1,1'-Thiocarbonyldiimidazole Property

Melting point:

98-102 °C(lit.)

Boiling point:

342°C (rough estimate)

Density 

1.3046 (rough estimate)

refractive index 

1.5500 (estimate)

storage temp. 

2-8°C

solubility 

Soluble in terahydrofuran, toluene and dichloromethane.

pka

1.96±0.10(Predicted)

form 

Powder

color 

Bright yellow

Water Solubility 

decomposes

Sensitive 

Moisture Sensitive

BRN 

609349

Stability:

Stable, but air and moisture sensitive. Incompatible with strong oxidizing agents, strong acids.

InChIKey

RAFNCPHFRHZCPS-UHFFFAOYSA-N

CAS DataBase Reference

6160-65-2(CAS DataBase Reference)

Safety

Hazard Codes 

Xi

Risk Statements 

22-34

Safety Statements 

22-24/25-45-36/37/39-26

WGK Germany 

3

F 

9-21

Hazard Note 

Irritant/Keep Cold/Moisture Sensitive

HS Code 

29332900

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Warning

Hazard statements

H315Causes skin irritation

H319Causes serious eye irritation

H335May cause respiratory irritation

Precautionary statements

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

P264Wash hands thoroughly after handling.

P264Wash skin thouroughly after handling.

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

P304+P340IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.

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

P405Store locked up.

1,1'-Thiocarbonyldiimidazole Chemical Properties,Usage,Production

Description

1,1'-Thiocarbonyldiimidazole (TCDI) is an imidazole compound that can be prepared by reacting thiophosphoryl chloride with two corresponding imidazoles.  Its structure has two imidazole rings, and the imidazole groups can be rapidly displaced, making it a safer alternative to thiophosphoryl chloride.  TCDI is used as an organic synthesis or chemical reaction reagent for the synthesis of thiosemicarbazones and thioamides.  It is also used in the Corey-Winter olefin synthesis and in the Barton-McCombie deoxygenation reaction.  In addition, it is the sulfur analogue of the peptide addition reagent carbodiimidazole (CDI), which is used to couple peptides.

Chemical Properties

yellow powder

Uses

1,1'-Thiocarbonyldiimidazole is used as a reagent for the deoxygenation of alcohols with tributyltin hydride and diols with lithium aluminum hydride. It is also used to deoxygenate carboxylic monosaccharide analogues. Further, it is a useful reagent involved in biochemical synthesis. In addition to this, it is used to prepare 1-[bis-(4-methoxy-phenyl)-methyl]-1H-imidazole by reacting with 4,4'-dimethoxy-benzhydrol.

Application

1,1′-Thiocarbonyldiimidazole (TCDI) is generally used as a reagent to carry out the deoxygenation of vicinal diols by forming cyclic thionocarbonate in Corey-Winter alkene synthesis.
It is used as a reagent in the enantioselective total synthesis of (+)-hapalindole Q, 12-epi-fischerindole U and welwitindolinone A.
It is also used in the preparation of trithiocarbonates, xanthates, and dithiocarbamates as chain transfer agents for the reversible addition fragmentation chain transfer and macromolecular design (RAFT/ MADIX) polymerization.

Uses

1,1’Thiocarbonyldiimidazole can be used to deoxygenate carboxylic monosaccharide analogues.

Synthesis Reference(s)

The Journal of Organic Chemistry, 43, p. 337, 1978 DOI: 10.1021/jo00396a035

Purification Methods

It forms yellow crystals on recrystallisation from tetrahydrofuran or by sublimation at 10-3torr (bath temperature 70-80o). It is hydrolysed by H2O and should be stored dry. [Staab & Walther Justus Liebigs Ann Chem 657 98 1962; Pullukat et al. Tetrahedron Lett 1953 1967, Hanessian et al. Can J Chem 65 1859 1987, Rajanbabu et al. J Am Chem Soc 111 1759 1989.] Thiochrome {2,7-dimethyl-5H -thiachromine-8-ethanol; 3,8-dimethyl-2-hydroxyethyl-5H -