13566-26-2

Upstream product

• 1829-60-3 dimethyl 7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate 
• 2684-60-8 2-diazopropane 
• 762-42-5 dimethyl acetylenedicarboxylate 
• 452336-02-6 2-(o-iodophenoxy)-2-phenoxy-5,5-dimethyl-Δ³-1,3,4-oxadiazoline 
• 452336-06-0 5,5-dimethyl-2-(o-methylphenoxy)-2-phenoxy-Δ³-1,3,4-oxadiazoline 
• 351197-69-8 5,5-dimethyl-2-(p-methylphenoxy)-2-phenoxy-Δ³-1,3,4-oxadiazoline 
• 198778-00-6 9-Benzenesulfonyl-3,3-dimethyl-4,6-dioxa-1,2,9-triaza-spiro[4.4]non-1-ene 
• 947-57-9 dimethyl bicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylate 
• 92573-96-1 2-methoxy-5,5-dimethyl-2-phenyl-Δ³-1,3,4-oxadiazoline 
• 119393-21-4 2-cyclopropyl-2-methoxy-5,5-dimethyl-Δ³-1,3,4-oxadiazoline 
• 77879-49-3 2-Methoxy-2,5,5-trimethyl-Δ³-1,3,4-oxadiazoline 

Relevant academic research and scientific papers

Ortho substituent effects on transfer of aryl groups from oxygen to carbon in adducts from diaryloxycarbenes and DMAD

Diaryloxycarbenes, generated by thermolysis of 2,2-diaryloxy-5,5-dimethyl-Δ3-1,3,4-oxadiazolines in benzene, reacted with dimethyl acetylenedicarboxylate (DMAD) to afford triesters. The triesters arose by aryl-group transfer from oxygen to carb

Ipso aromatic substitution from reaction of a carbene with DMAD

An aryloxy(methoxy)carbene reacted which DMAD (dimethyl acetylenedicarboxylate) by overall ipso aromatic substitution.

Chemistry of cyclic aminooxycarbenes

A series of oxazolidin-2-ylidenes and one tetrahydro-1,3-oxazin-2-ylidene, generated by thermolysis of Δ3-1,3,4-oxadiazolines in benzene at 90 °C, were intercepted by insertion into the OH bond of phenols. In two cases the initial products rearranged to N-(2-aryloxyethyl)-N-methylformamides. The activation energy for rotation about the amide CN bond of those ultimate products was measured as 20.4 kcal/mol. The aminooxycarbenes reacted with two equivalents of methyl or phenyl isocyanate to give spiro-fused hydantoins. Major products from the reactions of the N-carbonyl carbenes with dimethyl acetylenedicarboxylate or with methyl propiolate were 2-oxazolines resulting from apparent acyl transfers from N to C in the proposed dipolar intermediates; minor products of 1:2 (carbene:trap) stoichiometry were also observed.

Photolysis of 2-Alkoxy-Δ3-1,3,4-oxadiazolines. A New Route to Diazoalkanes

2-Alkoxy-2,5,5-trialkyl-Δ3-1,3,4-oxadiazolines (2), when photolyzed in solution with 300-nm light, afford the appropriate diazoalkane (3) and ester (4) in high yield.The diazoalkanes undergo intermolecular reaction, giving rise to azines (5), or they can be trapped in situ with 1,3-dipolarophiles to afford cycloadducts (7 or 11), which can in turn be photolyzed to the corresponding cyclopropenes (8) and cyclopropanes (12), respectively.

SITE SELECTIVITY IN THE REACTIONS OF 1,3-DIPOLES WITH NORBORNADIENE DERIVATIVES

The cycloadditions of arylazides, benzonitrile oxides and diphenylnitrile imine to norbornadiene derivatives 1a-c showed varying degree of site- and stereo-selectivity.With dipolarophile 1a arylazides and benzonitrile oxides attack, preferentially, the electron-poor tetrasubstituted double bond, while in the case of 1b and 1c is the substituted double bond which enters the cycloaddition.By contrast, 2-diazopropane and C-phenyl-N-methylnitrone react with the sole tetrasubstituted double bond of 1a-c in stereo- and site-specific cycloadditions.The quantitative evaluation of the two possible reaction paths was performed by glc analysis.The compounds detected were those arising from Diels-Alder cycloreversions of the thermally labile intermediate adducts 2 and 3 (Scheme 1).The results were rationalized on the basis of a qualitative perturbation treatment which considers frontier orbital interactions only.