Alcohol thiols

Nucleophilic Addition. Reagents with labile hydrogen atoms, such as alcohols, thiols, phenols, carboxyHc acids and amines, add to ketenes giving the corresponding carboxyHc acid derivatives (1) as shown ia Figure 1 (38). Not many are of practical importance, as there are better ways to such... 

Aziridinones undergo two types of selective ring opening by nucleophiles <68AG(E)25). Reaction with proton-containing nucleophiles, e.g. water, alcohols, thiols, amines and mineral acids, leads exclusively to amides (339), corresponding to an C —N bond rupture. 

Me3SiSEt. Alcohols, thiols, amines and carboxylic acids are silylated. 

Schwefel-. of sulfur, sulfur, sulfuric, sulfide of, thio-. siilfo-. -abdruck, m. sulfiir print, -alkali, n. alkali siilfide. -alkohol, m. siilfur alcohol, thiol carbon disulfide (old name), -ammonium, -ammon, n. ammonium sulfide, -antlmon, n. antimony sulfide, -antimonblei, n, antimony lead sulfide (Min.) boulanger-ite. 

Mino and Kaizerman [12] established that certain. ceric salts such as the nitrate and sulphate form very effective redox systems in the presence of organic reducing agents such as alcohols, thiols, glycols, aldehyde, and amines. Duke and coworkers [14,15] suggested the formation of an intermediate complex between the substrate and ceric ion, which subsequently is disproportionate to a free radical species. Evidence of complex formation between Ce(IV) and cellulose has been studied by several investigators [16-19]. Using alcohol the reaction can be written as follows ... 

In either the acid catalysis or the niekel carbonyl (or other metallic catalyst) method, if alcohols, thiols, amines, etc. are used instead of water, the product is the corresponding ester, thiol ester, or amide, instead of the carboxylic acid. 

Examples of name reactions can be found by first considering the nature of the starting material and product. The Wittig reaction, for instance, is in Section 199 (Alkenes from Aldehydes) and Section 207 (Alkenes frorm Ketones). The aldol condensation can be found in the chapters on difunctional compounds in Section 324 (Alcohol, Thiol-Aldehyde) and in Section 330 (Alcohol, Thiol-Ketone). 

How to Use the Book to Locate Examples of the Preparation of Difunctional Compounds. The difunctional index on p. xi gives the section and page corresponding to each difunctional product. Thus Section 327 (Alcohol, Thiol-Ester) contains examples of the preparation of hydroxyesters Section 323 (Alcohol, Thiol-Alcohol, Thiol) contains examples of the preparation of diols. 

A sulfonyl chloride group rapidly reacts with amines in the pH range of 9-10 to form stable sulfonamide bonds. Under these conditions, it also may react with tyrosine —OH groups, aliphatic alcohols, thiols, and histidine side chains. Conjugates of sulfonyl chlorides with sulf-hydryls and imidazole rings are unstable, while esters formed with alcohols are subject to nucleophilic displacement (Nillson and Mosbach, 1984 Scouten and Van der Tweel, 1984). The only stable derivative with proteins therefore is the sulfonamide, formed by reaction with e-lysine... 

From a structural point of view the OPLS results for liquids have also shown to be in accord with available experimental data, including vibrational spectroscopy and diffraction data on, for Instance, formamide, dimethylformamide, methanol, ethanol, 1-propanol, 2-methyl-2-propanol, methane, ethane and neopentane. The hydrogen bonding in alcohols, thiols and amides is well represented by the OPLS potential functions. The average root-mean-square deviation from the X-ray structures of the crystals for four cyclic hexapeptides and a cyclic pentapeptide optimized with the OPLS/AMBER model, was only 0.17 A for the atomic positions and 3% for the unit cell volumes. 

Amphoteric molecules of this type, where the acidic and basic sites are relatively close to each other but cannot interact directly, can heterolytically cleave H-X and C-X bonds where X is a halide, alkoxide, amide, alcohol, thiol, trimethylsilyl, or alkyl group.18,18a The ability to effect changes in the reactivity of borollide complexes by adjusting metal oxidation states and ligands allows fine-tuning of catalytic and other properties, which in turn advances the application of these compounds in synthesis. 

The thermolysis of isopropylidene 2-azacycloalkylidenemalonates (468, R2 = R4 = H, n = 0-2) gave unstable ketenes (1641), which were reacted with alcohols, thiols, and protic amines to afford Z-enamino ester derivatives (1642) in 63-98% yields (81TL963). 

Additional NMR information may be useful in difficult enantiomer analyses of alcohols, thiols, and primary and secondary amines. Reaction 32 illustrates the process for a chiral primary amine, RNIF, undergoing N-substitution with chiral reagent 185. Besides the 31P NMR spectra of the diasteroisomers 186, also 1H, 13C and 19F spectra may be taken. Addition of sulfur or selenium to the NMR tube will afford diasteroisomers 187, for which the corresponding spectra can also be taken397. 

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