The reaction of cis-2-methoxy-4-methyl-1,3-dioxane (4) with Grignard reagents proceeds in a totally regioselective manner via rupture of the less congested C(2)-0(1) bond remote from the 4-methyl substituent. The analogous r-2-methoxy-cis-4,cis-6-dimethyi-l,3dioxane (2) is totally inert to the acti
Studies on the grignard reactions III. competitive addition-reduction in the reaction of 2,4-dimethyl-3-pentanone with the grignard reagent from bromopropane.
โ Scribed by M.J. Anteunis; R. D'Hollander
- Publisher
- Elsevier Science
- Year
- 1962
- Tongue
- French
- Weight
- 250 KB
- Volume
- 3
- Category
- Article
- ISSN
- 0040-4039
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โฆ Synopsis
Th8 competitive addition-reduction of 2,kdlmethyl-3-pento rith %.PrHgRra vas studied using the procedure described earlier'.
The reaction vas followed by quantitative vapour pba8e chromatogra phY2 analysis of the products. The Grlgnard reagent was prepared by reaction of n.propylbromlde vlth magne-81~~ In ether; and the exce88 MgBr2 vas determined a8 being the dlfferenee between a Volhard titration and a new method bared on the reaction of the Grlgnard reagent ulth benzophe-non8 (to be publirhed). Moxane ~88 added until both ana-~~18 method8 gave the 88me result. wlraa the reagent was In large excess (t (nPr)#g&gBr2 = 0.579; t ketone = O&72) the ratio of addition compound (2aethgrl-3-lropro~l-3-hexanol) to reduction compound (2&-dlme-' Part I. M. Anteunls, J.Om.Chem. Part 11. H. Anteunis, J.Oz?g.Chem. ' The Instrument ased was a A-350-B a disc Integrator. 1275 a6, 4& (1961). a, 596 (1962).
๐ SIMILAR VOLUMES
The Stereochemistry of the Grignard -Ortho Ester Reaction Revisited: Regioselective Endocyclic Cleavage in the Reaction of Grignard Reagents with cis-2-Methoxy-4-methyl-1,3-dioxane. -cis-Dioxane (Ia) selectively reacts with Grignard reagents (cf. (II)) via rupture of the less congested C(2)-O(1) bo