14345-97-2

Basic information

• Product Name: 2-Chloro-3-methylthiophene
• Synonyms: 2-Chloro-3-methythiophene;2-CHLORO-3-METHYLTHIOPHENE 97%;N-ydroxymethylphthalimide;Thiophene, 2-chloro-3-methyl-;2-Chloro-3-methylthiophene ,98%;2-Chloro-3-methylthiophene,97%;2-Chloro-3-methylthi;Chloro-3-Methylthioph
• CAS NO: 14345-97-2
• Molecular Formula: C₅H₅ClS
• Molecular Weight: 132.61
• EINECS: 238-296-0
• Product Categories: Thiophenes;Thiophene&Benzothiophene;Thiophens;Functional Materials;Reagents for Conducting Polymer Research;Thiophene Derivatives (for Conduting Polymer Research);Halogenated Heterocycles;Heterocyclic Building Blocks;ThiophenesBuilding Blocks;Building Blocks;C4 to C6;Chemical Synthesis;Halogenated Heterocycles;Heterocyclic Building Blocks;Heterocycle-oher series
• Mol File: 14345-97-2.mol
• Article Data: 4

Chemical Properties

• Melting Point: 153-157 °C
• Boiling Point: 147-149 °C(lit.)
• Flash Point: 115 °F
• Appearance: clear yellow to yellow-brown liquid
• Density: 1.211 g/mL at 25 °C(lit.)
• Vapor Pressure: 4.99mmHg at 25°C
• Refractive Index: n20/D 1.5400(lit.)
• Storage Temp.: Keep in dark place,Inert atmosphere,Room temperature
• CAS DataBase Reference: 2-Chloro-3-methylthiophene(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Chloro-3-methylthiophene(14345-97-2)
• EPA Substance Registry System: 2-Chloro-3-methylthiophene(14345-97-2)

Safety Data

• Hazard Codes: Xn,Xi
• Statements: 10-22-41-36/37/38
• Safety Statements: 16-26-39-37/39
• RIDADR: UN 1993 3/PG 3
• WGK Germany: 3
• HazardClass: 3
• PackingGroup: III
• Hazardous Substances Data: 14345-97-2(Hazardous Substances Data)

Usage

Chemical Properties

clear yellow to yellow-brown liquid

InChI:InChI=1/C5H5ClS/c1-4-2-3-7-5(4)6/h2-3H,1H3

Synthetic route

N-chloro-succinimide (128-09-6) + 3-Methylthiophene (616-44-4) → 2-chloro-3-methylthiophene (14345-97-2)

N-chloro-succinimide (128-09-6) + 3-Methylthiophene (616-44-4) → 2-chloro-3-methylthiophene (14345-97-2) + 3-(chloromethyl)thiophene (2746-23-8)

Conditions	Yield
With tetrachloromethane; dibenzoyl peroxide

3-Methylthiophene (616-44-4) → 2-chloro-3-methylthiophene (14345-97-2)

Conditions	Yield
With sulfuryl dichloride
With aluminium trichloride; benzeneseleninyl chloride In chloroform for 3h; Ambient temperature;	78 % Chromat.
With sulfuryl dichloride at 15℃; for 1h;

3-Methylthiophene (616-44-4) + sodium thiosulfate → 2-chloro-3-methylthiophene (14345-97-2)

Conditions	Yield
With sulfuryl dichloride In acetonitrile

3-Methylthiophene (616-44-4) + SO2 Cl2 → 2-chloro-3-methylthiophene (14345-97-2)

Conditions	Yield
	35,3 g (52%)

2-chloro-3-methylthiophene (14345-97-2) + 3,5,5-Trimethylcyclohex-2-en-1-one (78-59-1) → 5,5-dimethyl-3-((3-methylthiophen-2-yl)methyl)cyclohex-2-enone

Conditions	Yield
With 2-(2,6-dimethoxyphenyl)-1-methyl-3-(diphenylphosphino)-1H-indole; palladium diacetate; lithium tert-butoxide In 1,4-dioxane at 100℃; for 1h; Schlenk technique; Inert atmosphere;	99%

2-chloro-3-methylthiophene (14345-97-2) + 4-chloro-1H-pyrazole (15878-00-9) → 4-chloro-1-(5-chloro-4-methylthiophen-2-yl)-1H-pyrazole

Conditions	Yield
With tert.-butylnitrite; 2,3-dicyano-5,6-dichloro-p-benzoquinone In 1,2-dichloro-ethane at 20℃; for 4h; Irradiation; Schlenk technique;	95%

2-chloro-3-methylthiophene (14345-97-2) + carbon dioxide (124-38-9) → 5-chloro-4-methylthiophen-2-carboxylic acid (74598-03-1)

Conditions	Yield
With n-butyllithium In diethyl ether 1.) reflux, 2 h, 2.) - 70 deg C;	89%

2-chloro-3-methylthiophene (14345-97-2) + ethyl acrylate (140-88-5) → ethyl (E)-3-(5-chloro-4-methylthiophen-2-yl)acrylate

Conditions	Yield
With dimethyl 2-((6-methylpyridin-3-yl)methylene)malonate; palladium diacetate; silver fluoride; acetic acid In N,N-dimethyl-formamide at 50℃; for 48h; Schlenk technique; Inert atmosphere; Sealed tube; regioselective reaction;	87%

2-chloro-3-methylthiophene (14345-97-2) + dicyanozinc (557-21-1) → 3-methylthiophene-2-carbonitrile (55406-13-8)

Conditions	Yield
bis(tri-t-butylphosphine)palladium(0); zinc In N,N-dimethyl acetamide at 95℃; for 6h;	86.4%

2-chloro-3-methylthiophene (14345-97-2) + 1-methoxy-4-(2-methyl-1-propenyl)benzene (877-99-6) → 2-chloro-5-(1-(4-methoxyphenyl)-2-methylpropyl)-3-methylthiophene

Conditions	Yield
With silver hexafluoroantimonate; 2,2':5',2''-terthiophene In dichloromethane at 20℃; Glovebox; Schlenk technique; regioselective reaction;	83%

2-chloro-3-methylthiophene (14345-97-2) + 2-phenylpyridine (1008-89-5) → 2-(2-(3-methylthien-2-yl)phenyl)pyridine

Conditions	Yield
With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; 1-methyl-2-phenyl-3-(diphenylphosphino)-1H-indole; potassium carbonate In 1-methyl-pyrrolidin-2-one at 120℃; for 24h; Schlenk technique; Inert atmosphere; Sealed tube;	80%

2-chloro-3-methylthiophene (14345-97-2) + 3-hexyl-2-bromothiophene (69249-61-2) → 2-chloro-3-methyl-5-(3-hexylthiophen-2-yl)thiophene

Conditions	Yield
Stage #1: 2-chloro-3-methylthiophene With 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex In tetrahydrofuran at 25℃; for 3h; Inert atmosphere; Schlenk technique; Stage #2: 3-hexyl-2-bromothiophene With Pd-PEPPSI-SIPr In tetrahydrofuran at 60℃; for 24h; Inert atmosphere; Schlenk technique;	79%

2-chloro-3-methylthiophene (14345-97-2) + tert-Butyl acrylate (1663-39-4) → tert-butyl (E)-3-(5-chloro-4-methylthiophen-2-yl)acrylate

Conditions	Yield
With 4-(ethylthio)-N,N-dimethylaniline; palladium diacetate; acetic acid; hydroquinone at 60℃; for 3h;	78%

2-chloro-3-methylthiophene (14345-97-2) + cyclohexenone (930-68-7) → 3-(5-chloro-4-methylthiophen-2-yl)cyclohexan-1-one

Conditions	Yield
With 4,5-Diazafluoren-9-one; palladium diacetate; acetic acid In acetonitrile at 50℃; for 36h;	78%
With 4,5-Diazafluoren-9-one; palladium diacetate; acetic acid In acetonitrile at 50℃; for 36h; Heck Reaction; Green chemistry;	78%

2-chloro-3-methylthiophene (14345-97-2) + 2,6-dimethylbenzene boronic acid (100379-00-8) → 2-(2,6-dimethylphenyl)-3-methylthiophene (1308652-76-7)

Conditions	Yield
With potassium phosphate; 9-(2-(dicyclohexylphosphino)phenyl)-9H-carbazole; palladium diacetate; phenylboronic acid In 1,4-dioxane at 120℃; for 24h; Suzuki coupling; Inert atmosphere;	75%

2-chloro-3-methylthiophene (14345-97-2) + 2-bromo-3-(4-bistrimethylsiloxysilylbutan-1-yl)thiophene → 2-chloro-3-methyl-5-(3-(4-(bis(trimethylsiloxy)(methyl)silyl)butan-1-yl)thiophen-2-yl)thiophene

Conditions	Yield
Stage #1: 2-chloro-3-methylthiophene With (2,2,6,6-tetramethylpiperidin-1-yl)magnesium halide Stage #2: 2-bromo-3-(4-bistrimethylsiloxysilylbutan-1-yl)thiophene With palladium catalyst	74%

2-chloro-3-methylthiophene (14345-97-2) + 2,4-dimethyl-3,6-dioxocyclohexa-1,4-dienylboronic acid (1130728-55-0) → 6-(5-chloro-4-methylthiophen-2-yl)-2,6-dimethylcyclohex-2-ene-1,4-dione (1262865-00-8)

Conditions	Yield
With iron(III) chloride hexahydrate In dichloromethane at 25℃; for 48h; Friedel Crafts alkylation; regioselective reaction;	72%

2-chloro-3-methylthiophene (14345-97-2) + 2-bromo-3-[4-(1,1,3,3,3-pentameth-yldisiloxan-1-yl)butan-1-yl]thiophene (1622149-27-2) → 2-chloro-3-methyl-5-{3-[4-(1,1,3,3,3-pentamethyldisiloxan-1-yl)butan-1-yl]thiophen-2-yl}thiophene

Conditions	Yield
Stage #1: 2-chloro-3-methylthiophene With 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex In tetrahydrofuran at 25℃; for 3h; Inert atmosphere; Schlenk technique; Stage #2: 2-bromo-3-[4-(1,1,3,3,3-pentameth-yldisiloxan-1-yl)butan-1-yl]thiophene With Pd-PEPPSI-SIPr In tetrahydrofuran at 60℃; for 24h; Inert atmosphere; Schlenk technique;	72%
Stage #1: 2-chloro-3-methylthiophene With (2,2,6,6-tetramethylpiperidin-1-yl)magnesium halide Stage #2: 2-bromo-3-[4-(1,1,3,3,3-pentameth-yldisiloxan-1-yl)butan-1-yl]thiophene With palladium catalyst	72%

2-bromothiophene (1003-09-4) + 2-chloro-3-methylthiophene (14345-97-2) → 2-chloro-3-methyl-5-(thiophen-2-yl)thiophene

Conditions	Yield
Stage #1: 2-chloro-3-methylthiophene With 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex In tetrahydrofuran at 25℃; for 3h; Inert atmosphere; Schlenk technique; Stage #2: 2-bromothiophene With Pd-PEPPSI-SIPr In tetrahydrofuran at 60℃; for 24h; Inert atmosphere; Schlenk technique;	72%

2-chloro-3-methylthiophene (14345-97-2) + 2-bromo-3-methylthiophene (14282-76-9) → 2-chloro-3-methyl-5-(3-methylthiophen-2-yl)thiophene

Conditions	Yield
Stage #1: 2-chloro-3-methylthiophene With 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex In tetrahydrofuran at 25℃; for 3h; Inert atmosphere; Schlenk technique; Stage #2: 2-bromo-3-methylthiophene With Pd-PEPPSI-SIPr In tetrahydrofuran at 60℃; for 24h; Inert atmosphere; Schlenk technique;	71%

2-chloro-3-methylthiophene (14345-97-2) + thiophene-2-carboxylic acid methyl ester (5380-42-7) → C11H9ClO2S2 (1430206-20-4) + C10H8Cl2S2

Conditions	Yield
With palladium diacetate; silver(l) oxide; 2-Biphenylcarboxylic acid In dimethyl sulfoxide at 80℃; for 8h;	A 70% B 28%

2-chloro-3-methylthiophene (14345-97-2) + Diphenylphosphine oxide (4559-70-0) → C17H14ClOPS

Conditions	Yield
With 1,10-Phenanthroline; tetrabutylammonium tetrafluoroborate; manganese (II) acetate tetrahydrate In acetic acid at 80℃; for 4h; Electrolysis; Inert atmosphere;	69%

2-chloro-3-methylthiophene (14345-97-2) + Methyl isobutyrate (547-63-7) → 2-methyl-3-(3-methyl-thiophen-2-yl)-propionic acid methyl ester (1258239-40-5)

Conditions	Yield
Stage #1: Methyl isobutyrate With lithium dicyclohexylamide In toluene at 20℃; for 0.25h; Inert atmosphere; Stage #2: With tris-(dibenzylideneacetone)dipalladium(0); DavePhos In toluene at 20℃; for 0.0833333h; Inert atmosphere; Stage #3: 2-chloro-3-methylthiophene In toluene at 50℃; for 1h; Inert atmosphere;	67%

2-chloro-3-methylthiophene (14345-97-2) + 2-hydroxy-2-methylpropanenitrile (75-86-5) → 3-methylthiophene-2-carbonitrile (55406-13-8)

Conditions	Yield
With [Pd(cinnamyl)Cl]2; N-ethyl-N,N-diisopropylamine; XPhos In isopropyl alcohol at 80℃; for 2h; Inert atmosphere;	67%

2-chloro-3-methylthiophene (14345-97-2) + cyclohexenone (930-68-7) → 3-(5-chloro-4-methylthiophen-2-yl)cyclohex-2-en-1-one

Conditions	Yield
With silver hexafluoroantimonate; silver carbonate; N-acetylglycine; palladium dichloride In 1,4-dioxane; dimethyl sulfoxide at 60℃; for 24h; Sealed tube;	67%
With silver hexafluoroantimonate; 1,1,1,3',3',3'-hexafluoro-propanol; silver carbonate; N-acetylglycine; palladium dichloride In 1,4-dioxane; dimethyl sulfoxide at 60℃; for 24h;	67%
With 4,5-Diazafluoren-9-one; oxygen; palladium diacetate; p-benzoquinone In acetonitrile at 80℃; for 24h; Heck Reaction; Green chemistry;	50%

2-chloro-3-methylthiophene (14345-97-2) + 4-Methoxystyrene (637-69-4) → C14H13ClOS

Conditions	Yield
With p-benzoquinone In acetic acid; dimethyl sulfoxide at 60℃; for 10h;	61%

2-chloro-3-methylthiophene (14345-97-2) + 1-phenyl-propan-1-one (93-55-0) → (E)-3-(5-chloro-4-methyl-2-thienyl)-1-phenyl-2-propen-1-one (1440662-26-9)

Conditions	Yield
With silver (II) carbonate; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; lithium acetate; palladium diacetate; tricyclohexylphosphine In 1,2-dimethoxyethane at 100℃; for 24h; Schlenk technique; Inert atmosphere;	60%

2-chloro-3-methylthiophene (14345-97-2) + 4-vinylbenzyl chloride (1073-67-2) → C13H10Cl2S

Conditions	Yield
With p-benzoquinone In acetic acid; dimethyl sulfoxide at 60℃; for 10h;	53%

2-chloro-3-methylthiophene (14345-97-2) + o-iodo-methyl-benzoic acid (610-97-9) + acrylic acid methyl ester (292638-85-8) → C17H15ClO4S

Conditions	Yield
With triphenyl-arsane; C9H13NO; silver(I) acetate; palladium diacetate; acetic acid; p-benzoquinone In ethyl acetate for 48h; Heating; Sealed tube; regioselective reaction;	51%

2-chloro-3-methylthiophene (14345-97-2) + 1-Brom-2-(2,4,6-trimethylphenyl)acetylen (33675-49-9) → 2-chloro-5-(mesitylethynyl)-3-methylthiophene

Conditions	Yield
With 1,4-pyrazine; (S)-2-acetylamino-3-phenylpropanoic acid; palladium diacetate; silver(l) oxide In dimethyl sulfoxide at 60℃; for 18h; Schlenk technique; Sealed tube; regioselective reaction;	45%

2-chloro-3-methylthiophene (14345-97-2) + 2-phenylpyridine (1008-89-5) + 5-chloro-2-methyl-benzenamine (95-79-4) → 4,4''-dimethyl-2'-(pyridin-2-yl)-[1,1':3',1''-terphenyl]-3,3''-diamine + 4-methyl-3'-(2-methylthiophen-3-yl)-2'-(pyridin-2-yl)-[1,1'-biphenyl]-3-amine + 4-methyl-2'-(pyridin-2-yl)biphenyl-3-amine

Conditions

Yield

Stage #1: 2-phenylpyridine; 5-chloro-2-methyl-benzenamine With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; 1-methyl-2-phenyl-3-(diphenylphosphino)-1H-indole; potassium carbonate In 1-methyl-pyrrolidin-2-one at 120℃; for 24h; Schlenk technique; Inert atmosphere; Sealed tube; Stage #2: 2-chloro-3-methylthiophene In 1-methyl-pyrrolidin-2-one at 140℃; for 24h; Schlenk technique; Inert atmosphere; Sealed tube;

A 16% B 41% C 28%

2-chloro-3-methylthiophene (14345-97-2) + diethyllaurylamine (4271-27-6) → diethyl-dodecyl-[2]thienylmethyl-ammonium; chloride

Conditions	Yield
With ethyl acetate
With ethanol

2-chloro-3-methylthiophene (14345-97-2) → 2-chloro-3-bromomethylthiophene (40032-81-3)

Conditions	Yield
With tetrachloromethane; N-Bromosuccinimide; dibenzoyl peroxide
With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane for 0.666667h; Inert atmosphere;

Upstream product

• 616-44-4 3-Methylthiophene 
• 128-09-6 N-chloro-succinimide 

Downstream Products

• 74598-03-1 5-chloro-4-methylthiophen-2-carboxylic acid 
• 55406-13-8 3-methylthiophene-2-carbonitrile 
• 40032-81-3 2-chloro-3-bromomethylthiophene 
• 14300-30-2 2-phenyl-3-methylthiophene 
• 1440662-26-9 (E)-3-(5-chloro-4-methyl-2-thienyl)-1-phenyl-2-propen-1-one 
• 1308652-76-7 2-(2,6-dimethylphenyl)-3-methylthiophene 
• 23806-24-8 3-methyl-2-thiophenecarboxylic acid 
• 1262865-00-8 6-(5-chloro-4-methylthiophen-2-yl)-2,6-dimethylcyclohex-2-ene-1,4-dione 
• 74598-11-1 ethyl thieno<3,2-d>isothiazole-5-carboxylate 
• 74598-06-4 ethyl 5-chloro-4-formylthiophen-2-carboxylate 

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