Organic precursors used

For some elements, there are a variety of possible precursors, sulfur for instance (Figure 11). Use of metal-organic precursors, used in MOMBE or MOVPE, are possible if they are soluble in water, or a nonaqueous solvent is used. Mixed aqueous-organic solvents could improve solubility. Overall, there would be an increased probability of carbon contamination, however. One of the benefits of using inorganic salts in aqueous solutions is that the number of constituents is limited, and thus the... 

Figure 1. Organic precursors used in this study, NAP = naphthenate, PTC = phthalocyanine, and POR = porphyrin.

The application of UV photoirradiation can also be extended when the film is not purely inorganic, which means that some of the organic precursors used in the synthesis have not been completely removed by postdeposition thermal treatment. This is in feet the case for titania and zirconia films whose synthesis requires control of the high reactivity of the transition metal alkoxides. Chelating agents or stabilizers have been used to control the reactivity of the precursors, such as acetylacetone, glycols [29], and alkanolamines [30], Just to name a few. 

Simple and Complex Organic Molecules. Using modem direct fluorination technology, the synthesis of even the most complex perfluorocarbon stmctures from hydrocarbon precursors is now possible. For example, syntheses of the first perfluoro crown ethers, perfluoro 18-crown-6, perfluoro 15-crown-5, and perfluoro 12-crown-4 (54) have been reported. Perfluoro crown ethers (54,55) are becoming important as the molecules of choice for many F-nmr imaging appHcations (56) in humans and are particularly effective in brain and spinal diagnostics when... 

Some hquid defoamers are preemulsified relatives of paste defoamers. In addition to the fatty components mentioned above, kerosene [8008-20-6] or an organic cosolvent such as 2-propanol have been used to enhance stabiUty of the oil—water emulsion and the solubiUty of the defoamer s active ingredients. These cosolvents are used less frequently as concerns increase about volatile organic emissions (VOCs) from the paper machine. Additionally, the use of ultrapure mineral oil in defoamers has become commonplace. Concern about the creation of 2,3,7,8-tetrachlorodibenzodioxin (TCDD) and 2,3,7,8-tetrachlorodibenzofuran (TCDF) in the pulping process has led to the discovery of unchlorinated precursor molecules, especially in recycled mineral oil and other organic cosolvents used in defoamer formulations (28). In 1995 the mineral oil that is used is essentially free of dibenzodioxin and dibenzofuran. In addition, owing to both the concern about these oils and the fluctuating cost of raw materials, the trend in paper machine defoamers is toward water-based defoamers (29). 

Caprolactam [105-60-2] (2-oxohexamethyleiiiiriiQe, liexaliydro-2J -a2epin-2-one) is one of the most widely used chemical intermediates. However, almost all of the aimual production of 3.0 x 10 t is consumed as the monomer for nylon-6 fibers and plastics (see Fibers survey Polyamides, plastics). Cyclohexanone, which is the most common organic precursor of caprolactam, is made from benzene by either phenol hydrogenation or cyclohexane oxidation (see Cyclohexanoland cyclohexanone). Reaction with ammonia-derived hydroxjlamine forms cyclohexanone oxime, which undergoes molecular rearrangement to the seven-membered ring S-caprolactam. 

Solution Deposition of Thin Films. Chemical methods of preparation may also be used for the fabrication of ceramic thin films (qv). MetaHo-organic precursors, notably metal alkoxides (see Alkoxides, metal) and metal carboxylates, are most frequently used for film preparation by sol-gel or metallo-organic decomposition (MOD) solution deposition processes (see Sol-GEL technology). These methods involve dissolution of the precursors in a mutual solvent control of solution characteristics such as viscosity and concentration, film deposition by spin-casting or dip-coating, and heat treatment to remove volatile organic species and induce crystaHhation of the as-deposited amorphous film into the desired stmcture. 

Essentially, carbonization entails the heating of organic precursors in the absence of air. In so doing, a solid carbon residue along with gaseous and volatile hydrocarbons is created. Bituminous coals are used to make metallurgical-grade coke while wood and other similar substances make charcoal. The condensed volatile material can be further refined to yield chermcals, pitches, or other useful commodities. 

Sol-gel primers use inorganic or metal-organic precursors (generally aluminum, silicon or titanium alkoxides) whose chemistry is closely related to the silane coupling agents discussed previously. These precursors are dissolved in alcohol, then hydrolyzed by the addition of water ... 

Thermal activation which typically takes place at high temperatures, i.e., >900°C, although the temperature can also be lowered considerably if metallo-organic precursors are used (MOCVD). 

Most metals can be deposited by MOCVD and in some cases the process is an important industrial operation. The metals most readily deposited by MOCVD are the non-transition metals. The following is a summary of the metallo-organic precursors and deposition condition presently used in development or production. 

Nitro compounds are versatile precursors for diverse functionalities. Their conversion into carbonyl compounds by the Nef reaction and into amines by reduction are the most widely used processes in organic synthesis using nitro compounds. In addition, dehydration of primary nitro compounds leads to nitrile oxides, a class of reactive 1,3-dipolar reagents. Nitro compounds are also good precursors for various nitrogen derivatives such as nitriles, oximes, hydroxylamines, and imines. These transformations of nitro compounds are well established and are used routinely in organic synthesis. 

Primary nitro compounds are good precursors for preparing nitriles and nitrile oxides (Eq. 6.31). The conversion of nitro compounds into nitrile oxides affords an important tool for the synthesis of complex natural products. Nitrile oxides are reactive 1,3-dipoles that form isoxazolines or isoxazoles by the reaction with alkenes or alky nes, respectively. The products are also important precursors for various substrates such as P-amino alcohols, P-hydroxy ketones, P-hydroxy nitriles, and P-hydroxy acids (Scheme 6.3). Many good reviews concerning nitrile oxides in organic synthesis exist some of them are listed here.50-56 Applications of organic synthesis using nitrile oxides are discussed in Section 8.2.2. 

The purpose of this book is to emphasize recent important advances in organic synthesis using nitro compounds. Historically, it was aromatic nitro compounds that were prominent in organic synthesis. In fact they have been extensively used as precursors of aromatic amines and their derivatives, and their great importance in industrial and laboratory applications has remained. 

Figure 14.2. Ultrasonic spray deposited CuInSe2 film for photovoltaic applications using mixed-metal organic precursors. XRD shows (left) the growth of nearly phase pure CuInSe2, and optical micrographs show reasonable morphologies (right).

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