Tertiary compounds

Fluorinated olefins react with nitrosyl fluoride [131], dinitrogen tetroxide and fluoride ion [131], or nitrosyl chloride and fluoride ion [19S, 199] (equations 35 and 36) to afford fluoronitioso compounds Tertiary fluoroniUoso compounds are a convenient source of tertiary perfluoroalcohols... 

This transformation is not common, but given the proliferation of nitriles in organic chemistry, it is potentially quite useful. In the presence of mercuric compounds, tertiary nitriles can be reduced to the hydrocarbon with sodium cyanoborohy-... 

Boron enolates are often used for aldol reactions. Boron enolates are usually prepared from the corresponding carbonyl compounds, tertiary amine, and a boron source (e.g., dibutylboron triflates). The aldol reactions proceed via a six-membered transition state to give high diastereo-selectivity which depends upon the geometry of the boron enolates. 

For the reaction of isocyanate with active hydrogen compounds, tertiary amines or tin compounds act on... 

Perhaps the best-known method of preparing aromatic azo compounds involves the coupling of diazonium salts with sufficiently reactive aromatic compounds such as phenols, aromatic amines, phenyl ethers, the related naphthalene compounds, and even sufficiently reactive aromatic hydrocarbons. Generally, the coupling must be carried out in media which are neutral or slightly basic or which are buffered in the appropriate pH range. The reaction may also be carried out in nonaqueous media. While some primary and secondary aromatic amines initially form an A-azoamine, which may rearrange to the more usual amino-C-azo compound, tertiary amines couple in a normal manner. 

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

If no absorption bands are present in the functional group region, with the exception of those arising from carbon-hydrogen stretching modes, consider the possibilities of ethers, alkyl halides, sulphur compounds, tertiary amines and nitro compounds as detailed in the sections below. 

The acid-catalysed reaction of hydrogen azide with electrophiles, such as carbonyl compounds, tertiary alcohols or alkenes. After a rearrangement and extrusion of N2, amines, nitriles, amides or imines are produced. 

Isocyanates also react with primary and secondary amine compounds. Tertiary amines cannot react with isocyanates because they do not contain active hydrogen atoms, but they are powerful catalysts for many other isocyanate reactions. Diamines are frequently used as chain extenders and curing agents in PU manufacture. The addition of a diamine to the reaction mixture increases the overall reactivity during polymerization. The reaction between an isocyanate group and an amine results in the formation of a urea bond. The polyurea segments present in the finished PU serve to increase the potential for both covalent and hydrogen bond crosslinks within the polymer. 

Figure 9. Proposed link between pyridine nucleotide-related release from rat liver mitochondria and ADP-ribosylation in the inner mitochondrial membrane. Oxidation of mitochondrial pyridine nucleotides can be brought about by various compounds tertiary butylhydroperoxide (BuOOH) is shown (1) glutathione peroxidase (2) glutathione reductase (3) energy-linked pyridine nucleotide transhydro-genase (4) NAD glycohydrolase (5) Ca /H antiporter, modified by ADP-ribose. NAm, nicotinamide. (From Richter et al., 1985).

The diketene (31) dimerises without loss of alcohol into dehydroacetic acid in the presence of basic electron-donor compounds (tertiary amines) (Meshcheryakova et al., 1970 Polyanskii and Meshcheryakova, 1971). 

Catalysts also include accelerators for two-pack polyurethane paints (e.g., tin and zinc compounds, tertiary amines) and initiators for unsaturated polyester resins that act as radical-forming agents. 

The DMC derivative is another preferred one for aromatization for practical reasons, as the eliminated acid is methylcarbonic acid, which decomposes to methanol and carbon dioxide. This DHCD-DMC aromatization process is catalyzed by alkali metal salts and a tertiary organic nitrogen compound. Tertiary bases such as n-octylamine, the oligo bases, and other bases of low volatility are the preferred catalysts for the process at 240°C using 0.5 mol%. Moreover, the base can be removed by volatilization at 350°C after the conversion is complete. This is definitely an advantage over using metal salts (Ballard et al. 1994). 

Various catalysts are used to prepare polyurethane at a relatively low temperature and with a much faster rate of polymerisation than would be the case with an uncatalysed reaction. Catalysts may be classified into two broad categories namely, amine (basic) compounds and organometalhc complex compounds. Tertiary amine is stiU one of the most frequently used urethane catalysts. Commonly used amine catalysts are triethylenedi-amine (TEDA), l,4-diazabicyclo[2.2.2]octane (DABCO), triethylamine (TEA), dimethylethanolamine (DMEA) and dimethylcyclohexylamine (DMCHA). The catalysis mechanism of tertiary amine catalysed urethane reaction involves complexation of the amine with isocyanate groups, followed by reaction of the complex with alcohol to produce polyurethane. A list of catalysts used in polyurethane preparation is given in Table 6.4. 

There are various specific colour tests for special classes of organophosphorus compounds. Tertiary phosphines, R3P, for example, produce a rose red colour in a carbon tetrachloride solution of m-dinitrobenzene. Trialkylphosphine oxides, R3PO, and dialkylphosphinic acids, RjPfOlOH produce a blue colour in a toluene solution of nickel bromide. A chloroform solution of PhjPO reacts with a chloroform solution of iodine to form an insoluble yellow compound and so forth. 

Paulov, S. 1987. The Effect of the Antiknock Compound tertiary-Butyl Ether on the Model Species Rana temporaria, L., Biologia (Bratislava), vol. 42, pp. 185-189 (in Czechosloveikitm, English abstract). 

The reaction of isocyanates with alcohols and with water can be catalyzed by amines and by organometallic compounds. Tertiary amines, such as l,4-diazo-[2.2.2]-bicyclooctane (DABCO) or triethylamine, are particularly effective in promoting the isocyanate-water reaction, while organometallic complexes, such as dibutyltin dilaurate or stannous octoate, are very useful for catalyzing isocyanate-alcohol reactions. Numerous articles have been written on various aspects of the catalysis of isocyanate reactions and representative examples are cited in refs. 8-10. 

The uncatalyzed epoxy reaction occurs far too slovdy for high-speed integrated circuit packaging procedures, which require reaction to be essentially complete in a few minutes at temperatures around 170°C. Tighter control over the reaction selectivity leads to greater product consistency and reliability. An appropiate catalyst or combination of catalysts can speed up the reaction and provide titter control over the reaction selectivity. Many types of catalysts have been used these include acids and bases, group 5a compounds (tertiary amines, phosphines), and quatemaiy ammonium complexes,... 

---