Sulfurous acid ester halides

Sulfonic acid halides Sulfurous acid ester halides Chlorosulfinates 5 Halogenosulfinic acid esters 15... 

Esterification. Esters are formed by the reaction of ethanol with inorganic and organic acids, acid anhydrides, and acid halides. If the inorganic acid is oxygenated, eg, sulfuric acid, nitric acid, the ester has a carbon—oxygen linkage that is easily hydrolyzed (24—26). 

Cellulose sulfated using sulfamic acid degrades less than if sulfated using sulfuric acid (23). Cellulose esters of sulfamic acids are formed by the reaction of sulfamyl halides in the presence of tertiary organic bases (see Cellulose esters). 

In sulfamation, also termed IV-sulfonation, compounds of the general structure I NSC H are formed as well as their corresponding salts, acid halides, and esters. The reagents are sulfamic acid (amido—sulfuric acid), SO3—pyridine complex, S03—tertiary amine complexes, aliphatic amine—S03 adducts, and chlorine isocyanate—S03 complexes (3). 

Preparation and Uses. Boric acid can be prepared in the laboratory by acid hydrolysis of a variety of boron compounds, including halides, esters, salts, and hydrides. It is prodnced commercially by reactions of snlfinic acid with sodium borates in the United States, and with sodium and calcium borates in Turkey. In Sonth America, boric acid is prodnced by reaction of sulfuric acid with ulexite, a mixed sodium-calcium borate. Boric acid is also produced in Rnssia from the borosilicate mineral datolite. 

Toluenes substituted with chloro, bromo, fluoro, or cyano groups can be dichlorinated or dibrominated and the resulting benzal halides hydrolyzed directly to the corresponding aldehydes in the presence of calcium carbonate or sulfuric acid (50-70%). o- and p-Xylene have been converted to the corresponding dialdehydes. ° In the halogenation of certain cresols, the carbonate or acetate esters are used in order to prevent nuclear halogenation. ... 

This reaction is analogous to similar methods for the preparation of ethers (methods 113 and 116), Both simple and mixed sulfides may be made from aliphatic mercaptans or thiophenols. The sodium mercaptides are formed from the mercaptans and aqueous or alcoholic solutions of sodium hydroxide or alcoholic sodium ethoxide. Alkylation is effected by halides, alkyl sulfates, or esters of sulfonic acids. The over-all yields of sulfides are usually above 70%. r-Butyl mercaptan is alkylated directly by /-butyl alcohol in strong sulfuric acid to give /-butyl sulfide in 87% yield. ... 

Various sulfuric and phosphoric acid esters have sometimes been used instead of alcohols as starting materials for the preparation of nitriles. Of more general importance are sulfonates, particularly from methane- or p-toluene-sulfonic acid, which react in an 5N2-type substitution with cyanide ions. The most common starting materials are, as described in Section 1.8.1.2.1, alkyl halides, and if their preparation creates problems, the use of sulfonates may be advantageous. The addition of crown ethers or the... 

Moreover, and more importantly for practical purposes, functionalized olefins with nearly all kinds of substituents attached to the olefin can be dihydroxylated. Thus, acrylic acid esters, unsaturated amides and ketones, dienes, enynes, vinyl silanes, acrolein acetals, and allylic halides, as well as allylic ethers and sulfur-... 

The thiol sulfur atom is a powerful nucleophile and can participate in nucleophilic substitution at a saturated carbon atom when this is attached to a good leaving group L (Scheme 5). An illustrative example is provided by the condensation of a thiol with an acyl halide to yield the corresponding thiolocarboxylic acid ester (Scheme 5). 

Crafts process is to generate carbonium ions from the alkyl or acyl halides. It would be expected, then, that a number of other combinations of starting materials and reagents which lead to carbonium ions should be capable of effecting acylation or alkylation. Indeed we find that olefins (p. 35), alcohols (p. 36), ethers (p. 36), and esters (p. 37) can be used as starting materials for aromatic alkylation reactions in the presence of such catalysts as boron trifluoride, sulfuric acid, or anhydrous hydrogen fluoride.69 Acylations can be carried out with acids (p. 37),64 acid halides (p. 230), and acid anhydrides (p. 37). The Fries reaction65 (in which phenolic esters are converted to hydroxy aromatic ketones by means of aluminum chloride) appears to be an example of a typical acylation reaction in which the ester itself acts as the source of an acyl carbonium ion ... 

Ethyl Alcohol and Higher Alcohols. Two general processes exist for hydrating olefins to alcohols. The first is by absorption of olefins in inorganic acids, primarily sulfuric acid, followed by hydrolysis of the intermediate ester. The second process is the direct catalytic hydration of the olefin. The literature on these processes, especially as applied to ethanol and 2-propanol manufacture, is well covered in the general works listed above, and especially by Brooks (22). German work on the catalytic hydration of olefins is described by Kammermeyer and Carpenter (55). The preparation of amyl alcohols via chlorination of pentanes and hydrolysis of the halides is described by Kenyon (56). 

---