Amines, tertiary compounds

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. 

Catalysis of the flexible polyurethane foaming operation is accompHshed through the use of tertiary amine compounds, often using two different amines to balance the blowing and gelling reactions. OrganometalHc compounds, usually staimous salts, are also used to faciHtate gelling and promote final cure. 

Photoredox systems involving carbonyl compounds and amines are used in many applications. Carbonyl compounds employed include benzophenone and derivatives, a-diketones [e.g. benzil, cainphoroquinone (85),2W 291 9,10-phenanthrene quinone], and xanthone and coumarin derivatives. The amines are tertiary and must have a-hydrogens [e.g. N,A7-dimethylani 1 ine, Michler s ketone (86)]. The radicals formed are an a-aminoalkyl radical and a ketyl radical. 

One of the exciting results to come out of heterogeneous catalysis research since the early 1980s is the discovery and development of catalysts that employ hydrogen peroxide to selectively oxidize organic compounds at low temperatures in the liquid phase. These catalysts are based on titanium, and the important discovery was a way to isolate titanium in framework locations of the inner cavities of zeolites (molecular sieves). Thus, mild oxidations may be run in water or water-soluble solvents. Practicing organic chemists now have a way to catalytically oxidize benzene to phenols alkanes to alcohols and ketones primary alcohols to aldehydes, acids, esters, and acetals secondary alcohols to ketones primary amines to oximes secondary amines to hydroxyl-amines and tertiary amines to amine oxides. 

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. 

The indole- and benzindole-cyanine dyes illustrated in Scheme 6 are used by many major manufacturers in optical disk recording applications. These types of dye tend to be more light-stable than many other readily synthesized polymethine dyes. To increase the photostability, the dyes are used in combination with various types of stabilizers such as nickel dithiolato complexes and selected tertiary aromatic amine compounds.199 The application of cyanine dyes for optical storage media was primarily developed in Japan203 and several dyes and compatible stabilizers are commercially available in pure form from Japanese suppliers.199... 

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

Sensitivities of 1 ng can be achieved by demethylation of the quarternary amines to tertiary amine analogs and analysis with FID detection (Tsai, 2000). However, the lack of volatility of these compounds makes them difficult to analyze satisfactorily with GC. Most work since the last edition of the Handbook of Neurochemistry on these compounds has utilized HPLC because these substances can be analyzed without demethylating or derivatizing (Tsai, 2000). 

N2. Nayak, P. K., and Schanker, L. S., Active transport of tertiary amine compounds into bile. Amer. J. Physiol. 217, 1639-1643 (1969). 

Even low doses of scopolamine have central effects. Sedation, amnesia, and drowsiness are common during the clinical use of this drug. Large doses of scopolamine can produce all of the responses seen with atropine. Other tertiary amine compounds with muscarinic receptor blocking activity have similar central effects. 

Nicotine is a tertiary amine compound composed of a pyridine and a pyrrolidine ring. It binds selectively to acetylcholine receptors at the autonomic ganglia in the adrenal medulla at neuro-muscular junction and in the brain. It exerts a stimulating effect in the cortex and a reward effect via the pleasure system in the limbic system. 

Based on comparisons with imipramine and amitriptyline, desipramine and nortriptyline (secondary amine compounds) are comparable in efficacy with their tertiary amine parent compounds and clearly superior to placebo (Table 7-5). Clinically, they are often preferred to the tertiary amine compounds because of their less... 

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... 

Reaction CXXXII. Action of Aliphatic Halogen Compounds on Aliphatic or Aromatic Primary Amines.—Secondary, tertiary and quaternary compounds may be formed. 

The major value of the vinylic halide-olefin-amine reaction is for synthesizing polyfunctional aliphatic compounds. The compounds are constructed from the vinylic halide, the olefinic reactant with the necessary substituents, and a secondary amine (or tertiary amine if activating groups are present in the appropriate positions). It is possible to have various functional groups present in either the halide or the olefinic compound and there is a choice of which part of the molecule is the olefinic reactant and which part is the vinylic halide. 

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. 

Amines may be primary, secondary, or tertiary. The C4HnN primary amines, compounds of the type C4H9NH2, and their systematic names are... 

Amines are classified as primary, secondary, or tertiary based upon the number of carbon-containing groups that are attached to the nitrogen atom. Those amine compounds that have only one group attached to the nitrogen atom are primary, while those with two or three groups attached to the nitrogen atom are secondary and tertiary, respectively. 

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. 

The most conspicuous property of aliphatic amines, apart from their fishy smell, is their high basicity, which usually precludes N-alkylations under acidic reaction conditions (last reaction, Scheme 6.3). Hence, alkylation of amines with tertiary alkyl groups is not usually possible without the use of highly stabilized carbocations which can be formed under basic reaction conditions. Rare exceptions are N-alkyla-tions of amines via radicals (Scheme 4.2), copper-catalyzed propargylations (Scheme 6.3), and the addition of amines to some Michael acceptors and allyl palladium or iridium complexes. Better strategies for the preparation of tert-alkylamines include the addition of Grignard reagents to ketone-derived imines [13] or the reduction of tert-alkyl nitro compounds. 

The pyridinium perchlorate (212), which is the precursor of the mesoionic oxazolone (213), is formed by the action of acetic anhydride and perchloric acid on l,2-dihydro-2-oxopyridin-l-acetic acid. The mesoion (213) is chemically unstable and is generated in solution for its reactions by treatment with a tertiary amine. Compound (213) is easily substituted at C-3, and with trifluoroacetic anhydride forms the stable 3-trifluoroacetyl mesoion (70JCS(C)1485). 

The most commonly used oxidant for selenium compounds is H202. " The oxidation procedure normally involves addition of 30% H2O2 to a THF or preferably dichloromethane solution of the selenide at 0 °C. The oxidation proceeds chemoselectively and, thus, many potentially oxidizable functional groups such as alkenes, sulfides, amines, sulfoxides, tertiary alcohols, esters, lactones, nitriles and carboxylic acids remain intact. Several selenoxides including (36) and (37) were isolated by this method. ... 

All the above copolymers and mixtures of poly(MBA) with low- and high-molecular-weight tertiary amine compounds display an appreciably higher activity, as measured by the maximum of polymerization rate (Rcmax), with respect to the corresponding mixtures involving the low-molecular-weight photoinitiator MBI. These results confirm previous observations [84] concerning the homopolymers of MBA and MBVE as well as their copolymers with MtA and MtVE as compared with MBAc and MB EE (Table 21). 

Amines, hydrazines, and hydroxylamines. Amine complexes are known for tetravalent complexes of the earliest actinides (Th, U), particularly for the halides, nitrates, and oxalates. The complexes are generated either in neat amine, or by addition of amine to the parent compound in a nonaqueous solvent. Some of the known simple amine compounds are presented in Table 6. The molecular structure of ThCl4(NMe3)3 has been determined. The coordination environment about the metal is a chloride capped octahedron. A very limited number of adducts exist in which a tetravalent actinide is coordinated by a hydrazine or hydroxylamine ligand the parent compound is generally a halide or sulfate complex. Cationic metal hydrates coordinated with primary, secondary, or tertiary amines have also been isolated with acetylacetonate, nitrate, or oxalate as counterions. 

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