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{{redirect|DPPA|the Driver's Privacy Protection Act|Driver's Privacy Protection Act}}
{{chembox {{chembox
| Verifiedfields = changed
| Watchedfields = changed | Watchedfields = changed
| verifiedrevid = 402003270 | verifiedrevid = 421089733
| ImageFile = Diphenylphosphoryl azide.png | ImageFile = Diphenylphosphoryl azide.png
| ImageSize = 200px | ImageSize =
| ImageFile1 = DPPA-3D-balls.png | ImageFile1 = DPPA-3D-balls.png
| ImageFile2 = DPPA-3D-vdW.png
| IUPACName = Diphenyl phosphorazidate
| ImageSize2 =
⚫ | OtherNames = Diphenylphosphonic azide<br>Diphenyl azidophosphate<br>Phosphoric acid diphenyl ester azide
| PIN = Diphenyl phosphorazidate<ref name=iupac2013>{{cite book | title = Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book) | publisher = ] | date = 2014 | location = Cambridge | pages=923, 931 | doi = 10.1039/9781849733069-FP001 | isbn = 978-0-85404-182-4}}</ref>
⚫ | Section1 = {{Chembox Identifiers
⚫ | OtherNames = Diphenoxyphosphoryl azide<br>Diphenylphosphonic azide<br>Diphenyl azidophosphate<br>Phosphoric acid diphenyl ester azide
⚫ | Abbreviations = DPPA
⚫ |Section1={{Chembox Identifiers
⚫ | Abbreviations = DPPA
⚫ | CASNo_Ref = {{cascite|correct|CAS}}
⚫ | CASNo = 26386-88-9
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} | ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 172597 | ChemSpiderID = 110011
| EINECS = 247-644-0
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = GXM91165AV
⚫ | PubChem = 123414
| InChI = 1/C12H10N3OP/c13-14-15-17(16,11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H | InChI = 1/C12H10N3OP/c13-14-15-17(16,11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H
| InChIKey = MKRTXPORKIRPDG-UHFFFAOYAD | InChIKey = MKRTXPORKIRPDG-UHFFFAOYAD
Line 18: Line 26:
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} | StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = MKRTXPORKIRPDG-UHFFFAOYSA-N | StdInChIKey = MKRTXPORKIRPDG-UHFFFAOYSA-N
⚫ | SMILES = C1=CC=C(C=C1)OP(=O)(N==)OC2=CC=CC=C2
⚫ | CASNo_Ref = {{cascite|correct|CAS}}
⚫ | CASNo = 26386-88-9
⚫ | PubChem = 199401
⚫ | SMILES = O=P(N==)(c1ccccc1)c2ccccc2
}} }}
| Section2 = {{Chembox Properties |Section2={{Chembox Properties
| C=12|H=10|N=3|O=3|P=1
| Formula = C<sub>12</sub>H<sub>10</sub>N<sub>3</sub>O<sub>3</sub>P
| MolarMass = 275.20 g/mol | MolarMass =
| Appearance = Colourless or faintly yellow liquid | Appearance = Colourless or faintly yellow liquid
| Density = 1.277 g/cm<sup>3</sup> | Density = 1.277 g/cm<sup>3</sup>
| MeltingPt = | MeltingPt =
| BoilingPt = 157 °C (0.2 mmHg) | BoilingPtC = 157
| BoilingPt_notes = (0.2 mmHg)
| Solubility = }} | Solubility = }}
| Section7 = {{Chembox Hazards |Section7={{Chembox Hazards
| ExternalMSDS = | ExternalSDS =
| GHS_ref=<ref>{{cite web |title=Diphenyl azidophosphate |url=https://pubchem.ncbi.nlm.nih.gov/compound/123414#section=Safety-and-Hazards |website=pubchem.ncbi.nlm.nih.gov |access-date=16 December 2021 |language=en}}</ref>
| EUClass = Toxic (C)
| GHSPictograms = {{GHS06}}{{GHS07}}
| EUIndex =
| GHSSignalWord = Danger
| MainHazards =
| HPhrases = {{H-phrases|301|311|315|319|331|335}}
| NFPA-H = 4
| PPhrases = {{P-phrases|260|261|262|264|270|271|280|284|301+310|302+350|302+352|304+340|305+351+338|310|311|312|320|322|330|332+313|337+313|361|362|363|403+233|405|501}}
| NFPA-F = 1
| NFPA-R = 0 | MainHazards =
| NFPA-O = | NFPA-H = 4
| RPhrases = | NFPA-F = 1
| SPhrases = | NFPA-R = 0
| RSPhrases = | NFPA-S =
| FlashPt = 112 °C | FlashPtC = 112
| Autoignition = | AutoignitionPtC =
| ExploLimits = | ExploLimits =
| LD50 = | LD50 =
| PEL = }} | PEL =
}}
}} }}


'''Diphenylphosphoryl azide''' ('''DPPA'''; ] name: '''Diphenyl phosphorazidate''') is an organic compound. It is widely used in synthesis of other organic compounds.<ref>Some Reactions of ''O'',''O''-Diphenylphosporyl Azide, '']'', 1973, 26, 1591-3.</ref> '''Diphenylphosphoryl azide''' ('''DPPA''') is an ]. It is widely used as a reagent in the ] of other organic compounds.<ref>{{cite journal | doi = 10.1071/CH9731591 | title = Some Reactions of ''O'',''O''-Diphenylphosporyl Azide | journal = ] | year = 1973 | volume = 26 | issue = 7 | pages = 1591–3 | author = R. J. W. Cremlyn| doi-access = free}}</ref>
==Synthesis==
Diphenylphosphoryl azide has been obtained by reaction of the ] with ]. The stability of the azide towards heating was shown by its distillation at 157 °C and by the fact that vigorous evolution of nitrogen was not observed until a temperature of 175 °C had been reached.{{Citation needed|date=March 2011}}

:]


== Uses == == Uses ==


This compound undergoes ] replacement of the azido group by treatment with nucleophilic reagents, such as water, butanol, ammonia, and various amines. DPPA undergoes ] replacement of the ] group by treatment with ] ], such as ] and various ].{{Citation needed|date=January 2017}}


This compound is used as a reagent for the synthesis of peptides by virtue of its reactions with carboxylic acids leading to either the urethane or the amide. The formation of the urethane is particularly valuable since it works with carboxylic acids which fail to undergo the ], and is believed to involve transfer of the azido group to the carboxylic acid. This compound is used as a reagent for the synthesis of ] by virtue of its reactions with carboxylic acids leading to either the ] or the ]. The formation of the urethane is particularly valuable since it works with carboxylic acids which fail to undergo the ], and is believed to involve transfer of the azido group to the carboxylic acid.


It is now suggested that this reaction proceeds through the intermediate mixed anhydride, resulting from attack by the nucleophilic carboxylate anion on the phosphorus atom, with expulsion of the azide ion. The latter then attacks the carbonyl carbon atom, to give the acyl azide and loss of the diphenyl phosphate anion, known to be a good leaving group. Finally, the acyl azide reacts in the normal manner to give the urethane. It is now suggested that this reaction proceeds through the intermediate mixed ], resulting from attack by the nucleophilic ] ] on the ] atom, with expulsion of the azide ion. The latter then attacks the carbonyl carbon atom, to give the ] and loss of the diphenylphosphate anion, known to be a good leaving group. Finally, the acyl azide reacts in the normal manner to give the urethane.


The present studies show that diphenylphosphoryl azide reacts with amines giving the corresponding phosphoramidates; it therefore appears that formation of the amide similarly involves the intermediate anhydride, followed by nucleophilic substitution by the amine. Studies show that DPPA reacts with amines giving the corresponding phosphoramidates; it therefore appears that formation of the amide similarly involves the intermediate anhydride, followed by ] by the amine.

In the synthesis of NSAIDs, DPPA is able to rearrange a propanoyl group into an isopropanoic acid.<ref name="KawaiKato1983">{{cite journal|last1=Kawai|first1=Nobutaka|last2=Kato|first2=Nobuharu|last3=Hamada|first3=Yasumasa|last4=Shioiri|first4=Takayuki|title=New methods and reagents in organic synthesis. 35. A new synthesis of some non-steroidal anti-inflammatory agents with the 2-arylpropionic acid skeleton by the use of diphenyl phosphorazidate (DPPA) as a 1,3-dipole|journal=Chemical & Pharmaceutical Bulletin|volume=31|issue=9|year=1983|pages=3139–3148|issn=0009-2363|doi=10.1248/cpb.31.3139|doi-access=free}}</ref>

DPPA is also used to prepare an acyl azide for use in the ].
==Safety==
DPPA is very ] and a potential ] like most other azide compounds.

==See also==
* ]
* ]


==References== ==References==
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