Hydrate isomerism

Positionalisomeri tion occurs most often duting partial hydrogenation of unsaturated fatty acids it also occurs ia strongly basic or acidic solution and by catalysis with metal hydrides or organometaUic carbonyl complexes. Concentrated sulfuric or 70% perchloric acid treatment of oleic acid at 85°C produces y-stearolactone from a series of double-bond isomerizations, hydration, and dehydration steps (57). 

Isomerism in the Metal-ammines.—Werner claimed for the coordination theory that in certain cases isomerism should occur, that isomerism being brought about by different causes. lie divided isomerism in the ammines into five groups, namely, structure isomerism, ionisation isomerism, hydrate isomerism, polymerism, and stereoisomerism. 

Isomerism in Metal-Ammines—Structure Isomerism—Ionisation Isomerism— Hydrate Isomerism—Polymerism—Stereo-isomerism. 

Vanadium Oxydichloride, V02C12.8H20.—By the action of dilute aqueous hydrochloric acid on the two isomeric hydrates of hypo-vanadic acid, two isomeric forms of this compound have been prepared. The green hydrate gives rise to deep green crystals, and the rose hydrate to blue crystals of the same empirical composition.2 Their constitutions are a matter of doubt.3... 

We use the term substitution with scheme (138) in the sense that it is used for aromatic compounds. Addition is reserved for processes in which a saturated intermediate is formed. To observe retention, we require only that k 2) > k(3) in (138). By analogy with the SB2 reactions at a saturated carbon (Rreevoy et al., 1967), it is probable that some demetalations with acid in a polar solvent proceed in this way. Certainly, the intermediates are wholly analogous to those proposed for the isomerization, hydration, or hydrogen halide addition to alkenes. 

Equation 15.3.2 Isomerization/hydration products from alpha-pinene 30... 

Ionization isomerism Hydration isomerism Coordination isomerism Linkage isomerism Polymerization isomerism... 

In fact, Werner played such a central and almost monopolistic role in coordination chemistry that his name is virtually synonymous with the field. Even today, almost 75 years after his death in 1919, coordination compounds, particularly metal-ammines, are still colloquially called Werner complexes. The coordination theory not only provided a logical explanation for known "molecular compounds, but also predicted series of unknown compounds, whose eventual discovery lent further weight to Werner s controversial ideas. He showed how ammonia could be replaced by water or other groups, and he demonstrated the existence of transition series between ammines, double salts, and hydrates. Werner recognized and named many types of inorganic isomerism such as coordination isomerism, polymerization isomerism, ionization isomerism, hydrate isomerism, salt isomerism, coordination position isomerism, and valence isomerism. He also postulated explanations for polynuclear complexes, hydrated metal ions, hydrolysis, and acids and bases. His view of the two types of chemical... 

X-Terpineol can be considered as a hydrate of limonene. Indeed, it is available by Markovnikov addition of trifluoroacetic acid to the latter, followed by hydrolysis [141]. The alcohol has a pleasant odor similar to lilac and is a constituent of cajuput, pine, and petitgrain oil. For technical applications, it is produced from a-pinene by acid-catalyzed isomerization/hydration [142]. Hydroformylation of a-terpineol has been conducted with an unmodified Rh catalyst at 69bar (Scheme 6.45) [132]. Under the conditions applied, besides the expected cyclic carbaldehydes also a linear aldehyde with a tertiary alcoholic group were obtained. The reaction product was distilled, and the main fraction collected showed a woody and nutty aroma with minty and floral topnotes. 

Although 2 methylpropene undergoes acid catalyzed hydration m dilute sulfuric acid to form tert butyl alcohol (Section 6 10) a different reaction occurs m more concentrated solutions of sulfuric acid Rather than form the expected alkyl hydrogen sulfate (see Sec tion 6 9) 2 methylpropene is converted to a mixture of two isomeric C Hig alkenes... 

By analogy to the hydration of alkenes hydration of an alkyne is expected to yield an alcohol The kind of alcohol however would be of a special kind one m which the hydroxyl group is a substituent on a carbon-carbon double bond This type of alcohol IS called an enol (the double bond suffix ene plus the alcohol suffix ol) An important property of enols is their rapid isomerization to aldehydes or ketones under the condi tions of their formation... 

Acid catalyzed hydration (Section 9 12) Water adds to the triple bond of alkynes to yield ketones by way of an unstable enol intermediate The enol arises by Markovnikov hydration of the alkyne Enol formation is followed by rapid isomerization of the enol to a ketone... 

Hydration and Dehydration. Maleic anhydride is hydrolyzed to maleic acid with water at room temperature (68). Fumaric acid is obtained if the hydrolysis is performed at higher temperatures. Catalysts enhance formation of fumaric acid from maleic anhydride hydrolysis through maleic acid isomerization. 

Uses ndReactions. a-Pinene (8) is useful for synthesizing a wide variety of terpenoids. Hydration to pine oil, acid-catalyzed isomerization to camphene, thermal isomerization to ocimene and aHoocimene, and polymerization to terpene resins are some of its direct uses. Manufacture of linalool, nerol, and geraniol has become an economically important use of a-pinene. 

Alkynes can be hydrated in concentrated aqueous acid solutions. The initial product IS an enol, which isomerizes to the more stable ketone. 

Hydrate isomerism of TiCl3.6H20, yielding [TiCl2(H20)4]" CU as one of the isomers, has already been referred to (p. 965) and analogous complexes are formed by a variety of alcohols. Neutral complexes, [T1L3X3] have been characterized for a variety of ligands such... 

Nuclear magnetic resonance spectra of all four parent compounds have been measured and analyzed.The powerful potentialities of NMR as a tool in the study of covalent hydration, tautomerism, or protonation have, however, as yet received no consideration for the pyridopyrimidines. NMR spectra have been used to distinguish between pyrido[3,2-d]pyrimidines. and isomeric N-bridgehead compounds such as pyrimido[l,2- ]pyrimidines and in several other structural assignments (cf. 74 and 75). 

The parent compounds undergo facile hydrolysis to aminoaldehydes subsequent to the covalent hydration and reversible ring-opening as described above for pyrido[4,3-d]pjrrimidines (Section IV, B). 2-(3-Pyridyl)pyTido[2,3-d]pyrimidine undergoes hydrolysis to yield 2-aminonicotinaldehyde and nicotinamide when treated with N—HCl under reflux for 3 hours. This mechanism also probably involves a covalent hydrate. 2-Methylpyrido[4,3-d]pyrimidin-4(3H)-one, although much more stable than the parent compound, is readily hydrolyzed with dilute acid, whereas the isomeric compounds from the other three systems are stable under such conditions. 

The above method is unsatisfactory when hydration takes place at two alternative sites in the molecule, although one hydrate is usually present in only a very small proportion, at equilibrium. Which oxo compound is preferentially formed in such a case depends on the rates of oxidation at the different sites and on the rate of isomerization of the water molecule from one position to the other, hence this method does not indicate which is the thermodynamically more stable hydrate. 

At the same time, the hydration of 3(5)-phenyl-5(3)-phenylethynylpyrazole 45 in sulfuric acid in the presence of mercury acetate leads to the formation of two isomeric ketones 46 (yield 44%) and 47 (yield 3%) (68LA117) (Scheme 88). 

In aqueous solutions, the prevailing process is the primary attack of the unsubstituted nitrogen atom of alkylhydrazines at the terminal carbon atom of diacetylene with predominant formation of l-alkyl-5-methylpyrazoles (18) (73DIS). The content of isomeric l-alkyl-3-methylpyrazoles is less than 10% (GLC). In the authors opinion, this different direction of the attack at diacetylene in aqueous media is related to the hydration of alkylhydrazines and the formation of ammonium base RN" H2(0H) NH2, in which the primary amino group becomes the major nucleophilic center. 

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