Sulfate ester hydrolysis

Volume V (Tentative) Hydrolysis (Sulfate Esters, Carboxyl Esters, Glycoside Bonds), Phosphoro/ysis, and Hydration... 

Sulfated Natural Oils and Fats. Sulfated natural triglycerides were the first nonsoap commercial surfactants introduced in the middle of the nineteenth century. Since then sulfates of many vegetable, animal, and fish oils have been investigated (see also Fats AND FATTY oils). With its hydroxyl group and a double bond, ricinoleic acid (12-hydroxy-9,10-octadecenoic acid) is an oil constituent particularly suited for sulfation. Its sulfate is known as turkey-red oil. Oleic acid is also suited for sulfation. Esters of these acids can be sulfated with a minimum of hydrolysis of the glyceride group. Polyunsaturated acids, with several double bonds, lead to dark-colored sulfation products. The reaction with sulfuric acid proceeds through either the hydroxyl or the double bond. The sulfuric acid half ester thus formed is neutralized with caustic soda ... 

Hydrolysis. The primary functions of hydrolysis are to remove some of the acetyl groups from the cellulose triester and to reduce or remove the combined acid sulfate ester to improve the thermal stabiUty of the acetate. 

Hydrolysis of Ethyl Esters. The hydrolysis of esters (other than ethyl sulfates) is not a commercial route for producing ethanol. An indirect hydration of ethylene actually takes place during the proposed (153) hydrolysis of ethyl sulfite cataly2ed by silver sulfate. 

Figure 5.28 Enantioselective hydrolysis of sulfate esters using S. acidocaldarius.

Scheme 5.14 Chemoenzymatic enantioconvergent deracemization of secondary alcohols via hydrolysis of their sulfate esters.

Although sulfate is formed by hydrolysis of both alkyl and aryl sulfates, the pathway of degradation for aryl sulfates is controlled by the source of sulfur (Cook et al. 1999). The complex issues surrounding the hydrolysis of sulfate esters have been discussed (Kertesz 1999), and are illustrated by the number and substrate specificity of alkyl sulfatases for the surfactant 2-butyloctyl sulfate in Pseudomonas sp. strain AE-A (Ellis et al. 2002). 

Fitzgerald JW (1976) Sulfate ester formation and hydrolysis a potentially important yet often ignored aspect of the sulfur cycle of aerobic soils. Bacterial Rev 40 698-721. 

For the intermediates in base-catalyzed hydrolysis of a sulfate ester (10), pseudorotation about any of the equatorial bonds will necessarily put at least one in an apical position, which is strongly disfavored. ... 

With TFA at a lower temperature, the results clearly indicate that the hydrolysis of the tyrosine 0-sulfate ester is sufficiently low to be acceptable for preparative purposes. 

Presently, FAB-MS spectra are routinely used to characterize synthetic tyrosine O-sulfate peptides.152,57,63-671 Since partial hydrolysis of the sulfate ester occurs in the gas phase, quantification of the tyrosine O-sulfate residue by mass spectrometry is not possible, but combined with one-peak assignment in HPLC, FAB-MS represents a powerful analytical tool. On the other hand, partial hydrolysis in the gas phase excludes the presence of sul-fonated species which should be perfectly stable. In early studies the presence of such species were excluded by quantitative recovery of tyrosine upon acid hydrolysis or upon hydrolysis with arylsulfatase.1361 Recently, even MALDI-TOF-MS spectra of CCK-peptides1441 and of conotoxins a-PnIA and a-PnlB 138 were reported which show that in the positive-ion mode the [M + H-S03]+ ions represent the base peaks, while in the negative-ion mode, [M-H]-ions consistently correspond to the base peaks. In the CCK peptides intramolecular salt bridging of the sulfate hemi-ester with proximal positive charges of arginine or lysine side chains was found to reduce the extent of hydrolysis in the gas phase significantly.144,1491... 

The polyethylenimines are also effective in the cleavage of nitrophenyl-sulfate esters and nitrophenylphosphate esters. These have not yet been studied as extensively as the acyl esters, but interesting kinetic accelerations are already apparent. Nitrocatechol sulfate, for example, is very stable in aqueous solution at ambient temperature. In fact, even in the presence of 2 M imidazole no hydrolysis can be detected at room temperature. At 95°C in the presence of 2 M imidazole cleavage is barely perceptible. In contrast, a modified polyethylenimine with attached imidazole groups cleaves the sulfate ester at 20°C.34 Some kinetic parameters are compared in Table VI. It is obvious that accelerations of many orders of magnitude are effected by the polymer. 

When alkenes react with concentrated sulfuric acid, the corresponding sulfate esters (alkyl hydrogen sulfate, dialkyl sulfate) are formed. Depending on the alkene structure and the acid concentration, ester formation is accompanied by polymer formation (see Section 13.1.1). Hydrolysis of the sulfate esters allows the synthesis of alcohols. The reaction, called indirect hydration, is applied in the manufacture of ethanol and 2-propanol (see Section 6.1.3). 

Whereas the phosphetanium (Sect. 2.2) derivatives undergo base-catalyzed hydrolysis with essentially complete retention of configuration, the reaction with the related thietanium salts proceeds with complete inversion of configuration and can be described simply as a direct nucleophilic substitution 35. As far as the author is aware, no exchange evidence of the type er countered in the acid-catalyzed hydrolysis of ethylene phosphate, has been found for the cyclic sulfate esters. Consequently despite the geometrical similarities between the cyclic sulfates and phosphates and the related hybridization of the central atoms, the situation in which a finite pentacovalent intermediate sulfur species exists has not been delineated (restricting the discussion to esters). 

Side chains may be modified in a very large number of different ways.282-284 These include acetylation and other kinds of acylation (Eq. 2-12),285-287 methyl-ation (Eqs. 2-14,2-15), phosphorylation (Eq. 2-16), phosphoadenylation,288 formation of sulfate esters (Eq. 2-17),289 290 and hydrolysis (Eqs. 2-18, 2-19)291 In at least a few proteins some L-amino acid residues are converted to d- 292-294... 

Sulfotransferases917 920a transfer sulfo groups to O and N atoms of suitable acceptors (reaction type ID, Table 10-1). Usually, transfer is from the "active sulfate," 3 -phosphoadenosine 5 -phosphosuIfate (PAPS),921 whose formation is depicted in Eq. 17-38. Sulfatases catalyze hydrolysis of sulfate esters. The importance of such enzymes is demonstrated by the genetic mucopolysaccharidoses. In four of these disease-specific sulfatases that act on iduronate sulfate, heparan N-sulfate, galactose-6-sulfate, or N-acetylglu-cosamine-4-sulfate are absent. Some of these, such as heparan N-sulfatase deficiency, lead to severe mental retardation, some cause serious skeletal abnormalities, while others are mild in their effects.922... 

---