Comprehensive Review on Synthesis, Properties, and Applications of Phosphorus (PIII, PIV, PV) Substituted Acenes with More Than Two Fused Benzene Rings

doi:10.3390/molecules27196611

Review

. 2022 Oct 5;27(19):6611.

doi: 10.3390/molecules27196611.

Comprehensive Review on Synthesis, Properties, and Applications of Phosphorus (P^III, P^IV, P^V) Substituted Acenes with More Than Two Fused Benzene Rings

Marek Koprowski¹, Krzysztof Owsianik¹, Łucja Knopik¹, Vivek Vivek¹, Adrian Romaniuk¹, Ewa Różycka-Sokołowska², Piotr Bałczewski^{1

2}

Affiliations

¹ Division of Organic Chemistry, Center of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Łódź, Poland.
² Institute of Chemistry, Faculty of Science and Technology, Jan Długosz University in Częstochowa, Armii Krajowej 13/15, 42-200 Częstochowa, Poland.

PMID: 36235148
PMCID: PMC9570788
DOI: 10.3390/molecules27196611

Review

Comprehensive Review on Synthesis, Properties, and Applications of Phosphorus (P^III, P^IV, P^V) Substituted Acenes with More Than Two Fused Benzene Rings

Marek Koprowski et al. Molecules. 2022.

. 2022 Oct 5;27(19):6611.

doi: 10.3390/molecules27196611.

Authors

Marek Koprowski¹, Krzysztof Owsianik¹, Łucja Knopik¹, Vivek Vivek¹, Adrian Romaniuk¹, Ewa Różycka-Sokołowska², Piotr Bałczewski^{1

2}

Affiliations

¹ Division of Organic Chemistry, Center of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Łódź, Poland.
² Institute of Chemistry, Faculty of Science and Technology, Jan Długosz University in Częstochowa, Armii Krajowej 13/15, 42-200 Częstochowa, Poland.

PMID: 36235148
PMCID: PMC9570788
DOI: 10.3390/molecules27196611

Abstract

This comprehensive review, covering the years 1968-2022, is not only a retrospective investigation of a certain group of linearly fused aromatics, called acenes, but also a presentation of the current state of the knowledge on the synthesis, reactions, and applications of these compounds. Their characteristic feature is substitution of the aromatic system by one, two, or three organophosphorus groups, which determine their properties and applications. The (P^III, P^IV, P^V) phosphorus atom in organophosphorus groups is linked to the acene directly by a P-C_sp2 bond or indirectly through an oxygen atom by a P-O-C_sp2 bond.

Keywords: acene; anthracene; diphosphene; phosphate; phosphine; phosphonate; phosphonium salt; phosphorane; properties; tri-, tetra-, pentacoordinated phosphorus.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

**Scheme 1**
The synthesis of sterically hindered phosphine ligands 4 and 5.

**Scheme 2**
The synthesis of (anthryl)(diphenyl)phosphine 7 and trianthrylphosphine 8 and the pentacarbonyltungsten complex 10.

**Scheme 3**
The synthesis of 8-chloro-1-(diphenylphosphino)anthracenes 12.

**Scheme 4**
Synthesis of 9-(1-phosphirano)anthracene 13, a precursor of the phosphinidene 15.

**Scheme 5**
The Rh-catalyzed arylation of 9-(diphenylphosphino)anthracene 7 with different aryl bromides.

**Scheme 6**
The synthesis of 1,2-ethylene bis(phosphine) 17.

**Scheme 7**
The synthesis of 1,8-bis(diphenylphosphino)anthracene 21 from 1,8-dichloro-9,10-anthraquinone 22.

**Scheme 8**
The Diels–Alder cycloaddition reaction of 1,8-bis-(diphenylphosphino)anthracene 21 with dialkyl fumarates.

**Scheme 9**
An example of the application of 26 in a red-light-controllable soft actuator system (photoisomerization of azotolane).

**Scheme 10**
Synthesis of repulsively interacting 1,8,9-tris(phosphino)anthracene 31 and 1,8-bis(phosphino)anthracene 35.

**Scheme 11**
The synthesis of single donor stabilized anthracenes 32 and 33 with metathio/selenophosphono groups.

**Scheme 12**
Synthesis of the doubly phosphine stabilized phosphenium salt 34.

**Scheme 13**
The synthesis of 2-(diphenylphosphinoyl)anthracene 39 using anthryl ammonium triflate 38.

**Scheme 14**
The synthesis of 2-(diphenylphosphinoyl)anthracene 39 using 2-anthroic acid 40.

**Scheme 15**
The synthesis of 9,10-bis(diphenylphosphinoyl)anthracene 41 from 9,10-dibromoanthracene 42.

**Scheme 16**
The synthesis of (9,10-diphenyl-2-phosphinoyl)anthracene 43 from 2-bromo-9,10-diphenylanthracene 44.

**Scheme 17**
The synthesis of trianthryl-substituted derivatives 8 and 45 reported by Yamaguchi and coworkers.

**Scheme 18**
Synthesis of phosphine oxides **46a**–h moiety containing carboxylic acid esters from 2-(dipenylphospinoyl)anthracene 39.

**Scheme 19**
The synthesis of 9-(diphenylphosphinoyl)anthracene 47, 9-(anthrylphenylphosphinoyl)anthracene 48, and the products of irradiation of 47 under N₂ and O₂ conditions, respectively.

**Scheme 20**
The synthesis of 9-[(methyl)(mesityl)phosphino)]anthracene 52 and the corresponding 9-[(methyl)(mesityl)phosphinoyl)]anthracene 53.

**Scheme 21**
Decarbonylation of 9-[(1-keto diphenylphosphinoyl)]anthracene 55.

**Scheme 22**
The synthesis of optically active 9-[(t-butyl)(phenyl)phosphinoyl)]anthracene 56.

**Figure 1**
Three positional isomers of 1-, 2- and 9-(diphenylthiophosphinoyl)anthracenes 58, 59, and 60.

**Scheme 23**
The preparation of 9-(diphenylthiophosphinoyl)anthracenes 58 and 61–63.

**Scheme 24**
The syntheses of 9-(diphenylthio- and diphenylselenophosphinoyl)anthracenes 58 and 70.

**Scheme 25**
The synthesis of 9-bromo-10-(diphenylphosphino)anthracene 6 and its oxo-, thio-, and seleno derivatives 71–73.

**Scheme 26**
The synthesis of phosphinoanthracenes 75, 76, and 77 and their oxo-, thio-, and seleno derivatives **78a**–f and 79.

**Scheme 27**
The synthesis of 9,10-bis(diphenylphosphinoyl)anthracene and thio- and seleno derivatives 80–82.

**Scheme 28**
The reaction of enantiomerically pure oxazaphospholidineborane 83 with anthryllithium.

**Scheme 29**
The synthesis of tridentate anthracene ligand **87a**/**87b**.

**Scheme 30**
An example of the preparation of the gold (I) complex [Au(NO₃)(PAnthPh₂)] 90.

**Scheme 31**
Synthesis of metalla(Au)cyclophane 91.

**Scheme 32**
The synthesis of the trinuclear Au(I) complex [Au₃(PAnthP)₃][ClO₄]₃ 93.

**Scheme 33**
The synthesis of Au/Ag/Sb complexes **94a**,b and **95a**,b.

**Figure 2**
The dinuclear silver complex 96 derived from 9,10-bis(diphenylphosphino)anthracene.

**Scheme 34**
The synthesis of the iron(0)tetracarbonyl complex 97.

**Figure 3**
Pincer iridium complexes 99.

**Scheme 35**
The synthesis of thermally stable iridium complexes **103** and **104**.

**Scheme 36**
The preparation of the europium complex **108**.

**Scheme 37**
The preparation of the coordination polymer **109**.

**Scheme 38**
The synthesis of the Ru-diphosphine-bridged complex **112**.

**Scheme 39**
The synthesis of tri-, tetra-, and penta-ruthenium clusters **113**, **114**, and **115**.

**Scheme 40**
The synthesis of the phosphine palladium complex **117**.

**Figure 4**
Structures of phosphapalladacycles **118a** and **118b**.

**Scheme 41**
The synthesis of the palladium complex **119** with 1-(diphenylphosphino)anthracene **120** (L) as a ligand.

**Scheme 42**
The synthesis of (Pd, Ni, Pt)-complexes **121a**–c via the Diels–Alder approach.

**Scheme 43**
The synthesis of the 1,8-bis(diphenylphosphino)anthracene ligand 21 and metal complexes **122a**, **122b**, and **123**.

**Scheme 44**
The synthesis of the Pt(II) complex **125** and the dimer **126**.

**Scheme 45**
The preparation of the platinum complex **129**.

**Scheme 46**
The synthesis of the dicyclometalated complexes **130**–**132** (*syn* and *anti*) and the monocyclometalated complex **133**.

**Scheme 47**
The synthesis of 9-(1-phosphirano)anthracene 13 and its platinum complex **137**.

**Scheme 48**
The synthesis of bis{1-(9-anthracene)phosphirano}dithiolatoplatinum(II) complexes **138a**–d.

**Scheme 49**
The synthesis of the Pt(II) pincer complex 50 and its sequential oxygenated products **140**, **141**, and **142**.

**Scheme 50**
The synthesis of tri(9-anthryl)difluorophosphorane **144**.

**Scheme 51**
The synthesis of N-trimethylsilyl-protected phosphinimine 1 and phosphiniminium salts **146a** and **146b**.

**Scheme 52**
The synthesis of the phosphonium salt **147**.

**Scheme 53**
The synthesis of the phosphonium bromide **149**.

**Scheme 54**
The synthesis of the phosphonium chloride **153a** and the phosphonium bromide **153b**.

**Scheme 55**
The synthesis of tri(9-anthryl)methylphosphonium iodide **154**.

**Scheme 56**
The synthesis of anthryl phosphonium salts **155** from diarylmethanols **156**.

**Scheme 57**
The synthesis of 9-difluoroanthracene **127**.

**Scheme 58**
The photodimerization of 14 and **127** and the reduction reaction of the dimer **126** to **157a**.

**Scheme 59**
The synthesis of 9-(dichlorophosphino)anthracene 18.

**Scheme 60**
The synthesis of (P-anthrylphosphino)phosphonium chloride **160a**/**160b** and the tetraphenylborate **162**.

**Scheme 61**
The synthesis of 9-(chlorophosphino)anthracenes 18, **163**, 9-(hydrophosphino)anthracenes 14, **165**, and the osmium complex **164**.

**Scheme 62**
The synthesis and transformation of bis(diethylamino)phosphino]anthracenes **166** and **167**.

**Scheme 63**
The synthesis of the phosphite **169** from PCl₃ and the dialcohol **170**.

**Scheme 64**
The synthesis of anthrylphosphinic acid **173**.

**Scheme 65**
The synthesis of the binuclear nickel complex **174** with the AnthP(H)O₂ ligand.

**Scheme 66**
The synthesis of the dinuclear cobalt complex **175** with the 9-anthrylphosphinic acid ligand.

**Scheme 67**
The synthesis of anthr-9-yl-H-phosphinic acid **173** from 9-bromoanthracene 1.

**Scheme 68**
The reaction of 9-bromoanthracene 1 with red phosphorus.

**Scheme 69**
The synthesis of the secondary phosphine oxide **177** from (n-butyltelluro)butenyne **178**.

**Scheme 70**
The synthesis of 2-(dihydroxyphosphoryl)anthracene **183**.

**Scheme 71**
The synthesis of 1-hydroxy-4-phenyl-2-(dimethoxyphosphoryl)anthracene **185**.

**Scheme 72**
The synthesis of 2-hydroxy-1-(dimethoxyphosphoryl)anthracene **188**.

**Scheme 73**
The cyclization of **191** to **192** upon irradiation with 365 nm monochromatic light.

**Scheme 74**
The synthesis of diethyl 2-amino-9-anthrylphosphonate **193**.

**Scheme 75**
The synthesis of zirconium bis(2-anthrylphosphonate) **196**.

**Scheme 76**
The synthesis of the bis(phosphonic acid) **197a** from 1,4-dibromobenzene **198**.

**Scheme 77**
The synthesis of 9,10-bis(diethoxyphosphoryl)anthracene **201**.

**Scheme 78**
The synthesis of bis(phosphonic acids) **202a** and **202b** from 9,10-diaryl-2,6-dibromoanthracenes **203a** and **203b**.

**Scheme 79**
The synthesis of 9,10-bis(phosphonic acid) **206** from 9,10-dibromoanthracene 42.

**Figure 5**
General structures of SAMPs **207**, **208**, and duplexes **209**.

**Scheme 80**
The *phospho*-Friedel–Crafts–Bradsher cyclization of phosphonates **211** to sterically hindered anthracenes **212**.

**Scheme 81**
The aerobic photochemical oxidation of the phosphate **213**.

**Scheme 82**
The synthesis of 9-bromo-1,8-dimethoxyanthracene **216** via 9-diethoxyphosphoryloxy-1,8-dimethoxy-anthracene **217** as the intermediate.

**Scheme 83**
The conversion of the phosphate **217** to 1,8,9-tribromoanthracene **219**.

**Scheme 84**
The synthesis of 4,4’-bianthryl phosphoric acid **223** from anthr-2-ol **220** using the vanadium complexes **221a** and **221b**.

**Scheme 85**
The synthesis of **224** and its application in the Diels–Alder reaction with maleic anhydride and acrylic acid.

**Scheme 86**
The synthesis of 9-dimethoxyphosphoryloxy-10-(phenylamino)anthracene **229** from anthraquinone anil **228**.

**Scheme 87**
The cyclization of **230** to **231** upon irradiation with a 365 nm monochromatic light.

**Scheme 88**
The synthesis of 9-diphospheno- **232** and 9,10-bis(diphospheno)anthracenes **233**.

**Scheme 89**
Sulfonation, selenation, and attempted telluration of **232a**.

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References

1. Zhao Y., Duan L., Zhang X., Zhang D., Qiao J., Dong G., Wang L., Qiu Y. White Light Emission from an Exciplex Based on a Phosphine Oxide Type Electron Transport Compound in a Bilayer Device Structure. RSC Adv. 2013;3:21453–21460. doi: 10.1039/c3ra43017k. - DOI
1. Wu C.L., Chang C.H., Chang Y.T., Chen C.T., Chen C.T., Su C.J. High Efficiency Non-Dopant Blue Organic Light-Emitting Diodes Based on Anthracene-Based Fluorophores with Molecular Design of Charge Transport and Red-Shifted Emission Proof. J. Mater. Chem. C. 2014;2:7188–7200. doi: 10.1039/C4TC00876F. - DOI
1. Kloß S., Selent D., Spannenberg A., Franke R., Börner A., Sharif M. Effects of Substitution Pattern in Phosphite Ligands Used in Rhodium-Catalyzed Hydroformylation on Reactivity and Hydrolysis Stability. Catalysts. 2019;9:1036. doi: 10.3390/catal9121036. - DOI
1. Takizawa S., Kodera J., Yoshida Y., Sako M., Breukers S., Enders D., Sasai H. Enantioselective Oxidative-Coupling of Polycyclic Phenols. Tetrahedron. 2014;70:1786–1793. doi: 10.1016/j.tet.2014.01.017. - DOI
1. Cattani-Scholz A., Liao K.-C., Bora A., Pathak A., Hundschell C., Nickel B., Schwartz J., Abstreiter G., Tornow M. Molecular Architecture: Construction of Self-Assembled Organophosphonate Duplexes and Their Electrochemical Characterization. Langmuir. 2012;28:7889–7896. doi: 10.1021/la301610a. - DOI - PubMed

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[1] Zhao Y., Duan L., Zhang X., Zhang D., Qiao J., Dong G., Wang L., Qiu Y. White Light Emission from an Exciplex Based on a Phosphine Oxide Type Electron Transport Compound in a Bilayer Device Structure. RSC Adv. 2013;3:21453–21460. doi: 10.1039/c3ra43017k. - DOI

[2] Zhao Y., Duan L., Zhang X., Zhang D., Qiao J., Dong G., Wang L., Qiu Y. White Light Emission from an Exciplex Based on a Phosphine Oxide Type Electron Transport Compound in a Bilayer Device Structure. RSC Adv. 2013;3:21453–21460. doi: 10.1039/c3ra43017k. - DOI

[3] Wu C.L., Chang C.H., Chang Y.T., Chen C.T., Chen C.T., Su C.J. High Efficiency Non-Dopant Blue Organic Light-Emitting Diodes Based on Anthracene-Based Fluorophores with Molecular Design of Charge Transport and Red-Shifted Emission Proof. J. Mater. Chem. C. 2014;2:7188–7200. doi: 10.1039/C4TC00876F. - DOI

[4] Wu C.L., Chang C.H., Chang Y.T., Chen C.T., Chen C.T., Su C.J. High Efficiency Non-Dopant Blue Organic Light-Emitting Diodes Based on Anthracene-Based Fluorophores with Molecular Design of Charge Transport and Red-Shifted Emission Proof. J. Mater. Chem. C. 2014;2:7188–7200. doi: 10.1039/C4TC00876F. - DOI

[5] Kloß S., Selent D., Spannenberg A., Franke R., Börner A., Sharif M. Effects of Substitution Pattern in Phosphite Ligands Used in Rhodium-Catalyzed Hydroformylation on Reactivity and Hydrolysis Stability. Catalysts. 2019;9:1036. doi: 10.3390/catal9121036. - DOI

[6] Kloß S., Selent D., Spannenberg A., Franke R., Börner A., Sharif M. Effects of Substitution Pattern in Phosphite Ligands Used in Rhodium-Catalyzed Hydroformylation on Reactivity and Hydrolysis Stability. Catalysts. 2019;9:1036. doi: 10.3390/catal9121036. - DOI

[7] Takizawa S., Kodera J., Yoshida Y., Sako M., Breukers S., Enders D., Sasai H. Enantioselective Oxidative-Coupling of Polycyclic Phenols. Tetrahedron. 2014;70:1786–1793. doi: 10.1016/j.tet.2014.01.017. - DOI

[8] Takizawa S., Kodera J., Yoshida Y., Sako M., Breukers S., Enders D., Sasai H. Enantioselective Oxidative-Coupling of Polycyclic Phenols. Tetrahedron. 2014;70:1786–1793. doi: 10.1016/j.tet.2014.01.017. - DOI

[9] Cattani-Scholz A., Liao K.-C., Bora A., Pathak A., Hundschell C., Nickel B., Schwartz J., Abstreiter G., Tornow M. Molecular Architecture: Construction of Self-Assembled Organophosphonate Duplexes and Their Electrochemical Characterization. Langmuir. 2012;28:7889–7896. doi: 10.1021/la301610a. - DOI - PubMed

[10] Cattani-Scholz A., Liao K.-C., Bora A., Pathak A., Hundschell C., Nickel B., Schwartz J., Abstreiter G., Tornow M. Molecular Architecture: Construction of Self-Assembled Organophosphonate Duplexes and Their Electrochemical Characterization. Langmuir. 2012;28:7889–7896. doi: 10.1021/la301610a. - DOI - PubMed

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Comprehensive Review on Synthesis, Properties, and Applications of Phosphorus (P^III, P^IV, P^V) Substituted Acenes with More Than Two Fused Benzene Rings

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Comprehensive Review on Synthesis, Properties, and Applications of Phosphorus (P^III, P^IV, P^V) Substituted Acenes with More Than Two Fused Benzene Rings

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Abstract

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