Boron trifluoride etherate as a catalyst in acylation of ferrocene

Darin, Vitor André; Neto, Alberto Federman; Miller, Joseph; Afonso, Márcia Maísa de Freitas; Fonsatti, Helen Cristina; Borges, Áurea Donizete Lanchote

doi:10.1002/(sici)1521-3897(199908)341:6<588::aid-prac588>3.0.co;2-9

Cited by 15 publications

(6 citation statements)

References 23 publications

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“…The synthetic methodologies to prepare the ferrocenyl-functionalized β-diketones 5 – 8 is shown in Scheme 1 . The therefore necessary starting compounds 1 – 3 were synthesized accordingly to references [ 79 , 80 , 81 ]. Ketone 4 was prepared by a Friedel-Crafts acylation of ferrocene with 2-[2-(2-methyoxyethoxy)ethoxy]acetyl chloride, which is accessible by refluxing the appropriate carboxylic acid with thionyl chloride in analogy to references [ 82 , 83 ], with ferrocene in presence of the Lewis acid catalyst AlCl 3 ( Section 4.6 ).…”

Section: Resultsmentioning

confidence: 99%

“…Ethyl ferrocenecarboxylate 1 was synthesized by mono lithiation of ferrocene with t BuLi and subsequent addition of ethyl chloroformate [ 79 ]. Acetylferrocene ( 2 ) was synthesized by acylation of ferrocene with acetic anhydride and boron trifluoride etherate [ 80 ]. Ferrocenyl ketone 3 was formed by a Friedel-Crafts acylation of ferrocene with hexanoyl chloride and anhydrous aluminum chloride as a catalyst [ 81 ].…”

Section: Methodsmentioning

confidence: 99%

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Synthesis, Characterization, and Electrochemistry of Diferrocenyl β-Diketones, -Diketonates, and Pyrazoles

Lehrich

Mahrholdt²,

Korb³

et al. 2020

Molecules

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The synthesis of FcC(O)CH(R)C(O)Fc (Fc = Fe(η5-C5H4)(η5-C5H5); R = H, 5; nBu, 7; CH2CH2(OCH2CH2)2OMe, 9), [M(κ2O,O′-FcC(O)CHC(O)Fc)n] (M = Ti, n = 3, 10; M = Fe, n = 3, 11; M = BF2, n = 1, 12), and 1-R’-3,5-Fc2-cC3HN2 (R’ = H, 13; Me, 14; Ph, 15) is discussed. The solid-state structures of 5, 7, 9, 12, 13, 15, and 16 ([TiCl2(κ2O,O′-PhC(O)CHC(O)Ph)2]) show that 7 and 9 exist in their β-diketo form. Compound 13 crystallizes as a tetramer based on a hydrogen bond pattern, including one central water molecule. The electrochemical behavior of 5–7 and 9–16 was studied by cyclic and square-wave voltammetry, showing that the ferrocenyls can separately be oxidized reversibly between −50 and 750 mV (5–7, 9, 12–15: two Fc-related events; 10, 11: six events, being partially superimposed). For complex 10, Ti-centered reversible redox processes appear at −985 (TiII/TiIII) and −520 mV (TiIII/TiIV). Spectro-electrochemical UV-Vis/NIR measurements were carried out on 5, 6, and 12, whereby only 12 showed an IVCT (intervalence charge-transfer) band of considerable strength (νmax = 6250 cm−1, Δν½ = 4725 cm−1, εmax = 240 L·mol−1·cm−1), due to the rigid C3O2B cycle, enlarging the coupling strength between the Fc groups.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Synthesis, Characterization, and Electrochemistry of Diferrocenyl β-Diketones, -Diketonates, and Pyrazoles

Lehrich

Mahrholdt²,

Korb³

et al. 2020

Molecules

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“…The so‐called “boron trifluoride‐alcohol complexes” in excess alcohol have been used for the esterification of carboxylic acids 28, 29. Because this system is not suitable for the acylation of erythritol, we turned to the RCOCl/BF 3 · Et 2 O system which was used by Darin et al 30 to acylate ferrocene (a Friedel–Crafts ketone synthesis reaction). As shown in Table 1, with this system the yields are inferior, e.g., with pentaerythritol with four primary OH groups.…”

Section: Resultsmentioning

confidence: 99%

Preparation and properties of fully esterified erythritol

Ioannou

Lala

Tsivgoulis

2011

Euro J Lipid Sci & Tech

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Pure tetraesters of erythritol with C 10 , C 12 , C 14 , C 16 , C 18 saturated, and C 18:1 unsaturated (oleoyl) fatty acyl chains have been prepared for the first time and characterized using the acylating systems fatty acid/ N,N 0 -dicyclohexylcarbodiimide/4-dimethylaminopyridine (DMAP), fatty acid anhydride/DMAP, fatty acyl chloride/pyridine, and fatty acyl chloride/boron trifluoride etherate. For the first three systems the yields were in the range of 80-90% while the fatty acyl chloride/pyridine system has the advantage of lower cost. The fatty acyl chloride/boron trifluoride etherate system gave lower (ca 70%) yields of the tetraesters. The tetraesters of erythritol may have applications analogues to those of triglycerides. In addition, new applications can be envisaged for these compounds, as a result of their differences in physical, chemical, and biochemical properties compared to triglycerides. Practical applications:The tetraesters of erythritol with saturated fatty acyl chains may have applications analogous to those of saturated triglycerides. However, tetraesters with unsaturated fatty acid chains may have greater prospects of having industrial uses after doing chemistry on the carbon-carbon double bonds.

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“…Acetylferrocene (5d). 34 1 H NMR (CDCl 3 , 400 MHz): d 2.37 (s, 3 H, CH 3 CO), 4.18 (s, 5 H, C 5 H 5 ), 4.48 (vt, J 0 = 2.0 Hz, 2 H, C 5 H 4 ), 4.75 (vt, J 0 = 2.0 Hz, 2 H, C 5 H 4 ).…”

Section: Catalytic Experimentsmentioning

confidence: 99%