1888-90-0

Upstream product

• 53723-50-5 2-methylenecyclohexyl acetate 
• 108776-78-9 {trans-2-[(dimethyl-oxy-amino)-methyl]-cyclohexyl}-dimethyl-amine oxide 
• 67-56-1 methanol 
• 1193-18-6 3-methylcyclohexen-2-one 
• 71-23-8 propan-1-ol 
• 75411-49-3 3-methyl-2-cyclohexen-1-yl acetate 
• 103668-33-3 3-hydroxymethylcyclohexene 
• 31171-59-2 N,N-dimethyl-1-cyclohexenylmethylamine 
• 930-68-7 cyclohexenone 
• 1822-00-0 trimethylsilylmethyllithium 
• 1779-49-3 Methyltriphenylphosphonium bromide 
• 30004-67-2 N,S-dimethyl-S-phenylsulfoximine 
• 681-06-1 dimethyl methylphosphonothionate 
• 104178-78-1 1-acetoxy-1-acetoxymethyl-cyclohexane 

Downstream Products

• 591-49-1 1-methylcyclohex-1-ene 
• 591-48-0 3-methyl-1-cyclohexene 
• 591-47-9 4-methylcyclohexene 
• 82166-21-0 methyl cyclohexane 
• 104190-00-3 2-methylene-7-oxabicyclo<4.1.0>heptane 
• 84099-15-0 N-(3-methyl-2-cyclohexenyl)aniline 
• 108125-75-3 Cyclohexen-⁽¹⁾-ylmethyl-p-tolylthioether 
• 102683-83-0 3-Bromo-3-bromomethanesulfonylmethyl-cyclohexene 

Relevant academic research and scientific papers

Palladium-catalyzed regio- and enantioselective fluorination of acyclic allylic halides

This report describes the Pd(0)-catalyzed fluorination of linear allylic chlorides and bromides, yielding branched allylic fluorides in high selectivity. Many of the significant synthetic limitations previously associated with the preparation of these products are overcome by this catalytic method. We also demonstrate that a chiral bisphosphine-ligated palladium catalyst enables highly enantioselective access to a class of branched allylic fluorides that can be readily diversified to valuable fluorinated products.

Flash vacuum pyrolysis over magnesium. Part 1 - Pyrolysis of benzylic, other aryl/alkyl and aliphatic halides

Flash vacuum pyrolysis over a bed of freshly sublimed magnesium on glass wool results in efficient coupling of benzyl halides to give the corresponding bibenzyls. Where an ortho halogen substituent is present further dehalogenation gives some dihydroanthracene and anthracene. Efficient coupling is also observed for halomethylnaphthalenes and halodiphenylmethanes while chlorotriphenylmethane gives 4,4′-bis(diphenylmethyl)biphenyl. By using α,α′-dihalo-o-xylenes, benzocyclobutenes are obtained in good yield, while the isomeric α,α′-dihalo-p-xylenes give a range of high thermal stability polymers by polymerisation of the initially formed p-xylylenes. Other haloalkylbenzenes undergo largely dehydrohalogenation where this is possible, in some cases resulting in cyclisation. Deoxygenation is also observed with haloalkyl phenyl ketones to give phenylalkynes as well as other products. With simple alkyl halides there is efficient elimination of HCl or HBr to give alkenes. For aliphatic dihalides this also occurs to give dienes but there is also cyclisation to give cycloalkanes and dehalogenation with hydrogen atom transfer to give alkenes in some cases. For 5-bromopent-1-ene the products are those expected from a radical pathway but for 6-bromohex-1-ene they are clearly not. For 2,2-dichloropropane and 1,1-dichloropropane elimination of HCl occurs but for 1,1-dichlorobutane, -pentane and -hexane partial hydrolysis followed by elimination of HCl gives E, E-, E,Z- and Z,Z- isomers of the dialk-1-enyl ethers and fully assigned 13C NMR data are presented for these. With 6-chlorohex-1-yne and 7-chlorohept-1-yne there is cyclisation to give methylenecycloalkanes and -cycloalkynes. The behaviour of 1,2-dibromocyclohexane and 1,2-dichlorocyclooctane under these conditions is also examined. Various pieces of evidence are presented that suggest that these processes do not involve generation of free gas-phase radicals but rather surface-adsorbed organometallic species.

Thermal reactions of anti- and syn-dispiro[5.0.5.2]tetradeca-1,8-dienes: Stereomutation and fragmentation to 3-methylenecyclohexenes. Entropy-dictated product ratios from diradical intermediates?

A series of cyclobutanes substituted 1,2- by polyenes of increasing radical-stabilizing power has been investigated to test the proposition that stabilization energies obtained independently from apposite, cis,-trans geometric isomerizations can be succes

Thermal pericyclic tandem reactions

Gas phase thermal isomerizations of twelve acetylenic systems, all of which can in principle undergo two successive pericyclic steps, are described. The substrates, the syntheses and spectroscopic properties of which are presented, are formal derivatives of but-2-yne, with different functional groups in the 1- and the 4-positions. The Cope, Claisen, Claisen ester, retro-ene, 1,5-hydrogen shift, and 1,5-homo hydrogen-shift processes were employed as the pericyclic steps from which the tandem processes were composed. The compositions of the pyrolysates obtained were determined over broad temperature ranges, and the mechanisms of the individual steps producing the pyrolysis products are discussed.

Reaction of cyclic allylic acetates with aliphatic alcohols in the presence of cerium(III) chloride

The reactions of selected allylic acetates with methanol, ethanol, n-propyl alcohol, isopropyl alcohol and tert-butyl alcohol in the presence of catalytic amounts of cerium(III) chloride are described. Allylic alkyl ethers, bis-allylic ethers and 1,3-dienes were obtained depending on the structure of the acetates.

The reaction of cyclic allylic alcohols with aliphatic alcohols in the presence of cerium(III) chloride

Cyclic secondary and tertiary allylic alcohols react with primary aliphatic alcohols in the presence of cerium(III) chloride heptahydrate to give alkyl allylic ethers. When secondary or tertiary aliphatic alcohols are used 1,3-dienes are obtained from allylic alcohols heaving the 3-methyl-2-en-1-ol moiety (3-8, 13-15).

Synthesis of Alkyl Allylic Ethers and 1,3-Dienes by the Reaction of Conjugated Cyclohexenones with Sodium Borohydride-Cerium(III) Chloride in Aliphatic Alcohols

The reaction of conjugated cyclohexenones 1,3-containing 3-methyl-2-en-1-one moiety with NaBH4/CeCl3*7H2O in primary aliphatic alcohols (MeOH, EtOH, n-PrOH) affords alkyl allylic ethers and 1,3-dienes.In isopropanol or tert-butanol only 1,3-dienes are obtained.Ketones 4-6 containing 2-methyl-2-en-1-one moiety are reduced under the same conditions to the corresponding allylic alcohols irrespective of the alcohol used.Key words: reduction, α,β-unsaturated ketones, allylic alcohols, alkyl allylic ethers, sodium borohydride, cerium(III) chloride

A new catalytic transformation of diazo esters: hydride abstraction in dirhodium(II)-catalysed reactions

Secondary benzylic and allylic diazoacetates undergo dirhodium(II)-catalysed diazo decomposition to form, competitively or exclusively, ketone and vinylidene products from intramolecular hydride abstraction in catalyst ligand-dependent molar ratios.

Synthese von Propellanen (n = 2,3,4)

A facile access to the parent propellanes 2, 3 and 4 is presented.Lithiation of methallyl alcohol with BuLi/TMEDA complex and reaction of the organometallic intermediate 8 with parformaldehyde, ethylene oxide, or oxetane affords the diols 9 which are converted via the dichlorides 10 into tetrahalides 11.The cyclization of 11 to the corresponding propellanes is effected with 2 equiv. of MeLi or BuLi via bromobicyclobutanes 12.As expected, 2 cannot be isolated; its formation is deduced from the structure of the consecutive products.Key Words: Small-ring propellanes / Bicyclobutane bridging