22082-46-8

Upstream product

• 103857-05-2 3-dimethylamino-1-(1-hydroxy-cyclohexyl)-propan-1-one; hydrochloride 
• 72252-03-0 (+/-)-2-(1-ethoxyethoxy)-but-3-enenitrile 
• 108-94-1 cyclohexanone 
• 161607-26-7 2-Ethoxy-2-vinyl-1-oxaspiro<2.5>octane 
• 161607-25-6 1-<1-(Benzotriazol-1-yl)-1-ethoxyprop-2-enyl>cyclohexanol 
• 93394-26-4 1-(1-Hydroxy-cyclohexyl)-3-phenylsulfanyl-propan-1-one 
• 22082-41-3 1-(1-Methoxypropadienyl)-cyclohexanol 

Downstream Products

• 72252-22-3 1-(1'-acetoxycyclohexyl)-2-propen-1-one 
• 1124-90-9 1-(1-hydroxycyclohexyl)propan-1-one 

Relevant academic research and scientific papers

A Novel Heterocycle-Stabilized Allylic Anion Route to Cyclopropanes, 1-Ethoxy-1-vinylethylene Oxides, 1-Hydroxyalkyl 2-Methoxyethyl Ketones, 1-Hydroxyalkyl Vinyl Ketones, β-Ethoxy-β-vinylalkyl Alcohols, γ-Lactones, and β,γ-Unsaturated Carboxylic Acids

Treatment of N-(α-ethoxyallyl)benzotriazole (8) with butyllithium followed by α,β-unsaturated esters at -78 deg C formed the 1,4-adducts 11 which underwent internal disolacement of the benzotriazolyl group at 20 deg C to give cyclopropanecarboxylic esters 14 and 15.In the presence of ZnBr2, addition of anion 13 to cyclic and methyl ketones gave 1-ethoxy-1-vinylethylene oxides 25 in good yields.Epoxides 25 were subsequently converted to 1-hydroxyalkyl 2-methoxyethyl ketones 24, 1-hydroxyalkyl vinyl ketones 26, and β-ethoxy-β-vinylalkyl alcohols 27.Treatment of anion 13 with aromatic ketones or sterically hindered aliphatic ketones produced γ-alkylated adducts 31 which were hydrolyzed to β,γ-unsaturated carboxylic acids 32 (R1,R2 = aromatic) or γ-lactones 33 (R1,R2 = aliphatic).

CONVENIENT SYNTHESIS OF VINYL KETONES VIA A NEW THREE CARBON HOMOLOGATING AGENT

Syntheses of vinyl ketones and the himachalene skeleton from 4-phenylthio-N,N-dimethylaminobutyronitrile were demonstrated.

Three-Carbon Annelations. Regiocontrolled Reactivity of Trimethylsilyl- and Ethoxyethyl-Protected Cyanohydrins. Versatile Homoenolate and Acyl Anion Equivalents

The trimethylsilyl- (2) and ethoxyethyl- (4) protected cyanohydrins of α,β-unsaturated aldehydes are utilized as three-carbon annelation reagents.Metalated reagent 2 displays exclusive α reactivity with aldehydes and ketones at -78 deg C.Metalated reagent 4 displays exclusive α reactivity at -78 deg C and exclusive γ reactivity at 0 deg C.Reagent 4 thus allows for complete regiocontrol in its addition to aldehydes and ketones which permits selective addition of either a homoenolate or an acyl anion equivalent.Metalation of the α product 11 at -78 deg C with subsequent warming to 0 deg C produces exclusively the γ product, confirming the reversible nature of the addition to the carbonyl.The derived α '-trimethylsiloxy enones 17 (R3=Me3Si), α '-hydroxy enones 17 (R3=H), α '-acetoxyenones 17 (R3=Ac), and γ-lactones 10 are useful cyclopentenone precursors.Treatment of 17 with p-TsOH in toluene at reflux produces cyclopentenones.The reaction proceeds via the postulated intermediacy of a pentadienyl cation 15 which undergoes in situ electrocyclic ring closure.