Chloroethyl chloroformate

Last updated
Chloroethyl chloroformate
1-chloroethyl chloroformate.svg
1-Chloroethyl chloroformate
2-chloroethyl chloroformate.svg
2-Chloroethyl chloroformate
Names
IUPAC names
1-Chloroethyl carbonochloridate
2-Chloroethyl carbonochloridate
Identifiers
3D model (JSmol)
ChemSpider
  • 454726 (1-chloroethyl chloroformate)
  • 11802 (2-chloroethyl chloroformate)
EC Number
  • 256-834-2
  • 210-982-4
PubChem CID
  • 521305  (1-chloroethyl chloroformate)
  • 12305  (2-chloroethyl chloroformate)
UNII
  • InChI=1S/C3H4Cl2O2/c1-2(4)7-3(5)6/h2H,1H3
    Key: QOPVNWQGBQYBBP-UHFFFAOYSA-N
  • InChI=1/C3H4Cl2O2/c4-1-2-7-3(5)6/h1-2H2
    Key: SVDDJQGVOFZBNX-UHFFFAOYAR
  • ClC(OC(Cl)C)=O
  • ClC(=O)OCCCl
Properties
C3H4Cl2O2
Molar mass 142.96 g·mol−1
Related compounds
Chloromethyl chloroformate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Chloroethyl chloroformates (chemical formula: C3H4Cl2O2) are any of three isomers of a structure consisting of ethyl chloroformate with a chloro group as substituent on the ethyl group. The 1-chloro isomers (a racemic pair) can be used for N-dealkylation of tertiary amines. [1]

Contents

2-Chloroethyl chloroformate is listed as an extremely hazardous substance. [2] Safety datasheets are available for both compounds. [3] [4]

Synthesis

1-Chloroethyl chloroformate can be manufactured by the reaction of acetaldehyde with phosgene in the presence of tetra-n-butyl urea [5] or benzyltributylammonium chloride. [6]

2-Chloroethyl chloroformate is the sole product of the reaction between ethylene oxide and phosgene in the presence of a small amount of pyridine. [7]

Uses

1-Chloroethyl chloroformate is a useful reagent, for example for the N-dealkylation of tertiary amines, especially their demethylation to produce drug metabolites for forensic investigations. [1] [6] [8]

2-Chloroethyl chloroformate is commonly used as a reagent, [9] [10] especially for making derivatives of amines and carboxylic acids for analysis by gas chromatography. [11] [12]

References

  1. 1 2 Olofson, R. A.; Martz, Jonathan T.; Senet, Jean Pierre; Piteau, Marc; Malfroot, Thierry (1984). "A new reagent for the selective, high-yield N-dealkylation of tertiary amines: Improved syntheses of naltrexone and nalbuphine". The Journal of Organic Chemistry. 49 (11): 2081–2082. doi:10.1021/jo00185a072.
  2. ↑ "40 CFR Part 355: Extremely Hazardous Chemicals" (PDF). Archived from the original (PDF) on 2012-07-20. Retrieved 2025-06-30.
  3. ↑ "Safety data sheet: 2-chloroethyl chloroformate". Sigmaaldrich.com. Retrieved 2025-06-30.
  4. ↑ "Safety data sheet: 1-chloroethyl chloroformate". Sigmaaldrich.com. Retrieved 2025-06-30.
  5. ↑ USpatent 4592874,Cagnon, G.C.; Piteau, M.D.& Senet, J-P.G.et al.,"Process for the synthesis of alpha-chlorinated chloroformates",issued 1986-06-03, assigned to Societe Nationale des Poudres et Explosifs
  6. 1 2 Armstrong, Alan (2001). "1-Chloroethyl Chloroformate". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rc102. ISBN   0-471-93623-5.
  7. ↑ Jones, J. Idris (1957). "530. The reaction of carbonyl chloride with 1 : 2-epoxides". Journal of the Chemical Society (Resumed): 2735. doi:10.1039/JR9570002735.
  8. ↑ Pelander, Anna; Ojanperä, Ilkka; a. Hase, Tapio (1997). "Preparation of N-demethylated drug metabolites for analytical purposes using 1-chloroethyl chloroformate". Forensic Science International. 85 (3): 193–198. doi:10.1016/S0379-0738(96)02088-9.
  9. ↑ Mousseau, James J. (2011). "β-Chloroethyl Chloroformate". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rn01309. ISBN   978-0-471-93623-7.
  10. ↑ Wu, Yikang; Shen, Xin (2000). "A high-yielding low-cost facile synthesis of 2-oxazolidinones chiral auxiliaries". Tetrahedron: Asymmetry. 11 (21): 4359–4363. doi:10.1016/S0957-4166(00)00415-8.
  11. ↑ Vreeken, Rob J.; Jager, Maria E.; Ghijsen, Rudy T.; Brinkman, Udo A. Th. (1992). "The derivatization of fatty acids by (Chloro)alkyl chloroformates in non-aqueous and aqueous media for GC analysis". Journal of High Resolution Chromatography. 15 (12): 785–790. doi:10.1002/jhrc.1240151203.
  12. ↑ Hušek, Petr (1998). "Chloroformates in gas chromatography as general purpose derivatizing agents". Journal of Chromatography B: Biomedical Sciences and Applications. 717 (1–2): 57–91. doi:10.1016/S0378-4347(98)00136-4. PMID   9832240.
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