Organic Solid-State Reactions with 100% Yield

Kaupp, Gerd

doi:10.1007/b100997

Cited by 216 publications

(88 citation statements)

References 107 publications

(275 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Liquid reagents can often be solidified at sufficiently low temperatures. A short review including AFM and crystallographic aspects [30] and a comprehensive review with more than 1000 quantitative gas-solid, solid-solid, and thermal intracrystal reactions (without coverage of photoreactions; for these see the references in Section 12) all along organic reaction types [31] appeared in 2005. Mechanochemical reactions that by definition imply the use of mechanical energy for the breakage of intramolecular bonds (e.g., milling of polymers) are not treated in this review, with the exception of the milling depolymerization of paraformaldehyde.…”

Section: Mechanismmentioning

confidence: 99%

“…Their inclusions may cover nonstoichiometric ranges. Importantly, the loadings of solid-state inclusions can be higher than obtainable by crystallization from solution [31]. The imbibition of gases into organic hosts has been pioneered in the research groups of Weber [41], Toda [42], Nassimbeni [43], and Kaupp [44] (Scheme 2).…”

Section: Cocrystalsmentioning

confidence: 99%

“…It must be synthesized by rapid cooling of the component's melt. This complex completely separates into the components by a remarkable solid-state reaction within some months upon standing at room temperature [31] (reflectance spectrum in Ref. [24]).…”

Section: Cocrystalsmentioning

confidence: 99%

See 2 more Smart Citations

Organic Solid-State Reactions

Kaupp

2016

Encyclopedia of Physical Organic Chemistry, 5 Volume Set

Self Cite

View full text Add to dashboard Cite

Section: Mechanismmentioning

confidence: 99%

Section: Cocrystalsmentioning

confidence: 99%

See 1 more Smart Citation

Organic Solid-State Reactions

Kaupp

2016

Encyclopedia of Physical Organic Chemistry, 5 Volume Set

Self Cite

View full text Add to dashboard Cite

“…Quantitative analyses of relative intensities of the product, made to quantify the reaction degree of typical solid-state organic reaction (SSOR), show a precision with RSDs of around 5% to 12%, though the RSDs for direct analysis of intensities of the reactant or the product in the solid-state are obviously larger. [20,21]. To our knowledge, however, effort focusing on MS monitoring of SSOR has never been discussed heretofore.…”

mentioning

confidence: 99%

“…Shortly after the discovery of DESI, a number of ambient ionization MS methods were reported for direct analysis of solid samples, including direct analysis in real time (DART) [14], desorption atmospheric pressure chemical ionization (DAPCI) [15], matrix-assisted laser desorption electrospray ionization (MALDESI) [16], desorption atmospheric pressure photoionization (DAPPI) [17], electrospray-assisted laser desorption/ionization (ELDI) [18], and atmosphericpressure solids analysis probe (ASAP) [19]. All of these MS techniques, as well as DESI-MS, are potentially applicable for direct following solid-state organic reactions (SSORs) [20,21]. To our knowledge, however, effort focusing on MS monitoring of SSOR has never been discussed heretofore.…”

mentioning

confidence: 99%

Desorption electrospray ionization mass spectrometry for monitoring the kinetics of Baeyer-Villiger solid-state organic reactions

Xie

Lin

et al. 2009

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

Desorption electrospray ionization mass spectrometry (DESI-MS) has been used for monitoring solid-state organic reaction in ambient air, specifically the Baeyer-Villiger (BV) type reaction involving the oxidation of ketones (benzophenone or deoxybenzoin) by m-chloroperbenzoic acid (m-CPBA) in solid-state. The DESI mass spectra obtained at regular intervals during the BV reaction processes are featured, with the amount of ester products increasing as those of ketone reactants decrease. Quantitative analyses of relative intensities of the product, made to quantify the reaction degree of typical solid-state organic reaction (SSOR), show a precision with RSDs of around 5% to 12%, though the RSDs for direct analysis of intensities of the reactant or the product in the solid-state are obviously larger. [20,21]. To our knowledge, however, effort focusing on MS monitoring of SSOR has never been discussed heretofore. Here we reported the first application using DESI-MS for direct characterization of kinetics of two representative SSORs, i.e., the BaeyerVilliger (BV) [22,23] type reactions of m-chloroperbenzoic acid (m-CPBA) with benzophenone (PhCOPh, 1) or deoxybenzoin (PhCOCH 2 Ph, 2). Unexpected kinetics of the BV reactions in solid-state, including reaction rate, kinetic curve, and concentration dependence, have been revealed to be different from those of the same reactions in solution. Experimental Materials and ChemicalsBenzophenone (98%) and chloroform (99%) were purchased from Sinopharm Chemical Reagent Co. Monitoring the BV Reaction by DESI-MSThe experiments were conducted at the temperature around 22°C. About 0.2 g of ketone (1 or 2) was mixed together with 2 mol equiv of m-CPBA to afford the reactant mixture. For the concentration-dependent experiments, the reactants "concentration" (60 and 80 wt%) of 2 and m-CPBA were changed depending on the Address reprint requests to Dr.

show abstract

Solvent‐Less Organic Synthesis

Kaupp

2012

Kirk-Othmer Encyclopedia of Chemical Technology

View full text Add to dashboard Cite

Solvent‐less reactions realize 100% yield of one product without involvement of any added solvent for reaction and workup. They occur in virtually all reaction types by proper choice of the states of aggregation and reaction technique. This article is subdivided into melting, kneading, dry milling, gas–solid reactions, and gas–liquid reactions. The choice depends on the crystal packing, melting points, and eutectic temperatures during a reaction. Temperature control is essential for achieving the full benefit of crystal packing or the maximal concentration in the absence of deactivating solvation. The reaction temperatures are decreased as a result of the most favorable kinetics that lead to complete conversions and mostly avoid catalysis. An additional advantage is the direct and perfect exclusion of moisture. A decreased reaction temperature often enables staying below the eutectic temperature, or allows for obtaining otherwise nonaccessible new products that directly crystallize without involving a liquid phase. If the yield is also quantitative with the product directly crystallizing from the melt, it may be easier to perform melt reactions with slight heating. The so‐called “solvent‐free” (rather than solvent‐less) reactions are mostly not quantitative and often not free of auxiliaries, which requires solvent‐consuming chromatography and separation of the auxiliary with usually difficult recovery (eg, catalysts or supports). The hype surrounding catalysis from “green chemistry” to perform reactions in “green‐solvents” or “solvent‐free” is counterproductive. Solvent‐less reactions without catalyst and with 100% yield of pure product are the better choice. It is therefore necessary to report the broad application and variability of solvent‐less techniques, for the sake of sustainability.

show abstract

Organic Solid-State Reactions with 100% Yield

Cited by 216 publications

References 107 publications

Organic Solid-State Reactions

Organic Solid-State Reactions

Desorption electrospray ionization mass spectrometry for monitoring the kinetics of Baeyer-Villiger solid-state organic reactions

Solvent‐Less Organic Synthesis

Contact Info

Product

Resources

About