6077-10-7

Upstream product

• 108230-30-4 tert-butyl(phenylethynyl)mercury 
• 100-56-1 phenylmercury(II) chloride 
• 74-86-2 acetylene 
• 33440-88-9 silver phenylacetylide 
• 536-74-3 phenylacetylene 
• 1600-27-7 mercury(II) diacetate 

Downstream Products

• 38151-51-8 phenyl-(3-phenyl-7,8-dihydro-imidazo[2,1-b][1,5,3]dithiazepin-5-ylidene)-amine 
• 55139-32-7 3-phenyl-7-(phenyl-thiocarbamoyl)-6,7-dihydro-5H-imidazo[2,1-b]thiazolium betaine 
• 38151-52-9 (3-phenyl-7,8-dihydro-imidazo[2,1-b][1,5,3]dithiazepin-5-ylidene)-o-tolyl-amine 
• 16458-77-8 3-phenylthiazolo<3,2-a>benzimidazole 
• 22902-44-9 6,7-dimethyl-3-phenylbenzo[4,5]imidazo[2,1-b]thiazole 
• 63124-72-1 (E)-1-phenylhex-4-en-1-yn-3-one 
• 1817-57-8 4-phenyl-3-butyne-2-one 
• 7338-94-5 1,3-diphenyl-2-propynone 
• 1129-65-3 (hex-1-yn-1-yl)benzene 
• 4250-82-2 (3,3-dimethyl-but-1-ynyl)benzene 
• 33414-83-4 1-(2-cyclohexylethynyl)benzene 
• 3450-67-7 diethyl phenylethynylphosphonate 
• 6907-75-1 N-(1-phenylethylidene)butylamine 
• 32897-40-8 N-methyl-N-(1-phenylethenyl)aniline 

Relevant academic research and scientific papers

The enthalpies of formation of bis-benzyl mercury and bis-phenylethynyl mercury and some associated bond-dissociation enthalpies

The two compounds Hg(C6H5CH2)2 and Hg(C6H5CC)2 have been burnt in a static combustion bomb and their vapour pressures have been measured by an effusion method: ΔfH0m = (189.3 +/- 4.1) kJ*mol-1; ΔsubHm = (88.7 +/- 2.1) kJ*mol-1; ΔfH0m = (621.3 +/- 5.2) kJ*mol-1; ΔsubHm = (99.2 +/- 1.4) kJ*mol-1.These values have been used to obtain the mean Hg-C bond-dissociation enthalpies.

Mercury-osmium carbonyl clusters resulting from facile Hg-C bond cleavage: Reactions of [Os3H2(CO)10] with [Hg(C≡CPh)2] and [RHgC≡CHgR] (R = Ph, Me or Et)

Reaction of the unsaturated cluster [Os3H2(CO)10] with Hg(C≡CPh)2 afforded two new Os-Hg clusters cis-[Os(CO)4{(μ-Hg)Os3(CO)10(μ-η 2-CH=CHPh)}2] 1 and [{Os3(CO)10(μ-η2-CH=CHPh)} 2(μ4-Hg)] 2 in 30 and 20% yield, respectively. Cluster 1 consists of two (μ-Hg)Os3(CO)10(μ-η2-CH=CHPh) subunits bonded to a central Os(CO)4 moiety in the cis configuration which under ambient conditions converts into 2 over 3-5 d with the extrusion of a HgOs(CO)4 unit. Cluster 2 comprises two skewed Os-Hg metal butterflies sharing a common wingtip Hg atom. In refluxing tetrahydrofuran (66°C) 2 underwent redistribution with the symmetrical mercurials [Hg{M(CO)3(η5-C5H5)} 2] (M = Cr, Mo or W) to afford respectively the heterometallic clusters [{Os3(CO)10(μ-η2-CH=CHPh)}(μ 3-Hg){M(CO)3(η5-C5H 5)}] (M = Cr 3, Mo 4 or W 5) in moderate yield. Alternatively, 3-5 can be obtained more readily from the reaction of cluster 1 with the corresponding symmetric mercurials at room temperature. Reactions of [Os3H2(CO)10] with [RHgC≡CHgR] (R = Ph, Me or Et) afforded the clusters [{Os3(CO)10(μ-η2-CH=CH 2)}(μ4-Hg){Os3(CO)10(μ-H)}] 6 (12%) and [{Os3(CO)10(μ-η2-CH=CH 2)}2(μ4-Hg)] 7 (25%). Cluster 7 is isostructural with 2, whilst 6 bears a central Hg atom connecting two structurally different osmium triangles. Clusters 1, 2, 6 and 7 all result from Hg-C bond cleavage of the parent organomercury species, hence the generality of this cleavage is demonstrated. The new clusters 1, 2, 4, 6 and 7 have been fully characterised by both spectroscopic and crystallographic techniques.

Acetodemercuration du bisphenylethynylmercure en solvant acide acetique at sa relation avec la catalyse d'addition d'acide acetique au phenylacetylene

Acetic acid reacts with phenylacetylene (PA) in presence of mercuric acetate and a strong acid to produce α-acetoxystyrene (EE) and acetophenone (Cet).We demonstrate that the key link in the reaction is the bisphenylethynylmercury BPEM, a product that is easy to isolate.We then study the acetolysis of BPEM in presence of BF3(CH3COOH)2.The disappearance of BPEM obeys to a general acid catalysis with a slow proton transfer.EE and PA are intermediate products but Cet, formed during the reaction, will stay irreversibly.The homogenous mixture of CH3COOH + BPEM + PA + BF3(CH3COOH)2 (when >> > ) yields important amounts of EE and Cet such as: 0 - = + .BPEM is regenerated and we propose a mechanism for this catalysis.A mathematical analysis of this cycle is made which only confirms the experimental findings.These results open the way to a practical synthesis of EE.

Electron-transfer processes. 43. Attack of alkyl radicals upon 1-alkenyl and 1-alkynyl derivatives of tin and mercury

Alkyl radicals, obtained by reaction of Bu3Sn? or ClHg? with alkylmercury halides, will undergo regioselective and in some cases stereospecific substitution by a free radical chain addition-elimination mechanism with 1-alkenylstannanes or -mercurials. The chain reaction is also observed for 1-alkynyl derivatives and in the photostimulated demercuration of mixed alkyl and 1-alkenyl- or 1-alkynylmercurials. Chain propagation with alkyl radical formation is also observed to occur in the reactions of β-eliminated ClHg? with Grignard reagents in PhH-THF solution. In competitive reactions of Bu3Sn? or ClHg? with pairs of alkylmercury chlorides, it is observed that a tert-butylmercurial is >1000 times more reactive than a n-butylmercurial, suggesting a concerted dissociate electron-transfer process not involving the intermediacy of RHg? species.

ETHYNYLGOLD(I) COMPLEXES

Reactions between R3PAuCl, NaOEt, and HCCR' under mild conditions produce R3PAuCCR' in excellent yield.When R' = H, a second step leading to the formation of R3PAuCCAuPR3 can take place.Exchange reactions of ethynyl for chloride between the ethynylgold complexes and HgCl2, cis-, cis-, and R 3PAuCl have been monitored, revealing R3PAuCCR' to be useful alkynylating agents.In the reaction with cis-, the first substitution step is non-specific.