10226-28-5

Usage

Chemical Properties

Colourless Oil

Uses

2-Methyl-3-carbethoxy-5,6-dihydropyran (cas# 10226-28-5) is a compound useful in organic synthesis.

Synthesis Reference(s)

Journal of the American Chemical Society, 68, p. 1294, 1946 DOI: 10.1021/ja01211a052

Upstream product

• 141-97-9 ethyl acetoacetate 
• 109-64-8 1,3-dibromo-propane 
• 1007476-32-5 sodium ethyl acetylacetate enolate 
• 14749-45-2 ethyl 2-(3-chloropropyl)acetoacetate 
• 570-08-1 diethyl acetylmalonate 
• 109-70-6 1.3-chlorobromopropane 
• 75-03-6 ethyl iodide 

Downstream Products

• 21856-89-3 6-hydroxy-2-hexanone 
• 10226-29-6 6-Bromo-2-hexanone 
• 15719-64-9 methylammonium carbonate 
• 20210-14-4 2-(4-Bromobutyl)-2-methyl-1,3-dioxolane 
• 324012-40-0 (3aS,6aR)-1,3-Dibenzyl-4-(5-oxohexylidene)tetrahydro-1H-thieno[3,4-d]imidazole-2(3H)-one 
• 5399-21-3 6-methyl-3,4-dihydro-2H-pyran-5-carboxylic acid 
• 1643935-77-6 (E)-phenyl 3-(benzhydryloxy)-2-methyl-4-(6-methyl-3,4-dihydro-2H-pyran-5-yl)-4-oxobut-2-enoate 
• 1643935-92-5 phenyl (S)-3-hydroxy-4-(3-hydroxypropyl)-1-methyl-5-methylene-2-oxocyclopent-3-ene-1-carboxylate 
• 1417917-57-7 N-(3,4-dihydro-2H-pyrano[2,3-d]pyridazin-5-yl)-2-(3-(4-(4-methoxybenzoyl)piperidin-1-yl)-2-oxopyrrolidin-1-yl)acetamide 
• 1417917-85-1 N-(2,4-dimethoxybenzyl)-3,4-dihydro-2H-pyrano[2,3-d]pyridazin-5-amine 

Relevant academic research and scientific papers

A one-step synthesis of tetrahydropyranopyranones from carbonyl compounds

A one-step synthesis of tetrahydropyranopyranones, a ring system present in the natural product FR182877, from carbonyl compounds is described.

Catalytic enantioselective nazarov cyclization: Construction of vicinal all-carbon-atom quaternary stereocenters

The diastereoselective asymmetric synthesis of vicinal all-carbon-atom quaternary stereocenters is a challenging problem in organic synthesis for which only few solutions have been described. A catalytic asymmetric Nazarov cyclization of fully substituted dienones that provides cyclopentenone derivatives with vicinal quaternary stereocenters in high optical purity and as single diastereoisomers is now reported.

An efficient and enantioselective synthesis of d-biotin

An efficient and enantioselective synthesis of d-biotin 1 starting from cis-1,3-dibenzyl-2-imidazo-lidone-4,5-dicarboxylic acid (6) is described. The key steps are the enantioselective reduction of meso-1,2-dicarboxylic thioanhydride 8 to prepare the (3as, 6ar)- thiolactone 9 and the introduction of the C6 side chain at C-2 in 9 via a modified Grignard reaction. This novel synthesis proceeded in six steps to afford 1 with 21% overall yield.

CATHODIC SYNTHESIS OF CYCLOBUTANES

Cathodic electrolysis of compounds with an activated methylene group in the presence of 1,3-dibromopropane affords 1,1-disubstituted cyclobutanes.

Metal ion effects on the rate of intramolecular O-alkylation of the anion of ethyl(3-chloropropyl)acetoacetate

The retarding effect of alkali metal and alkaline-earth metal ions on the rate of intramolecular O-alkylation of the title compound has been thoroughly investigated in 99% aqueous Me2SO at 25°C. Rate data have been dissected into contributions of free ions (ki) and ion pairs (kip). Comparison of the present results with available data for intramolecular C-alkylation of a strictly related system, reveals that rate-depressing effects due to cation pairing turn out to be remarkably similar in the two processes, which is at variance with the expectation of a more pronounced cation dependence of the kip/ki ratios for O-alkylation than for C-alkylation.

Sensitized Photooxygenation. 3. Mechanistic Studies on the Singlet Oxygenation of 5,6-Disubstituted 3,4-Dihydro-2H-pyrans

Studies on the photooxygenation of four 5,6-disubstituted 3,4-dihydro-2H-pyrans under singlet oxygen (1Δg) conditions are presented.For the 6-methyl-substituted substrates (1a,c), two hydroperoxides (2,3) are formed as the primary products, the ratio of which is solvent dependent, with the polar solvent favoring the production of 2.Hock cleavage of 5-hydroxyperoxide 2a and 2c is observed to occur via the possible intermediacy of dioxetane 4a and 4c.For the 6-phenyl analogue (1b,d), dioxetanes are observed to form directly, which decompose to ring-cleavageproducts (5b,d) readily. 6-Hydroperoxide 3a and 3c isomerize to 4-hydroperoxide 6a and 6c thermally, which further transform to 4-alcohol 7a and epoxy alcohols 8a and 8c.The singlet oxygenation reaction shows very significant effects of substitution and solvent.Both 6-phenyl and 5-acetyl substituents and polar solvents favor the "dioxetane-mode" process.Kinetic studies by the competition method indicate that the overall reaction rate decreases with increasing temperature, giving rise to a very significant negative enthalpy of activation.The experimental data is interpreted in terms of a prior formation of a reversible exciplex, which collapses to perepoxides, and the possible involvement of a zwitterionic transition state or intermediate along the "dioxetane" path.

CYCLOALKYLATION BY THE α,ω-DIBROMIDES OF COMPOUNDS CONTAINING AN ACTIVATED METHYLENE GROUP AS A METHOD FOR THE SYNTHESIS OF 1,1-DISUBSTITUTED CYCLOALKENES

A convenient preparative method was developed for the cycloalkylation of active methylene compounds, including β-diketones, by the dibromides BrCH2(CH2)nCH2Br (n = 0,1,2) in the presence of an excess of potassium carbonate in DMSO.The reaction gives high yields for the dibromides with n = 0 and 2, whereas the formation of cyclobutanes (n=1) is complicated by O,C-alkylation.The 1-substituted 1-acylcyclopropanes undergo thermal isomerization to the corresponding dihydrofuranes.