Triisopropylsilyl Trifluoromethanesulfonate Property

Boiling point:

45-46 °C/0.03 mmHg

Density 

1.14 g/mL at 25 °C (lit.)

refractive index 

n20/D 1.415(lit.)

Flash point:

213 °F

storage temp. 

under inert gas (nitrogen or Argon) at 2-8°C

solubility 

Miscible with chloroform and ethyl acetate.

form 

Liquid

Specific Gravity

1.14

color 

Clear light brown to orange-brown

Sensitive 

Moisture Sensitive

Hydrolytic Sensitivity

8: reacts rapidly with moisture, water, protic solvents

BRN 

3591541

InChI

InChI=1S/C10H21F3O3SSi/c1-7(2)18(8(3)4,9(5)6)16-17(14,15)10(11,12)13/h7-9H,1-6H3

InChIKey

LHJCZOXMCGQVDQ-UHFFFAOYSA-N

SMILES

C(F)(F)(F)S(O[Si](C(C)C)(C(C)C)C(C)C)(=O)=O

CAS DataBase Reference

80522-42-5(CAS DataBase Reference)

Safety

Hazard Codes 

C

Risk Statements 

34

Safety Statements 

26-36/37/39-45-28A-27

RIDADR 

UN 3265 8/PG 2

WGK Germany 

3

F 

3-10-21

TSCA 

No

HazardClass 

8

PackingGroup 

II

HS Code 

29319090

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Danger

Hazard statements

H314Causes severe skin burns and eye damage

Precautionary statements

P280Wear protective gloves/protective clothing/eye protection/face protection.

P303+P361+P353IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.

P305+P351+P338IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continuerinsing.

P363Wash contaminated clothing before reuse.

P405Store locked up.

Triisopropylsilyl Trifluoromethanesulfonate Chemical Properties,Usage,Production

Chemical Properties

clear light brown to orange-brown liquid

Physical properties

Colorless oil; bp 83–87 °C/1.7 mmHg; d 1.173 g cm?3.

Uses

Triisopropylsilyl Trifluoromethanesulfonate is a highly reactive silylating agent and Lewis acid capable of converting primary and secondary alcohols to the corresponding triisopropylsilyl ethers and converting ketones and lactones into their enol silyl ethers; protection of terminal alkynes; promoting conjugate addition of alkynylzinc compounds to α,β-enones; preparation of (triisopropylsilyl)diazomethane, participating in the following (but not limited to) reactions: Silylation of Alcohols, Formations of Enol Silyl Ethers, Alkynyltriisopropylsilanes, Conjugate Addition of Alkynylzinc Bromides, (Triisopropylsilyl)diazomethane, Triisopropylsiloxycarbonyl (Tsoc) and BIPSOP Protecting Groups for Amines, TIPS Protection for Oxazoles/Regioselective Trapping of C-2 Oxazole Anions, Benzannulation Using Triisopropylsilyl Vinyl Ketenes, Cyclization of 1-Silyloxy-1,5-diynes, Desymmetrization of Tartaric Acid Esters etc.

Uses

Triisopropylsilyl trifluoromethanesulfonate is used as a reagent for the introduction of triisopropylsilyl(TIPS) group in organic synthesis. It is involved in the synthesis of 2-substituted benzothiopyran-4-ones and silyloxy acetylenes. As a protecting group in organic synthesis, it is utilized especially for the protection of primary amines. Furthermore, it plays an important role in Takahashi Taxol total synthesis or for chemical glycosylation reactions.

Preparation

To 38.2 g (0.242 mol) of triisopropylsilane at 0°C under argon is added 23.8 mL (0.266 mol) of trifluoromethanesulfonic acid dropwise. The solution is stirred at 22°C for 16 h, at which time no further hydrogen gas evolves (removed through a bubbler). The resulting product is distilled through a 30-cm vacuum jacketed Vigreux column under reduced pressure: 71.7 g (97% yield) of TIPS triflate; bp 83–87°C/1.7 mmHg.

Reactivity Profile

Triisopropylsilyl Trifluoromethanesulfonate is a highly reactive silylating agent and Lewis acid capable of converting primary and secondary alcohols to the corresponding triisopropylsilyl ethers and converting ketones and lactones into their enol silyl ethers; protection of terminal alkynes; promoting conjugate addition of alkynylzinc compounds to α,β-enones; preparation of (triisopropylsilyl)diazomethane).

References

[1] Rücker, C. “1,3‐Bis(triisopropylsilyl)propyne.” 2001. 0.
[2] Fumihiko Yoshimura. “Nucleophilic Addition of Alkanenitriles to Aldehydes via N-Silyl Ketene Imines Generated In Situ.” Synlett 29 1 (2017): 1816–1820.