1165952-91-9

Basic information

• Product Name: cyclohexa-1,3-diene
• Synonyms: cyclohexa-1,3-diene
• CAS NO: 1165952-91-9
• Molecular Weight: 80.1295
• Mol File: 1165952-91-9.mol
• Article Data: 138

Chemical Properties

• CAS DataBase Reference: cyclohexa-1,3-diene(CAS DataBase Reference)
• NIST Chemistry Reference: cyclohexa-1,3-diene(1165952-91-9)
• EPA Substance Registry System: cyclohexa-1,3-diene(1165952-91-9)

Safety Data

• Hazardous Substances Data: 1165952-91-9(Hazardous Substances Data)

Upstream product

• 91-22-5 quinoline 
• 5401-62-7 1,2-dibromocyclohexane 
• 35076-92-7 1,4-dibromocyclohexane 
• 822-67-3 Cyclohex-2-enol 
• 821-07-8 (E)-1,3,5-hexatriene 
• 2441-97-6 3-chloro-cyclohexene 
• 141-52-6 sodium ethanolate 
• 69747-28-0 2-cyclohex-2-enylsulfanyl-benzothiazole 
• 3385-21-5 1,3-diaminocyclohexane 
• 76644-52-5 rac-3-acetoxycyclohexene 
• 2276-46-2 1,2-diacetoxy-cyclohexane 
• 51122-94-2 2-ethoxycyclohex-1-ene 
• 108-94-1 cyclohexanone 
• 71-43-2 benzene 

Downstream Products

• 102589-30-0 bicyclo<2.2.2>octa-2,5-diene-2-carboxylic acid 
• 71-43-2 benzene 
• 67504-35-2 3-methyl-endo-bicyclo<2.2.2>oct-5-ene-2,3-dicarboxylic anhydride 
• 40590-77-0 bicyclo(2.2.2)-5-octene-2-carboxaldehyde 
• 66819-70-3 1,2-dibutyl-cyclohexene 
• 769-44-8 5-nitro-bicyclo[2.2.2]oct-2-ene 
• 2969-21-3 5-nitro-6-phenyl-bicyclo[2.2.2]oct-2-ene 
• 1017-93-2 Bicyclo<2.2.2>oct-5-en-2,2,3,3-tetracarbonitril 
• 28871-80-9 bicyclo<2.2.2>oct-5-ene 2,3-endo,exo-dicarboxylic acid 
• 931-64-6 norbornene 
• 55005-81-7 3-bromo-6-trichloromethyl-cyclohexene 
• 99187-89-0 1-bicyclo[2.2.2]oct-5-en-2-yl-2-chloro-ethanone 
• 3540-84-9 4-bromocyclohexene 
• 1521-51-3 rac-3-bromocyclohexene 

Relevant articles and documents

Cyclization of Ethyne and Propyne over Lanthanide Catalysts Deposited from Eu or Yb Metal Solutions in Liquid Ammonia

Europium and ytterbium catalysts separated on active carbon from a solution of lanthanide metals dissolved in liquid ammonia were found to be effective for oligomerization of alkynes.Selective cyclic dimerization and trimerization of propyne and ethyne to cyclohexadiene and benzene occurred during the oligomerization, respectively, in which the active catalysts were characterized as lanthanide imides induced by the thermal treatment.

Regioselective Catalytic Transfer Hydrogenation of Dimethyl Bicyclohepta-2,5-diene-2,3-dicarboxylate, Dimethyl Bicyclohept-2-ene-2,3-dicarboxylate, and Related Compounds over Palladium on Carbon

The catalytic transfer hydrogenation (CTH) of dimethyl bicyclohepta-2,5-diene-2,3-dicarboxylate (3) on palladium on carbon is highly regioselective, giving predominant reduction at the least-substituted olefinic site.The CTH of dimethyl bicyclohept-2-ene-2,3-dicarboxylate also occurs with exclusive suprafacial exo addition of hydrogen to afford the endo isomer.An increase in the relative concentration of palladium on carbon (ca. 40-45 wt/wt percent based on the acceptor) accelerates the rate of CTH while the substituted cyclohexenes undergo CTH faster than cyclohexene with dimethyl bicyclohept-2-ene-2,3-dicarboxylate.

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Central and Lateral Bicyclo[1.1.0]butane Bond Cleavage with Subsequent Wagner-Meerwein Rearrangements or Carbene Formation in the 185-nm Photolysis of Tricyclo[3.1.0.02,6]hexane, Tricyclo[4.1.0.02,7]heptane, and Tricyclo[5.1.0.02,8]octane

The 185-nm photochemistry of tricyclop[3.1.0.02,6]hexane, tricyclo[4.1.0.02,7] heptane, [1,7-d2]tricyclo[4.1.0.02,7]heptane, tricyclo[5.1.0.02,8]octane, and [1-d]tricyclo[5.1.0.02,8]octane was investigated. Tricyclo[5.1.0.02,8]octane yields bicyclo[4.2.0]oct-7-ene, tricyclo[4.1.0.02,7]heptane yields 85% bicyclo[3.2.0]hept-6-ene and 15% 3-methylenecyclohexene, and tricyclo[3.1.0.02,6]hexane yields 39% 3-methylenecyclopentene, 15% 1,3-cyclohexadiene, 26% trans-1,3,5-hexatriene, and 20% cis-1,3,5-hexatriene. From the deuterium-labeling studies, it is concluded that, in the case of the tricyclooctane, the central bicyclobutane bonds cleave in the primary step to give radical cationic or zwitterionic species that undergo a Wagner-Meerwein rearrangement. Also, in the case of tricycloheptane, this is the dominating pathway but lateral C-C bond cleavage with subsequent carbene and product formation takes place to the extent of ca. 15%. For tricyclohexane, this pathway becomes the major route. Our photomechanistic observations are in good agreement with earlier theoretical investigations on the relative energetic ordering of the bicyclobutane HOMOs, in that the product composition reflects this.

NMR spectroscopic and computational investigations of RuHCl(CO)(PPh 3)3 catalyzed isomerization of 1,4-cyclohexadiene

Ruthenium catalysts with bulky ligands are particularly effective for diene isomerization reactions. Thermodynamics and the mechanism of RuHCl(CO)(PPh3)3 catalyzed 1,4-cyclohexadiene isomerization was probed experimentally through NMR spectroscopy and mod

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Chemistry of β-functionalized α-nitroso ethylenes. Methyl β-nitroso acrylate as heterodienophile in [4 + 2]-cycloaddition to cyclic dienes

(equation presented) β-Functionalized nitroso alkene 2, obtained from methyl β-nitropropionate 1 and W,O-bis(trimethylsilyl)acetamide, can function as a good heterodienophile in Diels-Alder reactions. Therefore, 2 was trapped by cyclic dienes to give adducts 4 with the corresponding stereoselectivity. Cycloadduct 4a undergoes refro-[4 + 2]-cycloaddition at 33 °C in solution; thus 4a can be used to generate nitroso alkene 2 in neutral medium. Cyclopentadiene reacts with adduct 4a according to an endo-[4 + 2]-cycloaddition scheme to give cycloadduct 5 in low yield.

Infrared Multiphoton Isomerization of cis- and trans-1,3,5-Hexatriene

The laser-induced infrared multiphoton isomerization reactions of cis- and trans-1,3,5-hexatriene have been investigated.Excitation of the trans isomer produces vibrationally excited cis molecules possessing sufficient energy to undergo electrocyclic ring closure to 1,3-cyclohexadiene.The ratio of primary (cis) to secondary (cyclohexadiene) products is dependent upon laser fluence and buffer gas pressure.Excitation of the cis isomer produces both trans and cyclohexadiene products.The fluence dependence of the product ratio is in accord with RRKM calculations for competing reactions of the highly excited (70-100 kcal/mol) cis parent isomer.

Kinetics of thermal dimerization of hexatriene

The thermal isomerization of cis-hexatriene (cHT) to cyclohexadiene (CHD) and the dimerization of CHD and trans-hexatriene (tHT) in the liquid phase in the temperature range 380 K-473 K are reported.

Dehydrogenation of cyclohexene over carbon deposited on alumina

The dehydrogenation of cyclohexene over carbon deposited on alumina, C/Al2O3, which was prepared by contacting hydrocarbons such as cyclohexane, cyclohexene, and cyclohexanone with alumina surface at ≥ 823 K, was studied under non-oxidative conditions. At 773 K, the conversion gradually decreased with process time, while the selectivity to the products slightly changed. Because the selectivity to dehydrogenated products such as benzene and 1,3-cyclohexadiene and their yields increased with increasing carbon content, the carbon deposited on alumina had dehydrogenation activity. The selectivities to the dehydrogenated products were maximized at a specific carbon content, while the selectivity to cyclohexane, hydrogenation product, increased with carbon content over the specific carbon content.

THE ABSENCE OF ETHYLENEDIONE ON PHOTOCHEMICAL BISCARBONYLATION REACTIONS

Photolyses of a number of bridged cyclohexenediones and vinylcyclobutanediones in argon or xenon matrices at 10 K at a variety of wavelengths produced carbon monoxide with no evidence for formation of ethylenedione, the elusive dimer of CO.

Dynamics of the thermal dissociation of unsaturated cyclic ketones: Nascent vibrational energy distributions in the products

It has been found that in thermal dissociation of both norbornenone and 3-cyclopentenone the CO is formed with less than half its statistical share of the energy released from the transition state. We have used (VV) coupling between the products, 1,3-cyclohexadiene and butadiene, respectively, to probe their nascent vibrational energy. They are both born vibrationally excited. It seems that much of the energy released appears as vibrational energy of these molecules. In the transition state the CO group must have a bond length close to that of the free molecule. These results do not permit a decision between symmetric and asymmetric bond cleavage. However, separate experiments in which the rotational distribution has been measured establish that the dissociation does not occur by symmetric bond rupture.

THERMAL BEHAVIOR OF TRANS,TRANS,TRANS-1,2,3,4-TETRAVINYLCYCLOBUTANE

Above 420 deg C the title compound decomposes to trans-hexatriene and cyclohexadiene-1,3.At temperatures above 770 deg C only cyclohexadiene-1,3 and benzene are found.

One- and Two-Electron Oxidation of Hydrazines by Dimethyldioxirane

Dimethyldioxirane (1) reacts with sesquibicyclic hydrazine 2 to give the expected (thermally labile) hydrazine N-oxide product and with the homologous hydrazine 5, principally by methyl group transfer, to produce the N-methylated hydrazinium cation acetate 6.

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THE THERMODYNAMIC EFFECT OF FLUORINE AS A SUBSTITUENT VINYLIC CF2 AND CFH AND ALLYLIC CF2C

I2-catalyzed isomerizations of 3-fluoropropene and 3,3-difluoropropene, and a Cope rearrangement of 1,1-difluoro-1,5-hexadiene provide thermodynamic data which allow the determination of a number of important group values for contributions to ΔHf0 which when combined with those determined in the preceding paper allow the calculations of ΔHf0's of most simple F-substituted hydrocarbons: d-(F)(H)>= -38.4, d(F)2>= -88.0, d)>= -103.9, = -104.9 kcal/mole.A kinetic study of the conversion of 1,1-difluoro- to 3,3-difluoro-1,5-hexadiene provided activation parameters for the process: Log A= 10.8, Ea= 33.0 kcal/mole and ΔS*= -12.2 e. u.Incremental geminal stabilizations of F and other substituents are discussed and contrasted.

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Dehydrobromination of 1,2-Dibromocyclohexane and Related Compounds by Lithium Chloride in Hexamethylphosphoric Triamide. An Improved Synthesis of 1,3-Cyclohexadiene and Some Deuterium-Labeled Analogues

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Low Valent Magnesium Chemistry with a Super Bulky β-Diketiminate Ligand

The steric bulk of the well-known DIPPBDI ligand (CH[C(CH3)N-DIPP]2, DIPP=2,6-diisopropylphenyl) was increased by replacing isopropyl for isopentyl groups. This very bulky DIPePBDI ligand could not stabilize the radical species (DIPePBDI)Mg.: reduction of (DIPePBDI)MgI with Na gave (DIPePBDI)2Mg2 with a rather long Mg-Mg bond of 3.0513(8) ?. Addition of TMEDA prior to reduction gave complex (DIPePBDI)2Mg2(C6H6), which could also be obtained as its THF adduct. It is speculated that combination of a bulky spectator ligand and TMEDA prevents dimerization of the intermediate MgI radical, which then reacts with the benzene solvent. Complex (DIPePBDI)2Mg2(C6H6), which formally contains the anti-aromatic anion C6H62?, reacted with tBuOH as a Br?nsted base to 1,3- and 1,4-cyclohexadiene and with H2 as a two electron donor to (DIPePBDI)2Mg2H2 and C6H6. It also reductively cleaved the C?F bond in fluorobenzene and gave (DIPePBDI)MgPh, (DIPePBDI)MgF, and C6H6.

Merging Halogen-Atom Transfer (XAT) and Cobalt Catalysis to Override E2-Selectivity in the Elimination of Alkyl Halides: A Mild Route towardcontra-Thermodynamic Olefins

We report here a mechanistically distinct tactic to carry E2-type eliminations on alkyl halides. This strategy exploits the interplay of α-aminoalkyl radical-mediated halogen-atom transfer (XAT) with desaturative cobalt catalysis. The methodology is high-yielding, tolerates many functionalities, and was used to access industrially relevant materials. In contrast to thermal E2 eliminations where unsymmetrical substrates give regioisomeric mixtures, this approach enables, by fine-tuning of the electronic and steric properties of the cobalt catalyst, to obtain high olefin positional selectivity. This unprecedented mechanistic feature has allowed access tocontra-thermodynamic olefins, elusive by E2 eliminations.

Challenging Thermodynamics: Hydrogenation of Benzene to 1,3-Cyclohexadiene by Ru@Pt Nanoparticles

Since the earliest reports on catalytic benzene hydrogenation, 1,3-cyclohexadiene and cyclohexene have been proposed as key intermediates. However, the former has never been obtained with remarkable selectivity. Herein, we report the first partial hydrogenation of benzene towards 1,3-cyclohexadiene under mild conditions in a catalytic biphasic system consisting of Ru@Pt nanoparticles (NPs) in ionic liquid (IL). The tandem reduction of [Ru(COD)(2-methylallyl)2] (COD=1,5-cyclooctadiene) followed by decomposition of [Pt2(dba)3] (dba=dibenzylideneacetone) in 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMI?PF6) IL under hydrogen affords core–shell Ru@Pt NPs of 2.9±0.2 nm. The hydrogenation of benzene (60 °C, 6 bar of H2) dissolved in n-heptane by these bimetallic NPs in BMI?PF6 affords 1,3-cyclohexadiene with an unprecedented 21 % selectivity at 5 % benzene conversion. Conversely, almost no 1,3-cyclohexadiene was observed when using monometallic Pt0 or Ru0 NPs under the same reaction conditions and benzene conversions. This study reveals that the selectivity is related to synergetic effects of the bimetallic composition of the catalyst material as well as to the performance under biphasic reaction conditions. It is proposed that colloidal metal catalysts in ILs and under multiphase conditions (“dynamic asymmetric mixtures”) can operate far from the thermodynamic equilibrium akin to chemically active membranes.