19064-90-5

Upstream product

• 60040-82-6 dimethyl 2,2'-(1,2-ethanediyl)bisbenzoate 
• 496-14-0 1,3-dihydroisobenzofuran 
• 138771-02-5 1,2-bis(3-formyl-4-phenyl)ethane 
• 95-46-5 2-methylphenyl bromide 
• 18887-51-9 2,2'-Bis-acetoxymethyl-diphenylacetylen 
• 5865-77-0 1,1'-ethyne-1,2-diylbis[2-(bromomethyl)benzene] 
• 5294-03-1 di-o-tolylethyne 
• 56526-10-4 o,o'-Bis(methoxycarbonyl)stilbene 
• 3433-80-5 1-Bromo-2-bromomethyl-benzene 
• 59485-34-6 1,2-bis(2-bromophenyl)ethane 
• 74785-02-7 (2-(bromomethyl)phenyl)methanol 
• 18887-49-5 2-[2-(2-hydroxymethylphenyl)-1-ethynyl]phenylmethanol 

Downstream Products

• 833-48-7 dibenzosuberane 
• 194666-00-7 2,2'-bis(chloromethyl)diphenylethane 
• 114504-92-6 (Z,Z,Z)-5,6-Dihydro-11,12-diphenyldibenzocycloocten 
• 96277-14-4 5,6-diphenyl-5,6,11,12-tetrahydro-dibenzo[a,e]cyclooctene 
• 5668-61-1 2,2'-bis(bromomethyl)bibenzyl 

Relevant academic research and scientific papers

New reactivity of functionalised organolithium compounds in the presence of Cu(I) or Cu(II) salts: Conjugate addition, acylation or dimerisation

The reaction of functionalised organolithium compounds 1 with electrophilic olefins 2 in the presence of copper(I) iodide and HMPA in THF at -78°C leads, after hydrolysis with a saturated solution of ammonium chloride, to the corresponding products 3 resulting from a conjugate addition. The same process but using an acyl chloride instead of the electrophilic olefins affords the expected ketone 4 from an acylation process. Finally, when intermediates 1 are treated with copper(II) chloride in THF at -78°C, the corresponding dimers 5 are isolated after the same hydrolytic treatment.

Preparation and coordinating properties of {CH2(o-C 6H4CH2SbMe2)}2, a novel wide-angle cis-chelating distibine

The unique wide-angle distibine, {CH2(o-C6H 4CH2SbMe2)}2, 1, has been prepared indirectly by reaction of Me2SbCl with the di-Grignard formed unexpectedly by coupling of o-C6H4(CH2MgCl) 2 in concentrated thf solution, and directly by treatment of the {CH2(o-C6H4CH2MgCl)}2 with Me2SbCl. The very oxygen-sensitive distibine 1 has been characterised by 1H and 13C{1H} NMR spectroscopy and high-resolution EIMS. Oxidation of 1 with Br2 gives the air-stable tetrabromide {CH2(o-C6H4CH 2SbMe2Br2)}2. Surprisingly, 1 shows a very strong tendency to function as a cis-chelate, e.g. to Pt(iv) in the complex [PtMe3I(1)], forming an 11-membered ring and providing a stable Pt(iv) stibine complex, the crystal structure of which shows the Sb-Pt-Sb angle to be 95.96(1)°. The yellow Pt(ii) complex [PtCl2(1)] is obtained from reaction of [PtCl2(MeCN)2] with 1 and IR spectroscopic data and a crystal structure determination confirm the Cl ligands are mutually cis in this species. Reaction of [W(CO)4(piperidine) 2] with 1 in refluxing EtOH gives [W(CO)4(1)], the IR spectrum of which shows four ν(CO) bands, also consistent with cis-Sb 2 coordination. The cis-chelation is also confirmed by single-crystal X-ray structure determinations of two polymorphs of [W(CO)4(1)]. The Royal Society of Chemistry 2006.

Copper(I) or (II)-mediated conjugate addition or dimerisation of functionalised organolithium compounds

The reaction of different functionalised organolithium intermediates 1- 3 with several electrophilic olefins 6 (2-cyclopentenone, 2-cyclohexenone, methyl vinyl ketone, benzylideneacetone, benzylideneacetophenone and ethyl acrylate) in the presence of copper(I) salts (bromide and iodide) in THF at -78°C gives, after hydrolysis with ammonium chloride, the expected products resulting from a conjugate addition. In the presence of copper(II) chloride intermediates 1-5 undergo dimerisation to yield the expected dimers. (C) 2000 Elsevier Science Ltd.

Efficient radical coupling of organobromides using dimanganese decacarbonyl

Wurtz-type radical coupling of a variety of allylic and benzylic bromides was observed on irradiation with dimanganese decacarbonyl in excellent yield (77-99%). Efficient cross-coupling of two different bromides was also readily achieved.

Selective Preparation of Polycyclic Aromatic Hydrocarbons. Part 7. A Preparative Route to 10,11-Dihydro-5H-dibenzo-cycloheptenes Using Friedel-Crafts Intramolecular Cyclobenzylation

Cyclobenzylation of 2-hydroxymethyldiphenylethanes 4 and 2,2'-bis(hydroxymethyl)diphenylethanes 13 in the presence of a solid perfluorinated sulfonic acid resin, Nafion-H, as a catalyst results in novel polycyclic aromatic hydrocarbons, dibenzocyclopentenes.Dibenzocyclopentenes were also prepared from diphenylethanes by a benzylation reaction, which incorporates chloromethylation of a hydrocarbon followed by Friedel-Crafts intramolecular cyclization reaction.The present method involving the action of ClCH2OMe and TiCl4 on a variety of diphenylethanes (constructed such that electrophilic substitution occurs ortho to the diphenylethane linkage) offers a convenient, mild one-pot synthesis of substituted dibenzocycloheptenes.The mechanism of these reactions is also discussed.

Electron-transfer-induced reductive cleavage of phthalans: Reactivity and synthetic applications

The behavior of phthalan (1a) was investigated under conditions of electron transfer from alkali metals in aprotic solvents. Reaction with lithium in the presence of a catalytic amount of naphthalene in THF led to the reductive cleavage of an arylmethyl carbon-oxygen bond, with formation of a stable dilithium compound. Trapping of this intermediate with several electrophiles (alkyl halides, carbonyl derivatives, CO2) was successful. The extension of this procedure to several substituted phthalans (1b-i) was investigated, and the regiochemistry as well as the synthetic usefulness of these reactions are discussed.