4282-31-9

Basic information

• Product Name: 2,5-Thiophenedicarboxylic acid
• Synonyms: 2,5-DICARBOXYTHIOPHENE;2,5-THIOPHENEDICARBOXYLIC ACID;RARECHEM AL BE 0623;OTAVA-BB BB7013911425;THIOPHENE-2,5-DICARBOXYLIC ACID;Thiophene-2,5-Dicarboxyl Acid;Thiophene-2,5-dicarboxylicacid,97%;2,5-THIOPHENEDICARBOXYLIC
• CAS NO: 4282-31-9
• Molecular Formula: C₆H₄O₄S
• Molecular Weight: 172.16
• EINECS: 224-284-2
• Product Categories: Thiophenes;FINE Chemical & INTERMEDIATES;Heterocycles;Thiophene&Benzothiophene;Organic acids;Heterocyclic Compounds;Thiophens;Functional Materials;Reagents for Conducting Polymer Research;Thiophene Derivatives (for Conduting Polymer Research);Thiophen;Building Blocks;Heterocyclic Building Blocks
• Mol File: 4282-31-9.mol
• Article Data: 14

Chemical Properties

• Melting Point: >300 °C(lit.)
• Boiling Point: 272.46°C (rough estimate)
• Flash Point: 222.7 °C
• Appearance: /solid
• Density: 1.473 (estimate)
• Vapor Pressure: 1.1E-08mmHg at 25°C
• Refractive Index: 1.5500 (estimate)
• Storage Temp.: Keep in dark place,Sealed in dry,Room Temperature
• PKA: 2.76±0.10(Predicted)
• Water Solubility: Very soluble in water.
• BRN: 136781
• CAS DataBase Reference: 2,5-Thiophenedicarboxylic acid(CAS DataBase Reference)
• NIST Chemistry Reference: 2,5-Thiophenedicarboxylic acid(4282-31-9)
• EPA Substance Registry System: 2,5-Thiophenedicarboxylic acid(4282-31-9)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36-37/39
• WGK Germany: 3
• TSCA: Yes
• HazardClass: IRRITANT
• Hazardous Substances Data: 4282-31-9(Hazardous Substances Data)

Usage

Chemical Properties

white to light yellow crystal powder

Uses

2,5-Thiophenedicarboxylic acid may be used as a thiophene based linker in the preparation of magnesium coordination networks. It may also be used as a precursor in the synthesis of 2,5-bis-benzoxazoyl-thiophene (EBF).It may be used in the synthesis of the following:new cobalt(II) thiophenedicarboxylate coordination polymernovel mesogenic thiophene based supramolecular liquid crystalstwo novel coordination polymers with the formula {[Ln2(2,5-tdc)3(dmso)2]H2O}n (Ln = Tb(III) and Dy(III)), (2,5-tdc2 = 2,5-thiophenedicarboxylate and dmso = dimethylsulfoxide)

Synthesis Reference(s)

Journal of the American Chemical Society, 72, p. 2109, 1950 DOI: 10.1021/ja01161a065

General Description

2,5-Thiophenedicarboxylic acid (2,5-TDCA, H2TDC) is an important building block in the preparation of fluorescent brightening agent, fungicides and anti-cancer drug. It has been generated by chlorination of adipic acid using thionyl chloride. Due to its diverse coordination modes, it is an excellent choice as an aromatic linker to generate coordination networks. The enthalpies of combustion and sublimation of 2,5-thiophenedicarboxylic acid have been evaluated by rotary-bomb combustion calorimetry.

InChI:InChI=1/C6H4O4S/c7-5(8)3-1-2-4(11-3)6(9)10/h1-2H,(H,7,8)(H,9,10)/p-2

Synthetic route

2,5-thiophenedicarbonitrile (18853-40-2) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With hydrogenchloride for 6h; Heating;	79%

Adipic acid (124-04-9) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
Stage #1: Adipic acid With dmap; thionyl chloride at 78 - 81℃; for 3.5h; Large scale; Stage #2: With sodium hydroxide In water at 70 - 72℃; for 2h; pH=9.3 - 10; Reagent/catalyst; Temperature; pH-value; Large scale;	75.58%

2,5‐diethyl thiophene‐2,5‐dicarboxylate (61755-85-9) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With potassium hydroxide In ethanol for 2h; Heating;	70%
With potassium hydroxide

2,5-diiodothiophene (625-88-7) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With n-butyllithium; carbon dioxide In tetrahydrofuran; water	60%
With diethyl ether; phenyllithium Behandeln des Reaktionsgemisches mit festem Kohlendioxid;

methanol (67-56-1) + 2,5-dibromothiophen (3141-27-3) + carbon monoxide (201230-82-2) → Thiophene-2,5-dicarboxylic acid (4282-31-9) + Dimethyl thiophene-2,5-dicarboxylate (4282-34-2)

Conditions	Yield
With tert-Amyl alcohol; sodium hydride; cobalt(II) acetate In tetrahydrofuran at 40℃; under 760 Torr; for 54h; Irradiation;	A 17% B 55%

2,5-dibromothiophen (3141-27-3) + carbon monoxide (201230-82-2) → Thiophene-2,5-dicarboxylic acid (4282-31-9) + Dimethyl thiophene-2,5-dicarboxylate (4282-34-2)

Conditions	Yield
With methanol; tert-Amyl alcohol; sodium hydride; cobalt(II) acetate In tetrahydrofuran at 40℃; under 760 Torr; for 54h; Irradiation;	A 17% B 55%

2,5-dibromothiophen (3141-27-3) + carbon dioxide (124-38-9) → 5-bromothiophene-2-carboxylic acid (7311-63-9) + Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
Stage #1: 2,5-dibromothiophen; carbon dioxide With tert.-butyl lithium In pentane at -70℃; Inert atmosphere; Stage #2: With sulfuric acid; water In pentane at 20℃; Inert atmosphere;	A 34% B 5%

thiophene (188290-36-0) + n-pentylsodium (1822-71-5) + sodium tert-pentoxide (14593-46-5) + methylammonium carbonate (15719-64-9, 15719-76-3, 97762-63-5) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
aufeinanderfolgender Umsetzung;

thiophene (188290-36-0) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With n-heptane; n-pentylsodium; sodium tert-pentoxide anschliessend Behandeln mit festem Kohlendioxid;

2,5-DIMETHYLTHIOPHENE (638-02-8) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With alkaline permanganate solution

2-Acetyl-5-methylthiophen (13679-74-8) → 2-methylthiophene-5-carboxylic acid (1918-79-2) + Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With potassium hydroxide; potassium permanganate Behandeln des Reaktionsprodukts mit wss. Wasserstoffperoxid;

2-Acetyl-5-methylthiophen (13679-74-8) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With alkaline permanganate solution
With sodium hydroxide; potassium permanganate Oxidation;

2,5-bis-chloromethyl-thiophene (28569-48-4) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With potassium hydroxide; potassium permanganate
With potassium permanganate; acetone

Glyoxal (131543-46-9) + diethyl thioglycolate (925-47-3) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With sodium ethanolate Abdampfen der mit Wasser versetzten Mischung und Ansaeuern mit Salzsaeure;

1-(5-ethyl-thiophen-2-yl)-ethanone (18761-46-1) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With alkaline permanganate solution

thiophene (188290-36-0) + carbon dioxide (124-38-9) → 2-thiophenylcarboxylic acid (527-72-0) + Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With n-butyllithium 1.) methylcyclohexane, THF, from 0 deg C to 25 deg C, 20 h, 2.) methylcyclohexane, THF, ether; Yield given. Multistep reaction. Yields of byproduct given;

2,5-dibromothiophen (3141-27-3) + carbon dioxide (124-38-9) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With n-butyllithium 1. THF/-50 - -55 deg C; Yield given. Multistep reaction;
Stage #1: 2,5-dibromothiophen With iodine; magnesium In tetrahydrofuran; 1,4-dioxane at 60℃; for 4h; Inert atmosphere; Stage #2: carbon dioxide In tetrahydrofuran; 1,4-dioxane Solvent; Temperature;

2-thiophenylcarboxylic acid (527-72-0) + carbon dioxide (124-38-9) → Thiophene-2,5-dicarboxylic acid (4282-31-9) + thiophene-2,3-dicarboxylic acid (1451-95-2)

Conditions	Yield
With n-butyllithium 1.) THF/hexane, -78 deg C, 30 min, 2.) THF/hexane, -78 -> -10 deg C; Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts;

5-chloromethyl-thiophene-2-carboxylic acid ethyl ester → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With nitric acid

5-ethyl-thiophene-carboxylic acid-(2) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With alkaline permanganate solution

5-methyl-thiophene-carboxylic acid-(2) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With alkaline permanganate solution

potassium salt of/the/ thiophene-disulfonic acid-(2.4) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With potassium cyanide Verseifen durch Kochen mit alkoh. Kali;

potassium-salt of/the/ thiophene-2-carboxylic acid → thiophene (188290-36-0) + Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With cadmium catalyst unter Kohlendioxid;

2-ethylthiophene (872-55-9) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: petroleum ether; aluminium chloride 2: alkaline permanganate solution View Scheme

Dimethyl thiophene-2,5-dicarboxylate (4282-34-2) → Thiophene-2,5-dicarboxylic acid (4282-31-9)

Conditions	Yield
With sulfuric acid In water at 60℃; for 2h; Large scale;	1679 g

Thiophene-2,5-dicarboxylic acid (4282-31-9) + ethanol (64-17-5) → 2,5‐diethyl thiophene‐2,5‐dicarboxylate (61755-85-9)

Conditions	Yield
With sulfuric acid Reflux;	100%
With sulfuric acid for 120h; Reflux;	90%
With graphene oxide at 100℃; for 24h;	67%
With sulfuric acid at 85℃; for 72h; Inert atmosphere;	3.2 g
for 6h; Reflux;

methanol (67-56-1) + Thiophene-2,5-dicarboxylic acid (4282-31-9) → Dimethyl thiophene-2,5-dicarboxylate (4282-34-2)

Conditions	Yield
With thionyl chloride at 0 - 20℃; for 3h; Heating / reflux;	99.9%
With thionyl chloride Reflux;	99%
With thionyl chloride Reflux;	99%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + Thiophene-2,5-dicarboxylic acid (4282-31-9) + zinc(II) nitrate hexahydrate + 1,2-dihydroxybutane (584-03-2) → [Zn12(thiophene-2,5-dicarboxylic acid)6(1,2-butanediol)6(1,4-diaza-bicyclo[2.2.2]octane)3]

Conditions	Yield
Stage #1: 1,4-diaza-bicyclo[2.2.2]octane; Thiophene-2,5-dicarboxylic acid; zinc(II) nitrate hexahydrate In N,N-dimethyl-formamide for 1h; Stage #2: 1,2-dihydroxybutane In N,N-dimethyl-formamide at 130℃; for 48h; Sealed tube;	99%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + 2-amino-4-tert-butylphenol (1199-46-8) → Uvitex OB (7128-64-5)

Conditions	Yield
With boric acid In toluene at 170 - 240℃; Solvent; Temperature; Inert atmosphere;	98.7%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + Thiophene-2,5-dicarboxylic acid (4282-31-9) + zinc(II) nitrate hexahydrate + ethylene glycol (107-21-1) → [Zn12(thiophene-2,5-dicarboxylic acid)6(ethylene glycol)6(1,4-diaza-bicyclo[2.2.2]octane)3]

Conditions	Yield
Stage #1: 1,4-diaza-bicyclo[2.2.2]octane; Thiophene-2,5-dicarboxylic acid; zinc(II) nitrate hexahydrate In N,N-dimethyl-formamide for 1h; Stage #2: ethylene glycol In N,N-dimethyl-formamide at 130℃; for 48h; Sealed tube;	98%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + benzoguanamine (91-76-9) → C15H11N5O3S

Conditions	Yield
In ethanol for 2h; Reflux;	97.9%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + (S)-2-aminobutan-1-ol (5856-62-2) → (-)-2,5-bis[4'-(S)-ethyloxazolin-2'-yl]thiophene

Conditions	Yield
In toluene for 24h; Reflux; water segregator;	96%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + propylene glycol (57-55-6) + Thiophene-2,5-dicarboxylic acid (4282-31-9) + zinc(II) nitrate hexahydrate → [Zn12(thiophene-2,5-dicarboxylic acid)6(1,2-propanediol)6(1,4-diaza-bicyclo[2.2.2]octane)3]

Conditions	Yield
Stage #1: 1,4-diaza-bicyclo[2.2.2]octane; Thiophene-2,5-dicarboxylic acid; zinc(II) nitrate hexahydrate In N,N-dimethyl-formamide for 1h; Stage #2: propylene glycol In N,N-dimethyl-formamide at 130℃; for 48h; Sealed tube;	96%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + Thiophene-2,5-dicarboxylic acid (4282-31-9) + zinc(II) nitrate hexahydrate + 1,2-pentanediol (5343-92-0) → [Zn12(thiophene-2,5-dicarboxylic acid)6(1,2-pentanediol)6(1,4-diaza-bicyclo[2.2.2]octane)3]

Conditions	Yield
Stage #1: 1,4-diaza-bicyclo[2.2.2]octane; Thiophene-2,5-dicarboxylic acid; zinc(II) nitrate hexahydrate In N,N-dimethyl-formamide for 1h; Stage #2: 1,2-pentanediol In N,N-dimethyl-formamide at 130℃; for 48h; Sealed tube;	96%

N,N’,N’’,N’’’-tetrakis(2-pyridylmethyl)-1,6-diaminohexane (190773-57-0) + Thiophene-2,5-dicarboxylic acid (4282-31-9) + cobalt(II) diacetate tetrahydrate (6147-53-1) → poly{[Co2(thiophene-2,5-dicarboxylato)2(N,N’,N’’,N’’’-tetrakis(2-pyridylmethyl)-1,6-diaminohexane)]·H2O}

Conditions	Yield
Stage #1: N,N’,N’’,N’’’-tetrakis(2-pyridylmethyl)-1,6-diaminohexane; cobalt(II) diacetate tetrahydrate In methanol at 20℃; Stage #2: Thiophene-2,5-dicarboxylic acid In methanol at 20℃;	96%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + tungsten 2,2-dimethylpropionate → [((pivalate)3W2)2(2,5-thienyldicarboxylate)]

Conditions	Yield
In toluene C4H2S(COOH)2 added to soln. of W2((CH3)3CCOO)4 in toluene; soln. stirredfor 7-10 d at rt; precipitate filtered off; detd. by elem. anal.;	95%
In toluene under Ar atm. to soln. (W2(O2C(t)Bu)4) in toluene 2,5-Th(COOH)2 was added and stirred at room temp. for 5-10 days; ppt. was filtered, washed with toluene and hexane, and dried in vacuo; elem. anal.;	95%

pyridine (110-86-1) + Thiophene-2,5-dicarboxylic acid (4282-31-9) + bismuth (III) nitrate pentahydrate → 2C6H2O4S(2-)*2.5H2O*Bi(3+)*C5H5N*H(1+)

Conditions	Yield
With acetic acid In ethanol at 20℃; for 120 - 168h; pH=4 - 5;	94%

1,4-diaza-bicyclo[2.2.2]octane (280-57-9) + Thiophene-2,5-dicarboxylic acid (4282-31-9) + zinc(II) nitrate hexahydrate + glycerol (56-81-5) → [Zn12(thiophene-2,5-dicarboxylic acid)6(glycerol)6(1,4-diaza-bicyclo[2.2.2]octane)3]

Conditions	Yield
Stage #1: 1,4-diaza-bicyclo[2.2.2]octane; Thiophene-2,5-dicarboxylic acid; zinc(II) nitrate hexahydrate In N,N-dimethyl-formamide for 1h; Stage #2: glycerol In N,N-dimethyl-formamide at 130℃; for 48h; Sealed tube;	94%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + 3-amino-4-hydroxytoluene (95-84-1) → 5,5'-dimethyl-2,2'-thiophene-2,5-diyl-bis-benzooxazole (3723-19-1)

Conditions	Yield
With boric acid; tin(ll) chloride In 1,2-dichloro-benzene at 220℃; for 24h; Inert atmosphere; Dean-Stark;	94%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + L-Phenylalaninol (3182-95-4) → (+)-2,5-bis[4'-(S)-benzyloxazolin-2'-yl]thiophene

Conditions	Yield
In toluene for 24h; Reflux; water segregator;	93%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + (2S)-2-phenylglycinol (20989-17-7) → (+)-2,5-bis[4'-(S)-phenyloxazolin-2'-yl]thiophene (1259933-47-5)

Conditions	Yield
In toluene for 24h; Reflux; water segregator;	93%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + N,0-dimethylhydroxylamine (1117-97-1) → N2,N5-dimethoxy-N2,N5-dimethylthiophene-2,5-dicarboxamide (821797-87-9)

Conditions	Yield
Stage #1: Thiophene-2,5-dicarboxylic acid; N,0-dimethylhydroxylamine In toluene at 0℃; for 0.166667h; Stage #2: With phosphorus trichloride In toluene at 20 - 60℃; for 0.5h;	92%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + manganese(II) chloride tetrahydrate + 2-(5-{6-[5-(pyrazin-2-yl)-1H-1,2,4-triazol-3-yl]-pyridin-2-yl}-1H-1,2,4-triazol-3-yl)pyrazine (1349082-74-1) + water (7732-18-5) → {[Mn2(ptptp)(Hbtc)(H2O)2]·2H2O}n

Conditions	Yield
With 3-ethyl-1-methyl-1H-imidazol-3-ium bromide In acetonitrile at 160℃; for 72h; Reagent/catalyst; Autoclave;	92%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + (S)-valinol (2026-48-4) → (-)-2,5-bis[4'-(S)-isopropyloxazolin-2'-yl]thiophene

Conditions	Yield
In toluene for 24h; Reflux; water segregator;	91%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + dimolybdenum tetrapivalate → [((pivalate)3Mo2)2(2,5-thienyldicarboxylate)]

Conditions	Yield
In toluene C4H2S(COOH)2 added to soln. of Mo2((CH3)3CCOO)4 in toluene; soln. stirred for 7-10 d at rt; precipitate filtered off; detd. by elem. anal., MALDI;	90%
In toluene under Ar atm. to soln. (Mo2(O2C(t)Bu)4) in toluene 2,5-Th(COOH)2 was added and stirred at room temp. for 5-10 days; ppt. was filtered; elem. anal.;	90%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + manganese(II) chloride tetrahydrate + water (7732-18-5) → Mn2(thiophene-2,5-dicarboxylate)2(H2O)3

Conditions	Yield
With NH3*H2O In water High Pressure; mixt. of MnCl2*4H2O, thiohene-2,5-dicarboxylic acid, H2O adjusted to pH 7.4 by aq. soln. of NH3*H2O, placed in autoclave, heated at 110°Cfor 3 d, slow cooled to room temp.; ppt. filtered, washed with H2O; elem. anal.;	90%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + cobalt(II) chloride hexahydrate + water (7732-18-5) → Co2(thiophene-2,5-dicarboxylate)2(H2O)3

Conditions	Yield
With NH3*H2O In water High Pressure; mixt. of CoCl2*6H2O, thiohene-2,5-dicarboxylic acid, H2O adjusted to pH 7.4 by aq. soln. of NH3*H2O, placed in autoclave, heated at 110°Cfor 3 d, slow cooled to room temp.; ppt. filtered, washed with H2O; elem. anal.;	90%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + zinc(II) nitrate hexahydrate + 2,5-bis(4-(pyridine-4-yl)phenyl)thiazolo[5,4-d]thiazole + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → [Zn2(2,5-bis(4-(pyridine-4-yl)phenyl)thiazolo[5,4-d]thiazole)2(2,5-thiophene dicarboxylate)2]n*2DMF

Conditions	Yield
at 120℃; for 72h;	90%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + aluminum(III) sulphate octadecahydrate + water (7732-18-5) → [Al(μ-OH)(2,5-thiophenedicarboxylate)]

Conditions	Yield
In N,N-dimethyl-formamide at 135℃; for 24h;	90%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + cobalt(II) diacetate tetrahydrate (6147-53-1) + N,N’-(1,4-phenylenebis(methylene))bis(1-(pyridin-2-yl)-N-(pyridin-2-ylmethyl)methanamine) (263713-26-4) → poly{[Co2(thiophene-2,5-dicarboxylato)2(N,N’-(1,4-phenylenebis(methylene))bis(1-(pyridin-2-yl)-N-(pyridin-2-ylmethyl)methanamine))]·6H2O}

Conditions	Yield
Stage #1: cobalt(II) diacetate tetrahydrate; N,N’-(1,4-phenylenebis(methylene))bis(1-(pyridin-2-yl)-N-(pyridin-2-ylmethyl)methanamine) In methanol at 20℃; Stage #2: Thiophene-2,5-dicarboxylic acid In methanol at 20℃;	90%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + 2-amino-phenol (95-55-6) → 2,2'-thiophene-2,5-diylbis(benzoxazole) (2866-43-5)

Conditions	Yield
With boric acid; tin(ll) chloride In 1,2-dichloro-benzene at 220℃; for 24h; Inert atmosphere; Dean-Stark;	89.23%
Stage #1: Thiophene-2,5-dicarboxylic acid; 2-amino-phenol at 150℃; for 2h; Inert atmosphere; Stage #2: With ammonia In water at 20℃; pH=~ 10 - 11; Cooling with cold water;	5.5%
With boric acid In 1-methyl-pyrrolidin-2-one; toluene at 20 - 185℃; for 13h;

Thiophene-2,5-dicarboxylic acid (4282-31-9) + (S)-tert-leucinol (112245-13-3) → (+)-2,5-bis[4'-(S)-tert-butyloxazolin-2'-yl]thiophene

Conditions	Yield
In toluene for 24h; Reflux; water segregator;	89%

Thiophene-2,5-dicarboxylic acid (4282-31-9) + manganese(II) chloride tetrahydrate + ISOPROPYLAMIDE (563-83-7) → Mn2(2,5-thiophenedicarboxylate)2(N,N-dimethylacetamide)2 + Mn2(2,5-thiophenedicarboxylate)2(acetate)*(dimethylammonium)

Conditions	Yield
at 120℃; for 120h; High pressure;	A 89% B n/a

formic acid (64-18-6) + Thiophene-2,5-dicarboxylic acid (4282-31-9) + zirconium(IV) chloride (10026-11-6) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → [Zr6O6(OH)2(2,5-thiophenedicarboxylate)4(formate)2(N,Ndimethylformamide)*(H2O)5]

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 120℃; for 48h; Sonication;	89%

formic acid (64-18-6) + Thiophene-2,5-dicarboxylic acid (4282-31-9) + zirconium(IV) chloride (10026-11-6) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → Zr6O6(OH)2(2,5-thiophenedicarboxylate)4(HCOO)2(DMF)2

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 80℃; for 48h;	89%

Upstream product

• 625-88-7 2,5-diiodothiophene 
• 188290-36-0 thiophene 
• 124-38-9 carbon dioxide 
• 3141-27-3 2,5-dibromothiophen 
• 18853-40-2 2,5-thiophenedicarbonitrile 
• 4282-34-2 Dimethyl thiophene-2,5-dicarboxylate 
• 124-04-9 Adipic acid 
• 872-55-9 2-ethylthiophene 
• 527-72-0 2-thiophenylcarboxylic acid 
• 201230-82-2 carbon monoxide 
• 67-56-1 methanol 
• 18761-46-1 1-(5-ethyl-thiophen-2-yl)-ethanone 
• 61755-85-9 2,5‐diethyl thiophene‐2,5‐dicarboxylate 
• 131543-46-9 Glyoxal 

Downstream Products

• 3857-36-1 thiophene-2,5-dicarbonyl dichloride 

Relevant articles and documents

Preparation method of thiophene carboxyl-substituted derivative

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Preparation method of refined thiophene-2,5-dicarboxylic acid

The invention provides a preparation method of refined thiophene-2,5-dicarboxylic acid. The preparation method specifically comprises the following steps: firstly taking 2,5-dichlorothiophene or 2,5-dibromothiophene as a raw material and reacting with magnesium chips in a solvent to prepare a corresponding format reagent solution; then introducing carbon dioxide gas or adding dry ice in batches, quenching a reaction system with water after the completion of reaction, extracting an organic solvent, drying by distillation to obtain a thiophene-2,5-dicarboxylic acid crude product; finally performing re-crystallization by adopting ethanol to obtain the refined thiophene-2,5-dicarboxylic acid. The invention can provide the preparation method of the refined thiophene-2,5-dicarboxylic acid, which is simple in process, short in step, low in production cost and high in product conversion rate.

Is carbon dioxide able to activate halogen/lithium exchange?

The unexpected effect of carbon dioxide on halogen-lithium exchange (HLE) reactions of selected haloarenes with tBuLi was investigated. In an aliphatic hydrocarbon solvent (pentane), the HLE does not occur at ca. -70 C but, surprisingly, pouring the mixture of reactants onto dry ice and subsequent aqueous acidic hydrolysis gave carboxylic acids resulting from the quench of the first-formed aryllithiums with carbon dioxide. This suggests that CO 2 acts as a promoter of the HLE and, subsequently, serves as an electrophile to trap the aryllithium intermediates that are generated in situ. Theoretical DFT calculations were used to develop a plausible mechanism for the reaction, which indicates that CO2 is a much weaker donor than tetrahydrofuran (THF) so the cleavage of inert tBuLi cubic tetramers into more reactive solvated dimeric species (tBuLi)2(CO2) 4 is disfavored by 42.8 kJ per mol of (tBuLi)4. It is possible that this deaggregation process occurs to some extent when a large excess of CO2 is used. Copyright