Trichloroacetonitrile Property

Melting point:

-42 °C

Boiling point:

83-84 °C(lit.)

Density 

1.44 g/mL at 25 °C(lit.)

vapor pressure 

58 mm Hg ( 20 °C)

refractive index 

n20/D 1.441(lit.)

Flash point:

None

storage temp. 

Store below +30°C.

solubility 

<0.1 g/100 mL at 21.5°C

form 

Liquid

color 

Clear colorless to very slightly yellow

Odor

odor of chloral and hydrogen cyanide

Water Solubility 

<0.1 g/100 mL at 21.5 ºC

Sensitive 

Lachrymatory

Merck 

14,9628

BRN 

605572

Dielectric constant

4.6（60℃）

Exposure limits

NIOSH: IDLH 25 mg/m3

Stability:

Stable, but water sensitive. Incompatible with acids, water, steam. May hydrolyze in alkali or acid conditions. Flammable.

CAS DataBase Reference

545-06-2(CAS DataBase Reference)

NIST Chemistry Reference

Acetonitrile, trichloro-(545-06-2)

IARC

3 (Vol. 52, 71) 1999

EPA Substance Registry System

Trichloroacetonitrile (545-06-2)

Safety

Hazard Codes 

T,N

Risk Statements 

23/24/25-51/53

Safety Statements 

45-61

RIDADR 

UN 3276 6.1/PG 3

WGK Germany 

3

RTECS 

AM2450000

Hazard Note 

Toxic/Lachrymatory

TSCA 

Yes

HazardClass 

8

PackingGroup 

II

HS Code 

29269095

Hazardous Substances Data

545-06-2(Hazardous Substances Data)

Toxicity

LD50 orally in rats: 0.25 g/kg (Smyth)

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Danger

Hazard statements

H411Toxic to aquatic life with long lasting effects

Precautionary statements

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

P273Avoid release to the environment.

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

P301+P310IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.

Trichloroacetonitrile Chemical Properties,Usage,Production

Chemical Properties

colourless to slightly yellow liquid

Uses

Trichloroacetonitrile is involved as a reagent in Overman rearrangement, which is used to prepare alylic amines from allylic alcohols. It is also used to prepare bistrichloroacetimidates from diols leading to dihyrooxazines through acid catalyzed cyclization. Further, it is utilized in the synthesis of trichloroacetimidates by 1,8-Diazobicyclo[5.4.0]undec-7-ene (DBU) catalyzed addition of allylic alcohols. It finds application in the study of the methoxy methyl (MOM) catalyzed aza-Claisen rearrangement.

Uses

Insecticide.

Definition

ChEBI: Trichloroacetonitrile is an aliphatic nitrile and an organochlorine compound.

Production Methods

Trichloroacetonitrile can be obtained by dehydration of trichloroacetamide with phosphorous pentoxide or by chlorination of acetonitrile with chlorine. Vapor phase chlorination in the presence of water and photochemical chlorination in the presence of catalysts such as HgCl2 or AlCl3 have been reported. Trichloroacetonitrile is an organic intermediate used, for example, in the synthesis of the fungicide etridiazole.

Reactions

Trichloroacetonitrile is an efficient dehydrating agent for a range of aldoximes, including aromatic and heterocyclic aldoxime, yielding the corresponding nitriles in moderate to good yields. The dehydration reactions can take place in non-acetonitrile media without the aid of a metal catalyst. In addition, it has been confirmed that trichloroacetonitrile was converted into trichloroacetamide in the reaction. Trichloroacetonitrile and triphenylphosphine convert carboxylic acids to acyl chlorides mildly and rapidly under acid-free conditions[1-2].

Air & Water Reactions

Highly flammable. Insoluble in water.

Reactivity Profile

May be sensitive to light and heat. Trichloroacetonitrile may react with water, steam, acid or acid fumes. Trichloroacetonitrile may hydrolyze under acidic or alkaline conditions. . The reaction of benzene and Trichloroacetonitrile evolves toxic chloroform and HCl gasses. (Hagedorn, F., H.-P. Gelbke, and Federal Republic of Germany. 2002. Nitriles. In Ullman Encyclopedia of Industrial Chemistry. Wiley-VCH Verlag GmbH & Co. KGaA.).

Hazard

Strong irritant to tissue. Questionable carcinogen.

Fire Hazard

Trichloroacetonitrile is combustible.

Safety Profile

Poison by ingestion and intravenous routes. Moderately toxic by inhalation and skin contact. Human mutation data reported. A skin and severe eye irritant. An experimental teratogen. Other experimental reproductive effects. When heated to decomposition or in reaction with water, steam, acid, or acid fumes it produces toxic fumes of CN-, Cl-, and NOx. Used as an insecticide. See also NITRILES and CYANIDE.

Toxicity evaluation

Trichloroacetonitrile (TCAN) is a by-product of the chlorine disinfection of water containing natural organic material. When administered by gavage to pregnant Long-Evans rats in a medium-chain triglyceride vehicle, tricaprylin oil (Tricap), at a volume of 10 ml/kg, TCAN induced fetal cardiovascular anomalies at doses as low as 1 mg/kg/d. Five groups of approximately 20 pregnant female rats received TCAN in CO at 15, 35, 55, and 75 mg/kg/d and in Tricap at 15 mg/kg/d (10 ml/kg closing volume). Corn oil, Tricap, and water served as vehicle controls. Animals were treated by oral intubation on gestation d 6-18 (vaginal plug -= d 0). Five out of 20 dams (75 mg/kg) died during treatment. Adjusted maternal weight gain was lower in females receiving 35 mg/kg TCAN or greater. The mean percent of nonlive implants per litter was elevated at 55 and 75 mg/kg TCAN (CO). The TCAN dose-response curve for fetal (but not maternal)effects was shifted to the right when CO was compared to Tricap. Fetal weight was reduced at 15 mg/kg TCAN (Tricap) and at 55 mg/kg TCAN (CO). When TCAN was administered in CO, the mean frequency of soft-tissue maliformations decreased with significantly fewer septal and great vessel cardiovascular defects observed. The lowest observed adverse effect level for TCAN (CO) was determined to be 35 kg/kg.

References

[1] István Vágó, István Greiner. “A useful acylation method using trichloroacetonitrile and triphenylphosphine for solid phase organic synthesis.” Tetrahedron Letters 43 34 (2002): Pages 6039-6041.
[2] Xiaoyun Ma, Zhengjian Chen, Dan Liu . “Dehydration of aldoximes to nitriles using trichloroacetonitrile without catalyst.” Synthetic Communications 51 21 (2021): Pages 3261-3266.