Hydrogen bonding acetals

The crystalline 1 1 complex of deoxycholic acid and acetic acid comprises chains of hydrogen-bonded acetic acid molecules occupying wide tunnels between... 

Hydrogen bonding. Acetic acid, HgCC—O—H, has a strong tendency to... 

Bfi and 022- However, in the second binary, intermolecular forces between unlike molecules are much stronger than those between like molecules chloroform and ethyl acetate can strongly hydrogen bond with each other but only very weakly with them-... 

FIGURE 19 2 Attrac tions between regions of positive (blue) and negative (red) electrostatic potential are responsible for intermo lecular hydrogen bonding between two molecules of acetic acid... 

Esters can participate m hydrogen bonds with substances that contain hydroxyl groups (water alcohols carboxylic acids) This confers some measure of water solubil ity on low molecular weight esters methyl acetate for example dissolves m water to the extent of 33 g/100 mL Water solubility decreases as the carbon content of the ester increases Fats and oils the glycerol esters of long chain carboxylic acids are practically insoluble m water... 

Like most other engineering thermoplastics, acetal resins are susceptible to photooxidation by oxidative radical chain reactions. Carbon—hydrogen bonds in the methylene groups are principal sites for initial attack. Photooxidative degradation is typically first manifested as chalking on the surfaces of parts. 

Halogen exchange with KF is not successful ia acetic acid (10). Hydrogen bonding of the acid hydrogen with the fluoride ion was postulated to cause acetate substitution for the haUde however, the products of dissolved KF ia acetic acid are potassium acetate and potassium bifluoride (11). Thus KF acts as a base rather than as a fluorinating agent ia acetic acid. 

Poly(vinyl acetate). The dielectric and mechanical spectra of hybrids produced by mixing a poly(vinyl acetate)—THE solution with TEOS, followed by the addition of HCl have been investigated (45). Mixtures were made which were beheved to be 0, 5, 10, 15, and 20 wt % Si02, respectively. These composites were transparent and Eourier transform infrared spectroscopy (ftir) revealed hydrogen bonding between the siUcate network and carbonyl units of the poly(vinyl acetate) (PVAc). No shift in the T of the composites from that of the pure PVAc was observed. Similarly, the activation... 

The hydroxyl groups in poly(vinyl alcohol) contribute to strong hydrogen bonding both intra- and intermolecularly, which reduces solubiUty in water. The presence of the residual acetate groups in partially hydrolyzed poly(vinyl alcohol) weakens these hydrogen bonds and allow solubiUty at lower temperatures. 

Acetate fibers are dyed usually with disperse dyes specially synthesized for these fibers. They tend to have lower molecular size (low and medium energy dyes) and contain polar groups presumably to enhance the forces of attraction by hydrogen bonding with the numerous potential sites in the cellulose acetate polymer (see Fibers cellulose esters). Other dyes can be appHed to acetates such as acid dyes with selected solvents, and azoic or ingrain dyes can be apphed especially for black colorants. However thek use is very limited. 

Isotope labeling by derivative formation with deuterated reagents is useful for the preparation of analogs such as dg-acetonides, da-acetates, da-methyl ethers, dg-methyl esters, etc. The required reagents are either commercially available or can be easily prepared. (The preparation of da-methyl iodide is described in section IX-F. Various procedures are reported in the literature for the preparation of dg-acetone, da-diazometh-ane57.i63.i73 and da-acetyl chloride. ) These reactions can be carried out under the usual conditions and they need no further discussion. A convenient procedure has been reported for the da-methylation of sterically hindered or hydrogen bonded phenolic hydroxyl functions by using da-methyl iodide and sodium hydroxide in dimethyl sulfoxide solution. This procedure should be equally applicable to the preparation of estradiol da-methyl ether derivatives. 

Systems usually fluonnated by electropositive fluorine reagents include acti-vated alkenes (enol ethers, enol acetates, silyl enol ethers, and enamines), activated aromatic systems, certain slightly activated carbon-hydrogen bonds, and selected organometallics. 

Bohlmann et al. (118-121) observed that an infrared absorption band between 2700-2800 cm is characteristic of a piperidine derivative possessing at least two axial carbon-hydrogen bonds in antiperiplanar position to the free-electron pair on the nitrogen atom. The possibility of forming an enamine by dehydrogenation can be determined by this test. Compounds which do not fulfill this condition cannot usually be dehydrogenated (50, 122,123). Thus, for example, yohimbine can be dehydrogenated by mercuric acetate,whereas reserpine or pseudoyohimbine do not react (124). The quinolizidine (125) enamines (Scheme 4), l-azabicyclo(4,3,0)-nonane, l-azabicyclo(5,3,0)decane, l-azabicyclo(5,4,0)undecane, and l-azabicyclo(5,5,0)dodecane have been prepared in this manner (112,126). 

One after the other, examine methanol dimer and acetic acid dimer. Do the hydrogen-bond lengths in these systems differ significantly from the optimum distance in water dimer Are the hydrogen-bond angles in these compounds significantly different from those in water dimer Rationalize your results. 

Factor b above is discussed in Sections II, B, 1 II, B, 4 and II, C. A hydrogen-bonded structure such as 221 can account for the facile reaction of 5-bromouracil or for the unique, so-called hydrolyzability of carboxymethylthio-azines (237). The latter may also react via the intramolecular mechanism indicated in 136. The hydrogen-bonded transition state 238 seems a reasonable explanation of the fact that 3,4,6- and 3,4,5-trichloropyridazines react with glacial acetic acid selectively to give 3-pyridazinones while other nucleophiles (alkoxides, hydrazine, ammonia, or sulfanilamide anion) react at the 4- and 5-positions. In this connection, 4-amino-3,5-dichloro-pyridazine in liquid hydrazine gives (95°, 3hr, 60%yield)the isomer-... 

When diazomethane is slowly added to excess lactam, the anions formed can interact with unreacted lactam by means of hydrogen bonds to form ion pairs similar to those formed by acetic acid-tri-ethylamine mixtures in nonpolar solvents. The methyldiazonium ion is then involved in an ion association wdth the mono-anion of a dimeric lactam which is naturally less reactive than a free lactam anion. The velocity of the Sn2 reaction, Eq. (7), is thus decreased. However, the decomposition velocity of the methyldiazonium ion, Eq. (6a), is constant and, hence, the S l character of the reaction is increased which favors 0-methylation. It is possible that this effect is also involved in kinetic dependence investigations have shown that with higher saccharin concentrations more 0-methylsaccharin is formed. 

Only the hydrophobic and steric terms were involved in these equations. There are a few differences between these equations and the corresponding equations for cyclo-dextrin-substituted phenol systems. However, it is not necessarily required that the mechanism for complexation between cyclodextrin and phenyl acetates be the same as that for cyclodextrin-phenol systems. The kinetically determined Kj values are concerned only with productive forms of inclusion complexes. The productive forms may be similar in structure to the tetrahedral intermediates of the reactions. To attain such geometry, the penetration of substituents of phenyl acetates into the cyclodextrin cavity must be shallow, compared with the cases of the corresponding phenol systems, so that the hydrogen bonding between the substituents of phenyl acetates and the C-6 hydroxyl groups of cyclodextrin may be impossible. 

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