Diethyl cyanomethylphosphonate

Diethyl cyanomethylphosphonate Property

Boiling point:

101-102 °C0.4 mm Hg(lit.)

Density 

1.095 g/mL at 25 °C(lit.)

refractive index 

n20/D 1.434(lit.)

Flash point:

>230 °F

storage temp. 

Inert atmosphere,2-8°C

solubility 

Chloroform (Soluble), Methanol (Slightly)

form 

Liquid

color 

Clear colorless to light yellow

Specific Gravity

1.1261.095

Water Solubility 

Miscible with water, chloroform, terahydrofuran, ethyl acetate and methylene chloride.

BRN 

1772981

InChI

InChI=1S/C6H12NO3P/c1-3-9-11(8,6-5-7)10-4-2/h3-4,6H2,1-2H3

InChIKey

KWMBADTWRIGGGG-UHFFFAOYSA-N

SMILES

P(CC#N)(=O)(OCC)OCC

CAS DataBase Reference

2537-48-6(CAS DataBase Reference)

NIST Chemistry Reference

Diethyl cyanomethylphosphonate(2537-48-6)

Safety

Hazard Codes 

Xi,Xn,C

Risk Statements 

38-36/37/38-20/21/22-34-36/38

Safety Statements 

26-28-36/37/39-23-45-27-36/37-9

RIDADR 

UN 1760 8/PG 2

WGK Germany 

3

Hazard Note 

Irritant

HazardClass 

6.1

PackingGroup 

III

HS Code 

29310095

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Danger

Hazard statements

H302Harmful if swallowed

H312Harmful in contact with skin

H315Causes skin irritation

H319Causes serious eye irritation

H331Toxic if inhaled

Precautionary statements

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

P264Wash hands thoroughly after handling.

P264Wash skin thouroughly after handling.

P270Do not eat, drink or smoke when using this product.

P271Use only outdoors or in a well-ventilated area.

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.

P403+P233Store in a well-ventilated place. Keep container tightly closed.

P405Store locked up.

P501Dispose of contents/container to..…

Diethyl cyanomethylphosphonate Chemical Properties,Usage,Production

Chemical Properties

clear colorless to light yellow liquid

Uses

Diethyl cyanomethyl phosphonate is used as an intermediate in Horner-Emmons reaction for the synthesis of substituted nitriles and their amide and heterocyclic derivatives. It is known as a modified Wittig reagent used in the preparation of alpha, beta-unsaturated nitriles from ketones or aldehydes like 3-hydroxy-3-methylbutanal. It reacts with epoxides and nitrones to prepare cyano-substituted cyclopropanes and aziridines respectively. It is actively involved in the synthesis of alpha-arylated alkanenitriles via reaction with aryl iodides in presence of CuI.

Uses

Wittig reagent.

Biological Functions

Diethyl cyanomethylphosphonate can be used to inhibit and/0r prevent the growth of undesirable algae, bacteria, fungi, yeast, and other microorganisms.

General Description

Diethyl cyanomethylphosphonate is a useful chemical and medical intermediate, which can be used as raw material to synthesize nitrogen-haloamine precursor AEP-ADCT containing triazine-phosphate group

reaction suitability

reaction type: C-C Bond Formation

Synthesis

The general procedure for the synthesis of diethyl cyanomethylphosphonate from chloroacetonitrile and triethyl phosphite is as follows: 677.5 g (4.0 mol) of triethyl phosphite is heated to 150 °C. At 150 °C, 152.4 g (2.0 mol) of chloroacetonitrile was slowly added dropwise, and the dropwise process lasted for 2 hours (during which the exhaust gas produced was chloroethane). After the dropwise addition was completed, the reaction mixture was continued to be stirred at 150 °C for 2 hours (until the gas escape stopped completely). Upon completion of the reaction, the mixture was distilled under reduced pressure using a small Vigreux fractionation column (height 10 cm). The fraction with a boiling range of 110-139 °C was collected at a reduced pressure of 1 mbar, which was the target product diethyl cyanomethyl phosphate. The product yield was 99% in chloroacetonitrile (based on GC area percentage).

References

[1] Patent: WO2005/63780, 2005, A1. Location in patent: Page/Page column 13
[2] Heterocycles, 2014, vol. 89, # 2, p. 375 - 397
[3] Phosphorus, Sulfur and Silicon and Related Elements, 2000, vol. 159, p. 37 - 46
[4] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1981, p. 433 - 436
[5] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1982, p. 25 - 30