26638-43-7

Usage

Uses

Used in Pharmaceutical Industry:
Methyl 2-(chlorosulfonyl)benzoate is used as an intermediate for the synthesis of pharmaceuticals, contributing to the development of new drugs and improving the efficacy of existing medications.
Used in Saccharin Production:
Methyl 2-(chlorosulfonyl)benzoate is utilized as an intermediate in the production of saccharin, a widely used artificial sweetener known for its ability to provide sweetness without adding calories.
Used in Dye Industry:
Methyl 2-(chlorosulfonyl)benzoate is employed as an intermediate in the synthesis of dyes, playing a crucial role in the creation of vibrant and long-lasting colorants for various applications.
Used in Pigment Industry:
Methyl 2-(chlorosulfonyl)benzoate is also used as an intermediate in the production of pigments, which are essential for creating a diverse range of colors in various industries, including paints, plastics, and cosmetics.

Synthesis Reference(s)

Synthesis, p. 1203, 1992 DOI: 10.1055/s-1992-26333

InChI:InChI=1/C8H7ClO4S/c1-13-8(10)6-4-2-3-5-7(6)14(9,11)12/h2-5H,1H3

Synthetic route

2-[(methoxymethyl)sulfanyl]benzoic acid methyl ester (146335-12-8) → 2-methoxycarbonylbenzenesulfonyl chloride (26638-43-7)

Conditions	Yield
With water; chlorine In dichloromethane at 5 - 10℃; for 1h;	96%
With water; chlorine In dichloromethane at 5 - 10℃; for 1h; Product distribution; other aryl(or benzyl) methoxymethyl sulfides, also with N-chlorosuccinimide;	96%

2-carbomethoxyaniline (134-20-3) → 2-methoxycarbonylbenzenesulfonyl chloride (26638-43-7)

Conditions	Yield
Stage #1: 2-carbomethoxyaniline With hydrogenchloride; sodium nitrite In water at 20℃; for 0.00555556h; Flow reactor; Stage #2: With hydrogenchloride; sodium hydrogensulfite; copper(l) chloride In water at 0 - 20℃; Temperature; Concentration; Time; Balz-Schiemann Reaction;	95%
Stage #1: 2-carbomethoxyaniline With hydrogenchloride; sodium nitrite In water at 80℃; for 0.0277778h; Large scale; Stage #2: With sodium hydrogensulfite In dichloromethane; water at 100℃; for 0.025h; Solvent; Reagent/catalyst; Temperature; Large scale;	94%
With sodium hypochlorite; sulfuric acid at 0℃; for 2h;

2-(methoxycarbonyl)benzenediazonium tetrafluoroborate (342-54-1) → 2-methoxycarbonylbenzenesulfonyl chloride (26638-43-7)

Conditions	Yield
With thionyl chloride; tris(bipyridine)ruthenium(II) dichloride hexahydrate In water; acetonitrile at 20℃; for 20h; Sealed tube; Irradiation;	85%

chloroamine-T (127-65-1) + Methyl thiosalicylate (4892-02-8) → methyl 2-[(N-chloro-4-methylbenzenesulfonamido)sulfinyl]benzoate + 2-methoxycarbonylbenzenesulfonyl chloride (26638-43-7)

Conditions	Yield
With N-chloro-succinimide In water; acetonitrile at 35℃; for 0.25h;	A 50% B 18%

methanol (67-56-1) + 2-chlorosulfonylbenzoyl chloride (34684-21-4) → 2-methoxycarbonylbenzenesulfonyl chloride (26638-43-7)

bis[2-(methoxycarbonyl)phenyl]disulfide (5459-63-2) → 2-methoxycarbonylbenzenesulfonyl chloride (26638-43-7)

Conditions	Yield
With water; chlorine

2-methoxycarbonyl-benzenesulfinic acid (119300-80-0) → 2-methoxycarbonylbenzenesulfonyl chloride (26638-43-7)

Conditions	Yield
With water; chlorine

2-methoxycarbonyl-benzenediazonium-chloride → 2-methoxycarbonylbenzenesulfonyl chloride (26638-43-7)

Conditions	Yield
With sulfur dioxide; copper(l) chloride

alkali salt of/the/ benzoic acid methyl ester-o-sulfinic acid → 2-methoxycarbonylbenzenesulfonyl chloride (26638-43-7)

Conditions	Yield
With water; chlorine

2-(methoxycarbonyl)benzenesulfonic acid (57897-77-5) → 2-methoxycarbonylbenzenesulfonyl chloride (26638-43-7)

Conditions	Yield
With phosphorus pentachloride at 95℃; for 2.5h;	2.51 g
With phosphorus pentachloride at 95℃; for 12h;	7.42 g

Conditions	Yield
Multi-step reaction with 2 steps 1: 1 h / Heating 2: 2.51 g / PCl5 / 2.5 h / 95 °C View Scheme
Multi-step reaction with 2 steps 1: 4 h / Reflux 2: phosphorus pentachloride / 12 h / 95 °C View Scheme

Upstream product

• 67-56-1 methanol 
• 34684-21-4 2-chlorosulfonylbenzoyl chloride 
• 5459-63-2 bis[2-(methoxycarbonyl)phenyl]disulfide 
• 81-08-3 2-sulfobenzoic acid cyclic anhydride 
• 7446-09-5 sulfur dioxide 
• 134-20-3 2-carbomethoxyaniline 
• 342-54-1 2-(methoxycarbonyl)benzenediazonium tetrafluoroborate 
• 85-44-9 phthalic anhydride 
• 127-65-1 chloroamine-T 
• 4892-02-8 Methyl thiosalicylate 
• 57897-77-5 2-(methoxycarbonyl)benzenesulfonic acid 
• 146335-12-8 2-[(methoxymethyl)sulfanyl]benzoic acid methyl ester 
• 119300-80-0 2-methoxycarbonyl-benzenesulfinic acid 

Downstream Products

• 55120-13-3 2-[methyl-(thiazol-2-ylcarbamoyl-methyl)-sulfamoyl]-benzoic acid methyl ester 
• 87223-34-5 2-(morpholinosulfonyl)benzoic acid 
• 63113-47-3 2-(p-tolyl)benzo[d]isothiazol-3(2H)-one-1,1-dioxide 
• 111874-90-9 2-Phenethylsulfamoyl-benzoic acid methyl ester 
• 87223-28-7 2-(benzyl-methyl-sulfamoyl)-benzoic acid 
• 87223-29-8 2-Diallylsulfamoyl-benzoic acid 
• 108293-25-0 (-)-<(-)-menthyl 2-carbomethoxybenzenesulfinate> 
• 88312-74-7 2-(2-bromo-4-methylphenyl)-1,2-benzisothiazol-3(2H)-one 1,1-dioxide 
• 145006-90-2 2-[2-(4-Bromo-phenyl)-ethylsulfamoyl]-benzoic acid methyl ester 
• 141556-86-7 2-[2-((1R,2S,6R,9R,12S)-12-Methoxy-9-methyl-10,11,13-trioxa-tricyclo[7.2.2.0^1,6]tridec-2-yl)-ethoxysulfonyl]-benzoic acid methyl ester 
• 145865-94-7 methyl 2-(hydrazinosulfonyl)benzoate 
• 6381-61-9 ammonium saccharinate 
• 57683-71-3 methyl 2-(aminosulfonyl)benzoate 
• 143850-22-0 2-But-3-ynyloxysulfonyl-benzoic acid methyl ester 

Relevant academic research and scientific papers

Sulfonium ion-promoted traceless Schmidt reaction of alkyl azides

Schmidt reaction by sulfonium ions is described. General primary, secondary, and tertiary alkyl azides were converted to the corresponding carbonyl or imine compounds without any trace of the activators. This bond scission reaction through 1,2-migration of C-H and C-C bonds was accessible to the one-pot substitution reaction.

Aromatic Chlorosulfonylation by Photoredox Catalysis

Visible-light photoredox catalysis enables the efficient synthesis of arenesulfonyl chlorides from anilines. The new protocol involves the convenient in situ preparation of arenediazonium salts (from anilines) and the reactive gases SO2and HCl (from aqueous SOCl2). The photocatalytic chlorosulfonylation operates at mild conditions (room temperature, acetonitrile/water) with low catalyst loading. Various functional groups are tolerated (e.g., halides, azides, nitro groups, CF3, SF5, esters, heteroarenes). Theoretical and experimental studies support a photoredox-catalysis mechanism.

Aminoxidation of Arenethiols to N-Chloro-N-sulfonyl Sulfinamides

A simple and efficient method to synthesize N-chloro-N-sulfonylsulfinamides by the direct aminoxidation of arenethiols under aqueous and mild conditions is disclosed, geminally installing the oxo and amino groups on the sulfur atom of arenethiols. The products have been primarily developed as sulfinylation reagents to convert Grignard reagents into sulfoxides, and as amination reagents to convert secondary amines into hydrazine derivatives.

Method of preparing 2-chlorosulfonylmethyl benzoate from phthalic anhydride and urea

The invention provides a method of preparing 2-chlorosulfonylmethyl benzoate from phthalic anhydride and urea. The method includes the steps of 1) adding solid phthalic anhydride and urea into a reaction kettle and heating the materials to 135-143 DEG C to carry out a reaction to prepare o-aminobenzene dicarboximide, feeding the o-aminobenzene dicarboximide with water and sodium hydroxide into a first tubular reactor, forcedly cooling the mixture to -12 - -15 DEG C; 2) adding methanol and a sodium hypochlorite solution to perform Hoffman degradation reaction, and separating the reaction product to obtain o-aminomethyl benzoate; 3) according to the same mass ratio, feeding the o-aminomethyl benzoate and a sodium nitrite solution to a second tubular reactor, cooling the reactants to 0 DEG C, and adding sulfuric acid to perform a diazo-reaction for 11.5-11.8 s; and 4) continuously performing a cyclic sulfurization oxidation tubular reaction for 2 h, when the reactants show a dark green color on an benzidine-ethylamine test paper, adding methylbenzene and separating the reactant to obtain the 2-chlorosulfonylmethyl benzoate. The method is safe and simple, is advanced and integrated, is high in synthesis efficiency, has less side reactions and greatly reduces influence due to human factors.

Continuous-Flow Diazotization for Efficient Synthesis of Methyl 2-(Chlorosulfonyl)benzoate: An Example of Inhibiting Parallel Side Reactions

An expeditious process for the highly efficient synthesis of methyl 2-(chlorosulfonyl)benzoate was described, which involved the continuous-flow diazotization of methyl 2-aminobenzoate in a three-inlet flow reactor via a cross joint followed by chlorosulfonylation in the tandem tank reactor. The side reaction such as hydrolysis was decreased eminently from this continuous-flow process even at a high concentration of hydrochloric acid. The mass flow rate of methyl 2-aminobenzoate was 4.58 kg/h, corresponding to an 18.45 kg/h throughput of diazonium salt solution. The potential of inhibiting parallel side reactions by conducting in a flow reactor was successfully demonstrated in this method.

Method for continuously preparing 2-(chlorosulfonyl) methyl benzoate and device adopted for method

The invention discloses a method for continuously preparing 2-(chlorosulfonyl) methyl benzoate and a device adopted for the method. The special device comprises a first mixer, a first tubular reactor, a second mixer, a second tubular reactor, a receiving tank, a fourth storage tank and a fifth storage tank. The first mixer, the first tubular reactor, the second mixer, the second tubular reactor and the receiving tank are sequentially connected. The fourth storage tank is connected with the second mixer sequentially through a fourth metering pump and a fourth flow meter. The fifth storage tank is connected with the second mixer sequentially through a fifth metering pump and a fifth flow meter. The first mixer is connected with a first storage tank, a second storage tank and a third storage tank. A first metering pump and a first flow meter are sequentially connected between the first storage tank and the first mixer. A second metering pump and a second flow meter are sequentially connected between the second storage tank and the first mixer. A third metering pump and a third flow meter are sequentially connected between the third storage tank and the first mixer. A backpressure valve is arranged between the second tubular reactor and an inlet of the receiving tank. The method and the device are environmentally friendly, safe and suitable for industrial production.

Arylphosphonylation and arylazidation of activated alkenes

Two radical-mediated processes of activated alkenes, namely arylphosphonylation and arylazidation, are described. The difunctionalization of alkenes by a tandem process that involves radical addition, 1,4-aryl migration, and desulfonylation generates α-ar

Hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins

The discovery, study, and implementation of the Co- and Mn-catalyzed hydrohydrazination and hydroazidation reactions of olefins are reported. These reactions are equivalent to direct hydroaminations of C-C double bonds with protected hydrazines or hydrazoic acid but are based on a different concept in which the H and the N atoms come from two different reagents, a silane and an oxidizing nitrogen source (azodicarboxylate or sulfonyl azide). The hydrohydrazination reaction using di-tert-butyl azodicarboxylate is characterized by its ease of use, large functional group tolerance, and broad scope, including mono-, di-, tri-, and tetrasubstituted olefins. Key to the development of the hydroazidation reaction was the use of sulfonyl azides as nitrogen sources and the activating effect of tert-butyl hydroperoxide. The reaction was found to be efficient for the functionalization of mono-, di-, and trisubstituted olefins, and only a few functional groups are not tolerated. The alkyl azides obtained are versatile intermediates and can be transformed to the free amines or triazoles without isolation of the azides. Preliminary mechanistic investigations suggest a rate-limiting hydrocobaltation of the alkene, followed by an amination reaction. Radical intermediates cannot be ruled out and may be involved.

A new and facile synthesis of sulfonyl chlorides

Several benzenesulfonyl and arylmethanesulfonyl chlorides 2 are synthesized in excellent yields by the aqueous chlorination of aryl (or benzyl) methoxymethyl sulfides 1. Functionalized sulfides 1 d-g can be prepared easily from bromophenyl methoxymethyl sulfides 1b,c.

Process for the preparation of N'-sulphonyl- and N',N"-bis-sulphonyl-guanidine derivatives

A process for the preparation of a guanidine derivative of the formula STR1 in which R1 represents hydrogen or the radical R5 --S(O)m --, m represents the numbers zero, 1 or 2 and R5 represents an optionally substituted radical from the series comprising alkyl, aralkyl, aryl and heteroaryl, R2 represents a six-membered aromatic heterocyclic structure which contains at least one nitrogen atom and is substituted, and R8 represents an optionally substituted radical from the series comprising C1 -C6 -alkyl, alkenyl, alkinyl, cycloalkyl, phenylalkyl and aryl, which comprises reacting a guanidine derivative of the formula STR2 with one or two molar equivalent(s), respectively, of a halogen/sulphur compound of the formula in which X1 represents fluorine, chlorine or bromine. The compounds are herbicidally active.