29837-07-8

Usage

Uses

Used in Fragrance and Flavoring Industry:
Cyclohexene, 4-(1,5-dimethyl-1,4-hexadienyl)-1-methyl-, (Z)is used as a key ingredient in the production of fragrances and flavorings due to its characteristic aromatic properties. Its natural presence in essential oils and plant extracts makes it a valuable component in creating authentic and appealing scents and tastes for various consumer products.
Used as a Precursor in Organic Synthesis:
Beyond its direct use in fragrances and flavorings, Cyclohexene, 4-(1,5-dimethyl-1,4-hexadienyl)-1-methyl-, (Z)also serves as a precursor in the synthesis of other organic compounds. Its unique structure and reactivity make it a versatile building block for creating a range of chemical products used across different industries.

Upstream product

• 40716-66-3 (E)-3,7,11-trimethyl-1,6,10-dodecatrien-3-ol 
• 24470-78-8 isopropyltriphenylphosphonium iodide 
• 120657-81-0 4-(4'-methylcyclohex-3'-en-1-yl)pent-3-en-1-al 
• 86105-39-7 (2S,3R)-3-(Diphenyl-phosphinoyl)-6-methyl-2-(4-methyl-cyclohex-3-enyl)-hept-5-en-2-ol 
• 89111-66-0 2(Z),6(E)-farnesyl iodide 
• 107259-61-0 catechol (Z,Z)-monofarnesyl ether 
• 107259-62-1 catechol (Z,E)-monofarnesyl ether 
• 86803-78-3 biphenol (Z,Z)-monofarnesyl ether 
• 86803-79-4 biphenol (Z,E)-monofarnesyl ether 
• 20484-24-6 1-trimethylstannyl-2-methyl-1-propene 
• 162132-42-5 (Z)-1-acetoxy-3-(4-methyl-3-cyclohexen-1-yl)-2-butene 
• 7560-64-7 4-methyl-cyclohex-3-enecarbaldehyde 
• 4342-60-3 4-methylcyclohex-3-enecarboxylic acid 
• 70286-15-6 methyl (Z)-3-(4-methyl-3-cyclohexen-1-yl)-2-butenoate 

Relevant academic research and scientific papers

Heteropoly acid catalyzed cyclization of nerolidol and farnesol: Synthesis of α-bisabolol

Heteropoly acid H3PW12O40 is an active and environmentally friendly homogeneous catalyst for the synthesis of α-bisabolol, a high-priced and highly demanded ingredient for the fragrance, cosmetic and pharmaceutical industries, starting from more abundant biomass-based sesquiterpenic alcohols. The solvent nature remarkably affects the reaction pathways and product selectivity. In acetone solutions, α-bisabolol can be obtained in 55-60% GC yields from nerolidol and 60-70% GC yields from farnesol at complete substrate conversions, which are probably the best results ever reported for these reactions. α-Bisabolol synthesized by this method contains no farnesol, which is a potentially allergenic compound and should be avoided in the commercially used α-bisabolol. This advantage is especially important because the distillative separation of α-bisabolol and farnesol is a troublesome task. The catalyst shows high turnover numbers and operates under mild nearly ambient conditions.

Structure of epi-isozizaene synthase from streptomyces coelicolor A3(2), a platform for new terpenoid cyclization templates

The X-ray crystal structure of recombinant epi-isozizaene synthase (EIZS), a sesquiterpene cyclase from Streptomyces coelicolor A3(2), has been determined at 1.60 A resolution. Specifically, the structure of wild-type EIZS is that of its closed conformation in complex with three Mg2+ ions, inorganic pyrophosphate (PPi), and the benzyltriethylammonium cation (BTAC). Additionally, the structure of D99N EIZS has been determined in an open, ligand-free conformation at 1.90 A resolution. Comparison of these two structures provides the first view of conformational changes required for substrate binding and catalysis in a bacterial terpenoid cyclase. Moreover, the binding interactions of BTAC may mimic those of a carbocation intermediate in catalysis. Accordingly, the aromatic rings of F95, F96, and F198 appear to be well-oriented to stabilize carbocation intermediates in the cyclization cascade through cation π interactions. Mutagenesis of aromatic residues in the enzyme active site results in the production of alternative sesquiterpene product arrays due to altered modes of stabilization of carbocation intermediates as well as altered templates for the cyclization of farnesyl diphosphate. Accordingly, the 1.64 A resolution crystal structure of F198A EIZS in a complex with three Mg2+ ions, PPi, and BTAC reveals an alternative binding orientation of BTAC; alternative binding orientations of a carbocation intermediate could lead to the formation of alternative products. Finally, the crystal structure of wild-type EIZS in a complex with four Hg 2+ ions has been determined at 1.90 A resolution, showing that metal binding triggers a significant conformational change of helix G to cap the active site.

PROCESS FOR REMOVING FARNESOL FROM MIXTURES WITH ALPHA-BISABOLOL

Process for esterification of farnesol in an initial mixture comprising alpha-bisabolol, farnesol and optionally other components, with the following steps: 1. Preparation or production of the initial mixture, 2. Adding (i) a transesterification catalyst and (ii) one or more compounds of formula (B) [in-line-formulae]R2YnCO2R1??(B) [/in-line-formulae] in which the following applies: R1 stands for an alkyl residue with 1 to 12 C atoms; R2 stands for hydrogen, an alkyl residue with 1 to 20 C atoms, a cycloalkyl residue with 5 to 20 C atoms, an aryl residue with 6 to 20 C atoms or a heteroaryl residue with 5 to 20 C atoms; and Y stands for CH2, CH(Me), CH(Et), C(Me)2, CH2—CH(Me), CH(Me)-CH2 or CH2—CH(Me)-CH2 and n stands for a whole number from 0 to 6; or R2 stands for a group CO2R3, R3 standing for an alkyl residue with 1 to 12 C atoms; and Y stands for CH2, CH(Me), CH(Et), C(Me)2, CH2—CH(Me), CH(Me)-CH2 or CH2—CH(Me)-CH2 and n stands for a whole number from 0 to 8, or Y stands for an optionally substituted phenyl or naphthyl ring with a total of at most four substituents on the ring, n=1 applying.

Termite trail attractants: New synthesis of racemic (E)-α-, (Z)-α- and β-bisabolenes

Racemic (E)-α-bisabolene (E)(1) was synthetized starting from 4-methyl-3-cyclohexenecarboxylic acid (3) by a reaction sequence involving the Pd(0)-catalyzed cross-coupling reaction between the (E)-2-methyl-1-alkenyltrimethylstannane 8 and 3-methyl-2-buten-1-yl acetate (9). Three different procedures, in which a common precursor was used as key intermediate, were tested for the synthesis of racemic (Z)-α-bisabolene (Z)(1). The best one, which involved the reaction between bromide 18 and lithium dialkenylcuprate 19, afforded a mixture of (Z)- and (E)-1 in a 93:7 molar ratio, respectively. Finally, racemic β-bisabolene (2) was synthetized by a simple reaction sequence involving the Zr-promoted methylenation of ketone 22 prepared from 3.

CYCLIZATION OF SOME LINEAR TERPENOLS INITIATED BY "ACTIVATED" DMSO

It was shown that the acylhydroxysulfonium salt generated in situ from DMSO and trifluoroacetic anhydride causes low-temperature cyclization of geraniol, linalool, and nerol in an aprotic medium to a mixture of p-menthane monoterpenoids, and the maximum yield is obtained in the case of the last two terpenols.A similar result was obtained for E-nerolidol.

Synthesis of cis-α-Bisabolene

The nitrile, 3-(4'-methylcyclohex-3'-en-1-yl)but-2-enylcyanide (3) was produced by the reaction of cuprous cyanide in DMSO on 3-(4'-methylcyclohex-3'-en-1-yl)but-2-enyl bromide (2).On alcoholysis, the above cyanide furnished methyl 4-(4'-methyl-cyclohex-3'-en-1-yl)pent-3-enoate (4) which was smoothly reduced to the corresponding carbinol (5).The key intermediate, 4-methylcyclohex-3'-en-1-yl)pent-3-en-1-al (6) was prepared by the oxidation of the carbinol (5) with CrO3/Py which upon Wittig reaction with isopropylidene triphenylphosphorane gave cis-α-bisabolene.

Applications of the Stereochemically-Controlled Horner-Wittig Reaction: Synthesis of Feniculin, (E)-Non-6-en-1-ol, a Pheromone of the Mediterranean Fruit Fly, (E)- and (Z)-Dec-5-en-1-ol, Tri-substituted Alkenes, and (Z)-α-Bisabolene

Stereoselective reduction of the appropriate α-diphenylphosphinoyl ketone or addition of the lithium derivative of an alkyl diphenylphospine oxide to an aldehyde or a ketone gives Horner-Wittig intermediates and hence the title compounds.

CHIRAL LEAVING GROUP: ASYMMETRIC SYNTHESIS OF LIMONENE AND BISABOLENE

The biogenetic-type asymmetric synthesis of limonene and bisabolenes is described.As model studies for the present asymmetric synthesis, the cyclization of catechol, biphenol and binaphthol mononeryl ethers 1, 4, and 5, with organoaluminium reagents are executed to furnish limonene as a major product.Since the reaction of 1, 4, and 5 has proved to proceed much faster than that of neryl phenyl ether under the similar conditions, the rate acceleration is attributed to the novel metal-anchimeric assistance of the aluminium reagents bound with the neighboring hydroxyl group for effecting the generation of the allyl cathion.This anchimeric effect is utilized for the enantioselective cyclization of (R)-(+)-1,1'-bi-2-naphthol mononeryl ether (8) upon treatment with modified aluminium reagent 9 to produce limonene with high optical purity (77percent ee).In a similar fashion, (R)-(+)-binaphtol (Z,Z)-monofarnesyl ether 16a undergoes the enantioselective cyclization to give β-bisabolene in 76percent ee.

AN ELECTROCHEMICAL METHOD SPECIFICALLY DIRECTED TO THE PREPARATION OF DL-BISABOLOL FROM DL-NEROLIDOL

A product-selective electrosynthesis of dl-bisabolol from dl-nerolidol was accomplished by a constant current electrolysis in commercial acetone containing a small amount of LiClO4

PHOTOCHEMICAL TRANSFORMATIONS-III; ORGANIC IODIDES (Part 3): GERANYL AND NERYL IODIDES AND 2(E),6(E)- AND 2(Z),6(E)-FARNESYL IODIDES

Solution photolysis of geranyl and neryl iodides, and 2(E),6(E)- and 2(Z),6(E)-farnesyl iodides has been carried out.Products arising from simple elimination as well as ?-participation are formed.Thus, both geranyl and neryl iodides furnished, besides some unidentified compounds, myrcene, cis-ocimene, limonene and terpinolene, though in different proportions.Likewise, the sesquiterpene analogues yielded different amounts of trans-β-farnesene, β-bisabolene, trans-α-bisabolene and ar-curcumene.Results have been discussed in terms of ionic intermediates.