On the preparation of acyl cyanides from aldehydes

Härle, Helmut; Jochims, Johannes C.

doi:10.1002/cber.19861190425

Cited by 18 publications

(6 citation statements)

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“…[1] Both of these dianhydrides can also be converted into diimides, which can either be used directly for applications from biomedicine to electronics or, in case of prior halogenation, as precursors for the synthesis of polymer semiconductors and other functional materials. [2] It has further been shown that naphthalenetetracarboxylic dianhydride can be used for the hydrothermal synthesis of fully conjugated small molecules and polymers, including the industrial organic pigment perinone. [3] Similarly, perylenetetracarboxylic dianhydride can be used for the synthesis of dyes and pigments, namely perylene diimides.…”

Section: Introductionmentioning

confidence: 99%

Squarephaneic Tetraanhydride: A Conjugated Square‐Shaped Cyclophane for the Synthesis of Porous Organic Materials**

et al. 2022

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Aromatic carboxylic anhydrides are ubiquitous building blocks in organic materials chemistry. In particular, dianhydrides and their conversion into imides have received considerable attention in the synthesis of organic semiconductors, pigments, and battery electrode materials. Here we extend the family of aromatic carboxylic anhydrides with a unique new member, a conjugated cyclophane with four anhydride groups. The cyclophane, named squarephaneic tetraanhydride due to its square shape, is obtained in a three-step synthesis; the anhydride groups are located at the corners and allow for efficient functionalisation, as shown by the conversion into imides and carboxylates. The crystal structures of the tetraanhydride and one of the imides demonstrate the high degree of porosity achievable with the new building block. Electrochemical measurements in solution and solid state are also presented. Considering the short synthesis and unique properties, we expect widespread use of the new building block in the development of organic materials.

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Section: Introductionmentioning

confidence: 99%

Squarephaneic Tetraanhydride: A Conjugated Square‐Shaped Cyclophane for the Synthesis of Porous Organic Materials**

et al. 2022

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“…Especially, synthesis of aroyl cyanides had to utilize strong toxic reagents as original cyanide sources, such as HgCN, 3 NaCN, 4 CuCN, 5 KCN, 6 and TMSCN, 7 which render the cyanation of aroyl chlorides unsafe and environmentally unfriendly. In addition, the corresponding phosphorus ylides, which are unstable to oxygen and moisture, also required to synthesize by reactions of triphenylphosphine with carbon tetrahalides prior to use.…”

Section: Introductionmentioning

confidence: 99%

One-pot four-component synthesis of 2-aryl-3,3-dihaloacrylonitriles using potassium hexacyanoferrate(II) as environmentally benign cyanide source

Zhao¹,

Li²

2011

J. Braz. Chem. Soc.

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Foi descrita uma rota eficiente para reações em uma etapa com quatro componentes incluindo cloretos de aroila, hexacianoferrato(II) de potássio, trifenilfosfina e tetrahaletos de carbono para sintetizar 2-aril-3,3-dicloroacrilonitrilas e 2-aril-3,3-dibromoacrilonitrilas. Este protocolo tem como vantagens o uso de uma fonte não-tóxica de cianeto, alto rendimento e procedimento experimental simples.An efficient route to one-pot four-component reactions of aroyl chlorides, potassium hexacyanoferrate(II), triphenylphosphine and carbon tetrahalides to synthesize 2-aryl-3,3-dichloroacrylonitriles and 2-aryl-3,3-dibromoacrylonitriles was described. This protocol has advantages of use of non-toxic cyanide source, high yield and simple work-up procedure.Keywords: cyanation, four-component synthesis, potassium hexacyanoferrate(II), cyanide source, triphenylphosphine, 2-aryl-3,3-dichloroacrylonitriles, 2-aryl-3,3-dibromoacrylonitriles Introduction 3,3-Dichloroacrylonitriles and 3,3-dibromoacrylonitriles are well-known as the most important synthetic intermediates.1 Although 2-aryl-3,3-dichloroacrylonitriles and 2-aryl-3,3-dibromoacrylonitriles could be prepared directly from phosphorus ylides with aroyl cyanides, 2 the commercially available aroyl cyanides are limited and comparatively expensive. Especially, synthesis of aroyl cyanides had to utilize strong toxic reagents as original cyanide sources, such as HgCN, 3 NaCN, 4 CuCN,5 KCN, 6 and TMSCN, 7 which render the cyanation of aroyl chlorides unsafe and environmentally unfriendly. In addition, the corresponding phosphorus ylides, which are unstable to oxygen and moisture, also required to synthesize by reactions of triphenylphosphine with carbon tetrahalides prior to use. Therefore, there is a need to explore environmentally benign cyanating agents and simple procedure for the synthesis of 2-aryl-3,3-dichloroacrylonitriles and 2-aryl-3,3-dibromoacrylonitriles.Potassium hexacyanoferrate(II), K 4 [Fe(CN) 6 ], is non-toxic and is even used in the food industry for metal precipitation. In addition, it has been described as an antiagglutinating auxiliary for Herein, we wish to report an efficient one-pot fourcomponent synthesis of 2-aryl-3,3-dichloroacrylonitriles and 2-aryl-3,3-dibromoacrylonitriles using potassium hexacyanoferrate(II) as an environmentally benign cyanide source. Results and DiscussionInitially, the reaction of benzoyl chloride, potassium hexacyanoferrate(II), triphenylphosphine and carbon tetrachloride was selected as a model reaction to examine the feasibility of one-pot four-component synthesis of 2-phenyl-3,3-dichloroacrylonitrile under different conditions (Scheme 1). It was found that the optimal mole ratio of benzoyl chloride to potassium hexacyanoferrate(II) and triphenylphosphine was 1:0.2:2 for the reaction, and the excess carbon tetrachloride were required because it acted both as a reactant and a solvent in this reaction. The 0.2 equivalent of potassium hexacyanoferrate(II) used in the reaction indicated that a small excess of CN -was utilized ...

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“…By contrast, use of methanesulfonic acid as the nucleophile afforded the α-methylsulfonated ketones (4f), likely derived from a double addition intermediate (see SI). 31 Interestingly, for arylsufonic acids, the oxo arylation products (4g-4i), a core substructure in bioactive natural products and functional materials, 32 were formed exclusively (see SI). 33…”

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confidence: 99%

Divergent Functionalization of Alkynes Enabled by Organic Photoredox Catalysis

Zhu

Qian

Nicewicz

2023

Synlett

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Direct Functionalization of alkynes under oxidative is challenging, as alkynes are usually recalcitrant towards typical oxidants. Herein, we communicate a strategy for the divergent functionalization of alkynes with photoexcited acridinium organic dyes, presumably via the formation of vinyl cation radicals as key intermediates. Based on the nature of the nucleophiles, different types of difunctionalized products were obtained in moderate to good yields. Addition of lithium Lewis acids resulted in a surprising reversal of diastereocontrol.

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On the preparation of acyl cyanides from aldehydes

Abstract: The 0-silylated cyanohydrins 3 prepared from the aldehydes 1 with trimethylsilyl cyanide are oxidized photochemically or thermally with N-bromosuccinimide to afford the acyl cyanides 427 -n. Scope and limitations of the procedure are discussed.

Cited by 18 publications

References 35 publications

Squarephaneic Tetraanhydride: A Conjugated Square‐Shaped Cyclophane for the Synthesis of Porous Organic Materials**

Squarephaneic Tetraanhydride: A Conjugated Square‐Shaped Cyclophane for the Synthesis of Porous Organic Materials**

One-pot four-component synthesis of 2-aryl-3,3-dihaloacrylonitriles using potassium hexacyanoferrate(II) as environmentally benign cyanide source

Divergent Functionalization of Alkynes Enabled by Organic Photoredox Catalysis

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