Schematic formula of the dipyrromethene molecule.
Schematic formula of dipyrromethene (fractional bonding view).
|Preferred IUPAC name
dipyrrin, pyrromethene, dipyrromethene
3D model (JSmol)
|Molar mass||144.177 g·mol−1|
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
2,2'-Dipyrromethene, often called just dipyrromethene or dipyrrin, is a chemical compound with formula C
2 whose skeleton can be described as two pyrrole rings C
5N connected by a methyne bridge =CH– through their nitrogen-adjacent (position-2) carbons; the remaining bonds being satisfied by hydrogen atoms. It is an unstable compound that is readily attacked by nucleophilic compounds above −40 °C.
2,2'-Dipyrromethene and its more stable and easily prepared derivatives—formally obtained by replacing one or more hydrogen atoms by other functional groups—are important precursors for the family of BODIPY fluorescent dies. The derivatives include salts of the dipyrrinato anion C
2 and of the cation C
2,2'-Dipyrromethene and its derivatives can be obtained from suitable pyrrole derivatives by several methods.
The unsubstituted compound can be prepared by oxidation of 2,2'-dipyrrolemethane with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) at −78 °C in dry dichloromethane solution. An alternative synthesis that avoids the oxidation step is the condensation of 2-formyl pyrrole and pyrrole catalyzed by trifluoroacetic acid, followed by deprotonation with N,N-diisopropylethylamine.
More generally, one starts with a pyrrole with suitable substituents at positions 3, 4, or 5 (but not 2). Condensation of two such molecules at their 2 positions with a bridging compound gives the corresponding 2,2'-dipyrromethane. The condensation may use, for example, the Knorr pyrrole synthesis, with an aromatic aldehyde in the presence of TFA. The dipyrromethane core is then oxidized to dipyrromethene using a quinone oxidant such as DDQ or p-chloranil.
Alternatively, one may use an activated carboxylic acid derivative, usually an acyl chloride. As another possibility, one may condense a substituted pyrroles with a 2-acylpyrrole; this route allows the synthesis of unsymmetrical dipyrromethenes.
The so-called BODIPY dyes can be obtained by reacting 2,2'-dipyrromethene or its derivatives with boron trifluoride-diethyl ether complex (BF
2O) in the presence of triethylamine or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
Dipyrrin and its derivatives for coordination complexes with transition metals. For example, the derivative anion 5-phenyl dipirrinato (pdp) forms the neutral iron(III) complex Fe(pdp)
3 (dark green monoclinic crystals, soluble in benzene, orange solution in dichloromethane), where the Fe3+
ion is coordinated to six nitrogen atoms of the dipyrrin cores in distorted octahedral geometry. A similar cobalt(III) complex has also been reported, as well as a complex with copper(II) Cu(pdp)
- =K. Tram, H. Yan, H. A. Jenkins, S. Vassiliev, and D. Bruce (2009): "The synthesis and crystal structure of unsubstituted 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)". Dyes and Pigments, volume 82, issue 3, pages = 392–395. doi:10.1016/j.dyepig.2009.03.001
- Burgess, Kevin (October 2007). "BODIPY Dyes and Their Derivatives: Syntheses and Spectroscopic Properties". Chemical Reviews. 107 (11): 4891–4932. doi:10.1021/cr078381n. PMID 17924696.
- A. Schmitt, B. Hinkeldey, M. Wild , and G. Jung (): "Synthesis of the core compound of the BODIPY dye class: 4,4′-difluoro-4-bora-(3a,4a)-diaza-s-indacene". Journal of Fluorescence, volume = 19, issue = 4, pages = 755–759 doi:10.1007/s10895-008-0446-7 PMID 19067126
- Brandon R. Groves, Sarah M. Crawford,a Travis Lundrigan, Chérif F. Matta, Shahin Sowlati-Hashjin, and Alison Thompson (2013): "Synthesis and characterisation of the unsubstituted dipyrrin and 4,4-dichloro-4-bora-3a,4a-diaza-s-indacene: improved synthesis and functionalisation of the simplest BODIPY framework." Chemical Communications, volume 49, pages 816-818. doi:10.1039/c2cc37480c
- Seth M Cohen and Sara R Halper (2002): "Dipyrromethene complexes of iron". Inorganica Chimica Acta, volume 341, pages 12-16.
- Sara R. Halper, Mitchell R. Malachowski, Heather M. Delaney, and Seth M. Cohen (2004): "Heteroleptic copperdipyrromethene complexes: synthesis, structure,and coordination polymers". Inorganic Chemistry, volume 43, pages 1242−1249