681164-27-2

Upstream product

• 60836-10-4 bis(trimethylsilylethynyl)ketone 
• 27329-60-8 diethyl (diphenylmethyl)phosphonate 
• 119-61-9 benzophenone 
• 2592-73-6 1,1-dibromo-2,2-diphenylethylene 
• 1066-54-2 trimethylsilylacetylene 

Downstream Products

• 195-19-7 benzo[c]phenathrene 
• 681164-28-3 (2-ethynylbut-1-en-3-yne-1,1-diyl)dibenzene 

Relevant academic research and scientific papers

Reductive Bergman-type cyclizations of cross-conjugated enediynes to fulvene and fulvalene anions: The role of the substituent

Various cross-conjugated enediynes undergo "Bergman-type" cycloaromatizations upon reduction with potassium metal, generating anions of fulvenes and fulvalene derivatives. This new anionic cyclization is considerably more facile than the classic Bergman cyclization with linear enediynes, creating highly reactive diradicals at -78 °C. Not all cross-conjugated enediynes yield cyclized dianions upon reduction; some give uncyclized, Y-shaped, cross-conjugated dianions, while others apparently yield radical-anions that either dimerize or persist as monomers. One system yields both a cyclized and an uncyclized dianion. The substituents are thus shown to be a critical factor in determining the outcome of the reduction. Cyclization occurs within a specific "window of opportunity" that is governed by the substituents.

Sandwich and half-sandwich metal complexes derived from cross-conjugated 3-methylene-penta-1,4-diynes

The cross-conjugated ethynyl-vinylidene [Ph2CC(CCH){C(H)CRu(PPh3)2Cp}]PF6 ([4a]PF6), and [FcC(H)C(CCH){C(H)CRu(PPh3)2Cp}]PF6 ([4b]PF6), and ethynyl-alkynyl Ph2CC(CCH){CCRu(PPh3)2Cp} (5a), and FcC(H)C(CCH){CCRu(PPh3)2Cp} (5b) compounds (Cp = η5-cyclopentadienyl) have been prepared from reactions of the known 3-methylene-penta-1,4-diynes Ph2CC(CCH)2 (3a) and [FcCHC(CCH)2] (3b) with [RuCl(PPh3)2Cp]. The compounds derived from 3b incorporating the more electron-rich alkene proved to be unstable during work-up, and attempts to prepare bis(ruthenium) complexes from 3a and 3b or from transmetallation reactions of the bis(alkynylgold) complex FcCHC(CCAuPPh3)2 (7) with RuCl(PPh3)2Cp were unsuccessful. The related bis-and tris(ferrocenyl) derivatives Ph2CC(CCFc)2 (6a) and FcCHC(CCFc)2 (6b) were more readily obtained from Pd(ii)/Cu(i) catalysed cross-coupling reactions of FcCCH with the 1,1-dibromo vinyl complexes PhCCBr2 (1a) and FcC(H)CBr2 (1b). Cyclic voltammetry of 6a and 6b using n-Bu4N[PF6] as the supporting electrolyte shows broad, overlapping waves arising from the sequential oxidation of the ferrocenyl moieties in electronically and chemically similar environments. Electrostatic effects between the ferrocenyl moieties are enhanced in solutions of the weakly ion-pairing electrolyte n-Bu4N[B{C6H3(CF3)2-3,5}4], leading to better resolution of the individual electrochemical processes. The comparative IR spectroelectrochemical response of 6a and 6b suggest the vinyl ferrocene moiety in 6b undergoes oxidation before the ethynyl ferrocene fragments. There is no evidence of electronic coupling between the metallocene moieties and [6a]+, [6b]n+ (n = 1, 2) are best described as Class I mixed-valence compounds.

TETRACATIONIC CYCLOPHANES AND THEIR USE IN THE SEQUESTRATION OF POLYAROMATIC HYDROCARBONS BY WAY OF COMPLEXATION

Novel tetracationic cyclophanes incorporating π-electron poor organic compounds into their ring structures, as well as methods of making the cyclophanes, are provided. The cyclophanes are able to form electron donor-acceptor complexes with a variety of polyaromatic hydrocarbons (PAHs) ranging in size, shape, and electron density. Also provided are methods of using the cyclophanes in the sequestration of PAHs in liquid or gaseous samples, the separation of PAHs from liquid or gaseous samples, the detection of PAHs in liquid samples, and the exfoliation of graphene via pseudopolyrotaxane formation.

ExBox: A polycyclic aromatic hydrocarbon scavenger

A template-directed protocol, which capitalizes on donor-acceptor interactions, is employed to synthesize a semi-rigid cyclophane (ExBox 4+) that adopts a box-like geometry and is comprised of π-electron-poor 1,4-phenylene-bridged ("extended") bipyridinium units (ExBIPY2+). ExBox4+ functions as a high-affinity scavenger of an array of different polycyclic aromatic hydrocarbons (PAHs), ranging from two to seven fused rings, as a result of its large, accommodating cavity (approximately 3.5 A? in width and 11.2 A? in length when considering the van der Waals radii) and its ability to form strong non-covalent bonding interactions with π-electron-rich PAHs in either organic or aqueous media. In all, 11 PAH guests were observed to form inclusion complexes with ExBox4+, with coronene being the largest included guest. Single-crystal X-ray diffraction data for the 11 inclusion complexes ExBox 4+?PAH as well as UV/vis spectroscopic data for 10 of the complexes provide evidence of the promiscuity of ExBox4+ for the various PAHs. Nuclear magnetic resonance spectroscopy and isothermal titration calorimetric analyses of 10 of the inclusion complexes are employed to further characterize the host-guest interactions in solution and determine the degree with which ExBox4+ binds each PAH compound. As a proof-of-concept, a batch of crude oil from Saudi Arabia was subjected to extraction with the water-soluble form of the PAH receptor, ExBox·4Cl, resulting in the isolation of different aromatic compounds after ExBox·4Cl was regenerated.

Assembly of organosilver coordination frameworks with aromatic ligands bearing a terminal enediyne group

In a series of five silver(I) complexes synthesized with (2-ethynylbut-1-en-3-yne-1,1-diyl)dibenzene (H2L1) and 9-(penta-1,4-diyn-3-ylidene)-9H-fluorene (H2L2), each resulting ethynide ligand is invariably inserted into a Agn/s

Elaboration of Diaryl Ketones into Naphthalenes Fused on Two or Four Sides: A Naphthoannulation Procedure

Transition metal-catalyzed double ring closures of 1,1-diaryl-2,2- diethynylethylenes yield polycyclic aromatic hydrocarbons and heterocycles that contain a newly formed naphthalene ring system embedded in a larger polycyclic network. The diynes required for this procedure are readily synthesized from diaryl ketones by the Corey-Fuchs olefination and subsequent Sonogashira coupling with trimethylsilylacetylene followed by desilylation. This procedure provides easy access to new compounds such as 3,11-di-tert-butyl[4]helicene and 1,8,9-perinaphthothioxanthene. Double naphthoannulation of 9,10-anthraquinone by this procedure closes four new benzene rings in a single operation to give coronene, although the yield in this case is presently low.