Sustainable application of calcium carbide residue as a filler for 3D printing materials.

Industrial activity results in ton-scale production of calcium carbide and generation of a significant amount of calcium carbide residue (CCR), which is often disposed of in the environment as waste. CCR is an active chemical, and rain washes away alkali from sludge, changing the pH of soils and water and damaging the environment. In this work, we explored new opportunities for the utilization of CCR in view of the coming industrial uptake of digital design and additive technologies. Amazingly, CCR can be successfully used as a filler for the modification of 3D printed materials towards the introduction of hybrid organic/inorganic frameworks. A series of commercially available plastics (PLA, ABS, Nylon, PETG, SBS) were successfully used as matrices for CCR-based composite production with high CCR contents up to 28%. Tensile analyses showed increases in tensile strength and Young's modulus of 9% and 60%, respectively. Moreover, in comparison with the pure plastics, the CCR-based materials better maintained the digitally designed shape (lower shrinkage). Importantly, CCR-filled materials are 3D printable, making them very promising components in the building sector. Considering the amount of already available CCR stored in the environment, this material is available in large quantities in the near future for hybrid materials, and anticipated opportunities exist in the additive manufacturing sector. The involvement of CCR in practical composite materials is equally important for environmental protection and reuse of already available multiple-ton wastes.

[13 C+D] Double Labeling with Calcium Carbide: Incorporation of Two Labels in One Step.

D-labeling is a valuable tool in advanced synthetic chemistry and pharmacy. However, D-incorporation significantly complicates the identification of products. In fact, D labels are invisible in 1 H-NMR spectra and cause undesirable splitting in 13 C-NMR spectra which decreases the detectable limits. At the same time, 2 H-NMR spectra are not effective for precise identification due to low sensitivity and the absence of correlations with 1 H atoms. Here, 13 C-label was considered as an accompanying label for D-label in [13 C+D] unit for identification of D-containing sites and to track D-labels. [13 C+D]-doubly labeled vinyl derivatives and triazoles were synthesized using 13 C-labeled calcium carbide as a source of 13 C-label and deuterium oxide as a source of D-label. The reaction occurred in one-step manner accompanied with in situ doubly labeled acetylene formation. Non-labeled, mono-labeled and doubly labeled substrates were isolated in 25-80% yields.

Towards Sustainable Carbon Return from Waste to Industry via C2-Type Molecular Unit.

A general possibility of a sustainable cycle for carbon return to high-value-added products is discussed by turning wastes into acetylene. Pyrolyzed solid municipal wastes, pyrolyzed used cationic exchangers, and other waste carbon sources were studied in view of the design of a sustainable cycle for producing calcium carbide and acetylene. The yields of calcium carbide from carbon wastes were as high as those from industrial fossil raw materials (coke, charcoal, etc.). Conversion of carbon-containing wastes to calcium carbide provides an excellent opportunity to make acetylene, which is directly compatible with modern industry. Overall, the process returns carbon-containing wastes back to sustainable cycles to produce high-value-added products involving only C2-type molecules (calcium carbide and acetylene). Calcium carbide may be stored and transported, and on-demand acetylene generation is easy to realize. Upon incorporation into the waste processing route, calcium carbide may be an efficient carbon reservoir for quick industrial uptake.

Thermal Mapping of Self-Promoted Calcium Carbide Reactions for Performing Energy-Economic Processes.

The syntheses of various chemical compounds require heating. The intrinsic release of heat in exothermic processes is a valuable heat source that is not effectively used in many reactions. In this work, we assessed the released heat during the hydrolysis of an energy-rich compound, calcium carbide, and explored the possibility of its usage. Temperature profiles of carbide hydrolysis were recorded, and it was found that the heat release depended on the cosolvent and water/solvent ratio. Thus, the release of heat can be controlled and adjusted. To monitor the released heat, a special tube-in-tube reactor was assembled using joining part 3D-printed with nylon. The thermal effect of the reaction was estimated using a thermoimaging IR monitor. It was found that the kinetics of heat release are different when using mixtures of water with different solvents, and the maximum achievable temperature depends on the type of solvent and the amount of water and carbide. The possibility of using the heat released during carbide hydrolysis to initiate a chemical reaction was tested using a hydrothiolation reaction-the nucleophilic addition of thiols to acetylene. In a model experiment, the yield of the desired product with the use of heat from carbide hydrolysis was 89%, compared to 30% in this intrinsic heating, which was neglected.

3D Printing to Increase the Flexibility of the Chemical Synthesis of Biologically Active Molecules: Design of On-Demand Gas Generation Reactors.

The development of new drugs is accelerated by rapid access to functionalized and D-labeled molecules with improved activity and pharmacokinetic profiles. Diverse synthetic procedures often involve the usage of gaseous reagents, which can be a difficult task due to the requirement of a dedicated laboratory setup. Here, we developed a special reactor for the on-demand production of gases actively utilized in organic synthesis (C2H2, H2, C2D2, D2, and CO2) that completely eliminates the need for high-pressure equipment and allows for integrating gas generation into advanced laboratory practice. The reactor was developed by computer-aided design and manufactured using a conventional 3D printer with polypropylene and nylon filled with carbon fibers as materials. The implementation of the reactor was demonstrated in representative reactions with acetylene, such as atom-economic nucleophilic addition (conversions of 19-99%) and nickel-catalyzed S-functionalization (yields 74-99%). One of the most important advantages of the reactor is the ability to generate deuterated acetylene (C2D2) and deuterium gas (D2), which was used for highly significant, atom-economic and cost-efficient deuterium labeling of S,O-vinyl derivatives (yield 68-94%). Successful examples of their use in organic synthesis are provided to synthesize building blocks of heteroatom-functionalized and D-labeled biologically active organic molecules.

Calcium Carbide Looping System for Acetaldehyde Manufacturing from Virtually any Carbon Source.

A vinylation/devinylation looping system for acetaldehyde manufacturing was evaluated. Vinylation of iso-butanol with calcium carbide under solvent-free conditions was combined with hydrolysis of the resulting iso-butyl vinyl ether under slightly acidic conditions. Acetaldehyde produced by hydrolysis was collected from the reaction mixture by simple distillation, and the remaining alcohol was redirected to the vinylation step. All the inorganic co-reagents can be looped as well, and the full sequence is totally sustainable. A complete acetaldehyde manufacturing cycle was proposed on the basis of the developed procedure. The cycle was fed with calcium carbide and produced the aldehyde as a single product in a total preparative yield of 97 %. No solvents, hydrocarbons, or metal catalysts were needed to maintain the cycle. As calcium carbide in principle can be synthesized from virtually any source of carbon, the developed technology represents an excellent example of biomass and waste conversion into a valuable industrial product.

Calcium-Based Sustainable Chemical Technologies for Total Carbon Recycling.

Calcium carbide, a stable solid compound composed of two atoms of carbon and one of calcium, has proven its effectiveness in chemical synthesis, due to the safety and convenience of handling the C≡C acetylenic units. The areas of CaC2 application are very diverse, and the development of calcium-mediated approaches resolves several important challenges. This Review aims to discuss the laboratory chemistry of calcium carbide, and to go beyond its frontiers to organic synthesis, life sciences, materials and construction, carbon dioxide capturing, alloy manufacturing, and agriculture. The recyclability of calcium carbide and the availability of large-scale industrial production facilities, as well as the future possibility of fossil-resource-independent manufacturing, position this compound as a key chemical platform for sustainable development. Easy regeneration and reuse of the carbide highlight calcium-based sustainable chemical technologies as promising instruments for total carbon recycling.

Acetylene in Organic Synthesis: Recent Progress and New Uses.

Recent progress in the leading synthetic applications of acetylene is discussed from the prospect of rapid development and novel opportunities. A diversity of reactions involving the acetylene molecule to carry out vinylation processes, cross-coupling reactions, synthesis of substituted alkynes, preparation of heterocycles and the construction of a number of functionalized molecules with different levels of molecular complexity were recently studied. Of particular importance is the utilization of acetylene in the synthesis of pharmaceutical substances and drugs. The increasing interest in acetylene and its involvement in organic transformations highlights a fascinating renaissance of this simplest alkyne molecule.

Vinylation of a Secondary Amine Core with Calcium Carbide for Efficient Post-Modification and Access to Polymeric Materials.

We developed a simple and efficient strategy to access N-vinyl secondary amines of various naturally occurring materials using readily available solid acetylene reagents (calcium carbide, KF, and KOH). Pyrrole, pyrazole, indoles, carbazoles, and diarylamines were successfully vinylated in good yields. Cross-linked and linear polymers were synthesized from N-vinyl carbazoles through free radical and cationic polymerization. Post-modification of olanzapine (an antipsychotic drug substance) was successfully performed.

[3 + 2]-Cycloaddition of in Situ Generated Nitrile Imines and Acetylene for Assembling of 1,3-Disubstituted Pyrazoles with Quantitative Deuterium Labeling.

A novel synthetic methodology for the preparation of 1,3-disubstituted pyrazoles from in situ generated nitrile imines and acetylene is reported. The reactions are performed in a simple two-chamber reactor. One part of the reactor is loaded with hydrazonoyl chloride precursors of active nitrile imine species and a base. The other part is used to generate acetylene from CaC2 and water. Partitioning of the reactants improves the yields of desired pyrazoles up to 99% and simplifies their isolation to a simple procedure of solvent evaporation. The approach requires no complex equipment and utilizes inexpensive, safe, and easy to handle calcium carbide as a starting material. A model deuterium incorporation is carried out according to the developed methodology, producing a series of novel 4,5-dideuteropyrazoles with excellent deuterium enrichment. Theoretical calculations on reaction mechanism and characterization of possible intermediate structures were performed.

A Green and Sustainable Route to Carbohydrate Vinyl Ethers for Accessing Bioinspired Materials with a Unique Microspherical Morphology.

Synthesizing chemicals and materials from renewable sources is one of the main aims of modern science. Carbohydrates represent excellent renewable natural raw materials that are ecofriendly, inexpensive, and biologically compatible. A green procedure has been developed for the vinylation of carbohydrates by using readily available calcium carbide. Various carbohydrates were utilized as starting materials, resulting in mono-, di-, and tetravinyl ethers in high to excellent yields (81-92 %). The synthesized biobased vinyl ethers were utilized as monomers in free radical and cationic polymerizations. A unique combination of a smooth surface and intrinsic microcompartments was achieved in the synthesized materials. Two types of biobased materials were prepared involving microspheres and intrinsic hollow compartments in polymers. Scanning electron microscopy with built-in ion beam cutting was applied to reveal the spatial hierarchical structures in 3D space.

Calcium Carbide: A Unique Reagent for Organic Synthesis and Nanotechnology.

Acetylene, HC≡CH, is one of the primary building blocks in synthetic organic and industrial chemistry. Several highly valuable processes have been developed based on this simplest alkyne and the development of acetylene chemistry has had a paramount impact on chemical science over the last few decades. However, in spite of numerous useful possible reactions, the application of gaseous acetylene in everyday research practice is rather limited. Moreover, the practical implementation of high-pressure acetylene chemistry can be very challenging, owing to the risk of explosion and the requirement for complex equipment; special safety precautions need to be taken to store and handle acetylene under high pressure, which limit its routine use in a standard laboratory setup. Amazingly, recent studies have revealed that calcium carbide, CaC2 , can be used as an easy-to-handle and efficient source of acetylene for in situ chemical transformations. Thus, calcium carbide is a stable and inexpensive acetylene precursor that is available on the ton scale and it can be handled with standard laboratory equipment. The application of calcium carbide in organic synthesis will bring a new dimension to the powerful acetylene chemistry.