ETHYL 5-CHLORO-METHYL PYRAZOLE-4-CARBOXYLATE

ETHYL 5-CHLORO-METHYL PYRAZOLE-4-CARBOXYLATE Property

Boiling point:

80-82 °C(Press: 0.2 Torr)

Density 

1.31±0.1 g/cm3(Predicted)

storage temp. 

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

pka

-1.13±0.10(Predicted)

Appearance

Colorless to light yellow Liquid

Safety

HS Code 

2933199090

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Warning

Hazard statements

H302Harmful if swallowed

H312Harmful in contact with skin

H315Causes skin irritation

H319Causes serious eye irritation

H332Harmful if inhaled

H335May cause respiratory irritation

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.

P301+P312IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.

P302+P352IF ON SKIN: wash with plenty of soap and water.

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.

P312Call a POISON CENTER or doctor/physician if you feel unwell.

P321Specific treatment (see … on this label).

P322Specific measures (see …on this label).

P330Rinse mouth.

P332+P313IF SKIN irritation occurs: Get medical advice/attention.

P362Take off contaminated clothing and wash before reuse.

P363Wash contaminated clothing before reuse.

P501Dispose of contents/container to..…

ETHYL 5-CHLORO-METHYL PYRAZOLE-4-CARBOXYLATE Chemical Properties,Usage,Production

Synthesis

General procedure for the synthesis of 5-chloro-4-ethoxycarbonyl-1-methylpyrazole from ethyl 5-amino-1-methylpyrazole-4-carboxylate: cuprous chloride (CuCl, 1.76 g, 1.77 mmol) was added to a solution of tert-butyl nitrite (tBuONO, 2.95 mL, 2.46 mmol) in acetonitrile (ACN), followed by the addition of 5-amino-1 -methylpyrazole-4-carboxylic acid ethyl ester (2.5 g, 1.48 mmol). The reaction mixture was stirred at room temperature for 2 h and then heated at 60 °C for 1 h. The reaction was carried out by thin layer chromatography (TLC). The reaction process was monitored by thin layer chromatography (TLC). After completion of the reaction, the mixture was cooled to room temperature, diluted with 2N aqueous hydrochloric acid and extracted with hydrochloric acid (3×). The combined organic phases were washed with brine, dried over anhydrous magnesium sulfate (MgSO4), filtered and concentrated, and finally purified by fast column chromatography to afford the target product 5-chloro-4-ethoxycarbonyl-1-methylpyrazole (2.08 g, 75% yield). The structure of the product was confirmed by 1H-NMR (300 MHz, CDCl3) with chemical shifts δ: 7.90 (1H, s), 4.30 (2H, q, J = 5.4 Hz), 3.86 (3H, s), 1.34 (3H, t, J = 5.4 Hz).

References

[1] Chemical and Pharmaceutical Bulletin, 2016, vol. 64, # 4, p. 326 - 339
[2] Patent: CN105164112, 2017, B. Location in patent: Paragraph 0439-0442
[3] Patent: US2007/225280, 2007, A1. Location in patent: Page/Page column 18
[4] Patent: US4872901, 1989, A
[5] Patent: US4620865, 1986, A