111823-35-9

Usage

Synthesis

Triphenylmethylphosphonium iodide (8.55 g, 21.2 mmoles) was weighed into a dry 100 mL round bottom flask, and 40 mL of dry tetrahydrofuran were cannulated into the reaction vessel. Phenyllithium in cyclohexane (11.8 mL of a 1.8 M solution, 21.2 mmoles) was added dropwise using an addition funnel. A color change from yellow to dark brown was observed. The mixture was stirred for 3 hrs at room temperature. 2,4-Dimethyl-3-pentanone (8) (2.4 g, 21.2 mmoles) was added slowly to the reaction mixture resulting in a color change from brown to gray. After stirring for an additional hour, a condenser was connected to the reaction vessel, and the mixture was heated at reflux for 24 hours.The mixture was allowed to cool to room temperature and extracted successively with aqueuos of 5% HCI, 10% NaHCO3, and distilled water. The organic layer was separated and dried over anhydrous MgSO4, and the drying agent was removed by gravity filtration. The solvent was removed by fractional distillation. Gas 61 chromatographic analysis indicated the presence of 1,- diisopropylethylene (-70%) (9), unreacted ketone (-20%) . The distillate was purified by column chromatography on silica gel (60-100 mesh, 2 in height and 2 in i.d.), using hexane as the eluant. The 1,1-diisopropylethylene was identified and characterized by 1 H and 13C-NMR spectroscopy.

InChI:InChI=1/C8H16/c1-6(2)8(5)7(3)4/h6-7H,5H2,1-4H3

Upstream product

• 3054-92-0 2,3,4-trimethyl-pentan-3-ol 
• 89354-72-3 1-isopropyl-1,2-dimethylpropyl acetate 
• 565-80-0 2,4-dimethylpentan-3-one 
• 7553-56-2 iodine 

Downstream Products

• 111848-52-3 {3-methyl-2-(2-propyl)-1-butene}{bis(dicyclohexylphosphino)ethane}platinum⁽⁰⁾ 
• 463-82-1 2,2-dimethylpropane 
• 1402011-50-0 N-(2-(3-(bromomethyl)-2,4-dimethylpentan-3-yloxy)-3-chloropropyl)-4-nitrobenzenesulfonamide 
• 1402011-60-2 C₁₇H₂₆BrClN₂O₅S 
• 1402011-70-4 6-(chloromethyl)-2,2-diisopropyl-4-nosylmorpholine 

Relevant academic research and scientific papers

Thermolytic Reactions of Esters. Part 12. Steric versus Polar Effects in Pyrolytic β-Elimination of Acetic Acid from (Tertiary) Alkyl Acetates

The vapour-phase pyrolysis of the crowded tertiary alkyl acetates AcOCMe2But (II) and AcOCMePri2 (III) to give acetic acid and the appropriate alkene(s) has been studied.Rates of formation of alk-1-ene and of isobutene from t-butyl acetate were compared.On this basis steric acceleration in pyrolysis of AcOR, employing known steric parameters Es' from groups R, is quantitatively analysed.Altough the steric effect can be quite substantial, the remarkable rate increase in the series AcOEt-AcOPri-AcOBut is largely due to a polar effect.A rationale is presented for the apparent inconsistency : the rate effect of α-alkylation in R is even larger than in SN1-type solvolysis of RBr, suggesting a large charge separation AcO-, R+ in the transition state for concerted β-elimination, whereas the Hammett ρ value observed for pyrolysis of e.g.AcOCH(Me)C6H4Z is only a few percent of that associated with formation of benzylic carbenium ions.

Enantioselective intramolecular oxidative aminocarbonylation of alkenylureas catalyzed by palladium-spiro bis(isoxazoline) complexes

(Chemical Equation Presented) An enantioselective synthesis of tetrahydropyrrolo[1,2-c]pyrimidine-1,3-diones via a palladium-catalyzed intramolecular oxidative aminocarbonylation is described. The carbon-carbon double bond of alkenylurea substrates has be

Alkylenation with Geminal Dialuminoalkane Reagents: The Synthesis of Olefins from Ketones

Bis(dichloroalumino)methane (BDAM, 1) has been synthesized in high yield from aluminum powder and methylene chloride by a published procedure carefully modified for safety.By the screening away of aluminum metal fine particles and the gradual addition of methylene bromide promoter over the course of reaction, a safe procedure was attained.Although 1 itself was a poor methylenating agent for ketones, its dietherate complex was distinctly more reactive.By exchanging half the halogens of 1 with Me3Al, MeMgBr, or Et3Al, two very effective methylenating agents for ketones, namely CH2(AlClMe)2 (2) and CH2(AlClEt)2 (3), were obtained.As diether ates with Et2O or THF, 2 and 3 smoothly converted a broad variety of ketones (aliphatic, alicyclic, and aromatic) into their corresponding methylene derivatives, with little or no competitive alkylation or reduction.A titanium-modified reagent, Cl2AlCH2TiCl3 (4), was also effective toward ketones, but gave only low conversions of esters to vinyl ethers.Finally, as an example of a multicarbon, alkylenating agent, the reagents 5-7 ((R2Al)2CH(CH2)4CH3, 5, R = Et; 6, R = Cl; and 7, R = Cl or Et) were examined.Good to fair yields of alkylenation were obtained with aromatic ketones, but aliphatic ketones underwent alkylation, hydride reduction, and/or aldol condension.The great influence of alkyl groups and donor solvent on the reactivity of 1-3 is briefly discussed.