70637-00-2

Usage

InChI:InChI=1/C12H14O3/c1-11-7-13-12(14-8-11,15-9-11)10-5-3-2-4-6-10/h2-6H,7-9H2,1H3

Upstream product

• 77-85-0 2-(hydroxymethyl)-2-methylpropane-1,3-diol 
• 707-07-3 orthobenzoic acid trimethyl ester 
• 173729-57-2 (3-Methyloxetan-3-yl)methyl benzoate 
• 3143-02-0 3-hydroxymethyl-3-methyloxethane 
• 90238-20-3 N,N-diethyl-α,α-difluorobenzylamine 

Downstream Products

• 58106-82-4 3-(methylthio)-6-phenyl-1,2,4,5-tetrazine 

Relevant academic research and scientific papers

Divergent Synthesis of Monosubstituted and Unsymmetrical 3,6-Disubstituted Tetrazines from Carboxylic Ester Precursors

Since tetrazines are important tools to the field of bioorthogonal chemistry, there is a need for new approaches to synthesize unsymmetrical and 3-monosubstituted tetrazines. Described here is a general, one-pot method for converting (3-methyloxetan-3-yl)methyl carboxylic esters into 3-thiomethyltetrazines. These versatile intermediates were applied to the synthesis of unsymmetrical tetrazines through Pd-catalyzed cross-coupling and in the first catalytic thioether reduction to access monosubstituted tetrazines. This method enables the development of new tetrazine compounds possessing a favorable combination of kinetics, small size, and hydrophilicity. It was applied to a broad range of aliphatic and aromatic ester precursors and to the synthesis of heterocycles including BODIPY fluorophores and biotin. In addition, a series of tetrazine probes for monoacylglycerol lipase (MAGL) were synthesized and the most reactive one was applied to the labeling of endogenous MAGL in live cells.

Facile synthesis of bicyclo orthoesters and bicyclo amide acetals using α,α-difluoroalkylamines

Bicyclo orthoesters and amide acetals were prepared from the corresponding triols or diethanolamines using α,α-difluoroalkylamines. The reaction proceeded under milder conditions than conventional methods. 4-tert-Butyl-1-(4-ethynylphenyl)trioxabicyclo[2.2.2]octane, a new class of insecticide, was prepared from a triol in three steps using a difluoroalkylamine.

Isomerization of cyclic ethers having a carbonyl functional group: New entries into different heterocyclic compounds

Oxiranes (epoxides) and oxetanes having a carbonyl functional group are chemoselectively isomerized to different heterocyclic compounds via Lewis acid-promoted 1,6- and 1,7-intramolecular nucleophilic attacks of the carbonyl oxygen on the electron-deficient carbon neighboring the oxonium oxygen: for example, cyclic imides to bicyclic acetals, esters to bicyclic orthoesters, sec-amides to 4,5-dihydrooxazole or 5,6-dihydro-4H-1,3-oxazines, and tert-amides to bicyclic acetals or azetidines. The intramolecular attack of a 1,5-positioned carbonyl oxygen predominantly results in a propagating-end isomerization polymerization. On the other hand, cyclic ethers having a 1,8- or farther positioned carbonyl group undergo conventional ring-opening polymerization. A tetrahydrofuran (oxolane) ring does not open, even with a 1,6-positioned carbonyl group.

Geminal Substituent Effects, 11. The Anomeric Effect in Orthoesters - The Concept of Geminal Pairwise Interactions for the Interpretation of Standard Enthalpies of Formation

New enthalpies of formation ΔH0f(g) are provided for the series of orthoesters 2a-2f, 3 and 4 from their enthalpies of combustion ΔH0c and their enthalpies of vaporization ΔH0vap or enthalpies of sublimation ΔH0sub.From these data and from literature data the following new thermochemical increments were calculated -1>: CH -106.4, C -103.7, and C -124.5.In addition the increment C -167.1 was calculated from literature data for ΔH0f(g) of the orthocarbonates 9a and 9b.The anomeric stabilization derived from these results and from previous results for acetals and ketals are reported in Table 3. - A new concept of additive structural increments for the quantitative analysis of the group increments of hydrocarbons, ethers, acetals, and ketals is proposed.It is shown that the increments for CH3, CH2, CH, and C groups with their different neighboring atoms (see Table 4) are determined by the number of hydrogen atoms in the group and by the number of pairwise geminal interactions between all atoms attached to the central carbon atom. - Using this procedure for orthoesters and orthocarbonates, deviations from additivity for the geminal interaction between oxygen atoms, i.e. the anomeric effect, are observed. - Keywords: Anomeric effect; Enthalpies of formation; Geminal substituents, energetic interaction of; Increments, thermochemical, of orthoesters; Group increments, interpretation of

Nature of the Slow Step in the Hydrolysis of Cyclic and Bicyclic Ortho Esters Containing 1,3-Dioxane Rings

A kinetic investigation is reported of the hydrolysis of a series of ortho esters containing 1,3-dioxane rings.Included are monocyclic 2-aryl-2-methoxy-1,3-dioxanes and bicyclic 1-aryl-4-methyl-2,6,7-trioxabicyclooctanes.Both types of compounds exh