Hydroxyl-containing compounds alcohols

Two different mechanisms have been proposed for the ROP of (di)lactones depending on the nature of the organometalhc derivatives. Metal halides, oxides, and carboxylates would act as Lewis acid catalysts in an ROP actually initiated with a hydroxyl-containing compound, such as water, alcohol, or co-hydroxy acid the later would result more hkely from the in-situ hydrolysis of the (di)lac-tone [11]. Polymerization is assumed to proceed through an insertion mechanism, the details of which depends on the metal compound (Scheme la). The most frequently encountered Lewis acid catalyst is undoubtedly the stannous 2-ethylhexanoate, currently referred to as stannous octoate (Sn(Oct)2). On the other hand, when metal alkoxides containing free p-, d-, or f- orbitals of a favo-... 

Acetic acid is an important industrial chemical. The reaction of acetic acid with hydroxyl-containing compounds, especially alcohols, results in the formation of acetate esters. The largest use of acetic acid is in the production ofvinyl acetate (Figure 1.1). Vinyl acetate can be produced through the reaction of acetylene and acetic acid. It is also produced from ethylene and acetic acid. Vinyl acetate is polymerized into polyvinyl acetate (PVA), which is used in the production of fibers, films, adhesives, and latex paints. 

It is well known 113,14 20 25> that the addition of hydroxyl-containing compounds (water, alcohols, phenols, acids) considerably promotes the interaction of epoxy compounds with amines and other nucleophilic reagents. In this case, the epoxy ring carbon atom becomes more sensitive to nucleophilic attack. The reaction proceeds through a trimolecular transition state initially suggested by Smith26 27) for the reactions of epoxy compounds with amines2... 

For the sensitive and selective detection of trace amounts of low-molecular-weight alcohols and other hydroxyl-containing compounds by means of the alkali FID, Vilceanu and Schulz [43] prepared phosphorus-containing derivatives. Derivatives 5.1 and 5.2 were prepared by the reaction with 2-chloro-l, 3,2-dioxaphosphorinane (5.3) and 2-chloro-1,3,2-dioxaphospholane (5.4), respectively, in the presence of triethylamine in benzene, which proceeds very quickly, and were particularly suitable for the determination of trace amounts of alcohols in non-alcoholic and anhydrous media. Retention indices of these derivatives of alcohols up to C5 are listed in Table 5.4. 

Thus, for instance, the formation of trimethylsilyl esters, alcohols and phenols or other hydroxyl-containing compounds not only improves chromatographic separations, but also is a method for the analysis of hydroxyl groups. The reagents used in this instance are, however, not very selective as they react with several classes of compounds. For instance, N,0-bis(trimethyl)acetamide also reacts with organic acids, amines, aromatic amides, urea derivatives and some enols [19, 20]. Therefore, this technique should desirably be used in combination with other methods or for converting involatile... 

Probably the most common preparative method involves the reaction of a sulphonyl chloride with a hydroxyl-containing compound, in the presence of a base. An extremely weak base, like sodium carbonate, may also be used in some instances353. The first reported example of this type of reaction being as early as I860354. This reaction occurs with both alcohols and phenols, in the presence of a base306-308,355-372, as shown in equation 81. 

In this respect, particular interest is attached to those studies which show a correlation between the O—H vibration frequencies measured in hydrogen-bonded associates of various hydroxyl-containing compounds (phenols, alcohols) with various donor molecules and the AH values for formation of the associates. 

The transesterification of dialkyl H-phosphonates with hydroxyl-containing compounds is accompanied by side reactions, resulting in the formation of ether compounds and H-phos-phonic acid monoalkyl esters [28,36,37]. The formation of these side products is due to the nucleophilic attack of the oxygen atom of the alcohol on the ot-carbon atom of the alkoxy group, the second electrophilic center in the molecule of dialkyl H-phosphonates. 

In hydroxyl-containing compounds with higher acidity, a transfer of proton from alcohol to amine is possible. 

A distinctive combination region of alcohols occurs between 4550 and 5550 cm" (1800-2200 nm). This broad peak, a combination of OH stretching and OH bending, has been used in a large number of quantitative analyses including hydroxyl number of polymers, alcohols in the presence of water, and ethylene vinyl alcohol content in copolymers. As shown in Figure 5.3, it is present to some extent in both dilute solution and neat spectra of hydroxyl-containing compounds. 

Germanes undergo oxidative condensation in the presence of Cu-powder with certain hydroxyl-containing compounds such as water, alcohols, phenols, carboxylic acids, and boric acid.— E ... 

We 11 Start by discussing m more detail a class of compounds already familiar to us alcohols Alcohols were introduced m Chapter 4 and have appeared regularly since then With this chapter we extend our knowledge of alcohols particularly with respect to their relationship to carbonyl containing compounds In the course of studying alco hols we shall also look at some relatives Diols are alcohols m which two hydroxyl groups (—OH) are present thiols are compounds that contain an —SH group Phenols, compounds of the type ArOH share many properties m common with alcohols but are sufficiently different from them to warrant separate discussion m Chapter 24... 

A number of ketones, pharmaceutical compounds, alcohols and hydroxy acids have also been resolved on this phase [724,765-767]. A chiral polysiloxane phase with tartramide substituents has been used for the separation of enantiomers capable of hydrogen bonding interactions with the stationary phase, such as enantiomers containing carboxylic, hydroxyl and amine functional groups [768]. 

An alcohol is an organic compound that contains the — OH functional group. Depending on the position of the hydroxyl group, an alcohol can be primary, secondary, or tertiary Figure 1.13 gives some examples of alcohols. 

Of the seven hydroxyl-containing peroxides listed in Table 2, six are tert-butylperoxy derivatives. Although the fert-butyl group kinetically stabilizes the peroxide so that its combustion enthalpy can be measured, its presence makes finding suitable reference compounds such as hydrocarbons and ethers to compare in reactions 2-9 more difficult. Reaction 6 is the only reaction for which there are enthalpy of formation data for the requisite comparison compounds. Three hydroxy peroxides, all from the same source, have remarkably consistent enthalpies of reaction 6 in both the liquid and gas phases. The mean values derived from the viciwaZ-dioxygen substimted alcohols, 2-tert-butylperoxyethanol, 2-fert-pentylperoxyethanol and 3-fert-butylperoxy-1,2-propanediol, are —304.0 + 4.1 kJmol (Iq) and —257.1 + 6.0 kJmol (g). However, these values... 

If the unknown, neutral, oxygen-containing compound does not give the class reactions for aldehydes, ketones, esters and anhydrides, it is probably either an alcohol or an ether. Alcohols are readily identified by the intense characteristic hydroxyl adsorption which occurs as a broad band in the infrared spectrum at 3600-3300 cm-1 (O—H str.). In the nuclear magnetic resonance spectrum, the adsorption by the proton in the hydroxyl group gives rise to a broad peak the chemical shift of which is rather variable the peak disappears on deuteration. 

The ability to oxidize to a corresponding hydroxyl-containing heterocycle is typical for dihydro derivatives of pyrazolo[l,5-a]pyrimidines 331 and pyri-mido[l,2- ]benzimidazoles 333. Simply dissolving these compounds in CHC13, DMF and alcohols at ambient conditions produces compounds 334 and 336 as major products together with heterocycles 340 and 342 (in some cases the latter products were not observed) [168, 293]. It is interesting to note that compounds 334-336 have a very high resistance to the action of... 

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