Waste‐free synthesis and production all across chemistry with the benefit of self‐assembled crystal packings

Abstract

A systematic mechanistic discussion of solid-state reactions (intracrystalline, intercrystalline, gas-solid thermal, or photochemical) at local molecular resolution is the basis for industrial sustainable production with waste-free solid-gas and stoichiometric solid-solid reactions at low energy requirement. These profit from the bargain of the self-assembled crystal packing. They rapidly complete to give 100% yield and require no solvent for workup. The basic requirements are thermodynamic feasibility and anisotropic molecular migrations at local pressure or suction in opposition to claims of 'minimal atomic and molecular movements' that do not know gas-solid and solid-solid reactions. Topochemical failures are settled on that experimental basis by atomic force microscopy (AFM), correlation with the crystal packing, scanning near field optical microscopy (SNOM), and nanoscratching. A general three-step phase rebuilding mechanism is derived that provides directions for all experimental situations including stereoregular polymerizations. Heat control in gas-solid equipment and solid-solid small-scale vibration or large-scale rotation ball-mills is essential. If AFM identifies (nano)liquids cooling is required. Also rare cases of surface passivation are detected by AFM. Molecular solid-state chemistry and mechanochemistry are differentiated. Solid-state techniques easily exclude moisture and are able to synthesize hitherto inaccessible compounds. Some of the latter are selected for discussion out of more than 1000 waste-free solid-state reactions in addition to already executed kg-scale productions using reasonably inexpensive starting materials with promise for industrial applications and extensions.

Suzuki cross-couplings of (hetero)aryl chlorides in the solid-state

“…In comparison to results 5 previously published for the cross-coupling of bromo-N-heteroarenes in a similar ball mill, 8 the yields obtained with the present catalyst are considerably higher, although the reaction times are longer.…”

Suzuki cross-couplings of (hetero)aryl chlorides in the solid-state

“…In comparison to results 5 previously published for the cross-coupling of bromo-N-heteroarenes in a similar ball mill, 8 the yields obtained with the present catalyst are considerably higher, although the reaction times are longer.…”

Kneading Ball‐Milling and Stoichiometric Melts for the Quantitative Derivatization of Carbonyl Compounds with Gas–Solid Recovery

“…Without heating of the mill, the milling times (1 a-h, p-q, x) ranged from 1 to 2 h. This result underlines the superiority of the heating/cooling device of the mill. [1,2,4,28] Melting points and spectral data of the reaction products 5 corresponded well with the literature values. [14] Importantly, no decomposition of the oxime hydrochloride products occurred under the specified conditions and this technique gave superior results to previous examples.…”

“…Unlike mechanochemical reactions that require mechanical impact for the breakage of intramolecular bonds for very diverse follow-up reactions, [1,20] molecular reactions with crystals are chemically driven, although at lower temperatures than the same reactions in liquids. [1,3] Milling is best suited for solid-state reactions of powders that do not melt, stick, or clot and allow a maximum contact between submicron crystallites. Temperature control, cooling below eutectics, and the use of sufficiently high-melting reagents guarantee the best results from the benefit of crystal packing.…”

More than Thousand Quantitative Wasteless Syntheses in 25 Reaction Types all Across Molecular Chemistry

“…No exception to these principles has been found: in one case from all of the numerous published ones with apparently not fitting stacking an initial phase transition gave the 4.90 Å polymorph before the polymerization started [14,16].…”

“…that also explains why these reactions come to a definite completion (zero order kinetics) in the preparative or production cases. These reactions are chemically driven; everything works without mechanical impact [16].…”

Suzuki cross-couplings of (hetero)aryl chlorides in the solid-state

“…In comparison to results 5 previously published for the cross-coupling of bromo-N-heteroarenes in a similar ball mill, 8 the yields obtained with the present catalyst are considerably higher, although the reaction times are longer.…”

Kneading Ball‐Milling and Stoichiometric Melts for the Quantitative Derivatization of Carbonyl Compounds with Gas–Solid Recovery

“…Without heating of the mill, the milling times (1 a-h, p-q, x) ranged from 1 to 2 h. This result underlines the superiority of the heating/cooling device of the mill. [1,2,4,28] Melting points and spectral data of the reaction products 5 corresponded well with the literature values. [14] Importantly, no decomposition of the oxime hydrochloride products occurred under the specified conditions and this technique gave superior results to previous examples.…”

“…Unlike mechanochemical reactions that require mechanical impact for the breakage of intramolecular bonds for very diverse follow-up reactions, [1,20] molecular reactions with crystals are chemically driven, although at lower temperatures than the same reactions in liquids. [1,3] Milling is best suited for solid-state reactions of powders that do not melt, stick, or clot and allow a maximum contact between submicron crystallites. Temperature control, cooling below eutectics, and the use of sufficiently high-melting reagents guarantee the best results from the benefit of crystal packing.…”

More than Thousand Quantitative Wasteless Syntheses in 25 Reaction Types all Across Molecular Chemistry

“…No exception to these principles has been found: in one case from all of the numerous published ones with apparently not fitting stacking an initial phase transition gave the 4.90 Å polymorph before the polymerization started [14,16].…”

“…that also explains why these reactions come to a definite completion (zero order kinetics) in the preparative or production cases. These reactions are chemically driven; everything works without mechanical impact [16].…”

Suzuki cross-couplings of (hetero)aryl chlorides in the solid-state

“…In comparison to results 5 previously published for the cross-coupling of bromo-N-heteroarenes in a similar ball mill, 8 the yields obtained with the present catalyst are considerably higher, although the reaction times are longer.…”

Kneading Ball‐Milling and Stoichiometric Melts for the Quantitative Derivatization of Carbonyl Compounds with Gas–Solid Recovery

“…Without heating of the mill, the milling times (1 a-h, p-q, x) ranged from 1 to 2 h. This result underlines the superiority of the heating/cooling device of the mill. [1,2,4,28] Melting points and spectral data of the reaction products 5 corresponded well with the literature values. [14] Importantly, no decomposition of the oxime hydrochloride products occurred under the specified conditions and this technique gave superior results to previous examples.…”

“…Unlike mechanochemical reactions that require mechanical impact for the breakage of intramolecular bonds for very diverse follow-up reactions, [1,20] molecular reactions with crystals are chemically driven, although at lower temperatures than the same reactions in liquids. [1,3] Milling is best suited for solid-state reactions of powders that do not melt, stick, or clot and allow a maximum contact between submicron crystallites. Temperature control, cooling below eutectics, and the use of sufficiently high-melting reagents guarantee the best results from the benefit of crystal packing.…”

More than Thousand Quantitative Wasteless Syntheses in 25 Reaction Types all Across Molecular Chemistry

“…No exception to these principles has been found: in one case from all of the numerous published ones with apparently not fitting stacking an initial phase transition gave the 4.90 Å polymorph before the polymerization started [14,16].…”

“…that also explains why these reactions come to a definite completion (zero order kinetics) in the preparative or production cases. These reactions are chemically driven; everything works without mechanical impact [16].…”