56-55-3Relevant articles and documents
One-Pot Synthesis of Tetraphene and Construction of Expanded Conjugated Aromatics
Wang, Jianbo,Yao, Jinzhong,Wang, Hailong,Chen, Hao,Dong, Jingcheng,Zhou, Hongwei
, p. 5250 - 5255 (2016)
Acene derivatives as a class of polycyclic aromatic hydrocarbons have attracted considerable interest because of their outstanding semiconductor properties. We developed a one-pot synthesis for fully conjugated tetraphene via a sequence of propargyl-allenyl isomerization, phosphine addition, intramolecular Wittig reactions, and Diels-Alder cyclization reactions. The derivative-conjugated aromatic compounds including carbazole or triphenylamine have been constructed via Pd-catalyzed coupling reaction with dibromotetraphene. These compounds show superior photophysical and electrochemical properties, which make them possible candidates for optoelectronic conjugated materials.
Industrial production method of benzo [a] anthracene
-
, (2021/06/22)
The invention discloses an industrial production method of benzo [a] anthracene, which belongs to the technical field of organic synthesis, and comprises the following steps of carrying out lithium substitution on 2-bromonaphthalene through 2, 2, 6, 6-tetramethylpiperidine lithium, and carrying out boron esterification and acidification through triisopropyl borate to obtain 2-bromo-3-naphthaleneboronic acid, carrying out Suzuki reaction on 2-bromo-3-naphthaleneboronic acid and iodobenzene to prepare 2-bromo-3-phenyl naphthalene, carrying out lithium substitution on 2-bromo-3-phenyl naphthalene and n-butyllithium, and preparing 2-formyl-3-phenyl naphthalene through DMF, carrying out Witting reaction on 2-formyl-3-phenyl naphthalene, chloromethyl ether triphenylphosphine salt and sodium tert-butoxide to prepare 2-methoxyvinyl-3-phenyl naphthalene, and enabling 2-methoxyvinyl-3-phenyl naphthalene to be subjected to ring closing through methanesulfonic acid, and preparing benzo [a] anthracene. Compared with an existing benzo [a] anthracene synthesis method, raw materials are cheap and easy to obtain, operation is easy, discharge of three wastes is small, preparation is environmentally friendly, and industrial production is facilitated.
Cascade reaction for the synthesis of polycyclic aromatic hydrocarbons via transient directing group strategy
Wang, Ziqi,Dong, Wendan,Sun, Bing,Yu, Qinqin,Zhang, Fang-Lin
supporting information, p. 4031 - 4041 (2019/07/03)
A Pd(II)-catalyzed cascade synthesis of diverse polycyclic aromatic hydrocarbons via transient directing group strategy has been developed, involving the consecutive arylation, cyclization and aromatization. The efficiency and practicality were demonstrated by wide substrate range, concise synthetic pathway and mild reaction conditions. The subsequent transformations of the benz[a]anthracene core accessed natural bioactive PAH molecules.
Reactivity Variation of Tetracyanoethylene and 4-Phenyl-1,2,4-Triazoline-3,5-Dione in Cycloaddition Reactions in Solutions
Kiselev, Vladimir D.,Kornilov, Dmitry A.,Anikin, Oleg V.,Shulyatiev, Alexey A.,Konovalov, Alexander I.
, p. 31 - 44 (2019/01/29)
The reasons for the very high reactivity and variability of reactivity of two dienophiles, tetracyanoethylene (1) and 4-phenyl-1,2,4-triazoline-3,5-dione (2), in the Diels–Alder reactions were considered. The data on the rate of reactions with anthracene (3), benzanthracene (4) and dibenzanthracene (5) in 14 solvents over a range of temperatures and high pressures, data on the change in the enthalpy of solvation of reagents, transition state, and adducts in the forward and backward reactions, and the enthalpies of these reactions in solution were obtained. Strong π-acceptor dienophile 1 has sharply reduced reactivity in reactions in π-donor aromatic solvents. It was observed that the π-acceptor properties of dienophile 1 disappear upon passage to the transition state and adduct. Large solvent effects on the reaction rate can be predicted for all types of reactions involving tetracyanoethylene. Very high reactivity of dienophiles 1 and, especially, 2 can be useful to catch such carcinogenic impurities such as 3–5 and neutralize them by transformation into less dangerous adducts.
Products of the Propargyl Self-Reaction at High Temperatures Investigated by IR/UV Ion Dip Spectroscopy
Constantinidis,Hirsch,Fischer,Dey,Rijs
, p. 181 - 191 (2017/06/07)
The propargyl radical is considered to be of key importance in the formation of the first aromatic ring in combustion processes. Here we study the bimolecular (self-) reactions of propargyl in a high-temperature pyrolysis flow reactor. The aromatic reaction products are identified by IR/UV ion dip spectroscopy, using the free electron laser FELIX as mid-infrared source. This technique combines mass selectivity with structural sensitivity. We identified several aromatic reaction products based on their infrared spectra, among them benzene, naphthalene, phenanthrene, indene, biphenyl, and surprisingly a number of aromatic compounds with acetylenic (ethynyl) side chains. The observation of benzene confirms that propargyl is involved in the formation of the first aromatic ring. The observation of compounds with acetylenic side chains shows that, in addition to a propargyl- and phenyl-based mechanism, the HACA (hydrogen abstraction C2H2 addition) mechanism of polycyclic aromatic hydrocarbons formation is present, although no acetylene was used as a reactant. On the basis of the experimental results we suggest a mechanism that connects the two pathways.
Facile Synthesis of Polycyclic Aromatic Hydrocarbons: Br?nsted Acid Catalyzed Dehydrative Cycloaromatization of Carbonyl Compounds in 1,1,1,3,3,3-Hexafluoropropan-2-ol
Fujita, Takeshi,Takahashi, Ikko,Hayashi, Masaki,Wang, Jingchen,Fuchibe, Kohei,Ichikawa, Junji
, p. 262 - 265 (2017/01/24)
The cycloaromatization of aromatic aldehydes and ketones was readily achieved by using a Br?nsted acid catalyst in 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP). In the presence of a catalytic amount of trifluoromethanesulfonic acid, biaryl-2-ylacetaldehydes and 2-benzylbenzaldehydes underwent sequential intramolecular cationic cyclization and dehydration to afford phenacenes and acenes, respectively. Furthermore, biaryl-2-ylacetaldehydes bearing a cyclopentene moiety at the α-position underwent unprecedented cycloaromatization including ring expansion to afford triphenylenes. HFIP effectively promoted the cyclizations by suppressing side reactions presumably as a result of stabilization of the cationic intermediates.
Ultrasound assisted Bradsher reaction in aqueous and non-aqueous media: First use of ultrasounds in electrophilic aromatic cyclisation leading to polyacenes
Kowalska, Emilia,Ba?czewski, Piotr
, p. 743 - 753 (2016/07/25)
The present work describes the first use of ultrasounds in the Bradsher cyclisation of activated and non-activated ortho-formyl diarylmethanes. This reaction is also the first example of electrophilic, aromatic cyclisation assisted by ultrasounds which leads to pure polycyclic, fused aromatic hydrocarbons containing 3 and 4 fused rings in excellent yields. The reaction proceeds not only in aqueous but also in non-aqueous media at milder conditions (room temperature) and in much shorter reaction times than in conventional protocols.
Microwave flash pyrolysis: C9h8 interconversions and dimerisations
Ajaz, Aida,Voukides, Alicia C.,Cahill, Katharine J.,Thamatam, Rajesh,Skraba-Joiner, Sarah L.,Johnson, Richard P.
, p. 1301 - 1308 (2014/11/07)
The pyrolysis of 2-ethynyltoluene, indene, fluorene, and related compounds has been studied by sealed tube microwave flash pyrolysis (MFP), in concert with modelling of putative mechanistic pathways by density functional theory (DFT) computations. In the MFP technique, samples are admixed with graphite and subjected to intense microwave power (150-300 W) in a quartz reaction tube under a nitrogen atmosphere. The MFP reaction of 2-ethynyltoluene gave mostly indene, the product of a Roger Brown rearrangement (1,2-H shift to a vinylidene) followed by insertion. An additional product was chrysene, the likely result of hydrogen atom loss from indene followed by dimerisation. The intermediacy of dimeric bi-indene structures was supported by pyrolysis of bi-indene and by computational models. Benzo[a]anthracene and benzo[c]phenanthrene are minor products in these reactions. These are shown to arise from pyrolysis of chrysene under the same MFP conditions. MFP reaction of fluorene gave primarily bi-fluorene, bifluorenylidene, and dibenzochrysene, the latter derived from a known Stone-Wales rearrangement.
Indium-catalyzed construction of polycyclic aromatic hydrocarbon skeletons via dehydration
Kuninobu, Yoichiro,Tatsuzaki, Tomohiro,Matsuki, Takashi,Takai, Kazuhiko
experimental part, p. 7005 - 7009 (2011/10/09)
Polycyclic aromatic compounds can be synthesized from 2-benzylic- or 2-allylbenzaldehydes using a catalytic amount of In(III) or Re(I) complexes. By using this method, polycyclic aza-aromatic compounds can also be prepared efficiently. In these reactions, only water is formed as a side product.
Synthesis of uniformly 13C-labeled polycyclic aromatic hydrocarbons
Zhang, Zhenfa,Sangaiah, Ramiah,Gold, Avram,Ball, Louise M.
, p. 5431 - 5435 (2011/09/14)
Convergent synthetic pathways were devised for efficient synthesis of a series of uniformly 13C labeled polycyclic aromatic hydrocarbons de novo from U-13C-benzene and other simple commercially-available 13C-starting compounds. All target products were obtained in excellent yields, including the alternant PAH U-13C-naphthalene, U-13C-phenanthrene, U-13C-anthracene, U- 13C-benz[a]anthracene, U-13C-pyrene and the nonalternant PAH U-13C-fluoranthene.
