tert-Butylchlorodiphenylsilane

tert-Butylchlorodiphenylsilane Property

Boiling point:

90 °C0.01 mm Hg(lit.)

Density 

1.057 g/mL at 25 °C(lit.)

refractive index 

n20/D 1.568(lit.)

Flash point:

>230 °F

storage temp. 

Inert atmosphere,2-8°C

solubility 

miscible in most organic solvents.

form 

Liquid

Specific Gravity

1.074

color 

Clear colorless to yellow or slightly brown

Water Solubility 

reacts

Sensitive 

Moisture Sensitive

Hydrolytic Sensitivity

7: reacts slowly with moisture/water

BRN 

644023

CAS DataBase Reference

58479-61-1(CAS DataBase Reference)

NIST Chemistry Reference

Silane, chloro(1,1-dimethylethyl)diphenyl-(58479-61-1)

EPA Substance Registry System

Silane, chloro(1,1-dimethylethyl)diphenyl- (58479-61-1)

Safety

Hazard Codes 

C,Xi

Risk Statements 

14-34-37-29-20/21/22-40

Safety Statements 

26-36/37/39-45-8

RIDADR 

UN 2987 8/PG 2

WGK Germany 

3

F 

10

Hazard Note 

Irritant/Corrosive

TSCA 

Yes

HazardClass 

8

PackingGroup 

II

HS Code 

29310095

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Danger

Hazard statements

H314Causes severe skin burns and eye damage

H335May cause respiratory irritation

Precautionary statements

P261Avoid breathing dust/fume/gas/mist/vapours/spray.

P271Use only outdoors or in a well-ventilated area.

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

P301+P330+P331IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.

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.

tert-Butylchlorodiphenylsilane Chemical Properties,Usage,Production

Chemical Properties

Tert-Butylchlorodiphenylsilane is a colorless to pale brown oily liquid with pungent odor, may be used as silylating agent for derivatization of alcohols, ketones, carboxylic acids, amines, amides and mercaptanes selectively into functional groups in different sterical environments.

Physical properties

colorless liquid, bp 93–95°C/0.015 mmHg; n20 D 1.5680; d 1.057 g cm?3.

Uses

tert-Butyldiphenylchlorosilane acts as a silylating reagent used to protect alcohols and in the preparation of silyl ethers. It plays a major role as a raw material and a precursor in organic synthesis and pharmaceuticals. It is also used for the synthesis of interphenylene phenyloxazoles which can be used for the treatment of circulatory disorders, angina and stroke.

Uses

tert-Butylchlorodiphenylsilane can be used to prepare 1-benzyloxy-3-(tert-butyldiphenylsilyloxy)propan-2-ol, a key intermediate for the synthesis of mono-O-protected pyrimidine acyclic nucleosides.

Uses

Several newmethods have been developed for using the reagent to protect primary and secondary alcohols as their TBDPS ethers. In the presence of ammonium nitrate or ammonium perchlorate, reaction between TBDPS-Cl and a primary alcohol, such as benzyl alcohol, in DMF provided excellent yields of the corresponding silyl ethers in just 15 min (eq 1).19 When silver nitrate was used as promoter, the reactions gave inferior yields under otherwise identical conditions.
When TBDPS-Cl is used to react with hemiacetals, it converts hemiacetals into ring-opened silyl ether carbonyl compounds, instead of mixed acetals.Presumably, the sizable TBDPS group presents too much steric hindrance for the formation of the corresponding mixed silyl acetals.

Preparation

a dry 1 L, three-necked round bottomed flask is equipped with a magnetic stirring bar, a 500mL equalizing dropping funnel fitted with a rubber septum, a reflux condenser, and nitrogen inlet tube. The flask is flushed with nitrogen, then charged with 127 g (0.5 mol) of diphenyldichlorosilane in 300mL of redistilled pentane. A solution of tbutyllithium in pentane (500 mL, 0.55 mol), is transferred under nitrogen pressure to the dropping funnel using a stainless steel, double-tip transfer needle. This solution is slowly added to the contents of the flask and when the addition is complete, the mixture is refluxed 30 h under nitrogen with stirring. The suspension is allowed to cool to rt, the precipitated lithium chloride is rapidly filtered through a pad of Celite, and the latter is washed with 200mL of pentane. The solvent is removed by evaporation, and the colorless residue is distilled through a short (10 cm), Vigreux column, to give 125–132 g of the colorless title compound.

Application

tert-Butylchlorodiphenylsilane (TBDPSCl) is a good reagent for chemical reaction, widely used in the fields of organic synthesis, thin film materials and medicine. The main applications are as follows:
(1) It can be used for the preparation of T - SSBR (SSBR end - capped by tert - Butylchlorodiphenylsilane). Since TBCSi end sealing can fix the free chain ends of T-SSBR (that is, reduce the frictional loss of molecular chains and generate a greater orientation degree in the force field), and adsorb carbon black, the performance of T-SSBR composites is superior to that of SSBR. Moreover, the performance of styrene-TBCSi terminated T-SSBR (TS-SSBR) is much better than that of butadiene-TBCSi terminated T-SSBR (TB-SSBR). Therefore, the former is applicable to the tread of green tires.^[1]
(2) TBDPSCl can be used to prepare fluorene-based polyimides (Si-PIs) containing silyl ether groups by silylation with hydroxyl-containing polyimides (OH-PIs). The optical, dielectric and solubility properties of the modified Si-PI films are simultaneously improved compared to the precursor OH-PI films. The modified Si–PI films demonstrate a meaningful enhancement in the transmittances at a wavelength of 400 nm (T400) to 74–81% from 42 to 55% of OH–PI films and the regeneration of fluorescence characteristics. The dielectric constant and loss of Si–PI films are also obviously reduced to 2.63–2.75 and 0.0024–0.0091 at 1 kHz from 4.19 to 4.78 and 0.0173–0.0295 of OH–PI films, respectively, due to substituted with the bulky nonpolar TBDPS groups to increase the free volume and hydrophobicity of Si–PI films. The solubility of Si–PIs in low- or nonpolar solvents (such as CHCl3, CH2Cl2, acetone, and toluene) is significantly improved. Furthermore, Si–PI films still maintain relatively good thermal properties with the 5% weight loss temperature (T5%) in the range 470–491 °C under a nitrogen atmosphere and the glass transition temperature (Tg) in the range 245–308 °C.^[2]

reaction suitability

reagent type: derivatization reagent
reaction type: Silylations

Synthesis

Example 2: To a 500 mL four-necked flask equipped with a reflux condenser, a charging funnel, a thermometer, and a stir bar was added 12.2 g (0.5 mol) of magnesium under nitrogen protection. After drying, tert-butyl Grignard reagent was prepared by adding 250 mL of tetrahydrofuran and 46.3 g (0.5 mol) of chlorinated tert-butane by stirring. At room temperature, 0.45 g (0.005 mol) of copper cyanide was added to the reaction system, followed by the slow dropwise addition of 126.6 g (0.5 mol) of diphenyl dichlorosilane under stirring. During the reaction, the system temperature was raised to 50°C. After reflux heating and stirring for 5 h, the reaction mixture was diluted by adding 100 mL of hexane and the insoluble material was removed by filtration. After distillation to remove the solvent, it was purified by vacuum distillation to give 103 g (75% yield) of tert-butyl diphenylchlorosilane.

Purification Methods

Purify it by repeated fractional distillaton. It is soluble in DMF and pentane [Hanessian & Lavalee Can J Chem 53 2975 1975, Robl et al. J Med Chem 34 2804 1991]. [Beilstein 4 IV 4076 for tert-butylchlorodimethylsilane.]

References

[1] LEI WANG . Study on the structure and properties of SSBR with large-volume functional groups at the end of chains[J]. Polymer, 2010, 51 9: Pages 2084-2090. DOI:10.1016/j.polymer.2010.03.006.
[2] YANCHENG WU*; Shumei L, JIANQING ZHAO; Simultaneously Improving the Optical, Dielectric, and Solubility Properties of Fluorene-Based Polyimide with Silyl Ether Side Groups[J]. ACS Omega, 2022, 7 14: 11939-11945. DOI:10.1021/acsomega.2c00069.