Oxalyl chloride

Not to be confused with phosgene.
Oxalyl chloride
Oxalyl chloride
  Carbon, C
  Oxygen, O
  Chlorine, Cl
Names
Preferred IUPAC name
Oxalyl dichloride[1]
Systematic IUPAC name
Ethanedioyl dichloride[1]
Other names
  • Oxalic acid chloride
  • Oxalic acid dichloride (1:2)
  • Oxalic dichloride
  • Oxaloyl chloride
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.001.092 Edit this at Wikidata
EC Number
  • 201-200-2
RTECS number
  • KI2950000
UNII
  • InChI=1S/C2Cl2O2/c3-1(5)2(4)6 ☒N
    Key: CTSLXHKWHWQRSH-UHFFFAOYSA-N ☒N
  • InChI=1/C2Cl2O2/c3-1(5)2(4)6
    Key: CTSLXHKWHWQRSH-UHFFFAOYAG
  • ClC(=O)C(=O)Cl
Properties
C2O2Cl2
Molar mass 126.92 g·mol−1
Appearance Colorless liquid
Odor Phosgene-like[2]
Density 1.4785 g/mL
Melting point −16 °C (3 °F; 257 K)
Boiling point 63 to 64 °C (145 to 147 °F; 336 to 337 K) at 1.017 bar
Reacts
1.429
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Toxic, corrosive, lachrymator[3]
GHS labelling:
GHS06: Toxic GHS05: Corrosive[3]
Danger[3]
H314, H331[3]
P261, P280, P305+P351+P338, P310[3]
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazard W: Reacts with water in an unusual or dangerous manner. E.g. sodium, sulfuric acid
3
1
2
W
Safety data sheet (SDS) External MSDS
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Oxalyl chloride is an organic chemical compound with the formula Cl−C(=O)−C(=O)−Cl. This colorless, sharp-smelling liquid, the diacyl chloride of oxalic acid, is a useful reagent in organic synthesis.[4]

Preparation

Oxalyl chloride was first prepared in 1892 by the French chemist Adrien Fauconnier, who reacted diethyl oxalate with phosphorus pentachloride.[5] It can also be prepared by treating oxalic acid with phosphorus pentachloride.[6]

Oxalyl chloride is produced commercially from ethylene carbonate. Photochlorination gives the perchloroethylene carbonate C2Cl4O2CO and hydrogen chloride HCl, which is subsequently degraded to oxalyl chloride and phosgene COCl2:[7]

C2H4O2CO + 4 Cl2 → C2Cl4O2CO + 4 HCl
C2Cl4O2CO → C2O2Cl2 + COCl2

Reactions

Oxalyl chloride reacts with water giving off gaseous products only: hydrogen chloride (HCl), carbon dioxide (CO2), and carbon monoxide (CO).

(COCl)2 + H2O → 2 HCl + CO2 + CO

In this, it is quite different from other acyl chlorides which hydrolyze with formation of hydrogen chloride and the original carboxylic acid.[citation needed]

Applications in organic synthesis

Oxidation of alcohols

Addition of a primary or secondary alcohol to a solution of oxalyl chloride in DMSO, followed by quenching with an organic base such as triethylamine converts alcohols to the corresponding aldehydes and ketones via the process known as the Swern oxidation.[8][9][10]

Synthesis of acyl chlorides

Oxalyl chloride is mainly used together with a N,N-dimethylformamide catalyst in organic synthesis for the preparation of acyl chlorides from the corresponding carboxylic acids. Like thionyl chloride, the reagent degrades into volatile side products in this application, which simplifies workup. One of the minor byproducts from the N,N-dimethylformamide catalyzed reaction, dimethylcarbamoyl chloride, is a potent carcinogen, stemming from the N,N-dimethylformamide decomposition.[11][12] Relative to thionyl chloride, oxalyl chloride tends to be a milder, more selective reagent. It is also more expensive than thionyl chloride so it tends to be used on a smaller scale.

This reaction involves conversion of N,N-dimethylformamide to the imidoyl chloride derivative (chloromethylene(dimethyl)ammonium ion (CH3)2N+=CHCl), akin to the first stage in the Vilsmeier–Haack reaction. The imidoyl chloride is the active chlorinating agent.

Formylation of arenes

Oxalyl chloride reacts with aromatic compounds in the presence of aluminium chloride to give the corresponding acyl chloride in a process known as a Friedel-Crafts acylation.[13][14] The resulting acyl chloride can be hydrolysed to form the corresponding carboxylic acid.

Preparation of oxalate diesters

Like other acyl chlorides, oxalyl chloride reacts with alcohols to give esters:

2 R−CH2−OH + Cl−C(=O)−C(=O)Cl → R−CH2−O−C(=O)−C(=O)−O−CH2−R + 2 HCl

Typically, such reactions are conducted in the presence of a base such as pyridine. The diester derived from phenol, phenyl oxalate ester, is Cyalume, the active ingredient in glow sticks.[citation needed]

Other

Oxalyl chloride was reportedly used in the first synthesis of dioxane tetraketone (C4O6), an oxide of carbon.[15]

Precautions

In March 2000, a Malaysia Airlines Airbus A330-300 was damaged beyond repair after a cargo of prohibited oxalyl chloride (falsely declared as hydroxyquinoline) leaked into the cargo bay.[16] It is toxic by inhalation, although it is over an order of magnitude less acutely toxic than the related compound phosgene.[17]

See also

References

  1. ^ a b Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 797. doi:10.1039/9781849733069-FP001. ISBN 978-0-85404-182-4.
  2. ^ Oxalyl chloride: odor
  3. ^ a b c d e Oxalyl chloride MSDS
  4. ^ Salmon, R. (2001). "Oxalyl Chloride". Encyclopedia of Reagents for Organic Synthesis. New York: John Wiley & Sons. doi:10.1002/047084289X.ro015. ISBN 0471936235.
  5. ^ Fauconnier, Adrien (1892). "Action du perchlorure de phosphore sur l'oxalate d'éthyle" [The action of phosphorus pentachloride on diethyl oxalate]. Comptes rendus hebdomadaires des séances de l'Académie des Sciences (in French). 114: 122–123.
  6. ^ DE patent 2840435, Vogel, A.; Steffan, G.; Mannes, K.; Trescher, V., "Process for the preparation of oxalyl chloride", issued 1980-03-27, assigned to Bayer 
  7. ^ Pfoertner, Karl-Heinz (2000). "Photochemistry". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_573. ISBN 3527306730.
  8. ^ Dondoni, A.; Perrone, D. (2004). "Synthesis of 1,1-Dimethyl Ethyl-(S)-4-formyl-2,2-dimethyl-3-oxazolidinecarboxylate by Oxidation of the Alcohol". Organic Syntheses; Collected Volumes, vol. 10, p. 320.
  9. ^ Bishop, R. (1998). "9-Thiabicyclo[3.3.1]nonane-2,6-dione". Organic Syntheses; Collected Volumes, vol. 9, p. 692.
  10. ^ Leopold, E. J. (1990). "Selective hydroboration of a 1,3,7-triene: Homogeraniol". Organic Syntheses; Collected Volumes, vol. 7, p. 258.
  11. ^ Clayden, Jonathan (2005). Organic chemistry (Reprinted(with corrections) ed.). Oxford [u.a.]: Oxford Univ. Press. pp. 296. ISBN 978-0-19-850346-0.
  12. ^ Levin, D. (1997). "Potential Toxicological Concerns Associated with Carboxylic Acid Chlorination and Other Reactions". Organic Process Research & Development. 1 (2). American Chemical Society: 182. doi:10.1021/op970206t.
  13. ^ Neubert, M. E.; Fishel, D. L. (1983). "Preparation of 4-Alkyl- and 4-Halobenzoyl Chlorides: 4-Pentylbenzoyl Chloride". Organic Syntheses. 61: 8; Collected Volumes, vol. 7, p. 420.
  14. ^ Sokol, P. E. (1964). "Mesitoic Acid". Organic Syntheses. 44: 69; Collected Volumes, vol. 5, p. 706.
  15. ^ Strazzolini, P.; Gambi, A.; Giumanini, A. G.; Vancik, H. (1998). "The reaction between ethanedioyl (oxalyl) dihalides and Ag2C2O4: a route to Staudinger's elusive ethanedioic (oxalic) acid anhydride". Journal of the Chemical Society, Perkin Transactions 1. 1998 (16): 2553–2558. doi:10.1039/a803430c.
  16. ^ "Firm told to pay $65 mln for ruining plane". Reuters. 2007-12-06. Retrieved 2007-12-06.
  17. ^ Barbee, S.J.; Stone, J.J.; Hilaski, R.J. (January 1995). "Acute Inhalation Toxicology of Oxalyl Chloride". American Industrial Hygiene Association Journal. 56 (1): 74–76. doi:10.1080/15428119591017358. ISSN 0002-8894. PMID 7872205.