Wittig;	74%

methyl (3,4,5-trimethoxyphenyl) ketone (1136-86-3) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → (2E,2’E)-3,3’-(2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-diyl)bis[1-(3,4,5-trimethoxyphenyl)prop-2-en-1-one]

Conditions	Yield
With sodium hydroxide In ethanol; water for 1h; Reflux;	74%

2,5-diamino-thiophene-3,4-dicarboxylic acid diethyl ester (80691-81-2) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → tetraethyl 5,5'-(1E,10E)-(2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-diyl)bis(methan-1-yl-1-ylidene)bis(azan-1-yl-1-ylidene)-bis(2-aminothiophene-3,4-dicarboxylate) (1239898-58-8)

Conditions	Yield
With trifluoroacetic acid In ethanol at 20℃; for 16h;	67%

2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) + diethyl (5-hexylthiophen-2-yl)methylphosphonate (609369-55-3) → (E,E)-2,5-bis[2-(5-hexyl-2-thienyl)-1-ethenyl]-3,4-ethylenedioxythiophene

Conditions	Yield
With potassium tert-butylate In tetrahydrofuran at 20℃; for 1h; Wittig-Horner reaction;	53%

3-cyano-2-amino-4,5,6,7-tetrahydrobenzo[b]thiophene (4651-91-6) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → 2,2'-(((1E,1'E)-(2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-diyl)bis(methanylylidene))bis(azanylylidene))bis(4,5,6,7-tetrahydrobenzo[b]thiophene-3-carbonitrile)

Conditions	Yield
With trifluoroacetic acid In ethanol at 40℃; for 16h;	52%

4-(N-isopropylamidino)-1,2-phenylene diamine (148344-30-3) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → 2,5-bis[(5-(N-isopropylamidino)benzimidazo-2-yl)]-3,4-ethylenedioxythiophene dihydrochloride

Conditions	Yield
Stage #1: 4-(N-isopropylamidino)-1,2-phenylene diamine; 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde With p-benzoquinone In ethanol for 4h; Reflux; Inert atmosphere; Stage #2: With hydrogenchloride In ethanol	50.7%

2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) + C11H20O3PS2(1-) → 2,5-bis<4,5-bis(n-propyl)-2H-1,3-dithiol-2-ylidenemethyl>-3,4-ethylenedioxythiophene

Conditions	Yield
	50%

2-(3,4-diaminophenyl)-imidazoline (66639-63-2) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → 2,5-bis[5-(3,4-dihydroimidazol-2-yl)benzimidazol-2-yl]-3,4-ethylenedioxythiophene dihydrochloride

Conditions	Yield
Stage #1: 2-(3,4-diaminophenyl)-imidazoline; 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde With p-benzoquinone In ethanol for 4h; Reflux; Inert atmosphere; Stage #2: With hydrogenchloride In ethanol	47.9%

4-amidino-1,2-phenylenediamine (68827-43-0) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → 2,5-bis[(5-amidinobenzimidazo-2-yl)]-3,4-ethylenedioxythiophene dihydrochloride

Conditions	Yield
Stage #1: 4-amidino-1,2-phenylenediamine; 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde With p-benzoquinone In ethanol for 4h; Reflux; Inert atmosphere; Stage #2: With hydrogenchloride In ethanol	42.6%

2-(Triphenyl-λ5-phosphanylidene)-[1,3]dithiole-4,5-dicarboxylic acid dimethyl ester (88430-82-4) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → 2,5-bis<4,5-bis(methoxycarbonyl)-2H-1,3-dithiol-2-ylidenemethyl>-3,4-ethylenedioxythiophene

Conditions	Yield
	40%

diethyl (3-hexylthiophen-2-yl)-methylphosphonate + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → C30H38O2S3

Conditions	Yield
With potassium tert-butylate In tetrahydrofuran at -78℃; for 2h; Inert atmosphere;	36%

1-(4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)phenyl)ethanone + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → C36H26O8S3

Conditions	Yield
With potassium hydroxide In ethanol for 12h; Claisen-Schmidt Condensation;	34%

C7H12O3PS4(1-) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → 2,5-bis<4,5-bis(methylsulfanyl)-2H-1,3-dithiol-2-ylidenemethyl>-3,4-ethylenedioxythiophene

Conditions	Yield
	27%

diethyl (3,4-ethylenedioxy-5-hexyl-2-thienyl)methylphosphonate + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → C34H42O6S3

Conditions	Yield
Stage #1: diethyl (3,4-ethylenedioxy-5-hexyl-2-thienyl)methylphosphonate With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.25h; Inert atmosphere; Stage #2: 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde In N,N-dimethyl-formamide at 20℃; for 18h; Horner-Wadsworth-Emmons Olefination; Inert atmosphere;	26%

1,3-bis(dicyanomethylidene)-indane (38172-19-9) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → 2-{2-[7-(1,3-Bis-dicyanomethylene-indan-2-ylidenemethyl)-2,3-dihydro-thieno[3,4-b][1,4]dioxin-5-ylmethylene]-3-dicyanomethylene-indan-1-ylidene}-malononitrile

2,5-diamino-thiophene-3,4-dicarboxylic acid diethyl ester (80691-81-2) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → C28H30N4O10S3 (1245748-31-5)

Conditions	Yield
In ethanol Acidic conditions;

diethyl 2-amino-5-benzamidothiophene-3,4-dicarboxylate (1586816-08-1) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → tetraethyl-5,5'-((1E,1'E)-((2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-diyl)bis(methanylylidene))bis(azanylylidene))bis(2-benzamidothiophene-3,4-dicarboxylate) (1586816-06-9)

Conditions	Yield
With trifluoroacetic acid In ethanol at 20℃; Inert atmosphere;

C17H19NO3 (347895-10-7) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → C42H40N2O8S

Conditions	Yield
With acetic acid In ethanol for 4h; Reflux; Inert atmosphere;

4-aminophenyl 4-(hexyloxy)benzoate (65388-44-5) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → C46H48N2O8S

Conditions	Yield
With acetic acid In ethanol for 4h; Reflux; Inert atmosphere;

4-aminophenyl 4-octyloxybenzoate (163856-08-4) + 2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-dicarboxaldehyde (211235-87-9) → C50H56N2O8S

Conditions	Yield
With acetic acid In ethanol for 4h; Reflux; Inert atmosphere;

Upstream product

• 75-27-4 bromodichloromethane 
• 126213-50-1 3,4-(ethylenedioxy)thiophene 
• 68-12-2 N,N-dimethyl-formamide 
• 204905-77-1 3,4-ethylenedioxythiophene-2-carboxaldehyde 
• 1269767-35-2 3,4-ethylenedioxythiophene-2,5-dicarbonitrile 
• 350474-52-1 2,5-di(hydroxymethyl)-3,4-ethylenedioxythiophene 

Downstream Products

• 1586816-06-9 tetraethyl-5,5'-((1E,1'E)-((2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-diyl)bis(methanylylidene))bis(azanylylidene))bis(2-benzamidothiophene-3,4-dicarboxylate) 
• 1141893-87-9 3,4-ethylenedioxythiophene-2,5-dicarbaldehyde di(N-methyl-N-phenylhydrazone) 
• 1141893-88-0 3,4-ethylenedioxythiophene-2,5-dicarbaldehyde di(N,N-diphenylhydrazone) 

Relevant articles and documents

Effect of 3,4-ethylenedioxy-extension of thiophene core on the DNA/RNA binding properties and biological activity of bisbenzimidazole amidines

Novel bisbenzimidazoles (4-6), characterized by 3,4-ethylenedioxy-extension of thiophene core, revealed pronounced affinity and strong thermal stabilization effect toward ds-DNA. They interact within ds-DNA grooves as dimmers or even oligomers and agglome

Synthesis and Optical Properties of New Chalcones Containing a 3,4-Ethylenedioxythiophene Fragment

Abstract: A new series of chalcones bearing two or more 3,4-ethylenedioxythiophene fragments were synthesized, and their optical properties were studied. The Stokes shifts (Δλ) and band gaps (Egopt) were calculated on the basis of the absorption and emission spectra. The largest Stokes shift (115 nm) was found for a symmetrical product of the terephthalaldehyde and 3,4-ethylenedioxythiophene-2-carbaldehyde condensation, and the smallest band gap (1.93 eV) is characteristic of a chalcone that contains a 2,2',5',2''-ter(3,4-ethylenedioxythiophene). Correlations were established between the band gap and mutual arrangement of the 3,4-ethylenedioxythiophene fragments in the prepared chalcones.

Palladium-catalyzed C-H formylation of electron-rich heteroarenes through radical dichloromethylation

A novel palladium-catalyzed C-H formylation of electron-rich N-, O-, and S-containing heteroarenes has been developed. The key to success is that the commercially available BrCHCl2 was used as a stoichiometric carbonyl source. Mechanistic investigations indicated that different from the known Reimer-Tiemann reaction, this net C-H formylation proceeded through an electrophilc radical-type path.

Carbazole-based π-conjugated polyazomethines: Effects of catenation and comonomer insertion on optoelectronic features

A series of carbazole-based polyazomethines have been synthesized under micro-wave irradiation and without transition-metal based catalyst. The impact of both the catenation brought by the carbazole subunits and the insertion of a co-monomer, i.e. 3,4 ethylene dioxythiophene (EDOT), on the optical and electrochemical properties have been studied. Among the different polyazomethines synthesized, the best in terms of optical and electrochemical properties has been found to be the one with the azomethine function linked in positions 2,7 of carbazole subunits. Upon the insertion of the EDOT comonomer, an increase of the molecular weight and a red-shift in the absorption spectra has been observed, corresponding to a diminution of the electronic gap.