Organic Synthesis in Solid State

The earlier belief that no reaction is possible without the use of a solvent is no more valid. It has been found that a large number of reactions occur in solid state without the solvent. In fact in a number of cases, such reactions occur more efficiently and with more selectivity compared to reactions carried out in solvents. Such reactions are simple to handle, reduce pollution, comparatively cheaper to operate and are especially important in industry. There is some literature available on different aspects of organic synthesis in solid state. It is believed that solvent-free organic synthesis and transformations are industrially useful and largely green. 

In the present discussion, the organic synthesis will be presented in two parts  

---

Organic Synthesis in Solid State 191 13.2.2 Hydrohalogenation (addition of HBr)... 

Organic Synthesis in Solid State 209 13.2.16.3 Synthesis of Azomethines... 

Organic Synthesis in Solid State 227 13.3.14 Synthesis of Thiadiazepines... 

When the polymer was prepared by the suspension polymerization technique, the product was crosslinked beads of unusually uniform size (see Fig. 16 for SEM picture of the beads) with hydrophobic surface characteristics. This shows that cardanyl acrylate/methacry-late can be used as comonomers-cum-cross-linking agents in vinyl polymerizations. This further gives rise to more opportunities to prepare polymer supports for synthesis particularly for experiments in solid-state peptide synthesis. Polymer supports based on activated acrylates have recently been reported to be useful in supported organic reactions, metal ion separation, etc. [198,199]. Copolymers are expected to give better performance and, hence, coplymers of CA and CM A with methyl methacrylate (MMA), styrene (St), and acrylonitrile (AN) were prepared and characterized [196,197]. 

Solid-state synthesis of /J-nitrostyrenes has been reported by Varma et al. in a process that uses readily available styrene and its substituted derivatives and inexpensive clay-supported nitrate salts, clayfen and clayan (Scheme 6.50) [170], In a simple experiment, admixed styrene with clayfen or clayan is irradiated in a MW oven (-100-110 °C, 3 min) or heated in an oil bath (-100-110 °C, 15 min). For clayan intermittent heating is recommended with 30-s intervals to maintain the temperature below 60-70 °C. Remarkably, the reaction proceeds only in solid state and leads to the formation of polymeric products in organic solvent. 

Several comprehensive reviews and books have been published, encompassing the preparation and use of Grignard reagents, their chemical and physical properties, mechanistic investigations of their formation and studies of their structures in solution and in solid state . In the present chapter, emphasis will be placed on synthetic methods for the preparation of functionalized organomagnesium compounds as well as their applications in organic synthesis. 

In this edition, we have incorporated new material in all the chapters and updated references to the literature. New sections dealing with porous solids, fullerenes and related materials, metal nitrides, metal tellurides, molecular magnets and other organic materials have been added. Under preparative strategies, we have included new types of synthesis reported in the literature, specially those based on soft chemistry routes. We have a new section covering typical results from empirical theory and electron spectroscopy. There is a major section dealing with high-temperature oxide superconductors. We hope that this edition of the book will prove to be a useful text and reference work for all those interested in solid state chemistry and materials science. 

The inclusion complex of an unstable reactant or reagent is sometimes useful in organic synthesis in the solid state. For example, very reactive anhydrous hydrazine can be trapped as a 1 1 inclusion complex with hydroquinone (24). This 1 1 inclusion compound (24) is a stable white powder that can easily be prepared by mixing aqueous hydrazine with powdered hydroquinone. Compound 24 is... 

Electronic Structure of Solids Fluorides Solid-state Chemistry Halides Solid-state Chemistry Macrocyclic Ligands Metallic Materials Deposition Metal-organic Precursors Oxides Solid-state Chemistry Periodic Table Trends in the Properties of the Elements Sol-Gel Synthesis of Solids Sohds Characterization by Powder Diffraction Structure Property Maps for Inorganic Solids Superconductivity Thin Film Synthesis of Solids. 

---