Oxalyl chloride: Difference between revisions

{{Distinguish|phosgene}}

| Verifiedfields = changed

| verifiedrevid = 447061304

| ImageFile = Oxalyl-chloride-2D.png

| ImageSize = 150 px

| ImageFileL2 = Oxalyl-chloride-3D-balls.png

| ImageFileR2 = Oxalyl-chloride-3D-vdW.png

| ImageCaptionR2 = {{legend|rgb(64,64,64)|Carbon, C}}{{legend|red|Oxygen, O}}{{legend|lime|Chlorine, Cl}}

| ImageName = Oxalyl chloride

| ImageFile3 = oxalyl chloride.jpg

| ImageSize3 = 150 px

| PIN = Oxalyl dichloride<ref name=iupac2013>{{cite book |title= Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013 (Blue Book) |publisher= [[Royal Society of Chemistry|The Royal Society of Chemistry]] |date= 2014 |location= Cambridge |page= 797 |doi= 10.1039/9781849733069-FP001 |doi-broken-date= 2024-06-29 |isbn= 978-0-85404-182-4}}</ref>

| SystematicName = Ethanedioyl dichloride<ref name=iupac2013/>

| OtherNames = {{ubl|Oxalic acid chloride|Oxalic acid dichloride (1:2)|Oxalic dichloride|Oxaloyl chloride}}

| IUPACName =

| SMILES = ClC(=O)C(=O)Cl

| CASNo_Ref = {{cascite|correct|CAS}}

| UNII_Ref = {{fdacite|correct|FDA}}

| UNII = R4Y96317DW

| RTECS = KI2950000

| PubChem = 65578

| EINECS = 201-200-2

| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}}

| ChemSpiderID = 59021

| InChI = 1/C2Cl2O2/c3-1(5)2(4)6

| InChIKey = CTSLXHKWHWQRSH-UHFFFAOYAG

| StdInChI_Ref = {{stdinchicite|changed|chemspider}}

| StdInChI = 1S/C2Cl2O2/c3-1(5)2(4)6

| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}}

| StdInChIKey = CTSLXHKWHWQRSH-UHFFFAOYSA-N

| Formula = {{chem2|C2O2Cl2}}

| C=2|O=2|Cl=2

| Appearance = Colorless liquid

| Odor = [[Phosgene]]-like<ref>Oxalyl chloride: odor</ref>

| Density = 1.4785 g/mL

| Solubility = Reacts

| MeltingPtC = -16

| BoilingPtC = 63 to 64

| BoilingPt_notes = at 1.017&nbsp;bar

| Viscosity =

| RefractIndex = 1.429

| Section3 =

| Section4 =

| Section5 =

| Section6 =

| ExternalSDS = [http://www.clayton.edu/portals/690/chemistry/inventory/MSDS%20oxalyl%20chloride.pdf External MSDS]

| GHSPictograms = {{GHS skull and crossbones}} {{GHS corrosion}}<ref name="COClCOCl">[http://www.clayton.edu/portals/690/chemistry/inventory/MSDS%20oxalyl%20chloride.pdf Oxalyl chloride MSDS]</ref>

| GHSSignalWord = '''Danger'''<ref name="COClCOCl"/>

| HPhrases = {{H-phrases|314|331}}<ref name="COClCOCl"/>

| PPhrases = {{P-phrases|261|280|305+351+338|310}}<ref name="COClCOCl"/>

| MainHazards = Toxic, corrosive, [[lachrymatory agent|lachrymator]]<ref name="COClCOCl"/>

| NFPA-H = 3

| NFPA-F = 1

| NFPA-R = 2

| NFPA-S = W

| Section9 = {{Chembox Related

| OtherFunction_label = [[acyl chloride]]s

| OtherFunction = {{ubl|[[Malonyl chloride]]|[[Succinyl chloride]]|[[Phosgene]]}}

| OtherCompounds = {{ubl|[[Oxalic acid]]|[[Diethyl oxalate]]|[[Oxamide]]|[[Oxalyl hydrazide]]|[[Cuprizon 1]]}}

'''Oxalyl chloride''' is an organic [[chemical compound]] with the [[chemical formula|formula]] {{chem2|Cl\sC(\dO)\sC(\dO)\sCl}}. This colorless, sharp-smelling liquid, the di[[acyl chloride]] of [[oxalic acid]], is a useful reagent in [[organic synthesis]].<ref name=eEROS>{{cite encyclopedia |author= Salmon, R. |chapter= Oxalyl Chloride |encyclopedia= Encyclopedia of Reagents for Organic Synthesis |year= 2001 |publisher= John Wiley & Sons |location= New York |doi= 10.1002/047084289X.ro015 |isbn= 0471936235}}</ref>

==Preparation==

Oxalyl chloride was first prepared in 1892 by the French chemist Adrien Fauconnier, who reacted diethyl oxalate with phosphorus pentachloride.<ref>{{cite journal|last1=Fauconnier|first1=Adrien|title=Action du perchlorure de phosphore sur l'oxalate d'éthyle|journal=Comptes rendus hebdomadaires des séances de l'Académie des Sciences|date=1892|volume=114|pages=122–123|url=https://babel.hathitrust.org/cgi/pt?id=umn.31951d00008437c;view=1up;seq=132|trans-title=The action of phosphorus pentachloride on diethyl oxalate|language=fr}}</ref> It can also be prepared by treating [[oxalic acid]] with [[phosphorus pentachloride]].<ref>{{cite patent |inventor= Vogel, A.; Steffan, G.; Mannes, K.; Trescher, V. |title= Process for the preparation of oxalyl chloride |country= DE |number= 2840435 |status= patent |gdate= 1980-03-27 |assign1= Bayer}}</ref>

Oxalyl chloride is produced commercially from [[ethylene carbonate]]. Photochlorination gives the [[perchloroethylene carbonate]] {{chem2|C2Cl4O2CO}} and [[hydrogen chloride]] HCl, which is subsequently degraded to oxalyl chloride and [[phosgene]] {{chem2|COCl2}}:<ref>{{Ullmann |doi=10.1002/14356007.a19_573|title=Photochemistry|year=2000|last1=Pfoertner|first1=Karl-Heinz|isbn=3527306730}}</ref>

:{{chem2|C2H4O2CO + 4 Cl2 → C2Cl4O2CO + 4 HCl}}

:{{chem2|C2Cl4O2CO → C2O2Cl2 + COCl2}}

==Reactions==

Oxalyl chloride reacts with [[water (molecule)|water]] giving off gaseous products only: [[hydrogen chloride]] (HCl), [[carbon dioxide]] ({{chem2|CO2}}), and [[carbon monoxide]] (CO).

:{{chem2|(COCl)2 + H2O → 2 HCl + CO2 + CO}}

In this, it is quite different from other [[acyl chloride]]s which hydrolyze with formation of hydrogen chloride and the original [[carboxylic acid]].{{citation needed|date=September 2024}}

==Applications in organic synthesis==

Addition of a primary or secondary alcohol to a solution of oxalyl chloride in [[dimethyl sulfoxide|DMSO]], followed by quenching with an organic base such as [[triethylamine]] converts [[Alcohol (chemistry)|alcohol]]s to the corresponding [[aldehyde]]s and [[ketone]]s via the process known as the [[Swern oxidation]].<ref>{{OrgSynth|author= Dondoni, A.|author2= Perrone, D.|title= Synthesis of 1,1-Dimethyl Ethyl-(''S'')-4-formyl-2,2-dimethyl-3-oxazolidinecarboxylate by Oxidation of the Alcohol|collvol= 10|collvolpages= 320|year= 2004|prep= v77p0064}}</ref><ref>{{OrgSynth|author= Bishop, R.|title= <nowiki>9-Thiabicyclo[3.3.1]nonane-2,6-dione</nowiki>|collvol= 9|collvolpages= 692|year= 1998|prep= cv9p0692}}</ref><ref>{{OrgSynth|author= Leopold, E. J.|title= Selective hydroboration of a 1,3,7-triene: Homogeraniol|collvol= 7|collvolpages= 258|year= 1990|prep= cv7p0258}}</ref>

===Synthesis of acyl chlorides===

Oxalyl chloride is mainly used together with a [[dimethylformamide|''N'',''N''-dimethylformamide]] catalyst in [[organic synthesis]] for the preparation of acyl chlorides from the corresponding [[carboxylic acid]]s. 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.<ref>{{cite book|last=Clayden|first=Jonathan|title=Organic chemistry|year=2005|publisher=Oxford Univ. Press|location=Oxford [u.a.]|isbn=978-0-19-850346-0|pages=[https://archive.org/details/organicchemistry00clay_0/page/296 296]|edition=Reprinted(with corrections)|url-access=registration|url=https://archive.org/details/organicchemistry00clay_0/page/296}}</ref><ref>{{cite journal |last=Levin |first=D. |title=Potential Toxicological Concerns Associated with Carboxylic Acid Chlorination and Other Reactions |journal=[[Organic Process Research & Development]] |publisher=[[American Chemical Society]] |year=1997 |volume=1 |issue=2 |page=182 |doi=10.1021/op970206t}}</ref> 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.

:[[File:Oxalyl chloride DMF catalyst.png|500px]]

This reaction involves conversion of ''N'',''N''-dimethylformamide to the [[imidoyl chloride]] derivative (chloromethylene(dimethyl)ammonium ion {{chem2|(CH3)2N+\dCHCl}}), 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 ring|aromatic]] compounds in the presence of [[aluminium chloride]] to give the corresponding [[acyl chloride]] in a process known as a [[Friedel-Crafts acylation]].<ref>{{OrgSynth|author= Neubert, M. E.|author2= Fishel, D. L.|title= Preparation of 4-Alkyl- and 4-Halobenzoyl Chlorides: 4-Pentylbenzoyl Chloride|year= 1983|volume= 61|pages= 8|collvol= 7|collvolpages= 420|prep= cv7p0420}}</ref><ref>{{OrgSynth|author= Sokol, P. E.|title= Mesitoic Acid|year= 1964|volume= 44|pages= 69|collvol= 5|collvolpages= 706|prep= CV5P0706}}</ref> 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:

:{{chem2|2 R\sCH2\sOH + Cl\sC(\dO)\sC(\dO)Cl → R\sCH2\sO\sC(\dO)\sC(\dO)\sO\sCH2\sR + 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 stick]]s.{{citation needed|date=September 2024}}

Oxalyl chloride was reportedly used in the first synthesis of [[dioxane tetraketone]] ({{chem2|C4O6}}), an [[oxocarbon|oxide of carbon]].<ref>{{cite journal |title= The reaction between ethanedioyl (oxalyl) dihalides and Ag₂C₂O₄: a route to Staudinger's elusive ethanedioic (oxalic) acid anhydride |author1=Strazzolini, P. |author2=Gambi, A. |author3=Giumanini, A. G. |author4=Vancik, H. |journal= Journal of the Chemical Society, Perkin Transactions 1 |year= 1998 |volume= 1998 |issue= 16 |pages= 2553–2558 |doi= 10.1039/a803430c}}</ref>

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.<ref>{{cite news |title= Firm told to pay $65 mln for ruining plane |date= 2007-12-06 |url= https://www.reuters.com/article/oddlyEnoughNews/idUSN0620441720071206 |publisher= [[Reuters]] |access-date= 2007-12-06}}</ref> It is toxic by inhalation, although it is over an order of magnitude less acutely toxic than the related compound [[phosgene]].<ref>{{cite journal|last1=Barbee|first1=S.J.|last2=Stone|first2=J.J.|last3=Hilaski|first3=R.J.|date=January 1995|title=Acute Inhalation Toxicology of Oxalyl Chloride|journal=American Industrial Hygiene Association Journal|language=en|volume=56|issue=1|pages=74–76|doi=10.1080/15428119591017358|pmid=7872205|issn=0002-8894}}</ref>

==See also==

*[[Oxalyl]]

*[[Swern oxidation]]

==References==

{{Reflist}}

{{Navbox acyl chlorides}}

{{Authority control}}

[[Category:Acyl chlorides]]

[[Category:Carbon oxohalides]]