Diphenylphosphoryl azide: Difference between revisions

| Verifiedfields = changed

| verifiedrevid = 421089733

| ImageSize =

| ImageFile2 = DPPA-3D-vdW.png

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| PIN = Diphenyl phosphorazidate<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 | pages=923, 931 | doi = 10.1039/9781849733069-FP001 | isbn = 978-0-85404-182-4}}</ref>

| OtherNames = Diphenoxyphosphoryl azide<br>Diphenylphosphonic azide<br>Diphenyl azidophosphate<br>Phosphoric acid diphenyl ester azide

|Section1={{Chembox Identifiers

| Abbreviations = DPPA

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

| CASNo = 26386-88-9

| ChemSpiderID = 110011

| EINECS = 247-644-0

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

| UNII = GXM91165AV

| PubChem = 123414

| SMILES = C1=CC=C(C=C1)OP(=O)(N=[N+]=[N-])OC2=CC=CC=C2

|Section2={{Chembox Properties

| C=12|H=10|N=3|O=3|P=1

| MolarMass =

| BoilingPtC = 157

| BoilingPt_notes = (0.2 mmHg)

|Section7={{Chembox Hazards

| 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>

| GHSPictograms = {{GHS06}}{{GHS07}}

| GHSSignalWord = Danger

| HPhrases = {{H-phrases|301|311|315|319|331|335}}

| 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}}

| MainHazards =

| NFPA-H = 4

| NFPA-F = 1

| NFPA-R = 0

| NFPA-S =

| FlashPtC = 112

| AutoignitionPtC =

| ExploLimits =

| LD50 =

| PEL =

}}

'''Diphenylphosphoryl azide''' ('''DPPA''') is an [[organic compound]]. It is widely used as a reagent in the [[Organic synthesis|synthesis]] of other organic compounds.<ref>{{cite journal | doi = 10.1071/CH9731591 | title = Some Reactions of ''O'',''O''-Diphenylphosporyl Azide | journal = [[Australian Journal of Chemistry]] | year = 1973 | volume = 26 | issue = 7 | pages = 1591–3 | author = R. J. W. Cremlyn| doi-access = free}}</ref>

DPPA undergoes [[pseudohalogen]] replacement of the [[azido]] group by treatment with [[nucleophilic]] [[reagents]], such as [[ammonia]] and various [[amines]].{{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 [[Carbamate|urethane]] or the [[amide]]. The formation of the urethane is particularly valuable since it works with carboxylic acids which fail to undergo the [[Schmidt reaction]], 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 diphenylphosphate anion, known to be a good leaving group. Finally, the acyl azide reacts in the normal manner to give the urethane.

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 [[nucleophilic substitution]] 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 [[Curtius reaction]].

==Safety==

DPPA is very [[toxic]] and a potential [[explosive]] like most other azide compounds.

==See also==

* [[Tosyl azide]]

* [[Trifluoromethanesulfonyl azide]]

[[Category:Azido compounds]]

[[Category:Phenol esters]]

[[Category:Phenyl compounds]]