4353-77-9

Basic information

• Product Name: TRIMETHYLSILYL CHLOROSULFONATE
• Synonyms: TRIMETHYLSILYL CHLOROSULFONATE;TRIMETHYLSILYLCHLOROSULPHONATE;trimethylsilyl chlorosulphate;Chloridosulfuric acid trimethylsilyl ester;Chlorosulfonic acid (trimethylsilyl) ester;Chlorosulfonic acid trimethylsilyl ester;Trimethyl(chlorosulfonyloxy)silane;TriMethylsilyl chlorosulfonate 99%
• CAS NO: 4353-77-9
• Molecular Formula: C₃H₉ClO₃SSi
• Molecular Weight: 188.71
• EINECS: 224-425-8
• Product Categories: Organic Building Blocks;Sulfonates/Sulfinates;Sulfur Compounds
• Mol File: 4353-77-9.mol
• Article Data: 6

Chemical Properties

• Melting Point: −26 °C(lit.)
• Boiling Point: 168-169 °C(lit.)
• Flash Point: 108 °F
• Appearance: /liquid
• Density: 1.225 g/mL at 25 °C(lit.)
• Vapor Pressure: 2.09mmHg at 25°C
• Refractive Index: n20/D 1.424(lit.)
• BRN: 1763675
• CAS DataBase Reference: TRIMETHYLSILYL CHLOROSULFONATE(CAS DataBase Reference)
• NIST Chemistry Reference: TRIMETHYLSILYL CHLOROSULFONATE(4353-77-9)
• EPA Substance Registry System: TRIMETHYLSILYL CHLOROSULFONATE(4353-77-9)

Safety Data

• Hazard Codes: C
• Statements: 10-34
• Safety Statements: 26-36/37/39-45
• RIDADR: UN 2920 8/PG 2
• WGK Germany: 3
• F: 10-21
• TSCA: No
• HazardClass: 3.2
• PackingGroup: III
• Hazardous Substances Data: 4353-77-9(Hazardous Substances Data)

Usage

Uses

Trimethylsilyl chlorosulfonate may be used:in the sulfonation of small organic molecules in the synthesis of sulfonated polysulfone as sulfonating agent in the preparation of nano-structured organic-inorganic membranes for proton exchange membrane fuel cells (PEMFC) based on methacrylate and epoxy polymeric structures in the preparation of sulfonated polysulfone (sPS)/titanium dioxide (TiO2) composite membranes for use in PEMFCs in the preparation of iodosobenzene sulfate, required for the synthesis of cyclic sulfates

General Description

Trimethylsilyl chlorosulfonate is commonly employed as sulfonating agent.

InChI:InChI=1/C3H9ClO3SSi/c1-9(2,3)7-8(4,5)6/h1-3H3

Synthetic route

bis(trimethylsilyl)sulphate (18306-29-1) → chloro-trimethyl-silane (75-77-4) + chlorosulfonate de trimethylsilyle (4353-77-9)

Conditions	Yield
With thionyl chloride at 120℃;	A 92% B 97%
With thionyl chloride at 70 - 120℃; Yields of byproduct given;	A n/a B 97%
With thionyl chloride at 80 - 120℃;	A n/a B 97%
With thionyl chloride at 120℃;	A n/a B 97%

chloro-trimethyl-silane (75-77-4) → chlorosulfonate de trimethylsilyle (4353-77-9)

Conditions	Yield
With sulfur trioxide at 50℃; for 0.166667h;	87%
With sulfur trioxide
With chlorosulphuric acid
With sulfur trioxide Ambient temperature;	91.5 g

Bis(trimethylsilyl)peroxodisulfat (29938-10-1) → chlorosulfonate de trimethylsilyle (4353-77-9) + bis(trimethylsilyl)sulphate (18306-29-1)

Conditions	Yield
In dichloromethane at -20 - 20℃;	A 6.2% B 2.5%

chloro-trimethyl-silane (75-77-4) + sulfur trioxide (7446-11-9) → chlorosulfonate de trimethylsilyle (4353-77-9)

Conditions	Yield
-30°C;	>99

chlorosulfonate de trimethylsilyle (4353-77-9) + 6-chloro-2-isopropylimidazo[1,2-a]pyridine-7-carbonitrile → 6-chloro-7-cyano-2-isopropylimidazo[1,2-a]pyridine-3-sulfonic acid

Conditions	Yield
In 1,2-dichloro-ethane at 90℃; for 5h; Cooling with ice;	99%

chlorosulfonate de trimethylsilyle (4353-77-9) + mercury bis(trifluoromethanethiolate) (21259-75-6) → S-(Trifluormethyl)thioschwefelsaeure-trimethylsilylester

Conditions	Yield
In tetrachloromethane at 20℃;	95%

chloro-trimethyl-silane (75-77-4) + chlorosulfonate de trimethylsilyle (4353-77-9) + recorcinol (108-46-3) → 2-Hydroxy-4-trimethylsiloxy-1-benzolsulfonsaeure-trimethylsilylester (81293-06-3)

Conditions	Yield
at 80℃; for 12h;	92%

chlorosulfonate de trimethylsilyle (4353-77-9) + ethoxycarbonylketene ethyltrimethylsilyl acetal (17906-37-5) → (Trimethylsiloxysulfonyl)malonsaeure-diethylester (89056-12-2)

Conditions	Yield
In 1,2-dichloro-ethane at 60℃; for 4h;	91%

chlorosulfonate de trimethylsilyle (4353-77-9) + 2,4-dimethyl-3-trimethylsilyloxy-2-pentene (55339-64-5) → 2,4-Dimethyl-2-(trimethylsiloxysulfonyl)-3-pentanon (72458-54-9)

Conditions	Yield
In 1,2-dichloro-ethane at 25℃; for 2.5h;	91%

chlorosulfonate de trimethylsilyle (4353-77-9) + 1-(Trimethylsilyl)imidazole (18156-74-6) → chloro-trimethyl-silane (75-77-4) + C6H12N2O3SSi

Conditions	Yield
In dichloromethane for 1h; Ambient temperature;	A n/a B 90%

chloro-trimethyl-silane (75-77-4) + p-cresol (106-44-5) + chlorosulfonate de trimethylsilyle (4353-77-9) → 5-Methyl-2-trimethylsiloxy-1-benzolsulfonsaeure-trimethylsilylester (81293-05-2)

Conditions	Yield
at 80℃; for 12h;	89%

chlorosulfonate de trimethylsilyle (4353-77-9) + silver(I) benzenesulphonate (39938-06-2) → Benzolpyrosulfonsaeure-trimethylsilylester (81293-11-0)

Conditions	Yield
In 1,2-dichloro-ethane at 0℃; for 0.5h;	89%

chlorosulfonate de trimethylsilyle (4353-77-9) + ((CH3)3Sn)C(CH2OCOCH3)CH(Sn(CH3)3) (180070-63-7) + sodium hydrogencarbonate (144-55-8) → Na(1+)*(CH3)3SnC(CH2OCH3)CHSO3(1-)*H2O=(CH3)3SnC(CH2OCH3)CHSO3Na*H2O

Conditions	Yield
In tetrachloromethane byproducts: Me3SnCl; Ar-atmosphere; slow addn. of 2 equiv. Sn-compd. to chlorosulfonate, standing at 20°C for 1 h, addn. of satd. aq. NaHCO3, stirring for 30 min; washing of aq. layer (Et2O), evapn., dissoln. in hot EtOH, filtration, evapn., washing (pentane), drying (vac., 80°C); elem. anal.;	88%

chlorosulfonate de trimethylsilyle (4353-77-9) + 3,3-dimethyl-2-(trimethylsilyl)oxy-1-butene (17510-46-2) → 3,3-Dimethyl-1-(trimethylsiloxysulfonyl)-2-butanon (72458-53-8)

Conditions	Yield
In 1,2-dichloro-ethane at 25℃; for 2.5h;	87%

chlorosulfonate de trimethylsilyle (4353-77-9) + trimethyl[(Z)-(1-phenyl-1-propenyl)oxy]silane (66323-99-7) → 1-Phenyl-2-(trimethylsiloxysulfonyl)-1-propanon (72458-56-1)

Conditions	Yield
In 1,2-dichloro-ethane at 25℃; for 2.5h;	87%

chlorosulfonate de trimethylsilyle (4353-77-9) + aniline (62-53-3) → chloro-trimethyl-silane (75-77-4) + anilinium phenylamidosulfate (1021-03-0)

Conditions	Yield
In tetrachloromethane at -15 - -10℃; for 3h;	A n/a B 87%

chlorosulfonate de trimethylsilyle (4353-77-9) + 2-(trimethylsilyl)-4-methoxy-1,3-difluorobenzene (114636-02-1) → 2,6-difluoro-3-methoxybenzenesulfonic acid

Conditions	Yield
In tetrachloromethane for 18h; Inert atmosphere; Reflux;	85.3%

chlorosulfonate de trimethylsilyle (4353-77-9) + 2-methyl-1-phenyl-1-trimethylsiloxy-1-propene (39158-85-5) → 2-Methyl-1-phenyl-2-(trimethylsiloxysulfonyl)-1-propanon (72458-57-2)

Conditions	Yield
In 1,2-dichloro-ethane at 25℃; for 2.5h;	85%

chlorosulfonate de trimethylsilyle (4353-77-9) + 1-phenoxy-1-trimethylsilyloxyprop-1-ene (86294-78-2, 86294-84-0, 65946-50-1) → 2-(Trimethylsiloxysulfonyl)propansaeure-phenylester (89056-10-0)

Conditions	Yield
In 1,2-dichloro-ethane at 60℃; for 4h;	85%

chlorosulfonate de trimethylsilyle (4353-77-9) + trimethyl-(4-trimethylsilanyloxy-phenyl)-silane (18036-81-2) → 4-Trimethylsiloxy-1-benzolsulfonsaeure-trimethylsilylester (81293-04-1)

Conditions	Yield
for 15h; Ambient temperature;	85%

chlorosulfonate de trimethylsilyle (4353-77-9) + m-xylene (108-38-3) → 2,4-Dimethyl-1-benzolsulfonsaeure-trimethylsilylester (81292-90-2)

Conditions	Yield
In 1,2-dichloro-ethane at 80℃; for 10h;	85%

Ethyl thiophene-2-carboxylate (2810-04-0) + chlorosulfonate de trimethylsilyle (4353-77-9) → 5-<(Trimethylsiloxy)sulfonyl>-2-thiophencarbonsaeure-ethylester (81293-10-9)

Conditions	Yield
In 1,2-dichloro-ethane at 80℃; for 18h;	84%

chlorosulfonate de trimethylsilyle (4353-77-9) + trimethyl(4-methylphenoxy)silane (17902-32-8) → 5-Methyl-2-trimethylsiloxy-1-benzolsulfonsaeure-trimethylsilylester (81293-05-2)

Conditions	Yield
With chloro-trimethyl-silane In 1,2-dichloro-ethane at 80℃; for 12h;	84%

heptamethyldisilazane (920-68-3) + chlorosulfonate de trimethylsilyle (4353-77-9) → methyl-trimethylsilanyl-amidosulfuric acid trimethylsilanyl ester (58584-42-2)

Conditions	Yield
In dichloromethane at 20℃; for 3h;	83%
In dichloromethane

p-cresol (106-44-5) + chlorosulfonate de trimethylsilyle (4353-77-9) → 2-Hydroxy-5-methyl-1-benzolsulfonsaeure-trimethylsilylester (81293-03-0)

Conditions	Yield
In 1,2-dichloro-ethane for 6h; Heating;	82%

1,2-dimethoxybenzene (91-16-7) + chlorosulfonate de trimethylsilyle (4353-77-9) → 3,4-Dimethoxy-1-benzolsulfonsaeure-trimethylester (81293-07-4)

Conditions	Yield
With chloro-trimethyl-silane In 1,2-dichloro-ethane at 80℃; for 10h;	82%

trimethylsilanyl-acetic acid ethyl ester (4071-88-9) + chlorosulfonate de trimethylsilyle (4353-77-9) → chloro-trimethyl-silane (75-77-4) + C7H16O5SSi (107716-49-4)

Conditions	Yield
Ambient temperature;	A n/a B 82%

chlorosulfonate de trimethylsilyle (4353-77-9) + o-xylene (95-47-6) → 3,4-Dimethyl-1-benzolsulfonsaeure-trimethylsilylester (81292-89-9)

Conditions	Yield
In 1,2-dichloro-ethane at 80℃; for 10h;	82%

chlorosulfonate de trimethylsilyle (4353-77-9) + methoxybenzene (100-66-3) → 4-Methoxy-1-benzolsulfonsaeure-trimethylester (74692-08-3)

Conditions	Yield
With chloro-trimethyl-silane In 1,2-dichloro-ethane at 80℃; for 10h;	82%

chlorosulfonate de trimethylsilyle (4353-77-9) + toluene (108-88-3) → 4-Methyl-1-benzolsulfonsaeure-trimethylsilylester (17872-98-9) + 2-Toluolsulfonsaeure-trimethylsilylester

Conditions	Yield
In 1,2-dichloro-ethane at 80℃; for 12h;	A 82% B 9%

chlorosulfonate de trimethylsilyle (4353-77-9) + 2,4-Dimethyl-3-(triethylsiloxy)-2-penten (80239-20-9) → triethylsilyl chloride (994-30-9) + 2,4-Dimethyl-2-(trimethylsiloxysulfonyl)-3-pentanon (72458-54-9)

Conditions	Yield
In 1,2-dichloro-ethane for 3.5h; Ambient temperature;	A n/a B 81%

1-styrenyloxytrimethylsilane (13735-81-4) + chlorosulfonate de trimethylsilyle (4353-77-9) → 1-Phenyl-2-(trimethylsiloxysulfonyl)-1-ethanon (89056-02-0)

Conditions	Yield
In 1,2-dichloro-ethane at 25℃; for 2.5h;	80%

Upstream product

• 18306-29-1 bis(trimethylsilyl)sulphate 
• 75-77-4 chloro-trimethyl-silane 
• 7446-11-9 sulfur trioxide 
• 29938-10-1 Bis(trimethylsilyl)peroxodisulfat 

Downstream Products

• 72458-57-2 2-Methyl-1-phenyl-2-(trimethylsiloxysulfonyl)-1-propanon 
• 81292-94-6 4-Fluor-1-benzolsulfonsaeure-trimethylsilylester 
• 76619-21-1 4-Brom-1-benzolsulfonsaeure-trimethylsilylester 
• 89056-02-0 1-Phenyl-2-(trimethylsiloxysulfonyl)-1-ethanon 
• 81292-88-8 4-tert-Butyl-1-benzolsulfonsaeure-trimethylsilylester 
• 74692-08-3 4-Methoxy-1-benzolsulfonsaeure-trimethylester 
• 75-77-4 chloro-trimethyl-silane 
• 1021-03-0 anilinium phenylamidosulfate 
• 81292-95-7 4-Chlor-1-benzolsulfonsaeure-trimethylsilylester 
• 81293-01-8 2,4-Dichlor-1-benzolsulfonsaeure-trimethylsilylester 
• 127-63-9 diphenyl sulphone 
• 17882-06-3 trimethylsilyl benzenesulfonate 
• 81293-02-9 4-Hydroxy-1-benzolsulfonsaeure-trimethylsilylester 
• 2004-90-2 Trimethyl-silyl-<3-methyl-benzol-sulfonat> 

Relevant articles and documents

-

-

Insertion of Sulfur Trioxide into the N-Si bond of Anilinotrimethylsilane. An Improved Method for the Preparation of Free Phenylamidosulfuric Acid

The reaction between anilinotrimethylsilane (1) and a variety of sulfonating agents has been studied.With SO3, 5, or a dioxane-sulfur trioxide complex a sulfur trioxide molecule was inserted selectively into the N-Si bond of 1 to yield trimethylsilyl phenylamidosulfate (2), which on treatment with acetic acid, trifluoroacetic acid, or methanol gave free phenylamidosulfuric acid (3).The reaction of 1 with ClSO3H afforded 3 directly, but the product was contaminated with slight amounts of anilinium hydrogensulfate and anilinium chloride.The reaction of 1 with 10 yielded a mixture containing dianilinium (4-sulfonatophenylamido)sulfate, 4-aminobenzenesulfonic acid, and ethyl phenylamidosulfate as major products (after desilylation).The reaction of 1 with 5 has been found to provide an improved method for preparing 3.

REACTION OF BIS(TRIMETHYLSILYL) SULFATE WITH HYDROGEN HALIDES AND WITH PHOSPHORUS AND SULFUR HALIDES AND OXYHALIDES

-