1489-56-1

Usage

Uses

Used in Chemical Synthesis:
1-METHYL-1,3-CYCLOHEXADIENE is used as a key intermediate in the synthesis of various organic compounds, particularly those with cyclohexane rings. Its presence of a double bond and a methyl group makes it a versatile building block for creating a wide range of molecules with different functional groups and properties.
Used in Pharmaceutical Industry:
1-METHYL-1,3-CYCLOHEXADIENE is used as a starting material for the production of pharmaceutical compounds. Its unique structure allows for the development of new drugs with potential therapeutic applications, such as anti-inflammatory, analgesic, or anti-cancer agents.
Used in Polymer Industry:
1-METHYL-1,3-CYCLOHEXADIENE can be used as a monomer in the polymer industry to create polymers with specific properties, such as improved strength, flexibility, or chemical resistance. These polymers can be utilized in various applications, including automotive, electronics, and packaging industries.
Used in Flavor and Fragrance Industry:
1-METHYL-1,3-CYCLOHEXADIENE may also find applications in the flavor and fragrance industry due to its potential to contribute unique scents or flavors when incorporated into complex mixtures.
Used in Research and Development:
As a synthetic intermediate, 1-METHYL-1,3-CYCLOHEXADIENE is used in research and development for exploring new chemical reactions, understanding reaction mechanisms, and developing novel synthetic routes for the production of various organic compounds.

Synthesis Reference(s)

Tetrahedron, 25, p. 4933, 1969 DOI: 10.1016/S0040-4020(01)83242-7

InChI:InChI=1/C7H10/c1-7-5-3-2-4-6-7/h2-3,5H,4,6H2,1H3

Upstream product

• 33866-90-9 4-methyl-N′-(3-methylcyclohex-2-en-1-ylidene)benzenesulfonohydrazide 
• 131179-51-6 2-methylcyclohex-2-enyl phenyl sulphone 
• 23758-27-2 1-methylcyclohex-2-en-1-ol 
• 7758-99-8 copper(II) sulfate 
• 1521-51-3 rac-3-bromocyclohexene 
• 108296-73-7 C₇H₁₂Pt(Cl)4 
• 63028-11-5 cyclohexa-1,3-dien-1-yl trifluoromethanesulfonate 
• 676-58-4 methylmagnesium chloride 
• 40648-22-4 (±)-3-bromo-1-methylcyclohex-1-ene 
• 930-68-7 cyclohexenone 
• 82166-21-0 methyl cyclohexane 
• 87413-32-9 (cyclohex-2-enylsulfonyl)benzene 
• 102860-22-0 2-phenylsulfonyl-1,3-cyclohexadiene 
• 1576-35-8 toluene-4-sulfonic acid hydrazide 

Downstream Products

• 125627-38-5 2,3-dihydroxy-3-methyl-cyclohexanone 
• 23156-00-5 1-Methyl-3-vinyl-cyclohexen 
• 92489-96-8 trans-1,4-Diacetoxy-1-methyl-2-cyclohexene 
• 18890-22-7 (R)-3-methylcyclohex-2-en-1-ol 
• 60733-10-0 (S)-seudenol 
• 62934-94-5 1-Methyl-bicyclo<2.2.2>octan-2-carbonsaeure-ethylester 
• 34069-21-1 (1S,2R)-4-methylcyclohex-3-ene-1,2-diol 

Relevant academic research and scientific papers

1,3-Dienylboronates in Diels-Alder reaction: Part III

New examples of Diels-Alder reactions involving 1,3-disubstituted 1,3-dienylboronates are reported. Various dienophiles were tested. With methyl acrylate as the dienophile, lower reaction temperature, shorter reaction time and better stereocontrol have been reached with the use of a steochiometric amount of Lewis acid EtAlCl2.

Catalytic (3+2) Palladium-Aminoallyl Cycloaddition with Conjugated Dienes

We describe the design and application of tailored aminoallyl precursors for catalytic (3+2) cycloaddition with conjugated dienes via a Pd-aminoallyl intermediate. The new cycloaddition reactions override the conventional (4+3) selectivity of aminoallyl cation cycloaddition through a sequence of Pd-allyl transfer and ring closure. A variety of highly substituted or fused pyrrolidine rings were synthesized using the cycloaddition, and can further undergo [1,3] N-to-C rearrangement to five-membered carbocycles with a different palladium catalyst. The utility of the (3+2) cycloaddition is also demonstrated by the preparation of various derivatives from the bicyclic pyrrolidine products.

Chiral Supramolecular U-Shaped Catalysts Induce the Multiselective Diels-Alder Reaction of Propargyl Aldehyde

The Diels-Alder reaction, which is a traditional [4 + 2] cycloaddition with two carbon-carbon bond formations, is one of the most powerful tools to synthesize versatile and unique six-membered rings. We show that chiral supramolecular U-shaped boron Lewis acid catalysts promote the unprecedented multiselective Diels-Alder reaction of propargyl aldehyde with cyclic dienes. Independent from the substrate control, enantio-, endo/exo-, π-facial-, regio-, site-, and substrate-selectivities could be controlled by the present U-shaped catalysts. The obtained reaction products could access the concise synthesis of chiral diene ligands and a key intermediate of (+)-sarkomycin. The results presented here might partially contribute to the development of artificial enzyme-like supramolecular catalysts for multiselective reactions, which will be able to target organic compounds that have thus far eluded synthesis.

(Guanidine)copper Complex-Catalyzed Enantioselective Dynamic Kinetic Allylic Alkynylation under Biphasic Condition

Highly enantioselective allylic alkynylation of racemic bromides under biphasic condition is furnished in this report. This approach employs functionalized terminal alkynes as pro-nucleophiles and provides 6- and 7-membered cyclic 1,4-enynes with high yields and excellent enantioselectivities (up to 96% ee) under mild conditions. Enantioretentive derivatizations highlight the synthetic utility of this transformation. Cold-spray ionization mass spectrometry (CSI-MS) and X-ray crystallography were used to identify some catalytic intermediates, which include guanidinium cuprate ion pairs and a copper-alkynide complex. A linear correlation between the enantiopurity of the catalyst and reaction product indicates the presence of a copper complex bearing a single guanidine ligand at the enantio-determining step. Further experimental and computational studies supported that the alkynylation of allylic bromide underwent an anti-SN2′ pathway catalyzed by nucleophilic cuprate species. Moreover, metal-assisted racemization of allylic bromide allowed the reaction to proceed in a dynamic kinetic fashion to afford the major enantiomer in high yield.

Synthesis and study of zeolites modified with cation metals as catalysts for the reaction of oxidative dehydrogenation of naphthenic hydrocarbons

A study of the catalytic activity of modified zeolites in the reaction of selective oxidative dehydrogenation of cyclohexane and methyl cyclohexane demonstrated that catalysts prepared based on natural clinoptilolite modified with Cu2+, Zn2+, Co2+, and Cr3+ cations showed the highest activity in the reactions considered. Specifcally, the natural zeolite, clinoptilolite, containing 0.5 wt % Co2+ and 0.25 wt % Cr3+ is an active catalyst for the reaction of oxidative dehydrogenation of methyl cyclohexane into cyclohexadiene-1,3. With the experimental data and the binding energies of the catalyst components with atomic oxygen considered, the active centers in the components of the catalyst for the reaction of oxidative dehydrogenation of cyclohexane, responsible for the formation of cyclohexadiene-1,3-cyclohexene, and benzene can be divided into groups. Principles to be used when selecting high-efficiency catalytic systems for the reaction of oxidative dehydrogenation of alicyclic hydrocarbons to the corresponding dienes are formulated.

Synthetic studies toward the kempane diterpenes. Diels-Alder additions to bicyclic dienes

Diels-Alder additions of 2,6-dimethyl-p-benzoquinone to the bicyclic dienes 24, 30 and 32 took place with very high regio-, stereo- and facial selectivity. Reduction and then alkylation of a tetracyclic adduct with 1,3-dithienium tetrafluoroborate provided compound 56, which has the correct stereochemistry at three key carbons for elaboration to the kempane diterpenes. Exploratory reactions with tricyclic model compounds and with tetracyclic adducts have been used to assess the development of the desired stereochemistry about the decalin moiety. X-Ray structures for 52, 53 and 59 were determined.

Isomer differentiation by tri-osmium cluster complexation of substituted 1,3-cyclohexadienes

A series of methyl- and dimethyl-substituted 1,3-cyclohexadienes have been prepared from their aromatic analogues via Birch reduction and subsequent isomerisation with Fe(CO)3 fragments. These ligands were reacted with [Os3(CO)10(CH3CN)2] to form tri-osmium decacarbonyl cluster compounds containing the η4-coordinated substituted 1,3-cyclohexadienes. The various isomers of the substituted dienes show a dramatic difference in their reactivity towards the tri-osmium cluster and it is likely that this is due to the steric interactions between the methyl substituents and the cluster framework, with this effect being more marked for the di-substituted ligands.

Regioselectivity in the gas - phase nucleophilic attack on O - protonated 3-methyl-2-cyclohexen-1-ol and 1-methyl-2-cyclohexen-1-ol

Our radiolytic study of the occurrence in the gas phase of concerted SN2' reactions on several open-chain allylic oxonium ions generated in the gas phase from the attack of gaseous GA+ acids (GA+ = CnH+5 (n = 1, 2), iC3H+7, and (CH3)2F+) on suitable substrates is now continued with cyclic allylic alcohols, such as 3-methyl-2-cyclohexen-1-ol (1) and 1-methyl-2-cyclohexen-1-ol (2), with both MeOH and NMe3 as neutral nucleophiles.With MeOH as the nucleophile, the substitution reaction exclusively takes place on 1 as the starting compound, whereas when the substrate is 2 it is accompanied by extensive elimination.With NMe3, only the elimination reaction is observed in the same systems.The analysis of the isomeric distribution of the substitution and elimination products allows definition of the corresponding reaction patterns.As for open-chain oxonium ions, the nucleophilic attack on O-protonated 1 and 2 is preceded by significant intramolecular interconversion.Partial unimolecular dissociation of the same ionic intermediates also takes place.After careful evaluation of the extent of these side processes, it is demonstrated that the O-protonated 1 undergoes the concerted SN2 process with MeOH almost exclusively ( 99percent).With O-protonated 2, however, the concerted SN2' pathway (84-95percent) prevails over the classical SN2 one (6-17percent).Concomitant (E2) and elimination (E2') pathways involve attack of the selected nucleophiles on the oxonium ions from 1 and 2.Their relative extent (E2'/E2:1.78-1.96 (1); 1.43-1.70 (2)) appears only slightly dependent on the nature of the ionic substrate, the nucleophile (whether MeOH or NMe3), and the leaving group (whether H2O or MeOH).The effects of both intrinsic structural factors and experimental conditions in determining the SN2'/SN2 and E2'/E2 branchings in the selected oxonium ions is discussed and compared with related gas-phase data. - Keywords: cyclohexenols; elimination reactions; gas-phase chemistry; mechanistic studies; nucleophilic substitutions

Thermal Decomposition of 2,3-Dihydro-1,4-benzodioxin and 1,2-Dimethoxybenzene

Rates and mechanisms of decomposition of 2,3-dihydro-1,4-benzodioxin (1) and 1,2-dimethoxybenzene (27) have been investigated in the gas phase near atmospheric pressure between 750 and 900 K in a tubular flow reactor in a large excess of radical trapping agents.The following rate expressions for decomposition have been determined: log kt/s-1 (1) = 15.7 - (271 kJ mol-1/2.303 RT); log kt/s-1 (27) = 15.7 - (251 kJ mol-1/2.303 RT).The main decomposition routes for 1 are the formation of o-benzoquinone (2) and 2-methyl-1,3-benzodioxole (7) through a biradical intermediate.The measured activation energy is 20 kJ mol-1 above the required C-O bond dissociation energy.Compound 2 rapidly loses CO to form cyclopenta-2,4-dien-1-one (6) which after dimerisation decomposes mainly into 3-phenylprop-2-enal (12) and indenols (14).The main product of the thermolysis of 27 is o-hydroxybenzaldehyde (33).The O-methyl bond is weakened by 16 kJ mol-1 compared to methoxybenzene as a result of the o-methoxy-substitution.