15366-08-2Relevant articles and documents
Disposable cartridge concept for the on-demand synthesis of turbo Grignards, Knochel–Hauser amides, and magnesium alkoxides
Adamo, Andrea,Berton, Mateo,McQuade, D. Tyler,Sheehan, Kevin
supporting information, p. 1343 - 1356 (2020/07/10)
Magnesium organometallic reagents occupy a central position in organic synthesis. The freshness of these compounds is the key for achieving a high conversion and reproducible results. Common methods for the synthesis of Grignard reagents from metallic magnesium present safety issues and exhibit a batch-to-batch variability. Tubular reactors of solid reagents combined with solution-phase reagents enable the continuous-flow preparation of organomagnesium reagents. The use of stratified packed-bed columns of magnesium metal and lithium chloride for the synthesis of highly concentrated turbo Grignards is reported. A low-cost pod-style synthesizer prototype, which incorporates single-use prepacked perfluorinated cartridges and bags of reagents for the automated on-demand lab-scale synthesis of carbon, nitrogen, and oxygen turbo magnesium bases is presented. This concept will provide access to fresh organomagnesium reagents on a discovery scale and will do so independent from the operator’s experience in flow and/or organometallic chemistry.
Production processes for triorganomonoalkoxysilanes and triorganomonochlorosilanes
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Page/Page column 21; 22; 23-24; 26; 28; 29, (2008/06/13)
A silane containing a bulky hydrocarbon group or groups R therein and having the formula (III) [in-line-formulae]R3-(x+y)(R1)x(R2)ySi(OR3) [/in-line-formulae] can be produced by reacting a silane of the formula (I) [in-line-formulae](R1)x(R2) ySiCl3-(x+y)(OR3) [/in-line-formulae] with a Grignard reagent of the formula (II) [in-line-formulae]RMgX [/in-line-formulae] Further, a tri-organo-chlorosilane of the formula (XIIa) [in-line-formulae](R1)(R2)(R3)SiCl [/in-line-formulae] can be produced by reacting a tri-organo-silane of the formula (XIa) [in-line-formulae](R1)(R2)(R3)SiZ1 [/in-line-formulae] with hydrochloric acid. Furthermore, a tri-organo-monoalkoxysilane of the formula (XXIII) [in-line-formulae]R3-(x+y)(R1)x(R2)ySi(OR3) [/in-line-formulae] can be produced when a silane of the formula (XXI) [in-line-formulae](R1)x(R2)ySiCl4-(x+y) [/in-line-formulae] is reacted with a Grignard reagent of the formula (XXII) [in-line-formulae]RMgX [/in-line-formulae] with addition of and reaction with an alcohol or an epoxy compound during the reaction.
Use of Magnesium Anthracene * 3 THF in Synthesis: Generation of Grignard Compounds and Other Reactions with Organic Halides
Bogdanovic, Borislav,Janke, Nikolaus,Kinzelmann, Hans-Georg
, p. 1507 - 1515 (2007/10/02)
The course (a), (b), (c) (Scheme 1) of the reaction of magnesium anthracene * 3 THF (1) with organic halides (RX) is dependent on the nature of RX.With alkyl halides in THF 1 reacts as a nucleophile, whereby primary as well as secondary alkyl halides produce dialkyldihydroanthracenes (4-4'') and tertiary alkyl halides yield primarily monoalkyl-substituted dihydroanthracenes (2, 2').With bromo- and iodobenzene in THF 1 reacts predominantly as a radical with H atom abstraction from the solvent affording benzene and 9.The formation of Grignard compounds (5) and anthracene (6), originating from primary and secondary alkyl and aryl halides and 1 in toluene or ether at elevated temperatures, is not caused by the reaction of 1 but by the "active magnesium" (Mg*) formed by decomposition of 1 in these solvents.In contrast, allyl, propargyl, and benzyl halides react with 1 independently of the solvent under mild conditions to produce 5 and 6.Allyl- and the difficultly accessible allenylmagnesium chloride can be prepared in THF at -78 and 0 deg C, respectively, from the corresponding halides and ordinary Mg powder via catalytic amounts of 1.
