Facile acidic hydrolysis and displacement reactions of 2‐chloro‐and 2,9‐dichloro‐1,10‐phenanthroline

Krapcho, A. Paul; Sparapani, Silvia

doi:10.1002/jhet.5570450435

Cited by 7 publications

(5 citation statements)

References 18 publications

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“…[Pd(OAc) 2 ], N‐acetylglycine, 2,2'‐bipyridine, 1,10‐phenanthroline, 6‐methyl‐2(1 H )‐pyridinone, the arenes and the alkenes used are commercially available and were used as received unless otherwise indicated. [Pd(bipy‐6‐OH)Br(C 6 F 5 ) ( 18 ), [38] (NBu 4 )[Pd(bipy‐6‐O)Br(C 6 F 5 )] ( 21 ), [38] [PdBr(CH 3 CN) 2 (C 6 F 5 )], [60] (NBu 4 ) 2 [Pd 2 (μ‐Br) 2 Br 2 (C 6 F 5 ) 2 ], [61] [2,2′‐bipyridin]‐6(1 H )‐one (bipy‐6‐OH), [62] 1,10‐phenanthrolin‐2(1 H )‐one (phen‐2‐OH), [63] 1,10‐phenanthrolin‐4(1 H )‐one (phen‐4‐OH), [64] [2,2'‐bipyridin]‐4(1 H )‐one (bipy‐4‐OH), [65,66] 6‐methoxy‐2,2'‐bipyridine (bipy‐6‐OMe), [62] and C 6 F 5 D, [54] were prepared according to the procedures in the literature.…”

Section: Methodsmentioning

confidence: 99%

Non‐Chelate‐Assisted Palladium‐Catalyzed Aerobic Oxidative Heck Reaction of Fluorobenzenes and Other Arenes: When Does the C−H Activation Need Help?

Villalba

Albéniz

2021

Adv Synth Catal

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The pyridone fragment in the ligand [2, 2’‐bipyridin]‐6(1H)‐one (bipy‐6‐OH) enables the oxidative Heck reaction of simple arenes with oxygen as the sole oxidant and no redox mediator. Arenes with either electron‐donating or electron‐withdrawing groups can be functionalized in this way. Experimental data on the reaction with toluene as the model arene shows that the C−H activation step is turnover limiting and that the ligand structure is crucial to facilitate the reaction, which supports the involvement of the pyridone fragment in the C−H activation step. In the case of fluoroarenes, the alkenylation of mono and 1,2‐difluoro benzenes requires the presence of bipy‐6‐OH. In contrast, this ligand is detrimental for the alkenylation of 1,3‐difluoro, tri, tetra and pentafluoro benzenes which can be carried out using just [Pd(OAc)2]. This correlates with the acidity of the fluoroarenes, the most acidic undergoing easier C−H activation so other steps of the reaction such as the coordination‐insertion of the olefin become kinetically important for polyfluorinated arenes. The use of just a catalytic amount of sodium molybdate as a base proved to be optimal in all these reactions.

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Section: Methodsmentioning

confidence: 99%

Non‐Chelate‐Assisted Palladium‐Catalyzed Aerobic Oxidative Heck Reaction of Fluorobenzenes and Other Arenes: When Does the C−H Activation Need Help?

Villalba

Albéniz

2021

Adv Synth Catal

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“…This fluorinated ligand was used to prepare 18 F radio-labelled Re complexes for positron emission tomography. 410 and 412 can both be obtained by reacting 396 and 397 , respectively, with HI in the presence of H 3 PO 2 as a stabilizer (reductant preventing I 2 formation). , Interestingly, it is possible to isolate mixed 409 by controlling the reaction time and temperature ( 409 is obtained on short time scales at low temperature, while 410 is obtained during overnight reflux conditions) (Scheme ). Mixed halogen-substituted phen products were envisioned as interesting building blocks allowing researchers to take advantage of the different reactivities of C–halogen bonds.…”

Section: Divergent Synthesis Pathwaysmentioning

confidence: 99%

“…Many classical nuclophiles have been used. Aromatic , or aliphatic alcoolates are usually generated in situ from the corresponding alcohol in the presence of sodium ,, or NaH ,− and reacted with 396 or 397 in DMSO or DMF. Tethering alkoxy chains in positions 2 or 2 and 9 of phen allows the study of the impact of both the steric and electron donating effects of those groups on the overall properties of the ligand itself and/or the corresponding complexes.…”

Section: Divergent Synthesis Pathwaysmentioning

confidence: 99%

Fifty Shades of Phenanthroline: Synthesis Strategies to Functionalize 1,10-Phenanthroline in All Positions

Queffélec,

Pati,

Pellegrin

2024

Chem. Rev.

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1,10-Phenanthroline (phen) is one of the most popular ligands ever used in coordination chemistry due to its strong affinity for a wide range of metals with various oxidation states. Its polyaromatic structure provides robustness and rigidity, leading to intriguing features in numerous fields (luminescent coordination scaffolds, catalysis, supramolecular chemistry, sensors, theranostics, etc.). Importantly, phen offers eight distinct positions for functional groups to be attached, showcasing remarkable versatility for such a simple ligand. As a result, phen has become a landmark molecule for coordination chemists, serving as a must-use ligand and a versatile platform for designing polyfunctional arrays. The extensive use of substituted phenanthroline ligands with different metal ions has resulted in a diverse array of complexes tailored for numerous applications. For instance, these complexes have been utilized as sensitizers in dye-sensitized solar cells, as luminescent probes modified with antibodies for biomaterials, and in the creation of elegant supramolecular architectures like rotaxanes and catenanes, exemplified by Sauvage’s Nobel Prize-winning work in 2016. In summary, phen has found applications in almost every facet of chemistry. An intriguing aspect of phen is the specific reactivity of each pair of carbon atoms ([2,9], [3,8], [4,7], and [5,6]), enabling the functionalization of each pair with different groups and leading to polyfunctional arrays. Furthermore, it is possible to differentiate each position in these pairs, resulting in non-symmetrical systems with tremendous versatility. In this Review, the authors aim to compile and categorize existing synthetic strategies for the stepwise polyfunctionalization of phen in various positions. This comprehensive toolbox will aid coordination chemists in designing virtually any polyfunctional ligand. The survey will encompass seminal work from the 1950s to the present day. The scope of the Review will be limited to 1,10-phenanthroline, excluding ligands with more intracyclic heteroatoms or fused aromatic cycles. Overall, the primary goal of this Review is to highlight both old and recent synthetic strategies that find applicability in the mentioned applications. By doing so, the authors hope to establish a first reference for phenanthroline synthesis, covering all possible positions on the backbone, and hope to inspire all concerned chemists to devise new strategies that have not yet been explored.

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“…For the preparation of cyclic diether 2d , 9‐chloro‐1,10‐phenanthrolin‐2(1 H )‐one ( 3b ) can be a good starting material, which can be prepared by hydrolysis of 2,9‐dichloro‐1,10‐phenanthroline ( 4b ) 13a with 36% (w/w) aqueous HCl . The same reaction condition described above for 1d was applied to 3b to yield 2d in 44% yield .…”

Section: Acknowledgmentsmentioning

confidence: 99%

Synthesis and Properties of 2,2′‐Oxybis(1,10‐phenanthroline) and 2,4‐Dioxa‐1,3(2,9)‐diphenanthrolinacyclobutaphane

Lü

Karim

Jahng

2018

Bulletin Korean Chem Soc

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Chemistry of 1,10-phenanthroline has long been of interest since first synthesis in 1898. 1 The importance of 1,10phenanthroline and its substituted analogues stems from their metal chelating properties and such ability has been widely applied in analytical chemistry for the analysis of metal cationic species. 2 The 1,10-phenanthroline moiety has been used not only as a single molecule but also as a part of macrocyclic ligand systems for molecular recognition, 3 cleavage of nucleic acids, 4 sensing agents, 5 catalysis for chemical reaction, 6 and photolysis, 7 and as therapeutic and bioanalytical applications, 8 which have been compiled in several reviews. 9 As the dimeric and cyclic 1,10-phenanthrolines are concerned, 2,2 0 -azabis(1,10-phenanthroline) (1b), 10 2,2 0 -thiobis(1,10-phenanthroline) (1c), 11 1,3(2,9)-diphenanthrolinacyclobutaphane (2a), 12 2,4-diaza-1,3(2,9)-diphenanthrolinacyclobutaphane (2b), 13 and 2,4-dithia-1,3(2,9)-diphenanthrolinacyclobutaphane (2c) 11c,14 were reported and have been attractive in variety of areas. 9c,10c,11c,13a,c However carbon-bridged di(1,10-phenanthrolin-2-yl)methane (1a) and the oxa-bridged 2,2 0 -oxybis (1,10-phenanthroline) (1d) and 2,4-dioxa-1,3(2,9)diphenanthrolinacyclobutaphane (2d), have not been reported. We herein described the preparation and properties of two new 1,10phenanthroline ethers, namely, 2,2 0 -oxybis(1,10-phenanthroline) (1d) and 2,4-dioxa-1,3(2,9)-diphenanthrolinacyclobutaphane (2d).Initial attempt for the synthesis of 1d involved a reaction of 1,10-phenanthrolin-2(1H)-one (3a) 15 and 2-chloro-1,10phenanthroline (4a) 16 in presence of KOH under the same condition for 1c. 11a,b The 1 H NMR spectrum of the product showed that it consisted of a mixture of 1d and 3a in a ratio of 1:4. To explain increased amount of 3a, we repeated the reaction with more reactive 2-bromo-1,10-phenanthroline 17 to give a 1.1:1 mixture of 1d and 3a. Formation of the same hydrolysis product, 3a, has also been reported in the reaction of 4a with 3c 18 reflecting that the low reactivity of 1a towards nucleophilic substitution and/or weak acidity of the amide proton of 3a might induce hydroxylation of 4a before it can undergo nucleophilic attack by the enolate anion. 19 Therefore, we used NaH to deprotonate 3a and the resulting enolate anion was then treated with excess of 4a, which led to 1d in 75% yield with a trace (7%) amount of 4a. 20 The 13 C NMR spectra of 1d showed resonances at δ 158.5 ppm for C2, which is comparable to those for C2 in 2c (δ 156.8) and in 3c (δ 181.0) 11a in CDCl 3 .For the preparation of cyclic diether 2d, 9-chloro-1,10phenanthrolin-2(1H)-one (3b) can be a good starting material, which can be prepared by hydrolysis of 2,9-dichloro-1,10-phenanthroline (4b) 13a with 36% (w/w) aqueous HCl. 21 The same reaction condition described above for 1d was applied to 3b to yield 2d in 44% yield. 22 1 H NMR spectrum of 2d showed two doublets at δ 8.00 and 6.65 (J = 9.5 Hz) for H3 and H4, respectively, and a singlet at δ 7.46 for H5, while 13 C NMR spectrum sho...

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Facile acidic hydrolysis and displacement reactions of 2‐chloro‐and 2,9‐dichloro‐1,10‐phenanthroline

Cited by 7 publications

References 18 publications

Non‐Chelate‐Assisted Palladium‐Catalyzed Aerobic Oxidative Heck Reaction of Fluorobenzenes and Other Arenes: When Does the C−H Activation Need Help?

Non‐Chelate‐Assisted Palladium‐Catalyzed Aerobic Oxidative Heck Reaction of Fluorobenzenes and Other Arenes: When Does the C−H Activation Need Help?

Fifty Shades of Phenanthroline: Synthesis Strategies to Functionalize 1,10-Phenanthroline in All Positions

Synthesis and Properties of 2,2′‐Oxybis(1,10‐phenanthroline) and 2,4‐Dioxa‐1,3(2,9)‐diphenanthrolinacyclobutaphane

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