39179-88-9

Upstream product

• 39179-87-8 4,4'-(2-bromoprop-1-ene-1,1-diyl)bis(methoxybenzene) 
• 81360-98-7 2-chloro-1,1-bis(p-methoxyphenyl)propene 
• 81360-99-8 1,11-bis(p-methoxyphenyl)-2-iodopropene 
• 4356-69-8 1,1-bis-(4-methoxyphenyl)ethylene 
• 75-25-2 Bromoform 
• 127349-06-8 N′-(bis(4-methoxyphenyl)-methylene)-4-methylbenzenesulfonohydrazide 
• 74-86-2 acetylene 
• 4663-13-2 1,1-bis(4-methoxyphenyl)propene 
• 128742-41-6 1,1-Bis-(4-methoxy-phenyl)-spiro[2.2]pentane 
• 22125-55-9 4,4'-(2,2-dibromocyclopropane-1,1-diyl)bis(methoxybenzene) 
• 67-56-1 methanol 
• 40938-16-7 (4,4'-dimethoxy-benzhydrylidene)-succinic acid 
• 696-62-8 para-iodoanisole 
• 13139-86-1 4-methoxyphenyl magnesium bromide 

Downstream Products

• 4663-13-2 1,1-bis(4-methoxyphenyl)propene 

Relevant academic research and scientific papers

Synthesis of Polycyclic Aromatic Hydrocarbons Decorated by Fluorinated Carbon Acids/Carbanions

The carboarylation reaction of biphenyl-alkynes was successfully triggered by electrophilic attack of 1,1-bis(triflyl)ethylene on the alkyne moiety to give polycyclic aromatic hydrocarbons (PAHs) decorated by superacidic carbon acid functionality. Neutralisation of thus obtained acids with NaHCO3 yielded the corresponding sodium salts, which showed improved solubility in both aqueous and organic solvents.

Regioselective Iron-Catalysed Cross-Coupling Reaction of Aryl Propargylic Bromides and Aryl Grignard Reagents

An iron-catalysed Kumada-type cross-coupling reaction between aryl substituted propargylic bromides and arylmagnesium reagents has been developed. Propargylic coupling products were the main or only outcome, and propargyl/allene regioselectivity was shown to depend on the electronic nature of the substituents on the triple bond of the substrate and on the arylmagnesium halide. Best selectivities were observed when electron donating substituents were present in either reagent. The process is stereoespecific, occurs with configuration inversion and no carbon-based radicals seem to be involved in the mechanism. (Figure presented.).

Regioselective Diboron-Mediated Semireduction of Terminal Allenes

A method for the regioselective reduction of the terminal double bond of 1,1-disubstituted allenes has been developed. In the presence of a palladium catalyst, tetrahydroxydiboron and stoichiometric water, allene semireduction proceeds in high yield to afford Z-alkenes selectively.

Chlorination of phenylallene derivatives with 1-chloro-1,2-benziodoxol-3-one: Synthesis of vicinal-dichlorides and chlorodienes

Allyl and vinyl chlorides represent important structural motifs in organic chemistry. Herein is described the chemoselective and regioselective reaction of aryl- and α-substituted phenylallenes with the hypervalent iodine (HVI) reagent 1-chloro-1,2-benz-iodoxol-3-one. The reaction typically results in vicinal dichlorides, except with proton-containing α-alkyl substituents, which instead give chlorinated dienes as the major product. Experimental evidence suggests that a radical mechanism is involved.

Fluorinative Rearrangements of Substituted Phenylallenes Mediated by (Difluoroiodo)toluene: Synthesis of α-(Difluoromethyl)styrenes

Phenylallenes undergo fluorinative rearrangement upon the action of (difluoroiodo)toluene in the presence of 20 mol % BF3?OEt2 to yield α-difluoromethyl styrenes. This unprecedented reaction was entirely chemoselective for the internal allene π bond, and showed remarkable regioselectivity during the fluorination event. Substituted phenylallenes, phenylallenes possessing both phenyl- and α-allenyl substituents, and diphenylallenes were investigated, and good functional-group compatibility was observed throughout. The ease with which allenes can be prepared on a large scale, and the operational simplicity of this reaction allowed us to rapidly access fluorine-containing building blocks that have not been accessed by conventional deoxyfluorination strategies.

Synthesis of terminal allenes through copper-mediated cross-coupling of ethyne with N-tosylhydrazones or α-diazoesters

Ethyne is employed as coupling partner in coppermediated cross-coupling reactions with N-tosylhydrazones and α-diazoacetate, leading to the development of a new synthetic method for terminal allenes. With this novel coupling method, the terminal allenes w

Lewis acid promoted reactions of ethenetricarboxylates with allenes: Synthesis of indenes and γ-lactones via conjugate addition/cyclization reaction

(Figure presented) Indenes are important core structures in organic chemistry. Few simple arylallenes have been used to construct indene skeletons by Friedel-Crafts reaction. Lewis acid catalyzed reaction of ethenetricarboxylates 1 and arylallenes has been examined in this study. The reaction of arylallenes and ethenetricarboxylate triesters with SnCl4 gave indene derivatives efficiently, via a conjugate addition/Friedel-Crafts cyclization reaction. On the other hand, the reactions of 1,1-diethyl 2-hydrogen ethenetricarboxylate and arylallenes or alkylallenes with SnCl4 at -78 °C or room temperature and subsequent treatment with Et3N gave γ-lactones. The reactions of triethyl ethenetricarboxylate and 1,1-dialkylallenes with SnCl4 at room temperature also gave γ-lactones.

Photoinduced skeletal rearrangement of 1,1-diarylspiropentanes

The photochemical reactivities of 1,1-diarylspiropentanes 1a-c have been investigated under various photolysis conditions. Upon direct photolysis or acetone-sensitized photolysis, 1 underwent skeletal rearrangement to afford methylidenecyclobutanes 2, 3 and 4. A mechanism involving diradical intermediates has been proposed. Also studied were the photochemical and thermal reactions of the electron donor-acceptor (EDA) complexes of 1 with tetracyanoethylene (TCNE). Photoirradiation of the charge-transfer (CT) absorption bands of the EDA complexes resulted in the skeletal rearrangement of 1 to 2 and 3, with concomitant formation of TCNE adducts 11b,c and 12a-c. The X-ray structure of 11c is reported. A mechanism involving ion radical pairs [1?+, TCNE?-] is proposed for the photoreaction. In contrast, no skeletal rearrangement was observed in the thermal reaction of the EDA complexes although i1b and 11c were produced.

Photoinduced skeletal rearrangement of 1,1-diphenylspiropentanes

Photoreactions of 1,1-diphenylspiropentanes have been investigated under various photochemical conditions. The exploratory studies have provided unprecedented examples of photochemically induced skeletal rearrangement of spiropentanes to methylenecyclobutanes.

Photocyclization between Quinones and Allenes via Photoinduced Electron Transfer

Photochemical reactions of halo-1,4-naphthoquinones with 1,1-diphenylallenes afforded spiropyran adducts derived from cycloaddition between carbonyl group of quinone and allene in good yield.In the photoreactions of 2,3-dichloro-1,4-naphthoquinone with monophenylallenes, cycloadducts were obtained in addition to spiropyran derivatives.Considering the relationship between formation of spiropyran adducts and the free energy changes (ΔG) together with substituent effects, solvent effects, and CIDNP (chemically induced dynamic nuclear polarization), we propose an electron-transfer mechanism.That is, radical ion pair formation from excited triplet quinone and allene is followed by conversion to a biradical.Subsequent bond formation between the ketyl radical in quinone moiety and ortho position of the phenyl substituents on the allene skeleton leads to the spiropyran adduct after subsequent 1,5-hydrogen shift.