2819-48-9

Usage

Uses

1. Used in Polymer Industry:
1,2-Dimethylene-cyclohexane is used as a monomer for the production of specialty polymers, such as norbornene-based polymers, due to its unique cyclic structure and reactivity. These polymers have applications in various fields, including coatings, adhesives, and elastomers.
2. Used in Chemical Synthesis:
1,2-Dimethylene-cyclohexane is used as a building block in the synthesis of various chemicals, such as pharmaceuticals, agrochemicals, and fragrances. Its conjugated diene structure allows for a range of chemical reactions, making it a valuable intermediate in the chemical industry.
3. Used in Material Science:
1,2-Dimethylene-cyclohexane is used as a precursor in the development of advanced materials, such as high-performance plastics and composites. Its unique properties contribute to the enhanced performance of these materials in various applications, including automotive, aerospace, and electronics.
4. Used in Research and Development:
1,2-Dimethylene-cyclohexane is utilized as a model compound in academic and industrial research to study the properties and reactivity of conjugated dienes. This helps in the development of new synthetic methods, catalysts, and applications for these types of compounds.

Synthesis Reference(s)

Journal of the American Chemical Society, 105, p. 6165, 1983 DOI: 10.1021/ja00357a041

InChI:InChI=1/C8H12/c1-7-5-3-4-6-8(7)2/h1-6H2

Upstream product

• 50-00-0 formaldehyd 
• 591-49-1 1-methylcyclohex-1-ene 
• 78426-32-1 2-(hydroxymethyl)-1-methylenecyclohexane 
• 43078-33-7 2-<(Dimethylamino)methyl>1,1-methylenecyclohexanone 
• 98516-00-8 cis-1,2-cyclohexanedimethanol diacetate 
• 110-89-4 piperidine 
• 86365-79-9 2-bromo-1,7-octadiene 
• 493-03-8 1,2,3,4,5,6,7,8-octahydro-naphthalene 
• 54730-18-6 bromomethanesulfonyl bromide 
• 15753-50-1 cis-1,2-cyclohexanedimethanol 
• 103261-98-9 1-Methylene-2-(acetoxymethyl)cyclohexane 
• 343250-59-9 CYCLOHEXANE-1,2-DIMETHANOL, DIACETATE 
• 123099-39-8 trimethyl-(2-methylene-cyclohexylmethyl)-ammonium; iodide 
• 108-94-1 cyclohexanone 

Downstream Products

• 39520-17-7 4-Methylene-1,1-diphenyl-spiro[2.5]octane 
• 55370-36-0 1,2-Bis-(brommethyl)-1-cyclohexen 
• 78156-47-5 5a,6,7,8,9,10,11,11a-Octahydro-naphtho[2,3-g]quinoline-5,12-dione 
• 97095-08-4 6a,7,8,9,10,11,12,12a-Octahydro-N-(4-methoxyphenyl)-6-oxo-6H-5-oxabenzanthracen-6a-carboxamid 
• 137958-33-9 1-(3-bromo-n-propyl)-1-methyl-2-methylenecyclohexane 
• 80754-56-9 2-Phenyl-1,3,4,5,6,7-hexahydro-isophosphindole 2-oxide 
• 137958-36-2 4-(1-methyl-2-methylenecyclohexyl)butyronitrile 
• 27723-50-8 1-Methylen-spiro<5.5>undecan 
• 97095-07-3 8a,9,10,11,12,13,14,14a-Octahydro-N-(4-methoxyphenyl)-8-oxo-8H-7-oxanaphth<1,2-a>anthracen-8a-carboxamid 
• 78172-07-3 2,5,12-trioxo-5a,6,7,8,9,10,11,11a-octahydro-1H-naphtho<2,3-g>quinoline 
• 134847-45-3 2-Diphenylvinylidene-2,3,4,5,6,7-hexahydro-1H-indene 
• 84183-26-6 3-<(E)-α-Chlorbenzyliden>-1,2,3,4,5,6,7,8-octahydro-2,2-dimethylnaphthalin 
• 96722-11-1 5,6,6a,7,8,9,10,11,12,12a-Decahydro-6-oxo-5-thiabenzanthracen-6a-carbonsaeure-(4-methoxyanilid) 

Relevant academic research and scientific papers

Quest for diatomic selenium

Metallocene pentaselenides and elemental selenium were employed in an effort to generate diatomic selenium (Se2) under thermal conditions. Trapping experiments were carried out with six dienes. A successful formation of a diselenium adduct was observed in the case of 5,6-dimethylene-cyclohexa-1,3- diene (1a). The other dienes produced the corresponding dihydroselenophenes. The in-depth study of the limitations of our method to generate Se2 is described; a plausible mechanism rationalizing the observed results is proposed.

Synthesis of highly substituted cyclobutane fused-ring systems from n-vinyl β-lactams through a one-pot domino process

In this contribution, aminocyclobutanes, as well as eight-membered enamide rings, have been made from N-vinyl β-lactams. The eightmembered products have been formed by a [3,3]-sigmatropic rearrangement, whereas the aminocyclobutanes have been derived from a domino [3,3]-rearrangement/6π- electrocyclisation process. The aminocyclobutanes have been obtained in a highly diastereoselective fashion. The cyclobutane ring system tolerates fusion even if adjacent quaternary centres are present. Systems containing up to four fused rings are readily accessible. The reaction profile has been investigated by using Gaussian 03. This study suggests that two reaction pathways for aminocyclobutane formation are possible. In one pathway the [3,3]-sigmatropic rearrangement is the rate-limiting step and in the second pathway the electrocyclisation is rate limiting. Taken together, these reactions should facilitate the construction of fused heterocycles.

Studies of the condensation of sulfones with ketones and aldehydes

The condensation of ketones or aldehydes with sulfunes was shown to give a variety of products. Condensation of 2-methylcyclohexanone with dimethyl sulfone using potassium t-butoxide as base gave useful yields of 1,2- dimethylenecyclohexane. Under the same conditions, cycloheptanone, 3-methyl-2-butanone, and 2-bulanone were converted to dienes. Remarkably, these reaction conditions converted acetophenone into p-terphenyl (10%) and (E)-1,4-diphenyl-3-penten-1-one (44%). Propiophenone was converted to 2′-methyl-p-terphenyl (61%). Using α-tetralone produced 1-methynaphthalene and naphthalene. No reaction took place with β-tetralone. Using diethyl sulfone with α-tetralone lead to pure naphthalene. Condensation of isobutyraldehyde and dimethyl sulfone using potassium t-butoxide gave isoprene in low yield. Using benzaldehyde and benzyl phenyl sulfone in N,N-dimethylcinnamide gave 1,2-diphenyl-1- phenylsulfonylethylene, N,N-dimethylcinnamide, and a complex condensation product. Only 1,2-diphenyl-1-phenylsulfonylethylene was obtained when the solvent was THF.

Hetero-Diels-Alder and cheletropic additions of sulfur dioxide to 1,2-dimethylidenecycloalkanes. Determination of thermochemical and kinetics parameters for reactions in solution and comparison with estimates from quantum calculations

Below -60° and without catalyst, 1,2-dimethylidenecyclopentane (16), 1,2-dimethylidenecyclohexane (13), 1,2-dimethylidenecycloheptane (17), and 1,2-dimethylidenecyclooctane (18) add to sulfur dioxide in the hetero-Diels-Alder mode, giving the correspondin

(2-Vinylcyclopropyl)carbenes. More stepwise mechanisms for ring-expansion

A simple vinyl group is sufficient to induce a stepwise mechanism for the ring expansion of cyclopropylcarbenes.

Asymmetric synthesis of bicyclic amino acid esters

The invention is an improved process for producing an optically active compound of formula IV: STR1 wherein R 1, R 2 and R 4 are herein described. The improved process to produce a compound of formula IV comprises:a). reacting a diene with a chiral compound, containing a chiral auxiliary to obtain an olefinic compound;b). removing the chiral auxiliary and reducing the olefin by hydrogenation to obtain a compound of formula IV.

Three bacteriorhodopsins with ring-didemethylated 6-s-locked chromophores and their properties

Three novel, 6-s-locked rigidified retinals, racemic all-E 1,5-didemethyl-8,16-methanoretinal, all-E, 1,1-didemethyl-8,18-methanoretinal and all-E 8a,18-didehydro-1,1-didemethyl-8,18-methanoretinal were prepared in good yield in high purity on a 100-mg scale.For the preparation of the key intermediate in the synthesis of 1,5-didemethyl-8,16-methanoretinal, reductive cyanation of an unsaturated cyanohydrin to the corresponding conjugated nitrile was accomplished using triethylsilane and trifluoroacetic acid.The three locked retinals interact with bacterioopsin to form bacteriorhodopsin with about the same rate as the native chromophore.This work proves that steric interaction of the 1,1-dimethyl group in the chromophore is an important factor in binding to bacterioopsin.

Evidence for 2-Hexene-1,6-diyl Diradicals Accompanying the Concerted Diels-Alder Cycloaddition of Acrylonitrile with Nonpolar 1,3-Dienes

The spontaneous reactions of a series of alkyl 1,3-dienes with acrylonitrile (AN) were investigated.Reproducible spontaneous copolymerizations were shown to compete with the expected concerted cycloadditions.For dienes which exist in s-cis/s-trans equilibrium, both copolymer and cycloadduct are formed.Kinetic measurements show that the alternating copolymerization and cycloaddition are two independent paralell second order reactions.With 1,3-cyclohexadiene and 1,2-dimethylenecyclohexane, for which s-gauche is in equilibrium with s-cis, copolymerization still competes with cycloaddition.The s-trans-locked verbenene forms only copolymer, while s-cis-locked cyclopentadiene and 1,2-dimethylenecyclopentane form only cycloadduct rapidly.Our explanation involves a 2-hexene-1,6-diradical, formed by combination between the terminal carbons of the s-gauche or s-trans diene and acrylonitrile.This does not cyclize but initiates copolymerization.Competitively s-cis conformer undergoes classical concerted addition.

Rearrangements of 1-Cyclohexenylmethylenes and Their Relevance to the Mechanism of the Phenylcarbene Rearrangement

Gas-phase pyrolysis of 1-cyclohexenyldiazomethane (17) and (2-methyl-1-cyclohexenyl)diazomethane (36) leads to the generation of cyclohexenylmethylenes, 13 and 27, respectively, whose intramolecular rearrangement mechanism can be inferred from the stable end products.These substituted vinylmethylenes undergo intramolecular ?-addition, but apparently do not participate in all-carbon Wolff rearrangement.The relevance of these results to the mechanism of the phenylcarbene rearrangement is discussed, and it is suggested that a ?-route with a bicycloheptatriene-like transition state may operate.An attempt to generate 1,3-cyclohexadienylmethylene is described.

Cleavage vs Rearrangement Ratios and Secondary Deuterium Kinetic Isotope Effects in the Thermolysis of Conformationally Fixed Cisoid Vinylcyclobutanes

The first-order rate constants for the thermally induced retro 2+2 cleavage and rearrangement of 5-methylenespirononane occur in a 1:2 ratio.In contrast, a 2:1 ratio of these rate constants is usual from conformationally unbiased vinylcyclobutanes.Comparison of the activation parameters suggests that the rearrangement in unbiased systems results from an unfavorable entropy of activation which suggests that the rearrangement is concerted.For the rearrangement of 5-methylenespirooctane, the secondary deuterium kinetic isotope effect at the exo-methylene carbon (kH/kD2) is 1.086 +/- 0.023.This is also consistent with concert in the rearrangement where exo-methylene rotation contributes to the reaction coordinate.The secondary KIE for cleavage of 5-methylenespirooctane is 1.025 +/- 0.027.