7403-46-5

Basic information

• Product Name: 2-CHLORO-1-METHYLPYRIDINIUM P-TOLUENESULFONATE
• Synonyms: Chloromethylpyridiniumtoluenosulfonate;2-chloro-1-methylpyridinium toluene-p-sulphonate;Nsc34626;2-Chloro-1-methylpyridinium tosylate;2-Chloro-1-Methylpyridin-1-iuM 4-Methylbenzenesulfonate;2-Chloro-1-methylpyridinium p-Toluenesulfonate;2-Chloro-1-methylpyridiniump-toluenesulfonate≥ 98%(Titration);2-CHLORO-1-METHYLPYRIDINIUM P-TOLUENESULFONATE
• CAS NO: 7403-46-5
• Molecular Formula: C₆H₇ClN*C₇H₇O₃S
• Molecular Weight: 299.77
• EINECS: 231-008-4
• Product Categories: Condensation & Active Esterification;Pyridinium Compounds;Synthetic Organic Chemistry
• Mol File: 7403-46-5.mol
• Article Data: 3

Chemical Properties

• Melting Point: 125°C
• Appearance: /
• Storage Temp.: 0-10°C
• Water Solubility: almost transparency
• CAS DataBase Reference: 2-CHLORO-1-METHYLPYRIDINIUM P-TOLUENESULFONATE(CAS DataBase Reference)
• NIST Chemistry Reference: 2-CHLORO-1-METHYLPYRIDINIUM P-TOLUENESULFONATE(7403-46-5)
• EPA Substance Registry System: 2-CHLORO-1-METHYLPYRIDINIUM P-TOLUENESULFONATE(7403-46-5)

Safety Data

• Statements: 36/37/38
• Safety Statements: 36/37/39
• Hazardous Substances Data: 7403-46-5(Hazardous Substances Data)

Usage

Uses

2-Chloro-1-methylpyridinium p-Toluenosulfonate is a dehydrating agent used in the Staudinger-type reaction of carboxylic acids with imines.

InChI:InChI=1/C7H8O3S.C6H7ClN/c1-6-2-4-7(5-3-6)11(8,9)10;1-8-5-3-2-4-6(8)7/h2-5H,1H3,(H,8,9,10);2-5H,1H3/q;+1

Synthetic route

2-chloropyridine (109-09-1) + methyl p-toluene sulfonate (80-48-8) → 2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5)

Conditions	Yield
at 80 - 85℃; for 1h;	88%
With benzene
at 70℃; for 6h; Methylation;
at 60℃; for 16h; Inert atmosphere; Neat (no solvent);

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) → 1-methyl-2-fluoropyridinium p-toluenesulfonate (58086-67-2)

Conditions	Yield
With potassium fluoride In acetonitrile for 1h; Product distribution / selectivity; Reflux;	90%

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + piperidinium O,O'-di-cyclohexylphosphorodithioate → bis(O,O'-di-cyclohexylphosphorothioyl) sulfide

Conditions	Yield
In dichloromethane at 30℃; for 1h;	86%

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + piperidinium O,O'-diethylphosphorodithioate (13604-49-4) → O,O,O,O-tetraethyl trithiopyrophosphate (4328-22-7)

Conditions	Yield
In dichloromethane at 30℃; for 1h;	77%

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + piperidinium O,O'-di-4-methoxybenzenephosphorodithioate → bis(O,O'-di-4-methoxybenzenephosphorothioyl) sulfide

Conditions	Yield
In dichloromethane at 30℃; for 1h;	75%

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + piperidinium O,O'-diphenylphosphorodithioate → bis-(O,O'-diphenylphosphorothioyl)-sulfide (29516-95-8)

Conditions	Yield
In dichloromethane at 30℃; for 1h;	66%

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + piperidinium diphenylphosphinodithioate (38194-90-0) → 1-methyl-2-pyridinethione (2044-27-1) + bis(diphenylphosphinothioyl) sulfide (6079-78-3)

Conditions	Yield
In dichloromethane at 30℃; for 1h;	A 65% B 62%

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + piperidinium O,O'-di-propylphosphorodithioate → bis(O,O'-di-propylphosphorothioyl) sulfide (61614-88-8)

Conditions	Yield
In dichloromethane at 30℃; for 1h;	65%

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + piperidinium O,O'-di-butylphosphorodithioate → bis(O,O'-di-butylphosphorothioyl) sulfide (29516-90-3)

Conditions	Yield
In dichloromethane at 30℃; for 1h;	63%

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + piperidinium O,O'-di-isopropylphosphorodithioate (19829-05-1) → O,O,O,O-tetraisopropyl pyrophosphorotrithioate (3253-29-0)

Conditions	Yield
In dichloromethane at 30℃; for 1h;	61%

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + piperidinium O,O'-di-p-tolylphosphorodithioate → 1-methyl-2-pyridinethione (2044-27-1) + bis(O,O'-di-p-tolylphosphorothioyl) sulfide (34789-58-7)

Conditions	Yield
In dichloromethane at 0℃; for 1h;	A 61% B 59%

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + potassium O,O'-diphenylphosphorodithioate (3514-82-7) → bis-(O,O'-diphenylphosphorothioyl)-sulfide (29516-95-8)

Conditions	Yield
In dichloromethane at 30℃; for 1h;	60%

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + piperidinium O,O'-di-4-chorobenzenephosphorodithioate → bis(O,O'-di-4-chlorobenzenephosphorothioyl) sulfide

Conditions	Yield
In dichloromethane at 30℃; for 1h;	57%

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + piperidinium O,O'-di-m-tolylphosphorodithioate → bis(O,O'-di-m-tolylphosphorothioyl) sulfide (34789-57-6)

Conditions	Yield
In dichloromethane at 30℃; for 1h;	54%

piperidinium 4-methylbenzenecarbodithiolate (42967-76-0) + 2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) → Toluene-4-sulfonate1-methyl-2-(4-methyl-thiobenzoylsulfanyl)-pyridinium; (129263-88-3)

Conditions	Yield
In methanol; chloroform at 0℃;	53%

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + piperidinium diphenylphosphinothioate → 1-methyl-2-pyridone (694-85-9) + diphenylphosphinothioic O-acid anhydride (3096-09-1)

Conditions	Yield
In dichloromethane at 0℃; for 0.5h;	A n/a B 45%

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + piperidinium O,O'-di-2-methoxybenzenephosphorodithioate → bis(O,O'-di-2-methoxybenzenephosphorothioyl) sulfide

Conditions	Yield
In dichloromethane at 30℃; for 1h;	30%

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + silver O,O'-diphenylphosphorodithioate → bis-(O,O'-diphenylphosphorothioyl)-sulfide (29516-95-8)

Conditions	Yield
In tetrahydrofuran at 66℃; for 1h;	10%
In tetrahydrofuran at 66°C for 1h; TLC (ethylacetate/hexane), recrystn. from dichloromethane/hexane, elem. anal., IR, NMR;	10%

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + zinc bis(O,O'-diphenylphosphorodithioate) → bis-(O,O'-diphenylphosphorothioyl)-sulfide (29516-95-8)

Conditions	Yield
In tetrahydrofuran at 66℃; for 1h;	5%
In tetrahydrofuran at 66°C for 1h; TLC (ethylacetate/hexane), recrystn. from dichloromethane/hexane, elem. anal., IR, NMR;	5%

1-(1-phenylvinyl)pyrrolidine (3433-56-5) + 2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) → 1-Methyl-2-[2-phenyl-2-(1-pyrrolidinyl)ethenyl]pyridinium hexafluoro-phosphate

Conditions	Yield
With ammonium hexafluorophosphate In acetonitrile at 80℃; Dehydrochlorination;

2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) → C14H14NO(1+)*F6P(1-)

Conditions	Yield
Multi-step reaction with 2 steps 1: NH4PF6 / acetonitrile / 80 °C 2: cc. HCl / 3 h / Heating View Scheme

5-(2-amino-4-methylbenzoyl)-1-(4-methoxybenzyl)-1,2,3-triazole-4-carboxylic acid (170989-07-8) + 4-(2-amino-4-methylbenzoyl)-1-(4-methoxybenzyl)-1,2,3-triazole-5-carboxylic acid (170989-00-1) + 2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + 3,4-dihydro-pyrido[1,2-a]pyrimidin-2-one (5439-14-5) → 3-(4-methoxybenzyl)-7-methyl-4(5H),10-dioxo-3H-1,2,3-triazolo[5,4-c][1]benzazepine (170988-19-9)

Conditions	Yield
With tributyl-amine In dichloromethane

4(2-amino-4-methoxycarbonylbenzoyl)-1-(4-methoxybenzyl)-1,2,3-triazole-5-carboxylic acid (170989-70-5) + 2-chloro-1-methylpyridinium p-toluenesulfonate (7403-46-5) + 3,4-dihydro-pyrido[1,2-a]pyrimidin-2-one (5439-14-5) → 3-(4-methoxybenzyl)-7-methoxycarbonyl-4(5H),10-dioxo-3H-1,2,3-triazolo[5,4-c][1]benzazepine

Conditions	Yield
With tributyl-amine In dichloromethane

Upstream product

• 109-09-1 2-chloropyridine 
• 80-48-8 methyl p-toluene sulfonate 

Downstream Products

• 58086-67-2 1-methyl-2-fluoropyridinium p-toluenesulfonate 
• 170988-19-9 3-(4-methoxybenzyl)-7-methyl-4(5H),10-dioxo-3H-1,2,3-triazolo[5,4-c][1]benzazepine 
• 29516-95-8 bis-(O,O'-diphenylphosphorothioyl)-sulfide 
• 694-85-9 1-methyl-2-pyridone 
• 3096-09-1 diphenylphosphinothioic O-acid anhydride 
• 2044-27-1 1-methyl-2-pyridinethione 
• 6079-78-3 bis(diphenylphosphinothioyl) sulfide 

Relevant articles and documents

Asymmetric syntheses of a GPR40 receptor agonist via diastereoselective and enantioselective conjugate alkynylation

Two asymmetric methods to synthesize a potent GPR40 receptor agonist are reported. Both synthetic routes utilize readily available, inexpensive starting materials and reagents. The first route relies on a highly diastereoselective conjugate alkynylation of an ephedrine-derived oxazepanedione acceptor. The second route features the enantioselective alkynylation of a Meldrum's acid-derived acceptor mediated by a chiral zinc cinchonidine reagent.

Pseudo Vilsmeier reagents a new protocol for regiospecific C-C bond formation in pyridines

2-Fluoro- and 2,6-difluoropyridine are readily quaternised with methyl p-toluenesulfonate and methyl triflate respectively. These salts readily undergo substitution of fluorine by enamines, the difluoro-derivatives being capable of specific mono- or disubstitution in a symmetrical or unsymmetrical manner. The products reduced to give keto-1, 2, 3, 6-tetrahydropyridines, can be hydrosed to the corresponding ketopyridines or hydrogenated to give ketopiperidines.