4668-64-8

Usage

InChI:InChI=1/C10H18O/c1-8(2)7-9-5-3-4-6-10(9)11/h8-9H,3-7H2,1-2H3

Upstream product

• 108-94-1 cyclohexanone 
• 115-11-7 isobutene 
• 2562-37-0 1-nitrocyclohexene 
• 100-99-2 triisobutylaluminum 
• 66806-69-7 2-Isobutylidenecyclohexanone 
• 72653-51-1 2-(1-phenylthio-2-methylpropyl)cyclohexanone 
• 936-67-4 2-(2-methyl-2-propenyl)cyclohexanone 
• 1116-39-8 triisobutylborane 
• 35307-20-1 (+/-)-3-chloro-2-pyrrolodinocyclohexene 
• 930-68-7 cyclohexenone 
• 77970-17-3 3-nitrocyclohex-2-ene-1-one 
• 823-45-0 2-(hydroxymethylene)cyclohexanone 
• 6651-36-1 1-(Trimethylsilyloxy)cyclohexene 
• 76059-98-8 1-isoxazolidin-2-ylcyclohexene 

Downstream Products

• 108-94-1 cyclohexanone 

Relevant academic research and scientific papers

One-pot synthesis of 2-alkyl cycloketones on bifunctional Pd/ZrO2 catalyst

2-Alkyl cycloketones are essential chemicals and intermediates for synthetic perfumes and pesticides, which are conventionally produced by multistep process including aldol condensation, separation and hydrogenation. In present work, a batch one-pot cascade approach using aldehydes and cycloketones as the raw materials, and a bifunctional Pd/ZrO2 catalyst was developed for the synthesis of 2-alkyl cycloketones, e.g., cyclohexanone and cycloheptanone. Very high aldehydes (except for paraldehyde with large steric hindrance) conversion and high yields for 2-alkyl cycloketones (e.g., 99 % of conversion for n-butanal and 76 wt.% of yield for 2-butyl cyclohexanone) were obtained at mild temperature of 140 °C. After 10 cycles of reuse, Pd/ZrO2 catalyst showed slight deactivation (ca. 5 % conversion and 10 % yield losses), due to the coke on the catalyst. However, the performance of the catalyst was completely recovered after an oxidative regeneration.

Nucleophilic α-arylation and α-alkylation of ketones by polarity inversion of N-alkoxyenamines: Entry to the umpolung reaction at the α-carbon position of carbonyl compounds

A new aspect of enamine chemistry: The formation of N-alkoxyenamines from ketones has led to an efficient umpolung reaction. The alkylation of N-alkoxyenamines with trialkylaluminum compounds proceeded smoothly and gave α-alkylated ketones (see scheme). This reaction offers a simple transformation of ketones into α-substituted ketones without the need to isolate enamines and intermediary imines.

A convenient transformation of 2-alkylidenecycloalkanones into alkyl-substituted bicyclo[ n.1.0]alkan-1-ols: Application to the synthesis of capsaicin

Treatment of 2-alkylidenecycloalkanones with hydrogen iodide in benzene and subsequent reaction of the obtained -iodo ketones with zinc dust in THF in the presence of chlorotrimethylsilane or titanium(IV) chlorotriisopropoxide led to exo- and endo-(n+3)-alkylbicyclo[n.1.0]alkan-1-ols in high yields. Cyclization of the intermediate -iodo ketones under these conditions proceeded in a moderate to good diastereoselectivity, and the resulted bicyclic cyclopropanols were easily separated by column chromatography over silica gel. exo-7- Isopropylbicyclo[4.1.0]heptan-1-ol obtained in this manner was efficiently employed as a key intermediate in the synthesis of capsaicin. Georg Thieme Verlag Stuttgart - New York.

The photochemistry of 3-nitro-2-cyclohexenone

3-Nitro-2-cyclohexenone appears to be unreactive when irradiated with ultra-violet light; no rearrangement of the nitro group to a nitrite ester or dimerization of the enone to cyclobutane adducts was observed. Cyclobutane containing photoadducts are also not formed when the electron poor alkenes, acrylonitrile or methyl acrylate are present. However, cyclobutane adducts are produced with more electron rich alkenes. The cycloadducts from reaction with cyclopentene can be reduced with zinc and acid to give a cyclooctanedione identical with the product of de Mayo reaction of cyclohexane-1,3-dione with cyclopentene. Photoadducts are also formed with 2-methylpropene; treatment of these with AIBN followed by hydrogenation yields products identical with those produced by hydrogenation of the photoadducts formed from ultra-violet light irradiation of 2-cyclohexenone with 2-methylpropene. The presence of the nitro group on the cyclohexenone increases the proportion of the head-to-head regioisomers from 13% of the adduct mixture to 63%. Copyright

Importance of Structure of α,β-Ethylenic Ketones during Their Reductive Coupling Promoted by the TiCl4-Mg Reagent

In most cases, the reductive coupling of α,β-ethylenic ketones by the TiCl4-Mg reagent leads to 1,3,5-trienes and bisallylic pinacols.Some α,β-enones of s-cis configuration, such as (+)-pulegone, show a particular reactivity: formation of dihydro ketones in the presence of tert-butyl alcohol and reductive alkylation with allylic halides or benzyl bromide.Results are accordance with a polymeric structure for the native low-valent titanium species, and in the case of some s-cis-enones, they can be explained by the intervention of a oxametallacyclopentene.

α-ALKYLATION AND α-ALKYLIDENATION OF CARBONYL COMPOUNDS BY O-SILYLATED ENOLATE PHENYLTHIOALKYLATION

For many reactions next to a carbonyl group, the use of O-silylated enolate chemistry offers improvements in yield and selectivity over the corresponding reactions of Group I metal enolates.In the case of α-alkylation of carbonyl compounds, Lewis acid (TiCl4 or ZnBr2) promoted phenylthioalkylation of O-silylated enolates 3 by α-chlorosulphides 4 (R3=H, Me, Prn, Pri, Bui, and Me3Si), followed by reductive sulphur removal by Raney nickel, 5->6, is found to be a reliable method for this synthetically important C-C bond forming step.An alternative sulphur elimination pathway via the sulphoxide, 5->7, allows the regio- and stereocontrolled α-alkylidenation of carbonyl compounds.The phenylthioalkylation reaction is applicable to ketones, aldehydes, esters, and lactones.

Efficient Conjugate Alkylation of α,β-Unsaturated Nitro Olefins by Triorganoalanes

Both trialkylaluminum (AlR3; R = Et, i-Bu) and triorganoaluminum etherates (AlR3*OEt2; R = Et, i-Bu, Ph) rapidly react with α,β-unsaturated nitro olefins to give only 1,4-monoalkylated products in high yields.The natures of substrates, the reaction conditions as well as the reagents molar ratio, do not cause significant variations on the recovered products.

One-pot Synthesis of 2-Substituted Cyclohexanones

The one-pot synthesis of 2-substituted cyclohexanones involves alkylation of 2-hydroxymethylenecyclohexanone (1) in the presence of solid KOH

α-Alkylation and α-alkylidenation of carbonyl compounds: Lewis acid-promoted phenylthioalkylation of o-silylated enolates

The O-silylated enolates of ketones, aldehydes, esters, and lactones can be phenylthioalkylated in the presence of Lewis acids; reductive or oxidative sulphur-removal gives the regiospecifically α-alkylated or alkylidenated carbonyl compounds.