Cathodic generation of reactive (phenylthio)difluoromethyl species and its reactions: mechanistic aspects and synthetic applications

• Sadanobu Iwase,
• Shinsuke Inagi and
• Toshio Fuchigami

Beilstein J. Org. Chem. 2022, 18, 872–880, doi:10.3762/bjoc.18.88

• bromodifluoromethyl phenyl sulfide (1) using o-phthalonitrile as a mediator generated the (phenylthio)difluoromethyl radical, which reacted with α-methylstyrene and 1,1-diphenylethylene to provide the corresponding adducts in moderate and high yields, respectively. In contrast, chemical reduction of 1 with SmI2

• resulted in much lower product yields. The detailed reaction mechanism was clarified based on the cathodic reduction of 1 in the presence of deuterated acetonitrile, CD3CN. Keywords: bis(phenylthio)difluoromethane; cathodic reduction; deuteration; o-phthalonitrile mediator; (phenylthio)difluoromethylation

• reduction of 1 using o-phthalonitrile as mediator At first, cyclic voltammetry was carried out to investigate the electrocatalytic reduction of bromodifluoromethyl phenyl sulfide (1) with o-phthalonitrile as a mediator. The cyclic voltammograms of o-phthalonitrile in the absence and presence of compound 1

Synthesis of dipolar molecular rotors as linkers for metal-organic frameworks

• Sebastian Hamer,
• Fynn Röhricht,
• Marius Jakoby,
• Ian A. Howard,
• Xianghui Zhang,
• Christian Näther and
• Rainer Herges

Beilstein J. Org. Chem. 2019, 15, 1331–1338, doi:10.3762/bjoc.15.132

• Sonogashira reaction [52]. The cross coupling following a Sonogashira protocol was problematic though in our case. Phthalonitrile (1,2-dicyanobenzene) units are known to form phthalocyanines and homologues, especially under harsher reaction conditions, such as the long reaction times and metal catalysis in

Synthesis and application of trifluoroethoxy-substituted phthalocyanines and subphthalocyanines

• Satoru Mori and
• Norio Shibata

Beilstein J. Org. Chem. 2017, 13, 2273–2296, doi:10.3762/bjoc.13.224

• )phthalonitrile (2) is synthesized by reacting commercially available tetrafluorophthalonitrile (1) with trifluoroethanol. Thereafter, tetramerization is carried out as a general synthesis of phthalocyanine to induce TFEO-Pc (Scheme 1). Since TFEO-Pcs have a large number of fluorine atoms, their solubility in

• phthalocyanines are synthesized by mixing two types of phthalonitrile, but symmetric A4 and A2B2 types are simultaneously produced as byproducts. It is usually difficult to remove these symmetrical A4 and A2B2 type Pc isomers from A3B type Pc, but TFEO-Pcs can be easily purified by silica gel column

• phthalocyanine can be synthesized by using phthalonitrile in which one trifluoroethoxy group was introduced at the α- or β-position (Scheme 9). The target DDPc was successfully obtained in moderate yield by heating trifluoroethoxy-substituted phthalonitrile in the presence of DBU and a lanthanoid acetylacetone

Improved syntheses of high hole mobility phthalocyanines: A case of steric assistance in the cyclo-oligomerisation of phthalonitriles

• Daniel J. Tate,
• Rémi Anémian,
• Richard J. Bushby,
• Suwat Nanan,
• Stuart L. Warriner and
• and Benjamin J. Whitaker

Beilstein J. Org. Chem. 2012, 8, 120–128, doi:10.3762/bjoc.8.14

• substrates from the chiral pool) or symmetrical, nonchiral R2CH-terminated chains, which we synthesised from commercially available carboxylic acids or alcohols. We discovered that bulky, branched-chain α-substituents provide steric assistance in the conversion of the phthalonitrile precursors to the

• scale. Results and Discussion Synthesis In synthesising many different α-alkylated phthalocyanines [17] we experimented with various routes to the phthalonitrile precursors 6 (Scheme 1). The route that we originally used was one described by Cook et al. for the octaoctyl compound 7a [18]. This involved

• nontemplated phthalonitrile cyclo-oligomerisation reactions and, although high-yielding nontemplated routes have been developed for some metal-free phthalocyanines [19][33][34][35], for the liquid-crystalline phthalocyanines, the low yield of the cyclo-oligomerisation step is a problem. Somewhat surprisingly

Synthesis of mesogenic phthalocyanine-C₆₀ donor–acceptor dyads designed for molecular heterojunction photovoltaic devices

• Yves Henri Geerts,
• Olivier Debever,
• Claire Amato and
• Sergey Sergeyev

Beilstein J. Org. Chem. 2009, 5, No. 49, doi:10.3762/bjoc.5.49

• example of LC phthalocyanine-C60 dyads. Keywords: donor–acceptor dyad; fullerene; liquid crystals; phthalocyanine; phthalonitrile; Introduction Among sustainable energy technologies, photovoltaic (PV) conversion of solar energy is considered as a promising solution. Although currently the market is

• unstructured multiplets from the protons of 1,2,4-substituted benzene rings. Inner-core protons in 4a–d and 10a–d are observed as a broad and concentration-sensitive high-field signal. It should be noted that 3 (as well as any phthalocyanine derivative prepared from a 4-substituted phthalonitrile) represents a

• (Fc/Fc+) couple (E°Fc/Fc+ = 0.425 V vs. Ag/AgCl) before and after each experiment. All potentials are reported versus saturated calomel electrode (SCE) (E°Fc/Fc+ = 0.405 V vs. SCE). Before each measurement, solutions were deaerated by 20 min nitrogen bubbling. 4-(2-Decyltetradecyloxy)phthalonitrile (5