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{{chembox |
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{{chembox |
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| verifiedrevid = 439308170 |
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| verifiedrevid = 472252233 |
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| Name = Diphosgene |
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| ImageFile = Diphosgene.png |
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| Name = Diphosgene |
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| ImageFile = Diphosgene structure.svg |
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| ImageSize = 160px |
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| ImageSize = 160px |
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| ImageName = Diphosgene |
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| ImageFile1 = Diphosgene-3D-vdW.png |
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| ImageName = Diphosgene |
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| ImageClass = skin-invert |
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| ImageSize1 = 160px |
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| ImageName1 = Diphosgene |
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| ImageFile1 = Diphosgene-3D-vdW.png |
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| ImageSize1 = 160px |
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| IUPACName = Diphosgene |
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| ImageName1 = Diphosgene |
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| OtherNames = trichloromethyl chloroformate |
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| PIN = Trichloromethyl carbonochloridate |
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| Section1 = {{Chembox Identifiers |
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| OtherNames = Trichloromethyl chloroformate, surpalite |
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| PubChem = |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID = 21154424 |
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| PubChem = 10426 |
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| SMILES = ClC(=O)OC(Cl)(Cl)Cl |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| InChI = 1/C2Cl4O2/c3-1(7)8-2(4,5)6 |
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| ChemSpiderID = 21154424 |
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| InChIKey = HCUYBXPSSCRKRF-UHFFFAOYAO |
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| StdInChI = 1S/C2Cl4O2/c3-1(7)8-2(4,5)6 |
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| SMILES = ClC(=O)OC(Cl)(Cl)Cl |
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| InChI = 1/C2Cl4O2/c3-1(7)8-2(4,5)6 |
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| StdInChIKey = HCUYBXPSSCRKRF-UHFFFAOYSA-N |
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| InChIKey = HCUYBXPSSCRKRF-UHFFFAOYAO |
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| CASNo_Ref = {{cascite|correct|??}} |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI = 1S/C2Cl4O2/c3-1(7)8-2(4,5)6 |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = HCUYBXPSSCRKRF-UHFFFAOYSA-N |
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| CASNo_Ref = {{cascite|correct|??}} |
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| CASNo = 503-38-8 |
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| CASNo = 503-38-8 |
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| RTECS = LQ7350000 |
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| RTECS = LQ7350000 |
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| EC_number = 207-965-9 |
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| UNII = PO4Q4R80LV |
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}} |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| Formula = C<sub>2</sub>Cl<sub>4</sub>O<sub>2</sub> |
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| Formula = C<sub>2</sub>Cl<sub>4</sub>O<sub>2</sub> |
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| MolarMass = 197.82 g/mol |
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| MolarMass = 197.82 g/mol |
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| Appearance = liquid at room temperature |
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| Appearance = liquid at room temperature |
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| Density = 1.65 g/cm<sup>3</sup> |
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| Density = 1.65 g/cm<sup>3</sup> |
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| Solubility = insol. |
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| Solubility = insoluble, reacts |
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| MeltingPt = -57 °C |
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| MeltingPtC = −57 |
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| BoilingPt = 128 °C |
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| BoilingPtC = 128 |
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| Section3 = {{Chembox Structure |
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|Section3={{Chembox Structure |
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| Dipole = |
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| Dipole = |
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| Section7 = {{Chembox Hazards |
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|Section7={{Chembox Hazards |
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| ExternalMSDS = |
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| ExternalSDS = |
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| MainHazards = toxic |
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| MainHazards = highly toxic, maybe corrosive; asphyxiant |
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| FlashPtC = 32 |
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| FlashPt = |
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| GHSPictograms = {{GHS05}}{{GHS06}} |
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| RPhrases = 26/28-34 |
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| GHSSignalWord = Danger |
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| SPhrases = 26-28-36/37/39-45 |
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| HPhrases = {{H-phrases|300|301|314|330}} |
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| PPhrases = {{P-phrases|260|264|270|271|280|284|301+310|301+330+331|303+361+353|304+340|305+351+338|310|320|321|330|363|403+233|405|501}} |
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}} |
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| Section8 = {{Chembox Related |
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|Section8={{Chembox Related |
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| OtherCpds = ], Cl<sub>2</sub>}} |
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| OtherCompounds = ], Cl<sub>2</sub>}} |
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}} |
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'''Diphosgene''' is a ] with the formula ClCO<sub>2</sub>CCl<sub>3</sub>. This colorless liquid is a valuable reagent in the ] of organic compounds. Diphosgene is related to ] but is more conveniently handled because it is a liquid, whereas phosgene is a gas. |
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'''Diphosgene''' is an organic ] with the formula ClCO<sub>2</sub>CCl<sub>3</sub>. This colorless liquid is a valuable reagent in the ] of organic ]s. Diphosgene is related to ] and has comparable ]ity, but is more conveniently handled because it is a liquid, whereas phosgene is a gas. |
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==Production and uses== |
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==Production and uses== |
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Diphosgene is prepared by ] chlorination of ] under ].<ref>{{OrgSynth |
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Diphosgene is prepared by ] chlorination of ] under ]:<ref>{{OrgSynth|author=Keisuke Kurita and Yoshio Iwakura |
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| year =1979 |
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| title =Trichloromethyl Chloroformate as a Phosgene Equivalent: 3-Isocyanatopropanoyl Chloride |
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|author=Keisuke Kurita1 and Yoshio Iwakura |
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| volume =59 |
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|year=1979 |
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| pages =195 |
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|title=TRICHLOROMETHYL CHLOROFORMATE AS A PHOSGENE EQUIVALENT: 3-ISOCYANATOPROPANOYL CHLORIDE |
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| collvol =6 |
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|volume=59 |
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| collvolpages =715 |
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|pages=195 |
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| prep =cv6p0715}} </ref> |
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|collvol=6 |
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|collvolpages=715 |
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|prep=cv6p0715}} </ref>: |
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:Cl-CO-OCH<sub>3</sub> + 3 Cl<sub>2</sub> —(hv)→ Cl-CO-OCCl<sub>3</sub> + 3 HCl |
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:Cl-CO-OCH<sub>3</sub> + 3 Cl<sub>2</sub> —(hv)→ Cl-CO-OCCl<sub>3</sub> + 3 HCl |
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Another method is the radical chlorination of methyl formate:<ref>Lohs, KH.: Synthetische Gifte; Berlin (east), 1974 (german).</ref> |
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Another method is the radical chlorination of methyl formate:<ref>Lohs, K. H.: ''Synthetische Gifte''; Berlin (east), 1974 (German).</ref> |
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:H-CO-OCH<sub>3</sub> + 4 Cl<sub>2</sub> —(hv)→ Cl-CO-OCCl<sub>3</sub> + 4 HCl |
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:H-CO-OCH<sub>3</sub> + 4 Cl<sub>2</sub> —(hv)→ Cl-CO-OCCl<sub>3</sub> + 4 HCl |
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Diphosgene converts to phosgene upon heating or upon ] with ]. It is thus useful for reactions traditionally relying on phosgene. For example, it convert ]s into ]s, secondary amines into ] chlorides, ]s into ]s, and ]s into ]s. Diphosgene serves as a source of two equivalents of phosgene: |
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Diphosgene converts to phosgene upon heating or upon ] with ]. It is thus useful for reactions traditionally relying on phosgene. For example, it convert ]s into ]s, secondary amines into ] chlorides, ]s into ]s, and ]s into ]s. Diphosgene serves as a source of two equivalents of phosgene: |
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:2 RNH<sub>2</sub> + ClCO<sub>2</sub>CCl<sub>3</sub> → 2 RNCO + 4 HCl |
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:2 RNH<sub>2</sub> + ClCO<sub>2</sub>CCl<sub>3</sub> → 2 RNCO + 4 HCl |
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With α-]s diphosgene gives the acid chloride-isocyanates, OCNCHRCOCl, or ''N''-carboxy-amino acid anhydrides depending on the conditions.<ref>Kurita, K. "Trichloromethyl Chloroformate" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. DOI: 10.1002/047084289.</ref> |
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With α-]s diphosgene gives the acid chloride-isocyanates, OCNCHRCOCl, or ''N''-carboxy-amino acid anhydrides depending on the conditions.<ref>{{citation | doi = 10.1002/047084289X | title = Encyclopedia of Reagents for Organic Synthesis | date = 2001 | hdl = 10261/236866 | isbn = 978-0-471-93623-7 | hdl-access = free }}</ref> |
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It hydrolyzes to release HCl in humid air. |
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It hydrolyzes to release HCl in humid air. |
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==Role in warfare== |
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==Role in warfare== |
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Diphosgene was originally developed as a ] for ], a few months after the first use of phosgene. It was used as a poison gas in ] shells by ] during ]. The first recorded battlefield use was in May 1916.<ref>{{cite book |
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Diphosgene was originally developed as a ] for ], a few months after the first use of phosgene. It was used as a poison gas in ] shells by ] during ]. The first recorded battlefield use was in May 1916.<ref>{{cite book |
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| first=Simon | last=Jones | coauthors=Hook, Richard |
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| first =Simon | last=Jones |author2=Hook, Richard |
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| title=World War I Gas Warfare Tactics and Equipment |
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| title =World War I Gas Warfare Tactics and Equipment |
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| year=2007 | publisher=Osprey Publishing |
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| year =2007 | publisher=Osprey Publishing |
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| isbn=1846031516 }}</ref> Diphosgene was developed because the vapors could destroy the filters in ]s in use at the time. |
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| isbn =978-1-84603-151-9 }}</ref> Diphosgene was developed because the vapors could destroy the filters of the ]s in use at the time. |
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==Safety== |
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==Safety== |
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Diphosgene has a relatively high ] of 10 mmHg (1.3 kPa) at 20 °C and decomposes to ] around 300 °C. Exposure to diphosgene is similar in hazard to phosgene and the MSDS should be consulted. |
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Diphosgene has a relatively high ] of 10 mm Hg (1.3 kPa) at 20 °C and decomposes to ] around 300 °C. Exposure to diphosgene is similar in hazard to phosgene. |
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==See also== |
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==See also== |
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==References== |
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==References== |
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{{Reflist}} |
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<references/> |
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==External links== |
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==External links== |
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*, includes treatment advice |
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*, includes treatment advice |
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* (PDF, for phosgene and diphosgene treated as one). |
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* (PDF, for phosgene and diphosgene treated as one). |
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{{Chemical warfare}} |
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{{Chemical warfare}} |
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